CN114744162A - Nickel-modified nitrogen-doped porous carbon lithium-loaded negative electrode and preparation method and application thereof - Google Patents

Nickel-modified nitrogen-doped porous carbon lithium-loaded negative electrode and preparation method and application thereof Download PDF

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CN114744162A
CN114744162A CN202210644541.2A CN202210644541A CN114744162A CN 114744162 A CN114744162 A CN 114744162A CN 202210644541 A CN202210644541 A CN 202210644541A CN 114744162 A CN114744162 A CN 114744162A
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lithium
nickel
porous carbon
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李哲东
符兵
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Zhongbo Longhui Equipment Group Co ltd
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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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
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    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a nickel-modified nitrogen-doped porous carbon lithium-loaded negative electrode and a preparation method and application thereof. The method comprises the steps of mixing and dissolving nickel nitrate and trimesic acid in DMF (dimethyl formamide), synthesizing Ni-MOFs (metal organic frameworks) materials through a hydrothermal reaction, then carrying out physical mixing on Ni-MOFs serving as precursors and melamine, starting pyrolysis, synthesizing Ni-NPCs, and then embedding metal lithium into the Ni-MOFs. In the preparation process, Ni-MOFs is a good precursor for synthesizing the porous carbon material, and porous carbon with uniform appearance, rich pores and stable structure can be synthesized; lithium embedded by adopting an electrodeposition method is more uniform, and dense large lithium blocks are divided into smaller domains to inhibit the growth of dendrites and minimize volume change, so that metal lithium can be stably de-embedded in the charging and discharging process; the Ni-NPCs-Li cathode prepared by the method is beneficial to the protection of a lithium cathode in a commercialization process, the safety of the battery is improved, and the cycle life of the battery can be effectively prolonged by applying the cathode to the lithium-sulfur battery.

Description

Nickel-modified nitrogen-doped porous carbon lithium-loaded negative electrode and preparation method and application thereof
Technical Field
The invention relates to the technical field of battery materials, in particular to a nickel-modified nitrogen-doped porous carbon lithium-loaded negative electrode and a preparation method and application thereof.
Background
In recent years, with the use of a large number of lithium ion batteries, some problems gradually emerge from the water surface, for example, the anode cost is not reduced permanently due to limited cobalt resources, the energy density gradually approaches the theoretical limit, the low-temperature performance is not good, and the like. Therefore, there is a need to develop a new electrochemical energy storage device to replace lithium ion batteries in certain application fields.
The lithium-sulfur battery is a battery system for storing energy based on multi-electron redox reaction between a sulfur positive electrode and a lithium negative electrode, and the theoretical energy density of the lithium-sulfur battery is as high as 2600Wh kg-1It is 5 times more than that of the traditional 'de-intercalation' type lithium ion battery. At present, the performance of the developed lithium-sulfur battery can reach 400Wh kg in the environment of-20 DEG C-1And can still work in an extremely cold environment at minus 60 ℃, which is the low-temperature performance that the lithium ion battery can not reach at present. However, lithium sulfur batteries have not been mass produced and used today due to limitations in sulfur positive electrode conductivity, intermediate product shuttling effects, and lithium negative electrode defects. However, after the research on the cathode material for about 10 years, the problem of the lithium cathode is a hot spot that researchers pay attention to, lithium dendrite is generated due to uneven deposition in the charging and discharging process, and grows up along with the charging and discharging process, and finally a Solid Electrolyte Interface (SEI) film on the surface of the cathode is damaged or a diaphragm is punctured, so that the cycle performance of the battery is reduced, even a short circuit is caused, the battery is spontaneously combusted, and a serious potential safety hazard is caused. Therefore, in order to further improve the long cycle performance of the lithium sulfur battery and accelerate the industrialization process of the lithium sulfur battery, it is imperative to develop a negative electrode capable of effectively inhibiting volume expansion and dendrite growth during the lithium exfoliation/deposition process.
