CN116130667A - Tin-copper composite current collector for lithium metal battery cathode and preparation method thereof - Google Patents
Tin-copper composite current collector for lithium metal battery cathode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a tin-copper composite current collector for a lithium metal battery cathode and preparation thereof; the Sn@Cu composite metal current collector with smooth and bright metal tin layers on the macroscopic surface and the microscopic surface being orderly-gully-shaped rough surfaces and uniformly and irregularly distributed with hilly micro-nano tin metal sites can be continuously prepared in batches in 3-10 min through an acid etching-laser ablation-complex redox tin plating process. The method has the advantages of simple process, controllable conditions, safety, high efficiency and wide universality, and is suitable for continuous batch production. The prepared Sn@Cu composite current collector has good lithium affinity, excellent direct lithium attachment performance and good electrochemical performance when used as a negative electrode current collector of a lithium metal battery.
Description
Technical Field
The invention belongs to the technical development field of lithium battery cathode materials, and particularly relates to a tin-copper (Sn@Cu) composite current collector for a lithium metal battery cathode and a preparation method thereof.
Background
Lithium batteries are widely used in various fields due to their advantages of high energy density, long cycle life, and the like. Lithium ion batteries are the most popular lithium batteries at present, but the energy density of the lithium ion batteries reaches a technical bottleneck due to the limit of specific capacity (372 mAh/g) of a negative electrode graphite material. The metallic lithium has a low oxidation-reduction potential (-3.04V) and a high theoretical specific capacity (3860 mAh/g) which is 10 times that of the traditional graphite negative electrode, and is an accepted final solution of the negative electrode of the high-energy-density lithium battery in the industry. Therefore, the development of lithium metal batteries and related technologies is a key to breaking through the energy density technology bottleneck of lithium batteries.
The metal lithium can be used as a negative electrode material and a current collector, and is an ideal negative electrode of a lithium battery. However, due to the special nature of the lithium metal, the development of the lithium metal battery is restricted by the problems of related manufacturing and processing technology, battery cathode cycle reversibility and the like. Limited by the specific physicochemical properties of lithium, metallic lithium products are generally less than 400mm wide and greater than 50 μm thick, and must provide a supporting framework for metallic lithium in the preparation of ultra-wide and ultra-thin metallic lithium products. At present, a lithium metal battery cathode is mainly prepared by directly compounding metal lithium and a cathode copper current collector, but due to the large difference of mechanical properties of two metals, the two metals have a plurality of problems in the compounding process, and the performance of the lithium metal battery cathode is far from expectations. In industry, a direct rolling method is commonly adopted to directly combine metallic lithium with a copper current collector by mechanical rolling to obtain the lithium-copper composite anode. In the direct rolling process, because the metal lithium has low hardness and low yield strength, the plastic deformation is large during pressure bonding, the copper has high hardness and high yield strength, the plastic deformation is small during pressure bonding, the metal lithium and the copper are extremely easy to generate defects such as surface wrinkles, bubbles, torsion and the like during the direct pressure bonding, and the surface metal lithium is extremely easy to fall off due to the weak interlayer composite strength. In view of the above problems, the optimization modification of the current collector is beneficial to improving the composite strength between the current collector and the metallic lithium and improving the composite effect of the current collector and the metallic lithium.
At present, the current collector modifying means mainly comprises the regulation and control of the surface morphology of the current collector and the loading of a surface lithium-philic layer. The surface morphology regulation and control of the current collector mainly comprises means of roughening, nanocrystallization and the like of the surface of the current collector, but has the problems of low process treatment efficiency, difficult efficient preparation and the like. The lithium-philic layer is supported mainly by means of surface mechanical coating (Rare met.2022,41, 1255-1264), electrochemical deposition (Nano res.2020,13, 45-51), chemical vapor deposition, surface in-situ growth (Nano energy.2021,87,106212), etc., but the method is mostly too lengthy and difficult to prepare in an efficient continuous manner. In order to solve the preparation difficulty of the lithium copper composite negative electrode in actual production, the development of a high-performance lithium metal battery negative electrode current collector and the high-efficiency preparation technology thereof are necessary.
Disclosure of Invention
The invention provides an Sn@Cu composite current collector for a lithium metal battery cathode and a preparation method thereof, and aims to provide a new reference for design and selection of the lithium metal battery cathode current collector.
The invention is realized by the following technical scheme:
the invention relates to a Sn@Cu composite current collector, wherein the macroscopic surface of the Sn@Cu current collector is provided with a smooth and bright metal tin layer, the microscopic surface is a gully-shaped rough surface and uniformly distributed hilly micro-nano tin metal sites in a dot manner, and the metal tin layer is formed by closely stacking 100-500 nm prismatic micro-nano tin metal particles and has the thickness of 0.1-5 mu m.
As an embodiment, the sn@cu composite current collector is composed of a surface micro-nano metallic tin layer with high lithium affinity, a tin-copper alloy transition layer with strong electron interaction among atoms and a metal inner copper skeleton layer with high electron conductivity, wherein all layers are tightly connected in an atomic intercalation composite state, and the sn@cu composite current collector has good charge conduction characteristics.
As an embodiment, the surface micro-nano metal tin layer with high lithium-philic property can perform spontaneous dry alloying reaction with the metal lithium, so that the metal lithium and the copper current collector are tightly combined, and meanwhile, the high lithium-philic metal tin layer can induce the metal lithium to be uniformly anchored on the surface of the copper current collector in an oriented manner, thereby being beneficial to the processing and manufacturing of the negative electrode of the lithium metal battery.
