CN109037594B - Self-healing polymer modified alkali metal negative electrode and preparation method and application thereof - Google Patents

Self-healing polymer modified alkali metal negative electrode and preparation method and application thereof Download PDF

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CN109037594B
CN109037594B CN201810703161.5A CN201810703161A CN109037594B CN 109037594 B CN109037594 B CN 109037594B CN 201810703161 A CN201810703161 A CN 201810703161A CN 109037594 B CN109037594 B CN 109037594B
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CN109037594A (en
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熊训辉
王钢
陈云华
杨成浩
林志华
林璋
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South China University of Technology SCUT
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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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/628—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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a self-healing polymer modified alkali metal cathode and a preparation method and application thereof. The invention firstly dissolves the polymer with self-healing function in organic solvent, and then uniformly coats the organic solvent on the surface of alkali metal, and the polymer can form chelate with alkali metal ions on the surface of metal and cover the surface of alkali metal as a strong Solid Electrolyte (SEI) film. The SEI film formed on the surface of the alkali metal is very uniform, so that the side reaction between interfaces is remarkably reduced, and the mechanical damage and cracks caused by volume expansion/contraction in the charge-discharge cycle process of the alkali metal can be spontaneously repaired, thereby effectively inhibiting the growth of dendrites, relieving the volume change of the alkali metal and ensuring the stable and efficient long-term cycle performance. The preparation method is simple, is suitable for large-scale production, is matched with a high-capacity anode material, can meet the use requirement of a novel high-energy-density power battery, and has wide application prospect.

Description

Self-healing polymer modified alkali metal negative electrode and preparation method and application thereof
Technical Field
The invention relates to the field of alkali metal ion battery cathode materials and electrochemistry, in particular to a self-healing polymer modified alkali metal cathode and a preparation method and application thereof.
Background
With the increasing development of electric vehicles and large-scale energy storage, the energy density of conventional lithium ion batteries has not increased at a rate to keep pace with the energy storage devices. Alkali metals have ultrahigh theoretical specific capacity and lowest electrochemical potential as the most ideal anode material. The alkali metal cathode can be applied to novel cathode materials such as air, sulfur and the like to be matched, and can also be assembled into a full battery with the traditional cathode materials, so that the requirements of high-power and high-energy-density power battery materials are met. However, the highly active alkali metal can react with most of the organic electrolyte and the salt in the electrolyte, consuming the alkali metal and the electrolyte too much, so that the coulombic efficiency of the alkali metal during the circulation process is not high enough and the circulation performance is poor. In addition, alkali metals tend to form dendrites during repeated plating/stripping processes, which can easily puncture the separator causing a series of safety problems. In order to solve the problems, researchers at home and abroad do a great deal of modification work on the method. For example, the courage research team permeates metal sodium into the gaps of the three-dimensional carbon felt through a hot melting method to form a three-dimensional flexible carbon felt/metal sodium composite negative electrode. The composite cathode not only provides sufficient space for pre-storing sodium in the preparation process, but also provides a carrier for receiving metal sodium in the circulation process, and can balance the distribution of sodium ions/electrons, thereby achieving the effects of suppressing dendrites and buffering volume expansion (Advanced Energy Materials,2018,8, 1702764). The Hulian subject group reported that a three-dimensional framework made of carbon fibers was used as a stable skeleton, and SnO was added2The Li/Na-Sn alloy with lithium affinity is formed after lithium/sodium is coated and melted, the alloy layer has rich electrochemical active sites, plays a key role in the lithium/sodium homogenization nucleation process, effectively inhibits the growth of dendrite by reducing local current density and limits the volume change in the charging and discharging process through a porous structure. (Advanced)Energy Materials,2018,1800635). The research results provide a new idea for solving the problem of dendritic crystal growth, but the methods are complex to operate and difficult to produce on a large scale.