The invention application with the publication number of CN112736252A discloses a mesoporous nickel oxide loaded nitrogen-doped porous carbon negative electrode material for improving the electrochemical performance of a lithium ion battery. Reacting starch with acrylonitrile to obtain cyanoethylated starch, carbonizing by using the starch as a carbon source and cyanoethyl as a nitrogen source to obtain a nitrogen-doped carbon material, and then making holes in the nitrogen-doped carbon material by using potassium hydroxide to prepare the nitrogen-doped porous carbon material, so that the specific surface area of the carbon material is improved, a large number of structures such as pyridine nitrogen and graphite nitrogen are introduced, and the electrochemical performance is improved in an auxiliary manner. And mixing and pyrolyzing the nitrogen-doped porous carbon material, nickel nitrate and citric acid, and performing air erosion on nickel oxide by using gas overflowing from decomposition of the citric acid to obtain the mesoporous nickel oxide-loaded nitrogen-doped porous carbon. The pore structures of the nitrogen-doped porous carbon enable nickel oxide to be uniformly loaded in the pore structures, so that the nickel oxide is prevented from being stacked, and the pore structures can also inhibit the volume expansion of the nickel oxide, so that the specific capacity and the cycling stability of the mesoporous nickel oxide are improved.
The invention application with the publication number of CN112573503A discloses a preparation method of a nitrogen-doped porous carbon material, which comprises the following steps: (1) preparing a yellow precursor by using nickel chloride, polyvinylpyrrolidone and 2-methylimidazole as raw materials; (2) heating and carbonizing the yellow precursor at 600-700 ℃ for 2h at the speed of 10 ℃/min in a nitrogen atmosphere to obtain a black sample; (3) ultrasonically dispersing a black sample in deionized water, and then adding mixed acid for reflux etching; (4) and washing and drying the sample subjected to the reflux etching to obtain the nitrogen-doped porous carbon material.
However, in the above prior art, the former is used for the negative electrode of the lithium ion battery, and the latter is used for the negative electrode of the potassium ion battery, which are not applied to the negative electrode of the lithium sulfur battery, and the problem of the growth of the lithium dendrite is not solved well.
Disclosure of Invention
Aiming at the defects in the prior art, the nickel-modified nitrogen-doped porous carbon lithium-loaded negative electrode and the preparation method and application thereof are provided, and the nickel-modified nitrogen-doped porous carbon lithium-loaded negative electrode can inhibit the growth of lithium crystals and improve the cycle life of a lithium-sulfur battery.
A preparation method of a nickel-modified nitrogen-doped porous carbon lithium-loaded negative electrode comprises the following steps:
(1) nickel nitrate and trimesic acid are mixed and dissolved in DMF (N, N-dimethylformamide) solvent, and Ni-MOFs material is synthesized through hydrothermal reaction;
(2) mixing the Ni-MOFs material prepared in the step (1) as a precursor with a nitrogen source, and then pyrolyzing the mixture to prepare a nickel modified nitrogen-doped porous carbon (Ni-NPCs) material;
(3) mixing the Ni-NPCs material prepared in the step (2) with acetylene black and PVDF (polyvinylidene fluoride) according to the mass ratio of 8: 1, adding N-methylpyrrolidone (NMP) to grind into slurry, coating the slurry on a copper foil, and drying to obtain a nickel-modified nitrogen-doped porous carbon electrode slice;
(4) and (4) carrying out electro-deposition lithium intercalation on the Ni-NPCs electrode slice prepared in the step (3) to prepare the nickel modified nitrogen-doped porous carbon lithium-loaded negative electrode (Ni-NPCs-Li).
The nickel nitrate used in this application may also be hydrated nickel nitrate, such as the common nickel nitrate hexahydrate.
Preferably, in the step (1), the molar ratio of the nickel nitrate to the trimesic acid is 1: 1.
Preferably, in step (1), 1mmol of nickel nitrate is dissolved in 30mL of DMF.
Preferably, in the step (1), the hydrothermal reaction temperature is 150 ℃ and the hydrothermal reaction time is 12 h.
Preferably, in step (2), the nitrogen source is melamine; the mass ratio of the Ni-MOFs material to the nitrogen source is 1: 1.