As one embodiment, the tin-copper alloy transition layer with strong electron interaction among atoms has the main effect that the strong electron interaction among tin-copper atoms is beneficial to the uniformity of the surface electric field of the current collector, so that the electric field effect is introduced in the process of compositing the current collector and the metal lithium, and the physical connection strength and the electric connection strength of the composite interface of the metal lithium and the copper current collector are improved under the coupling effect of a concentration field, a physical field and an electric field, thereby being beneficial to obviously improving the compositing effect of the copper current collector and the metal lithium.
As an embodiment, the copper skeleton layer inside the metal with high electronic conductivity has the main effects that copper has good electronic conductivity, machining property and chemical stability, and the copper skeleton material is a main support material of a current collector and provides space support for negative metal lithium.
As one implementation mode, the atomic mutually embedded composite state is tightly connected, and the main effect is that a metal tin layer is generated on the surface of a copper current collector framework in situ, and multiphase tin-copper alloy formed by tightly embedding tin atoms and copper atoms in different proportions exists among the metal tin layer, the tin-copper alloy transition layer and the copper framework layer, so that the effect of electron conduction among current collector layers is improved obviously.
As one embodiment, the prismatic micro-nano tin metal particles have irregular spherical overall morphology, and the surface of the spheres has a remarkable sharp prismatic structure. The micro-nano prismatic structure has lower surface energy, and can remarkably improve the wettability between the current collector and liquid and molten metal lithium. The surface formed by the arrangement of the prismatic particles has higher surface roughness compared with the surface formed by the arrangement of the prismatic particles, and the prismatic protrusions with micro-nano dimensions provide more attachment sites for the metal lithium, so that the compact combination of the current collector and the metal lithium is facilitated, the sliding deflection of the metal lithium on the surface of the current collector is prevented, and the composite processing effect between the current collector and the metal lithium is improved.
As one embodiment, the sn@cu composite current collector is prepared by an "acid etch-laser ablation-complex redox tin plating" process.
The invention also relates to a preparation method of the Sn@Cu composite current collector, which comprises the following steps:
s1, acid etching: and (3) carrying out acid etching treatment on the copper current collector at room temperature, and soaking the copper current collector in acid etching liquid with a certain concentration and treating for a certain time to obtain the acid etched copper current collector with the microscopic rough network topology structure on the surface.
S2, laser ablation: and (3) carrying out laser ablation treatment on the washed and dried acid etched copper current collector to obtain the double-etched copper current collector with the microscopic surface having the regular arranged gully-shaped structure and the disordered distributed rough network topological structure.
S3, complex redox tinning: and immersing the double-etched copper current collector in normal-temperature chemical tin plating solution at room temperature for complex redox tin plating treatment, and washing and drying to obtain the Sn@Cu composite current collector with the microcosmic surface being an ordered gully-shaped rough surface and uniformly and irregularly distributed hilly micro-nano tin metal sites in an unordered mode.
As one embodiment, the copper current collector in the S1 step of the preparation method of the sn@cu composite current collector includes a strip, a plate, a bar, a pipe, and other structural copper materials having a copper element component on the surface. Preferably, the copper foil is selected from micro copper foil, indentation copper foil, nano magnetron sputtering copper foil and foam copper. The normal-temperature in-situ wet chemical complex redox tinning process provided by the invention is suitable for any material with a copper simple substance layer on the surface, but copper foil or copper foil-like materials such as copper foil, foam copper and the like are commonly used in the negative current collector material of the lithium metal battery, so that micron copper foil, micropore copper foil, indentation copper foil, nano magnetron sputtering copper foil and foam copper are preferably selected as copper framework materials, and the Sn@Cu composite current collector with better comprehensive performance is favorably obtained.
As one embodiment, H of the acid etching solution in step S1 of the preparation method of the sn@cu composite current collector + The concentration is 0.1 to 1mol/L and preferably 0.5 to 1mol/L, and the acid etching treatment time is 5 to 30 minutes and preferably 10 to 15 minutes. The acid etching solution component is preferably HNO 3 、HCl、H 2 SO 4 The main purpose of the above parameters is to ensure that a microscopic coarse mesh topology with a mesh size of 1-10 μm is stably formed on the surface of the copper current collector during the acid etching process. The micro rough network topology structure is beneficial to regulating and controlling the surface morphology of the metal tin layer formed in the subsequent process, and is beneficial to forming hilly micro-nano tin metal sites which are uniformly interspersed and disordered.
As one implementation scheme, the laser ablation in the S2 step of the preparation method of the Sn@Cu composite current collector adopts a laser wavelength of 1000-1500 nm, the pulse duration is 30-100 ns, the repetition frequency is 10-30 kHz, the spot diameter is 5-10 mu m, the lens focal length is 150-200 mm, and the distance between adjacent laser scanning lines is 10-20 mu m. The above parameters are mainly aimed at ensuring a regular arrangement of the ravines with a pitch of 10-20 μm on the surface of the copper current collector. The regular arrangement of the ravines is beneficial to forming an orderly ravines-shaped rough surface in the subsequent process. Preferably, the laser is 1064nm, the pulse duration is 50ns, the repetition rate is 20kHz, the spot diameter is 50 μm, the lens focal length is 182mm, and the distance between adjacent laser scanning lines is 10 μm.