Disclosure of Invention
The invention aims to provide a self-healing polymer modified alkali metal cathode, and a preparation method and application thereof, aiming at the problems of poor cycle performance, low coulombic efficiency, poor safety and the like caused by dendritic crystal growth of the alkali metal cathode in the cycle process.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a self-healing polymer modified alkali metal negative electrode comprises the following steps:
dissolving a polymer with a self-healing function in an organic solvent to obtain a polymer solution; then under the protection of inert gas, the polymer solution is uniformly coated on the surface of alkali metal, and the polymer can form a chelate with alkali metal ions on the surface of alkali metal and cover the surface of alkali metal as a strong SEI film; after standing, the resulting cured polymer modified alkali metal negative electrode.
Preferably, the polymer is one or more of polypropylene (PP), Polyethylene (PE), polyvinyl chloride (PVC), Polystyrene (PS), polyethylene glycol (PEO), polyalkylene oxide (PEO), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), pyrimidinone (UPy), diimide (PTCDI).
Preferably, the mass fraction of the polymer in the polymer solution is 0.05% to 5%.
Preferably, the organic solvent is one or more of ethanol, acetone, Tetrahydrofuran (THF), N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), methyl salicylate (MeSA).
Preferably, the inert gas is one or more of helium, neon and argon.
Preferably, the alkali metal is lithium, sodium or potassium.
Preferably, the thickness of the SEI film is 10nm to 10 μm.
Preferably, the standing temperature is 20-60 ℃; the standing time is 2-24 h.
The self-healing polymer modified alkali metal negative electrode prepared by the method is provided.
The self-healing polymer modified alkali metal cathode is applied to assembling an alkali metal battery, and the alkali metal battery mainly adopts LiFePO4、MV3(PO4)3、MxCoO2(0.4≤x≤1)、MxMnO2(0.4≤x≤1)、xLiMnO2·(1-x)LiMO2(0<x<1)、LiNixCoyMn1-yO2(0.5≤x≤1,0≤y≤0.2)、LiNi0.5Mn1.5O4、Li2TiO3、FeF3·xH2O (x is more than or equal to 0 and less than or equal to 0.5), S or metal oxide/sulfide are taken as the positive/negative electrode materials, wherein M is Li, Na and K; taking an alkali metal cathode modified by a self-healing polymer as a counter electrode material; GF, PE, PP/PE or PP/PE/PP and the like are taken as membrane diaphragms; an ester electrolyte or an ether electrolyte is used as the electrolyte.
The invention adopts a simple and feasible surface treatment method of the alkali metal cathode with wide applicability, and an SEI film with a self-repairing function is formed on the surface of the alkali metal cathode through chelation. The SEI film can effectively inhibit side reactions and repair mechanical damage and cracks of alkali metals caused by volume expansion/contraction in the charging and discharging processes, and the formation of lithium dendrites and dead lithium is avoided, so that the cycle life of the battery is prolonged.
Compared with the prior art, the invention has the following technical effects:
(1) the method has the advantages of simple synthesis process, simple operation, wide adaptability, easy large-scale production and the like.
(2) According to the invention, a layer of self-healing polymer film is formed in situ on the surface of the alkali metal cathode, so that the side reaction between interfaces can be effectively reduced, and the mechanical damage and cracks of the alkali metal in the repeated electroplating/stripping process can be repaired spontaneously; the polymer protective layer inhibits the growth of dendritic crystals, remarkably improves the safety performance of the dendritic crystals, and effectively improves the electrochemical performance of a counter electrode material matched with the polymer protective layer when the polymer protective layer is applied to a metal alkali metal battery. Therefore, the method for modifying the interface of the alkali metal cathode by using the self-healing polymer provided by the invention has the advantages of excellent electrochemical performance, better safety performance and the like, can meet the use requirement of the advanced energy storage material with high energy density, and is beneficial to promoting the industrialization process of the alkali metal battery.
Drawings
Fig. 1 is an SEM image of metallic lithium without any treatment in example 1.
Fig. 2 is an SEM image of lithium metal modified with a self-healing polymer in example 1.
Fig. 3 is a charge-discharge curve diagram of a symmetric battery Li l Li assembled by the self-healing polymer modified lithium metal negative electrode in example 1.
Fig. 4 is a coulomb efficiency chart of the Li | | | Cu battery assembled by the self-healing polymer modified lithium metal negative electrode and the copper foil in embodiment 2.