Preferably, in the step (2), the pyrolysis is carried out in an inert gas atmosphere, the pyrolysis temperature is 800 ℃, and the time is 2 h.
Preferably, in step (3), the thickness of the slurry drawn down is 100 μm.
Preferably, in the step (4), the lithium intercalation current density is 0.5mA cm-2The time is 6-18 h, and the lithium embedding amount is 3-9 mAh cm-2。
The invention not only provides the nickel-modified nitrogen-doped porous carbon lithium-loaded cathode prepared by the preparation method, but also provides application of the nickel-modified nitrogen-doped porous carbon lithium-loaded cathode in preparation of a lithium-sulfur battery.
The invention has the beneficial effects that: the invention provides a preparation method of a Ni-NPCs-Li cathode and application thereof in a lithium-sulfur battery, the method comprises the steps of mixing nickel nitrate hexahydrate and trimesic acid according to a certain proportion, dissolving the mixture in a DMF solvent, and synthesizing a Ni-MOFs material through a hydrothermal reaction; then, Ni-MOFs serving as a precursor is physically mixed with melamine to start pyrolysis, Ni-NPCs are synthesized, and then metallic lithium is inserted into the Ni-MOFs. In the whole preparation process, Ni-MOFs is a good precursor for synthesizing the porous carbon material, and porous carbon with uniform appearance, rich pores and stable structure can be synthesized; in addition, when embedding lithium into the Ni-NPCs carrier material, an electrodeposition method is adopted, the lithium embedded by the method is more uniform, the embedding amount can be artificially regulated and controlled through the deposition time, and finally dense massive lithium is divided into smaller areas to inhibit the growth of lithium dendrites and minimize the volume change of the lithium dendrites, so that the metal lithium can be stably de-embedded in the charging and discharging process; the Ni-NPCs-Li cathode prepared by the method is beneficial to protecting the lithium cathode in the commercialization process, improves the safety of the battery, can effectively improve the cycle life of the battery when being used in the lithium-sulfur battery, and can be applied to other lithium metal batteries for protecting the lithium cathode. In addition, the steps involved in the preparation of the cathode are simple experimental methods, the requirement on equipment is low, and the method is suitable for rapid large-scale production.
Drawings
FIG. 1 is an SEM image of Ni-MOFs precursors and Ni-NPCs support materials prepared in example 1, wherein a: Ni-MOFs precursors; b: Ni-NPCs support material.
FIG. 2 is an XRD pattern of the Ni-NPCs support material prepared in example 1.
FIG. 3 is a graph showing the results of the rate and coulombic efficiency tests of the lithium-sulfur batteries assembled with the Ni-NPCs-Li cathodes in examples 1 to 3.
FIG. 4 is a graph showing the results of the cycle performance and coulombic efficiency tests of lithium-sulfur batteries assembled with Ni-NPCs-Li cathodes in comparative examples 1 to 3.
Fig. 5 is a graph showing the results of rate performance and coulombic efficiency tests on a lithium-sulfur battery assembled with a lithium metal negative electrode in test example 1.
Fig. 6 is a graph showing the results of cycle performance and coulombic efficiency tests of a lithium-sulfur battery assembled with a lithium metal negative electrode in test example 1.
Fig. 7 is a graph comparing charge and discharge curves of the assembled lithium sulfur batteries of example 2 and test example 1.
Fig. 8 is a graph showing the morphology of the negative electrode after cycling of the lithium sulfur battery assembled in example 2 and test example 1, wherein a: a metallic lithium negative electrode; b: Ni-NPCs-Li negative electrode.
Detailed Description
Example 1
(1) Preparing Ni-NPCs (nickel modified nitrogen-doped porous carbon) carrier materials and pole pieces.