As one embodiment, the main raw materials of the normal-temperature chemical tinning solution in the step S3 of the preparation method of the Sn@Cu composite current collector are divalent metal tin salt, thiourea and deionized water, wherein the divalent metal tin salt comprises at least one of stannous chloride dihydrate and stannous sulfate, the pH of the chemical tinning solution is 0-5, and Sn 2+ The concentration is 10-100 g/L, and the concentration of thiourea is 10-100 g/L. The complex redox tin plating is carried out by slow stirring and is arranged in a treatment tankThe solution is in a circulating state, sn is in a treatment pool 2+ And thiourea concentration float less than 0.1g/L. The main reason for selecting the stannous salt is that the stannous salt is common and low in price, so that the processing cost of the current collector is reduced, and meanwhile, the stannous salt has good water solubility, so that the electroless plating solution is prepared. Among these, stannous chloride dihydrate and stannous sulfate are the most common divalent metal tin salts, and therefore, the raw materials are preferably stannous chloride dihydrate and stannous sulfate. Because metallic copper cannot replace metallic tin at normal temperature, complexing agent or reducing agent is introduced into the electroless plating solution to realize the normal-temperature in-situ electroless tin plating on the surface of the copper current collector. Thiourea is a common complexing agent with low price, and thiourea solution with certain concentration can spontaneously carry out complexation reaction with copper at normal temperature to form copper-containing thiourea complex, so that the reaction path of surface tinning of a copper current collector is changed, and finally, the normal-temperature in-situ chemical tinning process of the copper current collector is realized, and therefore, thiourea is selected as a raw material. The pH value of the chemical tinning solution is 0-5, sn 2+ The concentration is 10-100 g/L, the thiourea concentration is 10-100 g/L, the chemical tinning liquid is ensured to be in a uniform liquid state at normal temperature, the technical effect of in-situ chemical tinning of the copper current collector at normal temperature can be realized, the pH value of the chemical tinning liquid is 0-2, and Sn 2+ The concentration is 20-50 g/L, the concentration of thiourea is 20-50 g/L, the quick plating in a short time can be realized, the plating layer is uniform and bright, and the process effect is better.
As one embodiment, the treatment duration of the S3 step of the preparation method of the Sn@Cu composite current collector is 0.5-30 min and preferably 3-10 min. The surface metal tin layer can be formed by using the process of the invention to treat the copper current collector for more than 0.5min, the treatment time is controlled to be 3-10 min, which is beneficial to uniformly bright micro-nano metal tin layer with certain roughness on the surface of the copper current collector and the thickness is 0.3-2 mu m, which is beneficial to improving the composite effect of the current collector and the metal lithium and ensuring the stability of the current collector.
As an implementation scheme, the auxiliary condition of the S3 step of the preparation method of the Sn@Cu composite current collector is that the solution in the treatment tank is in a circulating state and is assisted by slow stirring, and the Sn in the treatment tank is 2+ And thiourea concentration float of less than 0.1g/L, the main part of the auxiliary process The aim is to maintain the components of the chemical plating solution uniform and stable and ensure the stable processing effect of the process. The stirring process is favorable for improving the mass transfer state of the surface of the plating part and optimizing the process effect.
The invention also relates to application of the Sn@Cu composite current collector, and the Sn@Cu composite current collector and lithium metal are directly compounded to manufacture the lithium metal battery cathode. The compounding mode of the Sn@Cu composite current collector and the metallic lithium is a mechanical rolling method, a melting method and an electrodeposition method, and preferably, the lithium attaching method of the Sn@Cu composite current collector is a mechanical rolling method. The Sn@Cu composite current collector provided by the invention has excellent surface lithium affinity, and is suitable for various lithium attaching processes. The current collector preparation process provided by the invention is beneficial to be combined with continuous mass production, so that continuous mechanical rollers are preferred for attaching lithium.
Compared with the prior art, the invention has the following beneficial effects:
1) The Sn@Cu composite current collector provided by the invention has excellent lithium affinity and cycle stability, has good combination effect with metal lithium, can meet the continuous processing and preparation requirements of large-area ultrathin metal lithium materials, and has wide industrial application prospects.
2) The invention realizes the innovative use of the acid etching-laser ablation-complex redox tinning process in the processing of the lithium metal battery anode current collector material, provides chemical plating process parameters with rapid batch processing capability, and provides a process guide for the processing of the lithium metal battery anode current collector material.
3) The invention further optimizes the lithium metal battery negative electrode current collector material, and provides a new reference for the selection and design processing of the lithium metal battery negative electrode current collector.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, made with reference to the accompanying drawings in which:
fig. 1 is an SEM image of a sn@cu composite current collector structure;
FIG. 2 is a CV result of an assembled half cell of Sn@Cu composite current collector and metallic lithium;
FIG. 3 is a schematic diagram of a Sn@Cu composite current collector preparation flow and a surface structure;
fig. 4 is a schematic diagram of continuous processing of sn@cu current collector preparation and metallic lithium negative electrode manufacturing;
FIG. 5 is an SEM morphology graph of a Sn@Cu foil current collector; wherein, (a) is a cross-sectional topography, (b) is a bevel topography, and (c) and (d) are surface topography;
FIG. 6 is an XRD spectrum of Sn@Cu composite current collectors prepared in different treatment durations;
FIG. 7 is a Li deposition overpotential for the Sn@Cu current collector surface; wherein (a) is 0.05mA/cm 2 Current density of 1mAh/cm 2 The deposition amount of metallic lithium was 0.5mA/cm 2 Current density of 1mAh/cm 2 The deposition amount of metallic lithium was 1mA/cm 2 Current density of 1mAh/cm 2 The deposition amount of the metallic lithium, (d) is a summary comparison graph of the deposition overpotential;
FIG. 8 is a graph of the cycling performance of an Sn@Cu current collector and metallic lithium assembled half cell; wherein (a) is 0.2mA/cm 2 Current density of 0.2mAh/cm 2 Deposition/stripping amount of metallic lithium, (b) 0.5mA/cm 2 Current density of 1mAh/cm 2 The deposition/stripping amount of metallic lithium, (c) was 1mA/cm 2 Current density of 1mAh/cm 2 Metal lithium deposition/stripping amount;
FIG. 9 is an impedance diagram of a Sn@Cu composite current collector roll-laminated lithium assembled symmetric battery; the method comprises the steps of (a) assembling a symmetrical battery after lithium is attached to a pure copper foil, and (b) assembling a symmetrical battery after lithium is attached to a tin-copper composite tape;
FIG. 10 is a graph of the cycling performance of an assembled symmetric cell after mechanical roll-pressing of the Sn@Cu current collector to lithium; wherein (a) is 1mA/cm 2 Current density of 1mAh/cm 2 Deposition/stripping amount of metallic lithium, (b) 1mA/cm 2 Current density of 2mAh/cm 2 Deposition/stripping amount of metallic lithium.