FIG. 5 shows the LiNi and the self-healing polymer-modified and untreated lithium metal cathodes of example 20.6Co0.2Mn0.2O2And assembling to form the cycle performance diagram of the full cell.
FIG. 6 shows the LiNi and the self-healing polymer-modified and untreated lithium metal cathodes of example 20.6Co0.2Mn0.2O2And assembling into a full-battery charging and discharging curve diagram.
Detailed Description
Specific embodiments of the present invention will be described in further detail below with reference to examples and drawings, but the present invention is not limited thereto.
The experimental procedures in the following examples are conventional unless otherwise specified.
Example 1
Under the protection of argon gas, dissolving a self-healing polymer (PEO-UPy, wherein the molar ratio of PEO to UPy is 4:1) in DMSO, preparing a polymer solution with the mass fraction of 1.0%, taking 25 mu L of the solution by using a liquid-transferring gun, vertically dropping the solution on the surface of the metal lithium cathode, uniformly coating the solution, standing at room temperature for 20 hours, and obtaining the lithium metal cathode modified by the self-healing polymer, wherein the thickness of a protective layer is 110 nm.
The surface of the lithium metal negative electrode which is not modified is uneven and has obvious defects (shown in figure 1), and the surface of the lithium metal negative electrode which is modified by the polymer is flat (shown in figure 2). The polymer-coated lithium metal negative electrode obtained by this method was used as an electrolyte solution containing 1 wt% LiNO and a mixed solution of 1M LiTFSI dissolved in DOL/DME (volume ratio: 1)3As an additive, PP is a diaphragm, and the PP and the copper foil are assembled into a Li | | | Cu battery, and tests show that the current density is 1mA/cm2The deposition capacity is 1mAh/cm2Under the condition, the coulomb efficiency of the product is still 97 percent after 100 cycles. The lithium metal negative electrode modified by the self-healing polymer prepared by the method is assembled into a Li (I) Li symmetrical battery with the current density of 1mA/cm2The deposition capacity is 1mAh/cm2Under the condition, the charge-discharge curve is stable, the cycle time can reach 500h, and the hysteresis voltage is also obviously improved to be about 100mV (see figure 3). And ternary material LiNi0.6Co0.2Mn0.2O2Assembled into a full battery, the discharge specific capacity of the full battery is still as high as 130.5mAh/g under the current density of 10C (1C is 180mAh/g), and the full battery shows extremely excellent rate stability.
Example 2
Under the protection of argon gas, dissolving a self-healing polymer (PEO-UPy, wherein the molar ratio of PEO to UPy is 4:1) in THF, preparing a polymer solution with the mass fraction of 0.5%, taking 25 mu L of the solution by using a liquid-transferring gun, vertically dropping the solution on the surface of the lithium metal cathode, uniformly coating the solution, standing at room temperature for 2 hours to obtain the lithium metal cathode modified by the self-healing polymer, wherein the thickness of a protective layer is 50 nm.
The surface of the metal lithium cathode which is not modified is uneven, and has obvious defects. The polymer-coated lithium metal cathode prepared by the method is made of 1M LiFP6The Li [ I ] Cu battery is assembled by taking the mixed solution dissolved in EC/DMC (volume ratio of 1:1) as the electrolyte and PP as the diaphragm and copper foil, and tests show that the Li [ I ] Cu battery is assembled by using the mixed solution and the copper foil, wherein the current density of the Li [ I ] Cu battery is 1mA/cm2The deposition capacity is 1mAh/cm2Under these conditions, the coulombic efficiency remained 74% after 200 cycles (see FIG. 4). The lithium metal cathode modified by the polymer prepared by the method is assembled into a Li (I) Li symmetrical battery with the current density of 1mA/cm2The deposition capacity is 1mAh/cm2Under the condition, the charge-discharge curve is stable, the cycle time can reach 1000h, and the hysteresis voltage is greatly improved to about 25 mV. And ternary material LiNi0.6Co0.2Mn0.2O2The discharge specific capacity of the assembled full-cell is still as high as 161.2mAh/g after two hundred cycles under the current density of 1C, and the excellent cycle stability is shown (see figure 5 and figure 6).