Mixing 2mmoL nickel nitrate hexahydrate and 2mmoL trimesic acid, dissolving the mixture in 60mL of DMF (N, N-dimethylformamide) solvent, stirring for 30min, then carrying out hydrothermal reaction at 150 ℃ for 12h, washing the mixture with DMF and ethanol for 2-3 times after natural cooling, and then drying the mixture at 60 ℃ for 12h to obtain the Ni-MOFs (nickel-based metal organic framework) material, wherein the microstructure of the Ni-MOFs material is shown as a in figure 1. And then, physically mixing Ni-MOFs serving as a precursor with melamine according to the mass ratio of 1: 1, calcining for 2h at 800 ℃ in an argon atmosphere at the heating rate of 5 ℃/min to obtain the Ni-NPCs (nickel-modified nitrogen-doped porous carbon) carrier material, wherein the micro-morphology of the Ni-MOFs is shown in b in figure 1, and the XRD spectrogram is shown in figure 2. And then mixing Ni-NPCs, acetylene black and PVDF (polyvinylidene fluoride) according to the mass ratio of 8: 1, adding 150 muL NMP, grinding to prepare uniform negative electrode slurry, blade-coating the prepared slurry on smooth copper foil to prepare a Ni-NPCs pole piece, wherein the blade-coating thickness is 100 mu m, and drying at 60 ℃ for 12 hours.
(2) And preparing the Ni-NPCs-Li cathode.
Cutting the dried Ni-NPCs pole piece into small round pieces with the diameter of 14mm by using a slicer, assembling the small round pieces with a metal lithium piece to form the button cell, wherein the electrolyte solute is lithium trifluoromethanesulfonylimide (LiTFSI), the solvent is 1, 3-Dioxolane (DOL) and Dimethoxymethane (DME), the volume ratio is 1: 1, and the additive is 0.1M LiNO3The concentration of the electrolyte is 1 mol/L. After the cell was assembled, the current density was 0.5mA cm-2Under the condition of (1), constant current is deposited for 6h, and the Ni-NPCs pole piece is embedded by 3mAh cm-2The Ni-NPCs-Li (nickel modified nitrogen-doped porous carbon-loaded lithium) cathode can be prepared by using the metal lithium.
(3) Preparing a sulfur-carbon (C @ S) anode.
Mixing and grinding commercial activated carbon and sublimed sulfur according to the mass ratio of 7: 3, placing the mixture in a tubular furnace, keeping the temperature at 155 ℃ for 12 hours, and marking the obtained material as an AC @ S positive electrode. And then mixing and grinding the AC @ S, the acetylene black and the PVDF according to the mass ratio of 8: 1, adding 150 muL NMP after grinding uniformly, continuing grinding until uniform slurry is formed, then carrying out blade coating on the slurry onto a smooth aluminum foil by using a scraper, wherein the blade coating thickness is 100μm, and drying at 60 ℃ for 12 hours. And then cutting into small discs with the diameter of 14mm by using a slicing machine to obtain the AC @ S positive electrode.
(4) And assembling the CR2032 button lithium-sulfur battery by taking Ni-NPCs-Li as a negative electrode and AC @ S as a positive electrode.
A button cell is assembled by matching the cathode prepared in the step (2) of the example and the cathode prepared in the step (3) of the example, wherein the used separator is a commercial polypropylene (PP) separator, the electrolyte solute is lithium trifluoromethanesulfonylimide (LiTFSI), the solvent is 1, 3-Dioxolane (DOL) and Dimethoxymethane (DME), the volume ratio is 1: 1, and the additive is 0.1M LiNO3The concentration of the electrolyte is 1 mol/L.
Example 2
(1) Preparing Ni-NPCs (nickel modified nitrogen-doped porous carbon) carrier materials and pole pieces.
