CN116387463A - Preparation method and application of three-dimensional self-supporting composite lithium anode - Google Patents
Preparation method and application of three-dimensional self-supporting composite lithium anode 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
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Abstract
The invention discloses a preparation method and application of a three-dimensional self-supporting composite lithium anode. The modification method comprises the following steps: step 1: carrying out lithium-philic nitriding pretreatment on the self-supporting structure to obtain a three-dimensional self-supporting electrode with uniformly distributed lithium-philic sites; step 2: pre-storing lithium on the lithium-philic three-dimensional self-supporting electrode by an impregnation method or an electrochemical plating method to obtain a three-dimensional composite lithium anode; according to the invention, the three-dimensional porous substrate and the nitriding artificial SEI layer are effectively fused, the dissolution/deposition behavior of lithium ions in the battery is regulated and controlled, and the composite negative electrode is applied to a lithium metal secondary battery, so that a usable space is provided for lithium deposition, and volume deformation is buffered; inducing lithium ion to deposit homogeneously, inhibiting dendrite formation, maintaining high lithium depositing and eliminating reversibility and raising the cycling stability of the composite lithium metal negative electrode. The preparation method is simple, eliminates the traditional ammonia nitriding method, is environment-friendly, has strong operability, is suitable for large-scale production, and has good application prospect.
Description
Technical Field
The invention relates to the field of lithium ion battery anode materials and electrochemistry, in particular to a preparation method and application of a three-dimensional self-supporting composite lithium anode.
Background
Environmental friendly energy storage devices, including Lithium Ion Batteries (LIBs), have attracted considerable attention. LIB is still unavailable as a primary power source for consumer portable electronic productsThe method meets the requirements of other applications, such as mobility, for which higher specific energies and energy densities are highly desirable. These characteristics are determined by the capacity and operating voltage of the electrodes. For commercial lithium ion batteries relying on cobalt-based intercalation anodes and graphite cathodes, the specific energy density may actually exceed 250Wh kg -1 Although approaching the theoretical upper limit soon, the electric vehicle is still far below the expected value of high-energy equipment, and the limit of the driving mileage of the electric vehicle cannot be overcome. Development of high capacity cathode materials, such as lithium (Li) (or superlithium) rich cathodes and other high capacity cathode materials, and matching corresponding cathodes is an important strategy to increase the energy density of LIBs.
Lithium metal has an ultrahigh theoretical specific capacity (3860 mAh g) -1 (ii)) and the lowest electrochemical potential (-3.04V compared to a standard hydrogen electrode), and can be paired with a different cathode material (e.g., based on intercalation (e.g., liFePO) 4 ,LiNi x Co y Mn 1-x-y O 2 ) Or cathodes based on multiple electron conversion (e.g. Li-S or Li-O 2 Batteries), achieving different levels of energy density, is considered an ideal choice for large-scale energy storage systems, and has received great attention.
Unfortunately, the common problems of lithium cathodes in lithium metal batteries include uncontrolled dendrite growth, infinite volume deformation, low coulombic efficiency, poor cycle performance, especially dendrite lithium growth, which in severe cases can puncture the separator, leading to direct contact of the cathode with the positive electrode, resulting in internal shorting of the battery and failure, limiting the practical application of lithium metal as a negative electrode for lithium metal secondary batteries. In order to solve the above problems, inhibition of dendrite lithium growth has become a primary consideration in designing advanced lithium metal anodes. Heretofore, various countermeasures have been proposed to alleviate these problems of the negative electrode. For example, cao et al propose a robust organic-inorganic composite oxide artificial layered lithium metal anode. The artificial layer contains polyethylene glycol diacrylate (PEGDA), lithium difluoro (oxalic acid) boric acid LiBF 2 (C 2 O 4 ) (LiDFOB) and Azobisisobutyronitrile (AIBN) as initiators for in situ polymerization. Artificial SEI is produced by in situ polymerization by forming lithiated polymers with Li metal cathodesClose contact and with decomposition of LiDFOB provides a good lithium ion transport path and better chemical stability. In addition, the good mechanical property is favorable for forming a dendrite-free surface, and the serious side reaction between the lithium metal anode and the carbonate-based electrolyte is inhibited. In the Li NCM811 battery, the artificial SEI reached 58.4% high capacity retention after 300 cycles; for the Li symmetric battery of artificial SEI, 700h (0.5 mAcm -2 ,1mAh cm -2 ) The overpotential is about 60mV. (Nano Energy,2022,95,106983) the above study provides a new strategy for stable lithium metal cathodes, but these SEI layer strategies are not resistant to volume deformation during long-term cycling of the battery.