Example 3
Under the protection of high-purity argon gas, dissolving a self-healing polymer (PEG-UPy, wherein the molar ratio of PEG to UPy is 2:1)) in DMF, preparing a polymer solution with the mass fraction of 1.0%, taking 25 mu L of the solution by using a liquid-transferring gun, vertically dropping the solution on the surface of the metal lithium cathode, uniformly coating the solution, standing at room temperature for 3 hours to obtain the lithium metal cathode modified by the self-healing polymer, wherein the thickness of a protective layer is 80 nm.
The self-healing polymer modified lithium metal cathode prepared by the method is assembled into a symmetrical battery with the current density of 2mA/cm2The deposition capacity is 2mAh/cm2Under the condition, the charge-discharge curve is stable, the cycle time can reach 300h, and the hysteresis voltage is also greatly improved. The self-healing polymer modified lithium metal negative electrode can effectively inhibit the growth of lithium dendrites, and shows excellent electrochemical stability.
Example 4
Under the protection of high-purity argon gas, dissolving a self-healing polymer (PVC-UPy, wherein the molar ratio of PVC to UPy is 3:1) in DMAC (dimethylacetamide), preparing a polymer solution with the mass fraction of 0.1%, taking 25 mu L of the solution by using a liquid-transferring gun, vertically dripping the solution on the surface of the metal lithium cathode, uniformly coating the solution, standing the solution at 45 ℃ for 3 hours to obtain the lithium metal cathode modified by the self-healing polymer, wherein the thickness of a protective layer is 10 nm.
The self-healing polymer modified lithium metal cathode prepared by the method is matched with a lithium titanate material to assemble a full cell, and tests show that after 5C high current density is cycled for 500 circles, the specific discharge capacity and the capacity retention rate of the lithium metal cathode are higher than those of the untreated material.
Example 5
Under the protection of argon gas, dissolving a self-healing polymer (PS-PTCDI, wherein the molar ratio of PS to PTCDI is 5:1) in NMP, preparing a polymer solution with the mass fraction of 0.75%, taking 25 mu L of the solution by using a liquid-transferring gun, vertically dripping the solution on the surface of the metal sodium cathode, uniformly coating the solution, standing at 30 ℃ for 10 hours to obtain the sodium metal cathode modified by the self-healing polymer, wherein the thickness of a protective layer is 150 nm.
The self-healing polymer modified sodium metal cathode prepared by the method is prepared by 1M NaClO4The mixed solution dissolved in EC/DMC (volume ratio is 1:1) is used as electrolyte, GF is used as diaphragm, and Na | Cu battery is assembled by copper foil, and tests show that the current density is 0.5mA/cm2The deposition capacity is 1mAh/cm2Under the condition, the coulomb efficiency of the product is still 80 percent after 50 cycles. The metallic sodium cathode modified by the polymer prepared by the method is assembled into a Na-Na symmetrical battery with the current density of 0.5mA/cm2The deposition capacity is 1mAh/cm2Under the condition, the charge-discharge curve is stable, the cycle time can reach 150h, the hysteresis voltage is also obviously improved, about 400mV shows excellent stability. With NaV3(PO4)3The material is assembled into a full battery, the discharge specific capacity of the full battery is still as high as 144.6mAh/g under the current density of 2A/g, and the full battery shows extremely excellent rate capability.
Example 6
Under the protection of neon gas, dissolving a self-healing polymer (PMMA-PTCDI, wherein the molar ratio of PMMA to PTCDI is 2:1) in DMF, preparing a polymer solution with the mass fraction of 0.4%, taking 25 mu L of the solution by using a liquid-transferring gun, vertically dripping the solution on the surface of the metal lithium cathode, uniformly coating the solution, standing at 35 ℃ for 12 hours, and obtaining the lithium metal cathode modified by the self-healing polymer, wherein the thickness of a protective layer is 130 nm.
The self-healing polymer modified lithium metal prepared by the method is matched with a lithium iron phosphate material to be assembled into a full battery, and tests show that after the 2C high-current density cycle is performed for 300 circles, the specific discharge capacity and the capacity retention rate of the full battery are higher than those of the untreated material.
