CN112467147B - Lithium metal battery negative electrode current collector for inhibiting dendritic crystal growth and modification method thereof - Google Patents
Lithium metal battery negative electrode current collector for inhibiting dendritic crystal growth and modification method thereof Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 79
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 16
- 238000002715 modification method Methods 0.000 title abstract description 7
- 238000002109 crystal growth method Methods 0.000 title description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000004528 spin coating Methods 0.000 claims abstract description 18
- 210000001787 dendrite Anatomy 0.000 claims abstract description 15
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 229920002492 poly(sulfone) Polymers 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 229920012287 polyphenylene sulfone Polymers 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 9
- 229920006254 polymer film Polymers 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 229920013655 poly(bisphenol-A sulfone) Polymers 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 abstract description 20
- 229920006393 polyether sulfone Polymers 0.000 abstract description 20
- 239000003792 electrolyte Substances 0.000 abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011889 copper foil Substances 0.000 abstract description 8
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- 230000005501 phase interface Effects 0.000 abstract description 2
- 238000005137 deposition process Methods 0.000 abstract 1
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
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- 238000007599 discharging Methods 0.000 description 2
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- 239000002000 Electrolyte additive Substances 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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- 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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a lithium metal battery negative electrode current collector for inhibiting dendritic crystal growth and a modification method thereof, belonging to the field of dendritic crystal growth inhibition of a lithium battery negative electrode. According to the invention, a PES (polyether sulfone) film is modified on the surface of the current collector by using a spin-coating method, the PES film contains a large number of polar functional groups O = S = O, and the polar functional groups can induce uniform nucleation of lithium ions in the lithium deposition process, so that the growth of lithium dendrites is inhibited; meanwhile, the wettability of an electrode interface is improved, the impedance of a negative electrode and an electrolyte solid-liquid phase interface is reduced, and the transmission of interface lithium ions is improved; and the PES high polymer is covered on the copper foil, so that the direct contact between the electrode and the electrolyte can be prevented, and the consumption of the electrolyte in the circulation process can be prevented.
Description
Technical Field
The invention belongs to the field of dendritic crystal growth inhibition of a negative electrode of a lithium battery, and particularly relates to a negative electrode current collector of a lithium metal battery for inhibiting dendritic crystal growth and a modification method thereof.
Background
With the rapid development and application of portable charging and discharging equipment, in mobile energy storage equipment, a long-time charging interval is a new requirement for a high-energy-density battery. The lithium metal as the negative pole of the battery has extremely high theoretical specific capacity (3860 mAh-1) 10 times or more than that of the carbon material; the new generation rechargeable battery using the metallic lithium as the negative electrode has important research value and wide application prospect. The application of lithium metal batteries with higher energy density, lithium air batteries and lithium oxygen batteries is necessary to be premised on a mature lithium metal negative electrode technology.
The main current problem of the lithium metal negative electrode is that the electrons obtained by the lithium ions under the reduction potential of lithium are transformed from an ionic state to a metallic state and deposited on a current collector, and dendritic lithium metal, namely dendritic lithium metal, is formed due to the inherent characteristics of the lithium metal and the uneven distribution of current density. The lithium dendrites often break during multiple deposition/stripping cycles to form "dead lithium" which results in loss of the lithium metal negative active material and electrolyte, resulting in a sharp decrease in reversible capacity and a rapid decay in coulombic efficiency. Meanwhile, the dendrite in the deep part of the electrolyte often reduces the strength of an electrolyte interface film (SEI) on the surface of the lithium metal negative electrode, influences the stability of the battery structure and greatly shortens the service life of the battery. In the current method for inhibiting lithium dendrite, the regulation and control of electrolyte components and the use of electrolyte additives are the most convenient schemes, however, in the actual operation process of the battery, the additives can continuously generate irreversible chemical reactions, and the effect of the additives can continuously decline. The solid electrolyte has higher Young modulus, can inhibit the growth of lithium dendrite, and can effectively improve the safety performance of the lithium cathode, but the ionic conductivity of the solid electrolyte is far lower than that of a liquid electrolyte, so that the impedance of the battery is obviously increased, and the efficiency of the battery is low.