Mixing and dissolving 2mmoL nickel nitrate hexahydrate and 2mmoL trimesic acid in a 60mLDMF solvent, stirring for 30min, performing hydrothermal reaction for 12h at 150 ℃, washing for 2-3 times by DMF and ethanol in sequence after natural cooling, and drying for 12h at 60 ℃ to obtain the Ni-MOFs precursor. And then physically mixing Ni-MOFs serving as a precursor with melamine according to the mass ratio of 1: 1, calcining for 3h at 800 ℃ in an argon atmosphere at the heating rate of 5 ℃/min, and obtaining the Ni-NPCs (nickel-modified nitrogen-doped porous carbon) carrier material. And then mixing Ni-NPCs, acetylene black and PVDF (polyvinylidene fluoride) according to the mass ratio of 8: 1, adding 150 muL NMP, grinding to prepare uniform negative electrode slurry, blade-coating the prepared slurry on smooth copper foil to prepare the Ni-NPCs pole piece, wherein the blade-coating thickness is 100 mu m, and drying at 60 ℃ for 12 hours.
(2) And preparing the Ni-NPCs-Li cathode.
Cutting the dried Ni-NPCs pole piece into a small wafer with the diameter of 14mm by using a slicer, assembling the small wafer with a metal lithium piece to form the button cell, wherein the electrolyte solute is lithium trifluoromethanesulfonimide (LiTFSI), and the solvent is 1, 3-Dioxolane (DOL)And Dimethoxymethane (DME) in a volume ratio of 1: 1 with 0.1M LiNO as additive3The concentration of the electrolyte is 1 mol/L. After the cell was assembled, the current density was 0.5mA cm-2Under the conditions of (1), constant current is deposited for 12h, and a Ni-NPCs pole piece is embedded into 6mAh cm-2The Ni-NPCs-Li (nickel modified nitrogen-doped porous carbon-loaded lithium) cathode can be prepared by using the metal lithium.
(3) Preparing a sulfur-carbon (AC @ S) anode.
Mixing and grinding commercial activated carbon and sublimed sulfur according to the mass ratio of 7: 3, placing the mixture in a tubular furnace, keeping the temperature at 155 ℃ for 12 hours, and marking the obtained material as an AC @ S positive electrode. And then mixing and grinding the AC @ S, the acetylene black and the PVDF according to the mass ratio of 8: 1, adding 150 mu L of NMP after uniform grinding, continuing grinding until uniform slurry is formed, then blade-coating the slurry onto a smooth aluminum foil by using a scraper, wherein the blade-coating thickness is 100 mu m, and drying at 60 ℃ for 12 h. And then cutting into small discs with the diameter of 14mm by using a slicing machine to obtain the AC @ S positive electrode.
(4) And assembling the CR2032 button lithium-sulfur battery by taking Ni-NPCs-Li as a negative electrode and AC @ S as a positive electrode.
Matching and assembling the cathode prepared in the step (2) and the anode prepared in the step (3) into a button cell, wherein the used separator is a commercial polypropylene (PP) separator, the electrolyte solute is lithium trifluoromethanesulfonimide (LiTFSI), the solvent is 1, 3-Dioxolane (DOL) and Dimethoxymethane (DME), the volume ratio is 1: 1, and the additive is 0.1M LiNO3The concentration of the electrolyte is 1 mol/L.
Example 3
(1) Preparing Ni-NPCs (nickel modified nitrogen-doped porous carbon) carrier materials and pole pieces.
Mixing and dissolving 2mmoL nickel nitrate hexahydrate and 2mmoL trimesic acid in a 60mLDMF solvent, stirring for 30min, performing hydrothermal reaction for 12h at 150 ℃, washing for 2-3 times by DMF and ethanol in sequence after natural cooling, and drying for 12h at 60 ℃ to obtain the Ni-MOFs precursor. Then, physically mixing Ni-MOFs serving as a precursor with melamine according to the mass ratio of 1: 1, calcining for 3 hours at 800 ℃ in an argon atmosphere at the heating rate of 5 ℃/min, and obtaining the Ni-NPCs (nickel-modified nitrogen-doped porous carbon) carrier material. And then mixing Ni-NPCs, acetylene black and PVDF (polyvinylidene fluoride) according to the mass ratio of 8: 1, adding 150 muL NMP, grinding to prepare uniform negative electrode slurry, blade-coating the prepared slurry on smooth copper foil to prepare a Ni-NPCs pole piece, wherein the blade-coating thickness is 100 mu m, and drying at 60 ℃ for 12 hours.