Example 7
Under the protection of xenon gas, dissolving a self-healing polymer (PS-UPy, wherein the molar ratio of PS to UPy is 1:1) in NMP, preparing a polymer solution with the mass fraction of 1.2%, taking 25 mu L of the solution by using a liquid-transferring gun, vertically dripping the solution on the surface of the metal sodium cathode, uniformly coating the solution, standing at room temperature for 12 hours to obtain the sodium metal cathode modified by the self-healing polymer, wherein the thickness of a protective layer is 130 nm.
The self-healing polymer modified sodium metal cathode prepared by the method is prepared by 1M NaCF3SO3The mixed solution dissolved in DEG/DME (volume ratio is 1:1) is used as electrolyte, GF is used as diaphragm, and Na | | | Cu battery is assembled by copper foil, and tests show that the current density is 2mA/cm2The deposition capacity was 0.5mAh/cm2The coulombic efficiency of the product is still as high as 84 percent after 50 cycles of lower circulation. The material is matched with a tin sulfide material to be assembled into a full battery, and tests show that after the material is cycled for 600 cycles at a current density of 0.5A/g, the specific discharge capacity and the capacity retention rate of the material are higher than those of the untreated material.
Example 8
Under the protection of xenon gas, dissolving a self-healing polymer (PVDF-UPy, wherein the molar ratio of PVDF to UPy is 3:1) in DMAC (dimethylacetamide), preparing a polymer solution with the mass fraction of 2%, taking 25 mu L of the solution by using a liquid transfer gun, vertically dropping the solution on the surface of the potassium metal cathode, uniformly coating the solution, standing at room temperature for 18h to obtain the potassium metal cathode modified by the self-healing polymer, wherein the thickness of a protective layer is 150 nm.
The polymer-coated potassium metal negative electrode prepared by the method is subjected to 0.8M KPF6The mixed solution dissolved in EC/DEC (volume ratio of 1:1) is taken as electrolyte, GF is taken as diaphragm, and K [ I ] Cu battery is assembled with copper foil, and tests show that the current density is 0.2mA/cm2The deposition capacity is 1mAh/cm2Under the condition, the coulomb efficiency of the product is still 72 percent after 80 cycles. The polymer modified metal potassium cathode prepared by the method is assembled into a symmetrical battery with the current density of 0.5mA/cm2Deep and deepThe volume capacity is 1mAh/cm2Under the condition, the charge-discharge curve is stable, the cycle time can reach 80h, the hysteresis voltage is also obviously improved, and the excellent cycle stability is shown. And K0.6CoO2The anode material is assembled into a full battery, and the discharge specific capacity of the full battery is still 63.4mAh/g after 30 cycles under the current density of 40 mA/g.
Example 9
Under the protection of neon gas, dissolving a self-healing polymer (PMMA-UPy, wherein the molar ratio of PPMMA to UPy is 4:1) in DMAC (dimethylacetamide), preparing a polymer solution with the mass fraction of 5%, taking 25 mu L of the solution by using a liquid-transferring gun, vertically dripping the solution on the surface of a potassium lithium cathode, uniformly coating the solution, standing at 60 ℃ for 16 hours to obtain the self-healing polymer modified potassium metal cathode, wherein the thickness of a protective layer is 2 mu m.
The self-healing polymer modified potassium metal prepared by the method is matched with a titanium dioxide material to assemble a full cell, and tests show that after the current density of 0.2A/g is cycled for 60 circles, the discharge specific capacity of the full cell still has 120mAh/g, which is obviously higher than that of an untreated material.
Example 10
Under the protection of high-purity argon gas, dissolving a self-healing polymer (PEO-UPy, wherein the molar ratio of the PEO to the UPy is 2:1) in THF, preparing a polymer solution with the mass fraction of 2%, taking 25 mu L of the solution by using a liquid transfer gun, vertically dripping the solution on the surface of the metal sodium cathode, uniformly coating the solution, standing at room temperature for 12 hours, and obtaining the sodium metal cathode modified by the self-healing polymer, wherein the thickness of a protective layer is 300 nm.