Disclosure of Invention
The invention provides a lithium metal battery negative current collector for inhibiting dendritic crystal growth and a modification method thereof, which are used for correspondingly treating a current collector Cu, reducing the generation of 'lithium dendritic crystals' and the formation of 'dead lithium', and improving the coulombic efficiency and the cycle life of a lithium metal battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lithium metal battery negative electrode current collector for inhibiting dendritic crystal growth is characterized in that a layer of polysulfone polar polymer film containing a polar functional group O = S = O is modified on the surface of the current collector.
A modification method of a negative electrode current collector of a lithium metal battery for inhibiting dendritic crystal growth comprises the following steps:
step 1: cutting the processed current collector into a proper size;
step 2: adding the polysulfone polar high-molecular polymer into N-N-dimethylformamide or N-methylpyrrolidone, isolating air and moisture, and naturally dissolving and standing to form a polysulfone polar high-molecular polymer-DMF or NMP mixed solution;
and step 3: uniformly coating the polysulfone polar high molecular polymer-DMF or NMP mixed solution obtained in the step 2 on the surface of the current collector obtained in the step 1;
and 4, step 4: and (3) quenching the current collector coated in the step (3) and then drying the current collector in vacuum to obtain the current collector with the surface covered by the polymer film containing the polar functional group O = S = O.
In the above step, the polysulfone polar high-molecular polymer in step 2 is Polysulfone Ether (PES), bisphenol a Polysulfone (PSU) or polyphenylene sulfone (PPSU), and the concentration of the mixed solution of the polysulfone polar high-molecular polymer and DMF or NMP is 1.3-66.7 mg/mL, preferably 3.3 mg/mL;
and 3, coating the surface of the current collector by using a spin coating method, wherein the rotation speed of the spin coating is 3500r/min, and the amount of the spin coating is 2-5 mL.
In the step 4, the quenching temperature is 100 ℃, the quenching time is 30min, the vacuum drying temperature is 80 ℃, and the drying time is 24 h.
The method for modifying the current collector is applied to a battery system taking lithium metal as a negative electrode, and comprises the following steps: lithium metal batteries, lithium sulfur batteries, lithium air battery systems.
Has the advantages that: the invention provides a lithium metal battery negative electrode current collector for inhibiting dendritic crystal growth and a modification method thereof, wherein an artificial polymer film on the surface of the current collector is adopted to protect a lithium negative electrode and inhibit dendritic crystal growth, and the distribution of lithium ion current is induced by utilizing the polar functional group S = O = S of the polymer; the method has obvious effect, and the modified negative electrode has good consistency and is convenient to operate. Modifying a layer of polysulfone polar high-molecular polymer film on the surface of the Cu electrode by using a spin-coating method, wherein the polysulfone polar high-molecular polymer film contains a large number of polar functional groups O = S = O, and the polar functional groups can induce the uniform nucleation of lithium ions in the electrodeposition process, so that the growth of lithium dendrites is inhibited; meanwhile, the wettability of an electrode interface is improved, the impedance of a negative electrode and an electrolyte solid-liquid phase interface is reduced, and the transmission of interface lithium ions is improved; the PES high polymer is covered on the copper foil, and can also prevent the direct contact of the electrode and the electrolyte, prevent the consumption of the electrolyte in the circulation process, and improve the coulombic efficiency and the circulation life of the batteryThe life is greatly improved. The spin-coated PES protective film is very stable, can well protect the sensitive area of the electrode from ineffective consumption of electrolyte, and is beneficial to improving the stability of the lithium metal electrode. The lithium metal half cell assembled by the current collector of the invention is at 0.5 mA cm-2， 0.5 mAh cm-2The charge and discharge are carried out, the average coulombic efficiency reaches 90%, and the cycle can be stably carried out for 220 circles, which is three times that of a control group; increasing the charge-discharge current density to 2.0 mA cm-2The battery can stably circulate for 120 circles; 3.0 mA cm-2The cell was able to cycle stably for 100 cycles. For a Li/Li symmetric cell, the Cu-PES structure has a small and stable impedance value and a longer cell cycle life of 1mA cm-2, 1 mAh cm-2Can be stably charged and discharged for 500 h under the condition.