Fig. 11 is an SEM topography of the copper current collector surface after acid etching, (a) at 500 x magnification, and (b) at 1000 x magnification.
Fig. 12 is a SEM topography of a copper current collector surface subjected to laser ablation only, (a) 500 x magnification, and (b) 1000 x magnification.
Fig. 13 is a SEM topography of the surface of a copper current collector after acid etching and laser ablation, (a) at 500 x magnification, and (b) at 1000 x magnification.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that several modifications and improvements can be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Example 1
The Sn@Cu composite current collector material is prepared by treating a micron copper foil by an acid etching-laser ablation-complex redox tinning process, and consists of a surface micro-nano metallic tin layer with high lithium affinity, a tin-copper alloy transition layer with strong electron interaction among atoms and a metal inner copper framework layer with high electron conductivity (figure 1), wherein all layers are tightly connected in an atomic intercalation composite state, and the Sn@Cu composite current collector material has good charge conduction property. Specifically, in the surface micro-nano metal tin layer with high lithium-philic characteristic, the high lithium-philic metal tin can perform spontaneous dry alloying reaction with the metal lithium (figure 2), so that the metal lithium is tightly combined with the copper current collector, and meanwhile, the high lithium-philic metal tin layer can induce the metal lithium to be uniformly anchored on the surface of the copper current collector in an oriented manner, so that the processing and manufacturing of the negative electrode of the lithium metal battery are facilitated.
See flow chart (fig. 3):
s1, acid etching: the micro copper foil is subjected to an acid etching treatment at room temperature by immersing a copper current collector into H configured by HCl + And (3) treating the copper current collector in acid etching liquid with the concentration of 1mol/L for 10min to obtain the acid etching copper current collector with the surface having a micro rough network topology structure.
S2, laser ablation: and (3) carrying out laser ablation treatment on the washed and dried acid etched copper current collector, wherein the laser ablation parameters are laser wavelength 1064nm, pulse duration is 50ns, repetition frequency is 20kHz, spot diameter is 5 mu m, lens focal length is 182mm, and distance between adjacent laser scanning lines is 10 mu m, so as to obtain the double etched copper current collector with microscopic surfaces having a regular arranged gully-shaped structure and a disordered rough network topological structure.
S3, complex redox tinning: the double etched copper current collector was immersed at room temperature in a solution of stannous sulfate and thiourea at pH 0, sn 2+ And (3) in chemical tinning solution with the concentration of 20g/L and the thiourea concentration of 50g/L, carrying out slow stirring and soaking treatment for 5min at room temperature, and washing and drying to obtain the Sn@Cu composite current collector.
The Sn@Cu composite current collector provided by the embodiment has excellent surface lithium affinity, and is suitable for various lithium attaching processes. The current collector preparation process provided by the invention is beneficial to be combined with continuous mass production (fig. 4). The continuous production is to continuously convey the pretreated ultrathin copper foil coil to a process treatment line after being unwound by a roll shaft, control the belt speed to enable the material belt to be soaked in a treatment pool for 3-10 min, and continuously prepare the tin-copper composite belt. And continuously conveying the tin-copper composite belt to an environment with water and oxygen lower than 1ppm through a roll shaft after normal-temperature air blast drying, carrying out twin-roll compression compounding on the tin-copper composite belt and an ultrathin lithium belt conveyed by an additional roll shaft, continuously preparing an ultrathin lithium-tin-copper composite belt attached with lithium, and finally preparing the lithium-tin-copper composite belt through a roll shaft roll.
The macroscopic surface of the Sn@Cu composite current collector prepared under the condition is provided with a smooth and bright metal tin layer, the microscopic surface is a gully-shaped rough surface and uniformly distributed with hilly micro-nano tin metal sites in a spot mode, and the metal tin layer is formed by closely stacking prismatic micro-nano tin metal particles with the thickness of 200-300 nm and has the thickness of 0.4 mu m (shown in figures 5 and 6). The Sn@Cu composite current collector and a metal lithium sheet with the purity of 99.9 percent and the thickness of 1mm are assembled into a half battery and then are subjected to 0.5mA/cm 2 The overpotential for surface electrodeposition of metallic lithium at the current density of (C) was 86mV (FIG. 7), and was 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle over 300 cycles of coulombic efficiency remained 98% at the amount of metallic lithium deposition/stripping (fig. 8). The half-cell is assembled by adopting a CR2032 button cell shell, the electrolyte adopts 1M LiTFSI (DME: DOL=1:1) electrolyte, the diaphragm is a polypropylene (PP) diaphragm, and the positive electrode is a Sn@Cu composite current collectorThe negative electrode is a metal lithium sheet, and the addition amount of the positive and negative electrolyte is 40 mu l respectively. A lithium metal battery negative electrode having a low battery resistance (FIG. 9) and at 1mA/cm was fabricated by compounding a Sn@Cu composite current collector with a metal lithium foil having a purity of 99.9% and a thickness of 25 μm by a mechanical rolling method and assembling a symmetrical battery 2 And a current density of 2mAh/cm 2 The cycle life was over 550h (fig. 10) at a metallic lithium deposition/stripping amount of about 220 turns. The symmetrical battery is assembled by adopting a CR2016 button battery shell, the electrolyte adopts 1M LiTFSI (DME: DOL=1:1) electrolyte, the diaphragm is a polypropylene (PP) diaphragm, the anode and the cathode are Sn@Cu composite current collectors with lithium, and the addition amount of the electrolyte of the anode and the cathode is 40 mu l respectively.