Therefore, a modification method of a lithium metal negative electrode which is simple and easy to operate is researched, effective space is provided for lithium deposition to relieve volume deformation, and a lithium-philic site is provided to effectively inhibit side reaction, so that growth of lithium dendrite is inhibited, cycle performance of the lithium negative electrode is prolonged, and the method is a great thrust for promoting practical application of a lithium metal secondary battery.
Disclosure of Invention
According to the problems of the background technology, the invention aims to solve the problems of poor reversibility, low coulomb efficiency, poor safety and the like caused by dendrite growth and volume deformation in the current charge-discharge cycle process of the lithium metal battery cathode, and provides a preparation method and application of a novel three-dimensional self-supporting composite lithium cathode.
In order to achieve the above object, the present invention has the following technical scheme:
a novel three-dimensional self-supporting composite lithium negative electrode, which comprises a lithium-philic three-dimensional bracket and metallic lithium; the metal lithium is inserted and filled into the lithium-philic three-dimensional framework.
Correspondingly, the preparation method of the three-dimensional self-supporting composite lithium anode comprises the following steps of:
a) Taking urea as a nitriding agent, annealing and nitriding a stainless steel mesh wafer at a high temperature to obtain a three-dimensional nitrided stainless steel mesh (N-SSM) with nitrided lithium-philic sites on the surface;
b) And pre-storing lithium on the surface of the N-SSM by an immersion method or an electrochemical plating method, and cooling to room temperature to obtain the three-dimensional nitriding composite lithium anode (Li-N-SSM).
Further, in the step a), the stainless steel mesh has a pore diameter of 200 to 400 meshes, and the amount of the nitriding agent (g/g) and the area (cm) of the stainless steel mesh are used 2 ) The ratio of (2) is 1:1-3:2, the nitriding time is 1-60 min, the nitriding temperature is 300-700 ℃, and the nitriding atmosphere is vacuum.
Further, in the step b), the impregnation method is to immerse the N-SSM into molten metal lithium, wherein the temperature of the molten lithium is 250-350 ℃ and the impregnation time is 5-120 s, adsorb the molten lithium into the electrode through a lithium-philic site, and cool the electrode to room temperature to obtain the composite lithium anode Li-N-SSM; the electrochemical plating method is carried out for 2-10 h with plating current of 1-5 mAcm -2 。
The three-dimensional self-supporting composite lithium negative electrode prepared by the method is applied to a lithium metal secondary battery and is characterized by comprising a positive electrode, a three-dimensional self-supporting composite lithium negative electrode, a diaphragm, electrolyte, a positive and negative electrode shell, an elastic sheet and a gasket, wherein the assembly sequence is shown in the following figure.
Negative electrode shell, negative electrode plate, electrolyte, diaphragm, electrolyte, positive electrode plate, gasket, elastic sheet and positive electrode shell.
Further, the material of the positive electrode is selected from LiFeMnPO 4 、LiFePO 4 、LiCoO 2 、LiMnO 2 、LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NCM622)、LiNi 0.885 Co 0.1 Al 0.015 O 2 (NCA), metal oxide or metal sulfide, li, cu.
Further, the negative electrode is a three-dimensional self-supporting composite lithium negative electrode prepared by the method or a negative electrode prepared by the method.
Further, the separator is selected from a PP separator, a PE separator, PP/PE or PP/PE/PP separator.
Further, the electrolyte includes an ether-based electrolyte [1M LiTFSI/(DOL/DME)]Or ester-based electrolyte [1M LiPF 6 /(EC/DMC)]。
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, urea is used as a nitrogen source under a vacuum condition, and the nitriding three-dimensional self-supporting material with uniformly distributed structure complete nitrides is obtained by nitriding the stainless steel net by regulating and controlling the dosage of the nitriding agent and nitriding time, so that the original ammonia nitriding method is abandoned, and the method is safe and environment-friendly.
(2) According to the three-dimensional self-supporting lithium metal cathode, the three-dimensional porous structure can reduce local current density by dispersing current, regulate and control electric field distribution and homogenize lithium ion flow; the nitriding lithium-philic site on the three-dimensional porous support can form lithium nitride with high ion conductivity through spontaneous reaction with lithium, so that uniform deposition of lithium ions is promoted, and growth of dendrite lithium is further inhibited.