Drawings
FIG. 1 is SEM images of the growth of lithium on negative electrodes of examples and comparative examples of the present invention, wherein (a) is an unmodified Cu current collector lithium deposition topography, and (b) is a Cu-PES composite current collector lithium deposition topography;
FIG. 2 is a graph showing the cycle efficiency after the current collectors of the example of the present invention and the comparative example, in which (a) is a current density of 0.5 mA cm-2The electric quantity is 0.5 mAh cm-2A graph of the discharge efficiency of the cell at that time, and (b) a graph of the current density of 1.0 mA cm-2The electric quantity is 1.0 mAh cm-2A discharge efficiency chart of the time cell, wherein (c) is a current density of 1.0 mA cm-2The electric quantity is 1.0 mAh cm-2Time lithium/lithium symmetrical battery charging and discharging curve chart.
Detailed Description
The invention is described in detail below with reference to the following figures and specific examples:
preparing a Polysulfone Ether (PES), bisphenol A Polysulfone (PSU) or polyphenylene sulfone (PPSU) -DMF or NMP mixed solution:
0.04 g, 0.1 g, 0.16 g, 0.3 g, 2 g of Polysulfone Ether (PES), bisphenol A type Polysulfone (PSU) or polyphenylene sulfone (PPSU) was weighed and added to 30 mL of N-N-Dimethylformamide (DMF) or NMP, respectively, to form a Polysulfone Ether (PES), bisphenol A type Polysulfone (PSU) or polyphenylene sulfone (PPSU) -DMF or NMP mixed solution having a mass concentration of 1.3 mg/mL, 3.3 mg/mL, 5.3 mg/mL, 10 mg/mL, 66.7 mg/mL, respectively, to be dissolved naturally.
Modifying a current collector:
cutting a copper foil with a polished single surface and a clean and tidy surface into a square with the side length of 5 cm, spin-coating Polysulfone Ether (PES), bisphenol A Polysulfone (PSU) or polyphenylene sulfone (PPSU) -DMF or NMP mixed solution with different concentrations on the surface of the copper foil, putting the copper foil in a muffle furnace for quenching at 100 ℃, transferring a sample into a vacuum drying oven after 30min, and drying at 80 ℃ for 24h to cover the surface of the copper with a polymer film containing a polar functional group O = S = O;
preparation of lithium metal battery:
under the protection of an Ar atmosphere glove box, assembling the modified copper current collector composite electrode into a half cell, and dropwise adding 70 microliter of 1mol/L LiPF6The EC/DMC electrolyte of (1) is charged for the first time at a given current, followed by a charge-discharge cycle.
Example 1
In the embodiment, the PES precursor solution subjected to spin coating is a polyether sulfone-DMF mixed solution with the mass concentration of 1.3 mg/mL; after vacuum drying, taking the Cu-PES composite electrode modified under the concentration as a substrate, and taking a lithium sheet as an anode; the current density of the cathode of the half cell is 0.5 mA cm-2(ii) a Electricity 1 mAh cm-2。
Example 2
In the embodiment, the PES precursor solution subjected to spin coating is a polyether sulfone-DMF mixed solution with the mass concentration of 3.3 mg/mL; after vacuum drying, taking the Cu-PES composite electrode modified under the concentration as a substrate, and taking a lithium sheet as an anode; the current density of the cathode of the half cell is 0.5 mA cm-2(ii) a Electricity 1 mAh cm-2。
Example 3
In the embodiment, the PES precursor solution subjected to spin coating is a polyether sulfone-DMF mixed solution with the mass concentration of 5.3 mg/mL; after vacuum drying, taking the Cu-PES composite electrode modified under the concentration as a substrate, and taking a lithium sheet as an anode; the current density of the cathode of the half cell is 0.5 mA cm-2(ii) a Electricity 1 mAh cm-2。
Example 4