Example 2
Preparation of Sn@Cu composite current collector material by treating indentation copper foil by adopting acid etching-laser ablation-complex redox tinning process, and the specific process is shown in a flow chart (figure 3):
s1, acid etching: the indentation copper foil is subjected to acid etching treatment at room temperature by immersing a copper current collector into a copper film made of HNO 3 Configured as H + And (3) treating the copper current collector in acid etching liquid with the concentration of 0.5mol/L for 15min to obtain the acid etching copper current collector with the surface having a micro rough network topology structure.
S2, laser ablation: and (3) carrying out laser ablation treatment on the washed and dried acid etched copper current collector, wherein the laser ablation parameters are laser wavelength 1064nm, pulse duration is 50ns, repetition frequency is 20kHz, spot diameter is 5 mu m, lens focal length is 182mm, and distance between adjacent laser scanning lines is 10 mu m, so as to obtain the double etched copper current collector with microscopic surfaces having a regular arranged gully-shaped structure and a disordered rough network topological structure.
S3, complex redox tinning: the double etched copper current collector was immersed at room temperature at a pH of 0, sn, formulated from stannous chloride dihydrate and thiourea 2+ And (3) in the chemical tinning solution with the concentration of 50g/L and the thiourea concentration of 20g/L, carrying out slow stirring soaking treatment for 10min at room temperature, and washing and drying to obtain the Sn@Cu composite current collector.
The Sn@Cu composite current collector prepared under the condition has a macroscopic three-dimensional indentation-like structure and a macroscopic surfaceThe surface is provided with a smooth and bright metal tin layer, the microscopic surface is a gully-shaped rough surface and is uniformly provided with hilly micro-nano tin metal sites in a spot-interspersed mode, and the metal tin layer is formed by closely stacking 400-500 nm prismatic micro-nano tin metal particles and has the thickness of 1.9 mu m. The Sn@Cu composite current collector and a metal lithium sheet with the purity of 99.9 percent and the thickness of 1mm are assembled into a half battery and then are subjected to 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 42mV, and was 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle over 170 cycles coulombic efficiency remains 98% at the amount of metallic lithium deposition/stripping. A lithium metal battery negative electrode was fabricated by compounding Sn@Cu composite current collector with metallic lithium by mechanical roll method as in example 1 and assembling a symmetrical battery having a low battery resistance at 1mA/cm 2 And a current density of 2mAh/cm 2 The cycle life is over 280 hours, about 140 cycles, at the amount of metallic lithium deposited/stripped.
Example 3
The preparation method comprises the steps of preparing Sn@Cu composite current collector material by treating magnetron sputtering copper foil by adopting an acid etching-laser ablation-complex redox tinning process, and specifically comprises the following steps of:
s1, acid etching: the micro copper foil is subjected to acid etching treatment at room temperature by immersing a copper current collector until the copper current collector is immersed in a solution consisting of H 2 SO 4 Configured as H + And (3) treating the copper current collector in acid etching liquid with the concentration of 0.5mol/L for 10min to obtain the acid etching copper current collector with the surface having a micro rough network topology structure.
S2, laser ablation: and (3) carrying out laser ablation treatment on the washed and dried acid etched copper current collector, wherein the laser ablation parameters are laser wavelength 1064nm, pulse duration is 50ns, repetition frequency is 20kHz, spot diameter is 5 mu m, lens focal length is 182mm, and distance between adjacent laser scanning lines is 10 mu m, so as to obtain the double etched copper current collector with microscopic surfaces having a regular arranged gully-shaped structure and a disordered rough network topological structure.
S3, complex redox tinning: the double etched copper current collector was immersed at room temperature at a pH of 1, sn, prepared from stannous sulfate and thiourea 2+ Chemical with concentration of 30g/L and thiourea with concentration of 30g/L And (3) in the tinning liquid, carrying out slow stirring soaking treatment for 3min under the room temperature condition, and washing and drying to obtain the Sn@Cu composite current collector.
The macroscopic surface of the Sn@Cu composite current collector prepared under the condition is provided with a smooth and bright metal tin layer, the microscopic surface is a gully-shaped rough surface and uniformly distributed with hilly micro-nano tin metal sites in a spot mode, and the metal tin layer is formed by closely stacking 100-200 nm prismatic micro-nano tin metal particles and has the thickness of 0.3 mu m. The Sn@Cu composite current collector and a metal lithium sheet with the purity of 99.9 percent and the thickness of 1mm are assembled into a half battery and then are subjected to 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 90mV, and was 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle over 160 cycles of coulombic efficiency remains 98% at the amount of metallic lithium deposition/stripping. A lithium metal battery negative electrode was fabricated by compounding Sn@Cu composite current collector with metallic lithium by mechanical roll method as in example 1 and assembling a symmetrical battery having a low battery resistance at 1mA/cm 2 And a current density of 2mAh/cm 2 The cycle life is over 250 hours, about 120 cycles, at a metallic lithium deposition/stripping level.