(3) The three-dimensional porous structure can provide enough available space for lithium deposition, buffer volume change in the battery electroplating/stripping process, reduce side reaction, inhibit dead lithium generation, further improve the battery cycle stability and increase the safety of the lithium metal secondary battery.
Drawings
FIG. 1 is a surface topography of a stainless steel mesh before and after nitriding in example 2.
Fig. 2 is a composite lithium negative electrode diagram of example 2.
Fig. 3 is a graph showing the surface morphology of the lithium sheet after 100 cycles of the symmetrical battery of example 2.
Fig. 4 is a graph showing the morphology of the composite lithium negative electrode after 100 cycles of the symmetric battery in example 2.
Fig. 5 is a cycle stability test chart of the symmetrical battery assembled with the composite lithium anode and the common lithium sheet as the anode in example 2.
Fig. 6 is a nucleation overpotential diagram of a half cell assembled with a composite lithium anode and a common lithium sheet as the anode for the symmetric cell of example 2.
Fig. 7 is a cycle performance chart of a full cell assembled with a composite lithium anode and a common lithium sheet as the anode for the symmetrical cell of example 2.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The experimental methods in the following examples are conventional methods unless otherwise specified.
Example 1
(1) Preparation of three-dimensional self-supporting composite negative electrode
a) The purchased 200 mesh stainless steel mesh was cut into 14 mm diameter discs, which were then washed three times with ethanol and deionized water to remove surface impurities and dried overnight at 80 ℃.
b) 3 g of urea and 6 sheets of the wafer obtained in a) are placed in a tube furnace, and annealed for 5 minutes in Ar-Ar atmosphere at 400 ℃ to obtain a stainless steel mesh with partially nitrided surface;
c) Immersing the nitriding stainless steel network obtained in the step b) into molten lithium, wherein the temperature of the molten lithium is 270 ℃, the immersion time is 30s, and cooling to room temperature to obtain the three-dimensional self-supporting composite negative electrode.
(2) Battery assembly
(1) The three-dimensional self-supporting composite cathode obtained in the step (1) and the step c) is taken as an anode and a cathode, a PP film is taken as a diaphragm, and 1M LiPF is taken as a diaphragm 6 And/(ec+dmc) is the electrolyte, and the symmetrical cell is assembled.
(2) Taking lithium foil as a negative electrode, taking the nitrided stainless steel net obtained in the step (1) and b) as a positive electrode, taking a PP film as a diaphragm, and taking 1M LiPF 6 And/(ec+dmc) is the electrolyte, and the half cell is assembled.
(3) Taking the three-dimensional self-supporting composite negative electrode obtained in (1) and c) as a negative electrode, taking an NCM622 electrode plate as a positive electrode, taking a PP film as a diaphragm, and taking 1M LiPF 6 And/(ec+dmc) is the electrolyte, and the full cell is assembled.
(3) Electrochemical performance test
(1) At 2mAh/cm 2 Deposition capacity of 1mA/cm 2 And (3) carrying out charge-discharge cycle test on the symmetrical battery in the step (1) in the step (2) by current density.
(2) At 0.5mAh/cm 2 Deposition capacity of 0.5mA/cm 2 And (3) carrying out charge and discharge test on the battery in the step (2) by using the current density and the charging voltage of 1V.
(3) And (3) performing charge and discharge test on the full battery assembled in the step (3) of the step (2) at the current density of 1C.
Example 2
(1) Preparation of three-dimensional self-supporting composite negative electrode
a) The purchased 300 mesh stainless steel mesh was cut into 14 mm diameter discs, which were then washed three times with ethanol and deionized water to remove surface impurities and dried overnight at 80 ℃.
b) 4 g of urea and 10 tablets obtained in a) are placed in a tube furnace, and annealed for 20 minutes in Ar-Ar atmosphere at 600 ℃ to obtain a stainless steel mesh with partially nitrided surface;
c) Immersing the nitriding stainless steel network obtained in the step b) into molten lithium, wherein the temperature of the molten lithium is 350 ℃, the immersion time is 80s, and cooling to room temperature to obtain the three-dimensional self-supporting composite negative electrode.
(2) Battery assembly
(1) And (3) using the three-dimensional self-supporting composite cathode obtained in the step (1), c) as an anode and a cathode, using a PP/PE film as a diaphragm, and using 1M LiTFSI/(DOL/DME) as electrolyte to assemble the symmetrical battery.