This implementationIn the example, the PES precursor solution for spin coating is a polyethersulfone-DMF mixed solution with the mass concentration of 66.7 mg/mL; after vacuum drying, taking the Cu-PES composite electrode modified under the concentration as a substrate, and taking a lithium sheet as an anode; the current density of the cathode of the half cell is 0.5 mA cm-2(ii) a Electricity 1 mAh cm-2。
Example 5
In this example, the spin-coated bisphenol a Polysulfone (PSU) precursor solution was a bisphenol a polysulfone-DMF mixed solution with a mass concentration of 3.3 mg/mL; after vacuum drying, taking the Cu-PSU composite electrode modified under the concentration as a substrate, and taking a lithium sheet as an anode; the current density of the cathode of the half cell is 0.5 mA cm-2(ii) a Electricity 1 mAh cm-2。
Example 6
In this embodiment, the PES precursor solution for spin coating is a mixed solution of polyethersulfone-N-methylpyrrolidone (NMP) with a mass concentration of 3.3 mg/mL; after vacuum drying, taking the Cu-PES composite electrode modified under the concentration as a substrate, and taking a lithium sheet as an anode; the current density of the cathode of the half cell is 0.5 mA cm-2(ii) a Electricity 1 mAh cm-2。
Example 7
In the embodiment, the PES precursor solution subjected to spin coating is a polyether sulfone-DMF mixed solution with the mass concentration of 3.3 mg/mL; after vacuum drying, taking the Cu-PES composite electrode modified under the concentration as a substrate, and taking a lithium sheet as an anode; the current density of the cathode of the half cell is 1mA cm-2(ii) a Electricity 1 mAh cm-2。
Example 8
In the embodiment, the PES precursor solution subjected to spin coating is a polyether sulfone-DMF mixed solution with the mass concentration of 3.3 mg/mL; after vacuum drying, taking the Cu-PES composite electrode modified under the concentration as a substrate, and taking a lithium sheet as an anode; the current density of the cathode of the half cell is 2 mA cm-2(ii) a Electric quantity of 2 mAh cm-2. The rest is the same as example 1.
Comparative example 1
Preparation of lithium metal battery:
under the protection of an Ar atmosphere glove box, a commercial copper current collector and a lithium sheet are assembled into a half cell, and 70 microliter of 1mol/L LiPF is dropwise added6At a given current for the first timeCharging, followed by a charge-discharge cycle.
In the comparative example, the copper foil surface is coated with the DMF mixed solution without polyether sulfone; the current density of the cathode of the half cell is 0.5 mA cm-2(ii) a Electricity 1 mAh cm-2。
Comparative example 2
Preparation of lithium metal battery:
under the protection of an Ar atmosphere glove box, a commercial copper current collector and a lithium sheet are assembled into a half cell, and 70 microliter of 1mol/L LiPF is dropwise added6The EC/DMC electrolyte of (1) is charged for the first time at a given current, followed by a charge-discharge cycle.
In the present comparative example, in the present example, the surface of the copper foil was not subjected to any treatment; the current density of the cathode of the half cell is 0.5 mA cm-2(ii) a Electricity 1 mAh cm-2。
The lithium growth topography of the current collectors of the above examples and comparative examples is shown in fig. 1, fig. 1(a) is an unmodified Cu current collector lithium deposition topography, and fig. 1(b) is a Cu-PES composite current collector lithium deposition topography obtained by spin coating with a polyethersulfone-DMF mixed solution with a mass concentration of 3.3 mg/mL. The current density was 1mA cm-2The electric quantity is 1 mAh cm-2It can be seen that a large number of dendritic lithium dendrites grew over the unmodified Cu current collector; the Cu-PES composite current collector modified by the polyether sulfone-DMF mixed solution is subjected to electrodeposition, dendritic lithium dendrites are not generated, and compact nano-particle columnar lithium is formed, so that polyether sulfone can induce uniform nucleation of lithium ions, and the growth of the lithium dendrites is well inhibited.