The self-healing polymer modified sodium metal cathode prepared by the method is prepared by 1M NaPF6The mixed solution dissolved in EC/DME (volume ratio is 1:1) is used as electrolyte, GF/PE is used as diaphragm, and the electrolyte and copper foil are assembled into a Na | | Cu battery, and tests show that the current density is 5mA/cm2The deposition capacity is 1mAh/cm2The coulombic efficiency of the product is still as high as 79 percent after the product is circulated for 40 circles. The lithium iron oxide battery is matched with an iron oxide material to be assembled into a full battery, and tests show that after the lithium iron oxide battery is cycled for 1000 cycles at a current density of 1A/g, the discharge specific capacity and the capacity retention rate of the lithium iron oxide battery are higher than those of the untreated material.
Example 11
Under the protection of helium gas, dissolving a self-healing polymer (PMMA-UPy, wherein the molar ratio of PMMA to UPy is 3:1) in acetone to prepare a polymer solution with the mass fraction of 1.0%, taking 25 mu L of the solution by using a liquid-transferring gun, vertically dropping the solution on the surface of the metal lithium cathode, uniformly coating the solution, standing at room temperature for 6 hours to obtain the lithium metal cathode modified by the self-healing polymer, wherein the thickness of a protective layer is 150 nm.
Lithium metal and Li modified by self-healing polymer prepared by the method1.2Mn0.54Ni0.13C0.13O2The positive electrode material is matched and assembled into a full battery, and tests show that after the current density of 0.5C is cycled for 200 circles, the specific discharge capacity of the battery is 236.6mAh/g, which is obviously superior to that of an untreated material.
Example 12
Under the protection of high-purity argon gas, dissolving a self-healing polymer (PEG-PTCDI, wherein the molar ratio of PS to UPy is 4:1)) in DMAC (dimethylacetamide), preparing a polymer solution with the mass fraction of 0.8%, taking 25 mu L of the solution by using a liquid-transferring gun, vertically dripping the solution on the surface of the metal lithium cathode, uniformly coating the solution, standing the solution at 40 ℃ for 15 hours to obtain the lithium metal cathode modified by the self-healing polymer, wherein the thickness of a protective layer is 180 nm.
The self-healing polymer modified lithium metal cathode prepared by the method is assembled into a symmetrical battery with the current density of 1mA/cm2The deposition capacity is 3mAh/cm2Under the condition, the charge-discharge curve is stable, the cycle time can reach 600h, and the hysteresis voltage is also greatly improved. The self-healing polymer modified lithium metal negative electrode can effectively inhibit the growth of lithium dendrites, and shows excellent electrochemical stability.

Claims (9)

1. A preparation method of a self-healing polymer modified alkali metal negative electrode is characterized by comprising the following steps:
dissolving a polymer with a self-healing function in an organic solvent to obtain a polymer solution; then under the protection of inert gas, the polymer solution is uniformly coated on the surface of alkali metal, and the polymer can form a chelate with alkali metal ions on the surface of alkali metal and cover the surface of alkali metal as a strong SEI film; after standing, an alkali metal negative electrode modified by a healing polymer; the polymer is formed by compounding ureido pyrimidone with one or more of polypropylene, polyethylene, polyvinyl chloride, polystyrene, polyethylene glycol, polyalkylene oxide, polyvinylidene fluoride and polymethyl methacrylate.
2. The method of claim 1, wherein: the mass fraction of the polymer in the polymer solution is 0.05-5%.
3. The method of claim 1, wherein: the organic solvent is one or more of ethanol, acetone, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and methyl salicylate.