(2) And (3) taking a lithium foil as a negative electrode, taking the nitrided stainless steel net obtained in the step (1) and b) as a positive electrode, taking a PP/PE film as a diaphragm, and taking 1M LiTFSI/(DOL/DME) as an electrolyte to assemble the half cell.
(3) Taking the three-dimensional self-supporting composite anode obtained in the step (1) and the step c) as an anode, and LiFePO 4 The electrode plate is an anode, the PP/PE film is used as a diaphragm, and 1M LiTFSI/(DOL/DME) is used as electrolyte, so that the full battery is assembled.
(3) Electrochemical performance test
(1) At 5mAh/cm 2 Deposition capacity of 1mA/cm 2 And (3) carrying out charge-discharge cycle test on the symmetrical battery in the step (1) in the step (2) by current density.
(2) At 1mAh/cm 2 Deposition capacity of 1mA/cm 2 And (3) carrying out charge and discharge test on the battery in the step (2) by using the current density and the charging voltage of 1V.
(3) And (3) performing charge and discharge test on the full battery assembled in the step (3) of the step (2) at the current density of 1C.
Example 3
(1) Preparation of three-dimensional self-supporting composite negative electrode
a) The purchased 250 mesh stainless steel mesh was cut into 14 mm diameter discs, which were then washed three times with ethanol and deionized water to remove surface impurities and dried overnight at 80 ℃.
b) 4 g of urea and 12 tablets obtained in a) are placed in a tube furnace, and annealed for 30 minutes in Ar-Ar atmosphere at 500 ℃ to obtain a stainless steel mesh with partially nitrided surface;
c) Taking the nitriding stainless steel network obtained in the step b) as an anode, taking a metal Li sheet as a cathode to assemble the button cell, and carrying out 2mA/cm 2 Discharging for 3h under the current density, and disassembling the button cell after the discharging is finished, wherein the positive electrode is the three-dimensional self-supporting composite negative electrode.
(2) Battery assembly
(1) And (3) taking the three-dimensional self-supporting composite cathode obtained in the step (1), c) as an anode and a cathode, taking a PP film as a diaphragm, and taking 1M LiTFSI/(DOL/DME) as electrolyte to assemble the symmetrical battery.
(2) And (3) taking the copper foil as an anode, taking the three-dimensional self-supporting composite anode obtained in the step (1) and c) as an anode, taking the PP film as a diaphragm, and taking 1M LiTFSI/(DOL/DME) as electrolyte to assemble the half cell.
(3) And (3) taking the three-dimensional self-supporting composite anode obtained in the step (1), C) as an anode, taking the S/C composite material as a cathode, taking the PP film as a diaphragm, and taking 1M LiTFSI/(DOL/DME) as electrolyte to assemble the full battery.
(3) Electrochemical performance test
(1) At 3mAh/cm 2 Deposition capacity of 1mA/cm 2 And (3) carrying out charge-discharge cycle test on the symmetrical battery in the step (1) in the step (2) by current density.
(2) At 1mAh/cm 2 Deposition capacity of 3mA/cm 2 And (3) carrying out charge and discharge test on the battery in the step (2) by using the current density and the charging voltage of 1V.
(3) And (3) performing charge and discharge test on the full battery assembled in the step (3) of the step (2) at the current density of 1C.
Comparative example 1
(1) Assembled battery
(1) Lithium sheets are used as an anode and a cathode, a PP film is used as a diaphragm, and 1M LiPF is used 6 And/(ec+dmc) is the electrolyte, and the symmetrical cell is assembled.
(2) The lithium sheet is used as a negative electrode, the Cu foil is used as a positive electrode, the PP film is used as a diaphragm, and the 1MLiPF is used 6 And/(ec+dmc) is the electrolyte, and the half cell is assembled.
(3) The lithium sheet is used as a negative electrode, the NCM622 electrode sheet is used as a positive electrode, the PP film is used as a diaphragm, and the 1M LiPF is used 6 And/(ec+dmc) is the electrolyte, and the full cell is assembled.
(2) Electrochemical performance test
(1) At 2mAh/cm 2 Deposition capacity of 1mA/cm 2 Current density the symmetrical cells of step (1) were tested for charge and discharge cycles.