(2) And preparing the Ni-NPCs-Li cathode.
Cutting the dried Ni-NPCs pole piece into a small wafer with the diameter of 14mm by using a slicer, assembling the small wafer with a metal lithium piece to form the button cell, wherein the electrolyte solute is lithium trifluoromethanesulfonimide (LiTFSI), the solvent is 1, 3-Dioxolane (DOL) and Dimethoxymethane (DME), the volume ratio is 1: 1, and the additive is 0.1M LiNO3The concentration of the electrolyte is 1 mol/L. After the cell was assembled, the current density was 0.5mA cm-2Under the condition of (1), constant current is deposited for 18h, and 9mAh cm is embedded into the Ni-NPCs pole piece-2The Ni-NPCs-Li (nickel modified nitrogen-doped porous carbon-loaded lithium) cathode can be prepared by using the metal lithium.
(3) Preparing a sulfur-carbon (AC @ S) anode.
Mixing and grinding commercial activated carbon and sublimed sulfur according to the mass ratio of 7: 3, placing the mixture in a tubular furnace, keeping the temperature at 155 ℃ for 12 hours, and marking the obtained material as an AC @ S positive electrode. And then mixing and grinding the AC @ S, the acetylene black and the PVDF according to the mass ratio of 8: 1, adding 150 muL NMP after grinding uniformly, continuing grinding until uniform slurry is formed, then carrying out blade coating on the slurry onto a smooth aluminum foil by using a scraper, wherein the blade coating thickness is 100 mu m, and drying at 60 ℃ for 12 h. And then cutting into small discs with the diameter of 14mm by using a slicing machine to obtain the AC @ S positive electrode.
(4) And assembling the CR2032 button lithium-sulfur battery by taking Ni-NPCs-Li as a negative electrode and AC @ S as a positive electrode.
Matching and assembling the cathode prepared in the step (2) and the anode prepared in the step (3) into a button cell, wherein the used separator is a commercial polypropylene (PP) separator, the electrolyte solute is lithium trifluoromethanesulfonimide (LiTFSI), the solvent is 1, 3-Dioxolane (DOL) and Dimethoxymethane (DME), the volume ratio is 1: 1, and the additive is 0.1M LiNO3The concentration of the electrolyte is 1 mol/L.
Comparative example 1
Different from the embodiment 1, the cathode used this time is a lithium metal cathode with the thickness of 600 μm, and a finished product can be directly purchased. And also assembled into a CR2032 button lithium-sulfur battery.
Test example 1
(1) The rate capability of the button cell assembled in examples 1-3 was tested.
The CR2032 button cell assembled in examples 1 to 3 was sandwiched between three stainless steel electrodes, respectively, and rate performance test was performed at 30 ℃ using a new wil cell test system with a test voltage range of 1.7 to 2.8V. FIG. 3 shows Ni-NPCs-Li cathodes (3, 6, 9mAh cm) at different deposition amounts-2) The rate performance graph of the assembled lithium-sulfur battery shows that the discharge capacity of the lithium-sulfur battery gradually decreases due to the influence of internal polarization of the battery as the charge and discharge rate increases. When the deposition amount of the metallic lithium is 3 and 9mAh cm-2At 0.1C, the capacity of the cell was comparable (about 398mAh g)-1) When the deposition amount is 6mAh cm-2The initial capacity of the battery is the highest, and the discharge capacities at charge and discharge rates of 0.1, 0.2, 0.3, 0.5, 1.0 and 2.0C are 612, 516, 443, 344, 207 and 63mAh g in sequence-1. In addition, since the prepared negative electrode was gradually activated, the deposition amount of the negative electrode was 6mAh cm-2In this case, the coulombic efficiency of the lithium-sulfur battery gradually increases as the charge/discharge rate increases. When the charge and discharge rate is suddenly adjusted from 2.0C to 0.1C, the discharge capacity of the battery can be adjusted from 63mAh g-1Restore to 565mAh g-1。
(2) The long cycle performance of the button cell assembled in examples 1-3 was tested.