Example 4
The preparation method comprises the steps of preparing Sn@Cu composite current collector material by treating microporous copper foil by adopting an acid etching-laser ablation-complex redox tinning process, and specifically comprises the following steps of:
S1, acid etching: the micro copper foil is subjected to acid etching treatment at room temperature by soaking a copper current collector until the copper current collector is immersed in a copper film formed by HNO 3 Configured as H + And (3) treating the copper current collector in acid etching liquid with the concentration of 1mol/L for 10min to obtain the acid etching copper current collector with the surface having a micro rough network topology structure.
S2, laser ablation: and (3) carrying out laser ablation treatment on the washed and dried acid etched copper current collector, wherein the laser ablation parameters are laser wavelength 1064nm, pulse duration is 50ns, repetition frequency is 20kHz, spot diameter is 5 mu m, lens focal length is 182mm, and distance between adjacent laser scanning lines is 10 mu m, so as to obtain the double etched copper current collector with microscopic surfaces having a regular arranged gully-shaped structure and a disordered rough network topological structure.
S3, complex redox tinning: the double etched copper current collector was immersed at room temperature in a solution of stannous sulfate and thiourea at a pH of 0.3, sn 2+ And (3) in chemical tinning solution with the concentration of 30g/L and the thiourea concentration of 30g/L, carrying out slow stirring soaking treatment for 7min at room temperature, and washing and drying to obtain the Sn@Cu composite current collector.
The macroscopic surface of the Sn@Cu composite current collector prepared under the condition is provided with a smooth and bright metal tin layer, the microscopic surface is a gully-shaped rough surface and uniformly distributed with hilly micro-nano tin metal sites in a spot mode, and the metal tin layer is formed by closely stacking and arranging prismatic micro-nano tin metal particles with the thickness of 300-400 nm and has the thickness of 0.9 mu m. The Sn@Cu composite current collector and a metal lithium sheet with the purity of 99.9 percent and the thickness of 1mm are assembled into a half battery and then are subjected to 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 60mV, and at 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle over 180 cycles of coulombic efficiency remains 98% at the amount of metallic lithium deposition/stripping. The Sn@Cu composite current collector and the metallic lithium are compounded to prepare a lithium metal battery cathode by adopting an electrodeposition method, and a symmetrical battery is assembled, wherein the electrodeposition process is that 0.5mA/cm is adopted on the surface of the current collector 2 Is 5mAh/cm 2 The symmetrical battery assembly process is the same as example 1. The battery has low battery impedance and is at 1mA/cm 2 And a current density of 2mAh/cm 2 The cycle life is over 300 hours, about 150 cycles, at a metallic lithium deposition/stripping amount.
Example 5
Preparation of Sn@Cu composite current collector material by treating foam copper by adopting acid etching-laser ablation-complex redox tinning process, and the specific process is shown in a flow chart (figure 3):
s1, acid etching: the micro copper foil is subjected to an acid etching treatment at room temperature by immersing a copper current collector into H configured by HCl + And (3) treating the copper current collector in acid etching liquid with the concentration of 1mol/L for 15min to obtain the acid etching copper current collector with the surface having a micro rough network topology structure.
S2, laser ablation: and (3) carrying out laser ablation treatment on the washed and dried acid etched copper current collector, wherein the laser ablation parameters are laser wavelength 1064nm, pulse duration is 50ns, repetition frequency is 20kHz, spot diameter is 5 mu m, lens focal length is 182mm, and distance between adjacent laser scanning lines is 10 mu m, so as to obtain the double etched copper current collector with microscopic surfaces having a regular arranged gully-shaped structure and a disordered rough network topological structure.
S3, complex redox tinning: the double etched copper current collector was immersed at room temperature at a pH of 1.5, sn, formulated from stannous chloride dihydrate and thiourea 2+ And (3) in chemical tinning solution with the concentration of 20g/L and the thiourea concentration of 50g/L, carrying out slow stirring soaking treatment for 10min at room temperature, and washing and drying to obtain the Sn@Cu composite current collector.
The macroscopic surface of the Sn@Cu composite current collector prepared under the condition is provided with a smooth and bright metal tin layer, the microscopic surface is a gully-shaped rough surface and uniformly distributed with hilly micro-nano tin metal sites in a spot mode, and the metal tin layer is formed by closely stacking 400-500 nm prismatic micro-nano tin metal particles and has the thickness of 1.2 mu m. The Sn@Cu composite current collector and a metal lithium sheet with the purity of 99.9 percent and the thickness of 1mm are assembled into a half battery and then are subjected to 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 50mV, and at 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle over 170 cycles coulombic efficiency remains 98% at the amount of metallic lithium deposition/stripping. And compounding the Sn@Cu composite current collector with metal lithium by adopting a melting method to prepare a lithium metal battery cathode and assembling the symmetrical battery, wherein the melting lithium attaching process is prepared by immersing the current collector in the molten metal lithium and immersing for 30s, and the symmetrical battery assembling process is the same as that of the embodiment 1. The battery has low battery impedance and is at 1mA/cm 2 And a current density of 2mAh/cm 2 The cycle life is over 260h at a metallic lithium deposition/stripping amount of about 130 turns.
Example 6
Preparation of Sn@Cu composite current collector material by treating micro copper foil by adopting acid etching-laser ablation-complex redox tinning process, and the specific process is shown in a flow chart (figure 3):
s1, acid etching: the micron copper foil is subjected to acid etching treatment at room temperatureBy immersing a copper current collector into H configured from HCl + And (3) treating the copper current collector in acid etching liquid with the concentration of 0.1mol/L for 30min to obtain the acid etching copper current collector with the surface having a micro rough network topology structure.