(2) At 0.5mAh/cm 2 Deposition capacity of 0.5mA/cm 2 And (3) carrying out charge and discharge test on the battery in the step (2) in the step (1) by using a current density and a charging voltage of 1V.
(3) And (3) performing charge and discharge test on the full battery assembled in the step (3) of the step (1) at the current density of 1C.
Comparative example 2
(1) Assembled battery
(1) And (3) taking a lithium sheet as an anode and a cathode, taking a PP/PE film as a diaphragm, and taking 1 MLiTFSI/(DOL/DME) as electrolyte to assemble the symmetrical battery.
(2) The half cell was assembled with lithium sheet as negative electrode, cu foil as positive electrode, PP film as separator, and 1 mliffsi/(DOL/DME) as electrolyte.
(3) Lithium sheet is used as negative electrode, liFePO 4 The electrode plate is an anode, the PP film is used as a diaphragm, and 1M LiTFSI/(DOL/DME) is used as electrolyte, so that the full battery is assembled.
(2) Electrochemical performance test
(1) At 5mAh/cm 2 Deposition capacity of 1mA/cm 2 Current density the symmetrical cells of step (1) were tested for charge and discharge cycles.
(2) At 1mAh/cm 2 Deposition capacity of 1mA/cm 2 And (3) carrying out charge and discharge test on the battery in the step (2) in the step (1) by using a current density and a charging voltage of 1V.
(3) And (3) performing charge and discharge test on the full battery assembled in the step (3) of the step (1) at the current density of 1C.
Comparative example 3
(1) Battery assembly
(1) And (3) taking a lithium sheet as an anode and a cathode, taking a PP/PE film as a diaphragm, and taking 1 MLiTFSI/(DOL/DME) as electrolyte to assemble the symmetrical battery.
(2) The half cell was assembled with lithium sheet as negative electrode, cu foil as positive electrode, PP film as separator, and 1 mliffsi/(DOL/DME) as electrolyte.
(3) And (3) taking a lithium sheet as a negative electrode, taking an S/C composite material as a positive electrode, taking a PP film as a diaphragm, and taking 1 MLiTFSI/(DOL/DME) as electrolyte to assemble the full battery.
(2) Electrochemical performance test
(1) At 3mAh/cm 2 Deposition capacity of 1mA/cm 2 Current density the symmetrical cells of step (1) were tested for charge and discharge cycles.
(2) At 1mAh/cm 2 Deposition capacity of 3mA/cm 2 And (3) carrying out charge and discharge test on the battery in the step (2) in the step (1) by using a current density and a charging voltage of 1V.
(3) And (3) performing charge and discharge test on the full battery assembled in the step (3) of the step (1) at the current density of 1C.
After high-temperature annealing and nitridation, nitriding the surface of the stainless steel mesh to generate a nitriding lithium-philic site, as shown in figure 1; after pre-storing lithium in the nitrided stainless steel mesh, a composite lithium anode with a smooth surface is obtained, as shown in fig. 2. Comparative example 2 and comparative example 2 symmetrical cell cycle performance graph (fig. 5) it can be observed that the three-dimensional composite lithium anode was at 5mA/cm 2 The current density of (2) can be stably cycled for more than 900 hours with lower overpotential, and the overpotential of a symmetrical battery assembled by bare lithium without any modification is rapidly increased after tens of hours of charge/discharge cycles, and the surface morphology of the battery after the cycle is observed after the battery is disassembled, so that the three-dimensional composite lithium negative electrode surface presents smooth, uniform and dendrite-free morphology and no lithium is deposited outside a hole, as shown in figure 3; the bare lithium negative electrode after the reverse cycle had a large amount of dendrite lithium on the surface with dead lithium build-up (fig. 4), which coincides with the rapid increase in overpotential of the symmetric battery assembled from bare lithium. The results show that the three-dimensional self-supporting lithium anode prepared by the method can effectively inhibit the growth of lithium dendrites and limit the volume deformation in the lithium deposition process. In addition, from compositing lithium in three dimensionsAs can be seen from a comparison of the voltage capacity diagrams of half cells with the positive electrode and the copper foil as the positive electrode (fig. 6), the nucleation overpotential of lithium on the three-dimensional composite lithium negative electrode is far lower than that on the copper foil, which indicates that the three-dimensional self-supporting composite negative electrode prepared by the method can effectively reduce the lithium nucleation overpotential. More importantly, the full battery prepared by matching and assembling the three-dimensional self-supporting composite lithium anode and the commercial anode can stably circulate for more than 200 circles with higher capacity retention rate (figure 7), the circulation stability is far higher than that of a full battery with a lithium sheet as the anode, and the ultrahigh coulombic efficiency is maintained.