The CR2032 button cell assembled in examples 1 to 3 was sandwiched between three stainless steel electrodes, and a long cycle performance test was performed at 30 ℃ using a new wiler cell test system, with a test voltage range of 1.7 to 2.8V and a test charge-discharge rate of 1.0C, and the test results are shown in fig. 4. It can be seen that when the deposition amount of metallic lithium in the Ni-NPCs-Li negative electrode was 3mAh cm-2Although the initial capacity of the battery was the highest (about 218mAh g)-1) However, after 400 cycles, the capacity retention rate was as low as 61%. In contrast, when the anode deposition amount isIs 6mAh cm-2The initial discharge capacity of the assembled lithium-sulfur battery at 1.0C was 170mAh g-1After 400 cycles, the capacity retention rate is 86%, and the performance is superior to the capacity of 3mAh cm-2The charge-discharge efficiency of the battery is always stable and is higher than 90% in the whole process, because the Ni-NPCs-Li negative electrode can inhibit the growth and volume expansion of lithium dendrites in the circulating process, and the attenuation of the battery capacity is effectively reduced.
Detection example 2
(1) The rate performance of the assembled button cell of comparative example 1 was tested.
The CR2032 button cell assembled in the comparative example 1 is respectively clamped between stainless steel electrodes, and a multiplying power performance test is carried out at 30 ℃ by using a new Wille cell test system, wherein the test voltage range is 1.7-2.8V. FIG. 5 is a graph showing rate performance of a lithium-sulfur battery assembled with a lithium metal negative electrode, and when compared with FIG. 3, it can be seen that the discharge capacities of the lithium-sulfur battery assembled with the lithium metal negative electrode at 0.1, 0.2, 0.3, 0.5, 1.0 and 2.0C charge-discharge rates are 622, 423, 293, 179, 125 and 18mAh g-1. Obviously, the discharge capacity of the lithium-sulfur battery assembled by the lithium metal negative electrode is lower than that of the lithium-sulfur battery assembled by the Ni-NPCs-Li negative electrode along with the increase of the charge-discharge rate. Meanwhile, the lithium metal negative electrode has low charge and discharge efficiency at a high rate and becomes unstable when adjusted back to a low rate, and the lithium sulfur battery assembled by the Ni-NPCs-Li negative electrode has stable charge and discharge efficiency even after the lithium sulfur battery is adjusted back to the low rate from the high rate.
(2) The assembled button cell of comparative example 1 was tested for long cycle performance.
The CR2032 type button cell assembled in comparative example 1 was sandwiched between stainless steel electrodes, and a long cycle performance test was performed at 30 ℃ using a new wiler cell test system, with a test voltage range of 1.7-2.8V and a test charge-discharge rate of 1.0C. As can be seen from fig. 6, although the capacity fading of the lithium-sulfur battery assembled by the metallic lithium negative electrode is not obvious under the same conditions, the discharge capacity is low and the charge-discharge efficiency is unstable because the SEI film is continuously destroyed by the severe volume expansion and dendrite growth of the lithium during the charge-discharge process of the pure lithium negative electrode, so that fresh lithium is continuously exposed to have side reactions with the shuttling lithium polysulfide.
(3) The charge and discharge curves of the assembled button cells of example 2 and comparative example 1 were tested.
The CR2032 button cell batteries assembled in example 2 and comparative example 1 were respectively sandwiched between two stainless steel electrodes, and a charge and discharge test was performed at 30 ℃ using a new wil cell test system, with a test voltage range of 1.7 to 2.8V and a test charge and discharge rate of 0.1C, and the test results are shown in fig. 7. The lithium-sulfur battery assembled by the Ni-NPCs-Li cathode has obvious discharge platforms in the vicinity of 2.3V and 2.1V in sequence, and respectively corresponds to the conversion of elemental sulfur to long-chain lithium polysulfide and further to short-chain lithium sulfide. In contrast, although the discharge capacity of lithium sulfur assembled by a metallic lithium negative electrode at 0.1C is not much different from that of a lithium sulfur battery assembled by a Ni-NPCs-Li negative electrode, the charge-discharge platform is not clear enough and the polarization voltage is higher, which indicates that the shuttle effect of polysulfide and the passivation of the negative electrode surface are more serious.