S2, laser ablation: and (3) carrying out laser ablation treatment on the washed and dried acid etched copper current collector, wherein the laser ablation parameters are that the laser wavelength is 1000nm, the pulse duration is 100ns, the repetition frequency is 15kHz, the spot diameter is 10 mu m, the lens focal length is 200mm, the distance between adjacent laser scanning lines is 15 mu m, and the double etched copper current collector with a micro surface having a regular arranged gully-like structure and a disordered rough network topological structure is obtained.
S3, complex redox tinning: the double etched copper current collector was immersed at room temperature at a pH of 3, sn, formulated from stannous chloride dihydrate and thiourea 2+ And (3) in the chemical tinning solution with the concentration of 10g/L and the thiourea concentration of 60g/L, carrying out slow stirring soaking treatment for 15min at room temperature, and washing and drying to obtain the Sn@Cu composite current collector.
The macroscopic surface of the Sn@Cu composite current collector prepared under the condition is provided with a smooth and bright metal tin layer, the microscopic surface is a gully-shaped rough surface and uniformly distributed with hilly micro-nano tin metal sites in a spot mode, and the metal tin layer is formed by closely stacking 400-500 nm prismatic micro-nano tin metal particles and has the thickness of 2.3 mu m. The Sn@Cu composite current collector and a metal lithium sheet with the purity of 99.9 percent and the thickness of 1mm are assembled into a half battery and then are subjected to 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 36mV, and was at 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle of more than 120 cycles of coulombic efficiency still maintains 98% at the deposition/stripping amount of metallic lithium. A lithium metal battery negative electrode was fabricated by compounding Sn@Cu composite current collector with metallic lithium by mechanical roll method as in example 1 and assembling a symmetrical battery having a low battery resistance at 1mA/cm 2 And a current density of 2mAh/cm 2 The cycle life is over 200 hours, about 100 cycles, at a metallic lithium deposition/stripping amount.
Example 7
Preparation of Sn@Cu composite current collector material by treating 0.5mm copper plate by adopting acid etching-laser ablation-complex redox tinning process, and the specific process is shown in a flow chart (figure 3):
s1, acid etching: the micro copper foil is subjected to an acid etching treatment at room temperature by immersing a copper current collector into H configured by HCl + And (3) treating the copper current collector in acid etching liquid with the concentration of 1mol/L for 20min to obtain the acid etching copper current collector with the surface having a micro rough network topology structure.
S2, laser ablation: and (3) carrying out laser ablation treatment on the washed and dried acid etched copper current collector, wherein the laser ablation parameters are that the laser wavelength is 1500nm, the pulse duration is 30ns, the repetition frequency is 30kHz, the spot diameter is 10 mu m, the lens focal length is 150mm, the distance between adjacent laser scanning lines is 20 mu m, and the double-etched copper current collector with a micro surface having a regular arranged gully-like structure and a disordered rough network topological structure is obtained.
S3, complex redox tinning: the double etched copper current collector was immersed at room temperature at pH 4, sn, formulated from stannous chloride dihydrate and thiourea 2+ And (3) in chemical tinning solution with the concentration of 100g/L and the concentration of thiourea of 100g/L, carrying out slow stirring soaking treatment for 30min at room temperature, and washing and drying to obtain the Sn@Cu composite current collector.
The macroscopic surface of the Sn@Cu composite current collector prepared under the condition is provided with a smooth and bright metal tin layer, the microscopic surface is a gully-shaped rough surface and uniformly distributed with hilly micro-nano tin metal sites in a spot mode, and the metal tin layer is formed by closely stacking 400-500 nm prismatic micro-nano tin metal particles and has the thickness of 4.5 mu m. The Sn@Cu composite current collector and a metal lithium sheet with the purity of 99.9 percent and the thickness of 1mm are assembled into a half battery and then are subjected to 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 20mV, and at 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle over 150 cycles of coulombic efficiency remains 98% at the amount of metallic lithium deposition/stripping. A lithium metal battery negative electrode was fabricated by compounding Sn@Cu composite current collector with metallic lithium by mechanical roll method as in example 1 and assembling a symmetrical battery having a low battery resistance at 1mA/cm 2 And a current density of 2mAh/cm 2 Metal lithium deposition of (2)The cycle life was over 160 hours at peel level, about 80 cycles.
Example 8
Preparation of Sn@Cu composite current collector material by treating micro copper foil by adopting acid etching-laser ablation-complex redox tinning process, and the specific process is shown in a flow chart (figure 3):
s1, acid etching: the micro copper foil is subjected to acid etching treatment at room temperature by soaking a copper current collector until the copper current collector is immersed in a copper film formed by HNO 3 Configured as H + And (3) treating the copper current collector in acid etching liquid with the concentration of 1mol/L for 5min to obtain the acid etching copper current collector with the surface having a micro rough network topology structure.
S2, laser ablation: and (3) carrying out laser ablation treatment on the washed and dried acid etched copper current collector, wherein the laser ablation parameters are laser wavelength 1275nm, pulse duration is 60ns, repetition frequency is 20kHz, spot diameter is 5 mu m, lens focal length is 160mm, and distance between adjacent laser scanning lines is 15 mu m, so as to obtain the double etched copper current collector with microscopic surfaces having a regular arranged gully-shaped structure and a disordered rough network topological structure.
S3, complex redox tinning: the double etched copper current collector was immersed at room temperature in a solution of stannous sulfate and thiourea at pH 5, sn 2+ And (3) in the chemical tinning solution with the concentration of 60g/L and the thiourea concentration of 10g/L, carrying out slow stirring soaking treatment for 20min at room temperature, and washing and drying to obtain the Sn@Cu composite current collector.