In conclusion, the three-dimensional self-supporting composite lithium cathode prepared by the method can effectively induce lithium ion flow, promote uniform deposition of lithium ions and inhibit generation of dendrite lithium by performing nitriding pretreatment on a stainless steel mesh to generate a lithium-philic active site; and can provide a storage space for lithium deposition, buffer volume deformation in the lithium electroplating/stripping process, reduce deposition overpotential of lithium ions, and improve the cycling stability of the lithium metal secondary battery.
Table 1 data obtained for example 1, comparative example 1, example 3, comparative example 3
| Symmetrical battery life (h)/overpotential (mV) | Full cell cycle number/specific capacity (mAh/g) | |
| Example 1 | 1100/～90 | 300/140 |
| Comparative example 1 | 300/gradually increase to 400 | 150/118 |
| Example 3 | 1280/～150 | 300/765 |
| Comparative example 3 | 450/380 | 169/523 |
Claims (10)
1. The preparation method of the three-dimensional self-supporting composite lithium anode is characterized by comprising the following steps of;
a) Taking urea as a nitriding agent, annealing and nitriding a stainless steel mesh wafer at a high temperature to obtain a three-dimensional nitrided stainless steel mesh N-SSM with a nitride lithium-philic site on the surface;
b) And pre-storing lithium on the surface of the N-SSM by an immersion method or an electrochemical plating method, and cooling to room temperature to obtain the three-dimensional nitriding composite lithium anode Li-N-SSM.
2. The method for preparing a three-dimensional self-supporting composite lithium anode according to claim 1, wherein in the step a), the stainless steel mesh has a pore diameter of 200-400 meshes, and the ratio of the amount of nitriding agent to the area of the stainless steel mesh is 1:1-3:2 g/cm 2 Nitriding time is 1-60 min, nitriding temperature is 300-700 ℃, and nitriding atmosphere is vacuum.
3. The method for preparing a three-dimensional self-supporting composite lithium anode according to claim 1, wherein in the step b), the impregnation method is to immerse the N-SSM into molten metal lithium, and adsorb the molten lithium into the electrode through a lithium-philic site, thereby obtaining the composite lithium anode Li-N-SSM.
4. The method for preparing a three-dimensional self-supporting composite lithium negative electrode according to claim 1, wherein in the step b), the electrochemical plating method is to assemble an electrochemical cell by using an N-SSM electrode, a metal lithium sheet, an electrolyte and the like, and to plate lithium metal on the N-SSM electrode by setting a discharging step, thereby obtaining the composite lithium negative electrode Li-N-SSM.
5. The method for preparing a three-dimensional self-supporting composite lithium anode according to claim 3, wherein the lithium melting temperature used in the impregnation method is 250-350 ℃ and the impregnation time is 5-120 s.
6. The method for preparing the three-dimensional self-supporting composite lithium anode according to claim 4, wherein the electrochemical plating method is carried out for 2-10 h with a plating current of 1-5 mA-2
cm。
7. The three-dimensional self-supporting composite lithium anode prepared by the method according to any one of claims 1 to 6 is applied to a lithium metal secondary battery, and is characterized by comprising a positive electrode, a three-dimensional self-supporting composite lithium anode, a diaphragm, electrolyte, a positive electrode shell, a negative electrode shell, an elastic sheet and a gasket.
8. The use according to claim 7, wherein the material of the positive electrode comprises LiFe x Mn 1-x PO 4 、LiFePO 4 、LiCoO 2 、LiMn 2 O 4 、LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NCM622)、LiNi 0.885 Co 0.1 Al 0.015 O 2 (NCA), metal oxide or metal sulfide, li or Cu.
9. Use according to claim 7, wherein the membrane comprises a PP membrane, a PE membrane, PP/PE or PP/PE/PP membrane.
10. The use according to claim 7, wherein the electrolyte comprises an ether-based electrolyte [1M LiTFSI/(DOL/DME)]Or ester-based electrolyte [1M LiPF 6 /(EC/DMC)]。
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| CN116936815B (en) * | 2023-09-18 | 2024-02-27 | 宁德时代新能源科技股份有限公司 | Negative current collector, preparation method thereof, negative electrode plate, lithium metal battery and power utilization device |
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