(4) SEM images after cycling of the cells in example 2 and test example 1 were tested.
The CR2032 button type sample obtained by recycling step 2 of detection examples 1 and 2 was disassembled in a glove box to deposit lithium metal in an amount of 6mAh cm-2The Ni-NPCs-Li negative electrode and the metal lithium negative electrode are sealed, then the glove box is removed, samples are rapidly prepared, SEM characterization is carried out, and the result is shown in figure 8. In fig. 8, a is a cycled lithium metal negative electrode, and cracks, protrusions and crushed lithium metal appear on the surface of the lithium metal negative electrode, while b is a cycled SEM image of the Ni-NPCs-Li negative electrode in fig. 8, which has a relatively dense surface, has protrusions, but is small and uniformly distributed. Therefore, the modified composite negative electrode has a certain inhibiting effect on the formation of lithium dendrites and volume expansion on one hand, and the existence of the Ni-NPCs carrier material can reduce the direct contact between metal lithium and polysulfide and reduce the probability of side reaction between the metal lithium and the polysulfide on the other hand, which are two reasons that the Ni-NPCs-Li negative electrode has better cycle performance than a lithium-sulfur battery assembled by a pure lithium negative electrode.

Claims (10)

1. A preparation method of a nickel-modified nitrogen-doped porous carbon lithium-loaded negative electrode is characterized by comprising the following steps:
(1) nickel nitrate and trimesic acid are mixed and dissolved in a DMF solvent, and a Ni-MOFs material is synthesized through a hydrothermal reaction;
(2) mixing the Ni-MOFs material prepared in the step (1) as a precursor with a nitrogen source, and then pyrolyzing to prepare a nickel modified nitrogen-doped porous carbon material;
(3) mixing the nickel-modified nitrogen-doped porous carbon material prepared in the step (2) with acetylene black and PVDF according to the mass ratio of 8: 1, adding N-methyl pyrrolidone, grinding to prepare slurry, then blade-coating the slurry on copper foil, and drying to prepare a nickel-modified nitrogen-doped porous carbon electrode slice;
(4) and (4) carrying out electrodeposition lithium intercalation on the nickel-modified nitrogen-doped porous carbon electrode slice prepared in the step (3) to prepare the nickel-modified nitrogen-doped porous carbon lithium-loaded cathode.
2. The method according to claim 1, wherein in the step (1), the molar ratio of the nickel nitrate to the trimesic acid is 1: 1.
3. The method according to claim 1, wherein 1mmol of nickel nitrate is dissolved in 30mL of DMF solvent in the step (1).
4. The method according to claim 1, wherein in the step (1), the hydrothermal reaction is carried out at a temperature of 150 ℃ for 12 hours.
5. The process according to claim 1, wherein in the step (2), the nitrogen source is melamine; the mass ratio of the Ni-MOFs material to the nitrogen source is 1: 1.
6. The method according to claim 1, wherein in the step (2), the pyrolysis is performed in an inert gas atmosphere at a pyrolysis temperature of 800 ℃ for 2 hours.
7. The production method according to claim 1, wherein in the step (3), the thickness of the slurry drawn down is 100 μm.
8. The production method according to claim 1, wherein in the step (4), the lithium intercalation current density is 0.5mA cm-2The time is 6-18 h, and the lithium embedding amount is 3-9 mAh cm-2。
9. The nickel-modified nitrogen-doped porous carbon lithium-loaded negative electrode prepared by the preparation method according to any one of claims 1 to 8.
10. The use of the nickel-modified nitrogen-doped porous carbon-supported lithium negative electrode of claim 9 in the preparation of a lithium-sulfur battery.
CN202210644541.2A 2022-06-09 2022-06-09 Nickel-modified nitrogen-doped porous carbon lithium-loaded negative electrode and preparation method and application thereof Pending CN114744162A (en)

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Application publication date: 20220712