The battery cycling efficiency is shown in FIG. 2, and it can be seen that the current density is 0.5 mA cm-20.5 mAh cm of electric quantity-2In the case (as shown in fig. 2 (a)), the coulombic efficiency of the Li-Cu half cell assembled by the unmodified Cu current collector is reduced sharply when the Li-Cu half cell circulates for 60 cycles, while the cell assembled by the copper foil modified by the polyethersulfone-DMF mixed solution has higher discharge efficiency and longer service life, the PES concentration is 3.3 mg/mL, the cell can stably circulate for 230 cycles, and the number of effective charge-discharge cycles is more than 3 times that of the unmodified half cell. The current density was 1mA cm-2(ii) a Electricity 1 mAh cm-2When (1)As shown in fig. 2 (b)), it can be seen that the cycle life of the Cu-PES composite current collector modified by the polyethersulfone-DMF mixed solution with the mass concentration of 3.3 mg/mL is also best in terms of cycle efficiency. For a lithium symmetric cell (as shown in fig. 2 (c)), it can be found that the voltage polarization rapidly increases and the cell fails when the control system is cycled for 220 h, while the Cu-PES structure has a more stable impedance value and a longer battery cycle life of 1mA cm-2， 1 mAh cm-2Can be stably charged and discharged for 500 h under the condition. In conclusion, the Cu-PES composite current collector obtained by spin-coating the polyether sulfone-DMF mixed solution provided by the invention has an active effect on uniform deposition of a metal lithium cathode, can better inhibit dendritic crystal growth in a lithium ion deposition stripping process, enables electrodeposition of lithium metal on a cathode to be more uniform, and can greatly improve the coulombic efficiency and stability of the lithium metal battery cathode.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (9)
1. A method for modifying a negative electrode current collector of a lithium metal battery for inhibiting dendritic growth is characterized by comprising the following steps of:
step 1: cutting the processed current collector into a proper size;
step 2: adding the polysulfone polar high-molecular polymer into N-N-dimethylformamide or N-methylpyrrolidone, isolating air and moisture, and naturally dissolving and standing to form a polysulfone polar high-molecular polymer-DMF or NMP mixed solution;
and step 3: uniformly coating the polysulfone polar high molecular polymer-DMF or NMP mixed solution obtained in the step 2 on the surface of the current collector obtained in the step 1;
and 4, step 4: and (3) quenching the current collector coated in the step (3) and then drying the current collector in vacuum to obtain the current collector with the surface covered by the polymer film containing the polar functional group O = S = O.
2. The method for modifying the negative electrode current collector of the lithium metal battery for inhibiting the dendritic growth according to claim 1, wherein the polysulfone-based polar high molecular polymer is polysulfone ether, bisphenol a polysulfone, or polyphenylene sulfone.
3. The method for modifying the lithium metal battery negative electrode current collector capable of inhibiting dendrite growth according to claim 2, wherein the concentration of the polysulfone polar high-molecular polymer-DMF or NMP mixed solution in the step 2 is 1.3-66.7 mg/mL.
4. The method for modifying the lithium metal battery negative electrode current collector capable of inhibiting dendrite growth according to claim 3, wherein the concentration of the polysulfone polar high-molecular polymer-DMF or NMP mixed solution in the step 2 is 3.3 mg/mL.
5. The method for modifying the negative electrode current collector of a lithium metal battery for suppressing dendrite growth according to claim 1, wherein step 3 is performed by applying the coating on the surface of the current collector by using a spin coating method.
6. The method for modifying the negative electrode current collector of the lithium metal battery for inhibiting the dendritic growth according to claim 5, wherein the rotation speed of the spin coating is 3500r/min, and the amount of the spin coating solution is 2-5 mL.
7. The method for modifying the negative electrode current collector of the lithium metal battery for inhibiting dendrite growth according to claim 1, wherein the quenching temperature in step 4 is 100 ℃, the quenching time is 30min, the vacuum drying temperature is 80 ℃, and the drying time is 24 h.
8. The negative electrode current collector for a lithium metal battery for suppressing dendrite growth prepared by the method of any one of claims 1-7, wherein the surface of the current collector is modified with a polymer film containing polar functional groups O = S = O.
9. The dendrite growth inhibiting negative electrode current collector for a lithium metal battery of claim 8 is applied to a lithium metal battery, a lithium sulfur battery, or a lithium air battery system.
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