4. The method of claim 1, wherein: the inert gas is one or more of helium, neon and argon.
5. The method of claim 1, wherein: the alkali metal is lithium, sodium or potassium.
6. The method of claim 1, wherein: the thickness of the SEI film is 10 nm-10 mu m.
7. The method of claim 1, wherein: the standing temperature is 20-60 ℃; the standing time is 2-24 h.
8. A self-healing polymer modified alkali metal negative electrode made by the method of any one of claims 1-7.
9. The self-healing polymer modified alkali metal cathode of claim 8 applied to assembly of alkaliA metal battery, characterized in that: the alkali metal battery is made of LiFePO4、MV3(PO4)3、MxCoO2、MxMnO2、xLiMnO2·(1-x)LiMO2、LiNixCoyMn1-yO2、LiNi0.5Mn1.5O4、Li2TiO3、FeF3·xH2O, S, metal oxide or metal sulfide as positive electrode material or negative electrode material, wherein, M is Li, Na or K, MxCoO2Wherein x is more than or equal to 0.4 and less than or equal to 1, and MxMnO2Wherein x is more than or equal to 0.4 and less than or equal to 1, and xLiMnO2·(1-x)LiMO2Wherein x has a value range of 0<x<1，LiNixCoyMn1-yO2Wherein x and y have the value ranges of 0.5-1, 0-0.2 and FeF3·xH2The value range of x in O is more than or equal to 0 and less than or equal to 0.5; taking an alkali metal cathode modified by a self-healing polymer as a counter electrode material; GF, PE, PP/PE or PP/PE/PP are taken as diaphragms; ester electrolyte or ether electrolyte is used as electrolyte.
CN201810703161.5A 2018-06-30 2018-06-30 Self-healing polymer modified alkali metal negative electrode and preparation method and application thereof Active CN109037594B (en)

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CN113629246A (en) * 2020-05-09 2021-11-09 深圳新宙邦科技股份有限公司 Metal electrode and battery
CN112186134A (en) * 2020-09-11 2021-01-05 中国航发北京航空材料研究院 Preparation method of lithium metal electrode with protective layer
CN113314709A (en) * 2021-05-26 2021-08-27 长沙理工大学 Supermolecule polymer modified metal negative electrode and preparation method and application thereof
CN113782730A (en) * 2021-08-18 2021-12-10 武汉理工大学 Carbon cloth-based potassium metal composite electrode and preparation method and application thereof
CN114933706B (en) * 2022-05-12 2023-03-21 华南理工大学 Biomass dynamic gel polymer based on Schiff base reaction, lithium metal negative electrode, and preparation methods and applications thereof
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102315420A (en) * 2010-07-05 2012-01-11 中国科学院上海硅酸盐研究所 Metal cathode structure with protection layer and preparation method thereof
CN103779581A (en) * 2012-10-25 2014-05-07 华为技术有限公司 Porous negative pole piece and preparation method thereof, and lithium ion battery
CN107394115A (en) * 2016-04-29 2017-11-24 三星电子株式会社 Negative pole for lithium metal battery and the lithium metal battery including it
WO2018046494A1 (en) * 2016-09-06 2018-03-15 Oxis Energy Limited Anode for an electrochemical cell
CN108075106A (en) * 2017-11-22 2018-05-25 中国科学院化学研究所 A kind of adaptive elastic nano decorative layer preparation method of lithium anode

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102140129B1 (en) * 2016-09-28 2020-07-31 주식회사 엘지화학 Anode with mesh type insulating layer, lithium secondary battery containing the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102315420A (en) * 2010-07-05 2012-01-11 中国科学院上海硅酸盐研究所 Metal cathode structure with protection layer and preparation method thereof
CN103779581A (en) * 2012-10-25 2014-05-07 华为技术有限公司 Porous negative pole piece and preparation method thereof, and lithium ion battery
CN107394115A (en) * 2016-04-29 2017-11-24 三星电子株式会社 Negative pole for lithium metal battery and the lithium metal battery including it
WO2018046494A1 (en) * 2016-09-06 2018-03-15 Oxis Energy Limited Anode for an electrochemical cell
CN108075106A (en) * 2017-11-22 2018-05-25 中国科学院化学研究所 A kind of adaptive elastic nano decorative layer preparation method of lithium anode

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"A Flexible Solid Electrolyte Interphase Layer for Long-Life Lithium Metal Anodes";Nian-WuLi等;《Angew.Chem. Int.Ed.》;20180105;第57卷;第1505-1509页 *
"A Quadruple-Hydrogen-Bonded Supramolecular Binder for High-Performance Silicon Anodes in Lithium-Ion Batteries";Guangzhao Zhang等;《Small》;20180622;第14卷;第1-10页 *
"High-Performance Lithium Metal Negative Electrode with a Soft and Flowable Polymer Coating";Guangyuan Zheng等;《ACS Energy Lett.》;20161114;第1卷;第1247-1255页 *

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