The macroscopic surface of the Sn@Cu composite current collector prepared under the condition is provided with a smooth and bright metal tin layer, the microscopic surface is a gully-shaped rough surface and uniformly distributed with hilly micro-nano tin metal sites in a spot mode, and the metal tin layer is formed by closely stacking 400-500 nm prismatic micro-nano tin metal particles and has the thickness of 3.2 mu m. The Sn@Cu composite current collector and a metal lithium sheet with the purity of 99.9 percent and the thickness of 1mm are assembled into a half battery and then are subjected to 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 30mV, and at 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle of more than 130 cycles of coulombic efficiency still maintains 98% at the deposition/stripping amount of metallic lithium. Sn@Cu was compounded by electrodeposition as in example 4Current collector and lithium metal are compounded to prepare lithium metal battery cathode and assembled symmetrical battery, the battery has low battery impedance and is 1mA/cm 2 And a current density of 2mAh/cm 2 The cycle life is over 180 hours, about 90 turns, at the amount of metallic lithium deposited/stripped.
Example 9
Preparation of Sn@Cu composite current collector material by treating micro copper foil by adopting acid etching-laser ablation-complex redox tinning process, and the specific process is shown in a flow chart (figure 3):
s1, acid etching: the micro copper foil is subjected to acid etching treatment at room temperature by immersing a copper current collector until the copper current collector is immersed in a solution consisting of H 2 SO 4 Configured as H + And (3) treating the copper current collector in acid etching liquid with the concentration of 0.5mol/L for 20min to obtain the acid etching copper current collector with the surface having a micro rough network topology structure.
S2, laser ablation: and (3) carrying out laser ablation treatment on the washed and dried acid etched copper current collector, wherein the laser ablation parameters are laser wavelength 1064nm, pulse duration is 50ns, repetition frequency is 20kHz, spot diameter is 5 mu m, lens focal length is 182mm, and distance between adjacent laser scanning lines is 10 mu m, so as to obtain the double etched copper current collector with microscopic surfaces having a regular arranged gully-shaped structure and a disordered rough network topological structure.
S3, complex redox tinning: the double etched copper current collector was immersed at room temperature in a solution of stannous sulfate and thiourea at pH 0, sn 2+ And (3) in chemical tinning solution with the concentration of 30g/L and the thiourea concentration of 30g/L, carrying out slow stirring soaking treatment for 0.5min at room temperature, and washing and drying to obtain the Sn@Cu composite current collector.
The macroscopic surface of the Sn@Cu composite current collector prepared under the condition is provided with a smooth and bright metal tin layer, the microscopic surface is a gully-shaped rough surface and uniformly distributed with hilly micro-nano tin metal sites in a spot mode, and the metal tin layer is formed by closely stacking 100-200 nm prismatic micro-nano tin metal particles and has the thickness of 0.1 mu m. The Sn@Cu composite current collector and a metal lithium sheet with the purity of 99.9 percent and the thickness of 1mm are assembled into a half battery and then are subjected to 0.5mA/cm 2 Is the overpotential of the surface electrodeposited metallic lithium under the current density of (2)103mV, and at 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle over 90 cycles of coulombic efficiency remains 98% at the amount of metallic lithium deposition/stripping. A lithium metal battery negative electrode was fabricated by compounding Sn@Cu composite current collector with metallic lithium by mechanical roll method as in example 1 and assembling a symmetrical battery having a low battery resistance at 1mA/cm 2 And a current density of 2mAh/cm 2 The cycle life is over 100 hours, about 50 cycles, at a metallic lithium deposition/stripping amount.
Example 10
Preparation of Sn@Cu composite current collector material by treating micro copper foil by adopting acid etching-laser ablation-complex redox tinning process, and the specific process is shown in a flow chart (figure 3):
s1, acid etching: the micro copper foil is subjected to acid etching treatment at room temperature by soaking a copper current collector until the copper current collector is immersed in a copper film formed by HNO 3 Configured as H + And (3) treating the copper current collector in acid etching liquid with the concentration of 0.2mol/L for 5min to obtain the acid etching copper current collector with the surface having a micro rough network topology structure.
S2, laser ablation: and (3) carrying out laser ablation treatment on the washed and dried acid etched copper current collector, wherein the laser ablation parameter is 1300nm of laser wavelength, the pulse duration is 30ns, the repetition frequency is 15kHz, the spot diameter is 10 mu m, the lens focal length is 150mm, the distance between adjacent laser scanning lines is 10 mu m, and the double-etched copper current collector with a micro surface having a regular arranged gully-like structure and a disordered rough network topological structure is obtained.
S3, complex redox tinning: the double etched copper current collector was immersed at room temperature at a pH of 1, sn, prepared from stannous sulfate and thiourea 2+ And (3) in chemical tinning solution with the concentration of 20g/L and the thiourea concentration of 50g/L, carrying out slow stirring soaking treatment for 1min at room temperature, and washing and drying to obtain the Sn@Cu composite current collector.
The macroscopic surface of the Sn@Cu composite current collector prepared under the condition is provided with a smooth and bright metal tin layer, the microscopic surface is a gully-shaped rough surface and uniformly distributed with hilly micro-nano tin metal sites in a point-by-point manner, the metal tin layer is formed by closely stacking 100-200 nm prismatic micro-nano tin metal particles, and the metal tin layer is formed byThe thickness was 0.2. Mu.m. The Sn@Cu composite current collector and a metal lithium sheet with the purity of 99.9 percent and the thickness of 1mm are assembled into a half battery and then are subjected to 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 94mV, and at 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle over 100 cycles of coulombic efficiency remains 98% at the amount of metallic lithium deposition/stripping. A lithium metal battery negative electrode was fabricated by compounding Sn@Cu composite current collector with metallic lithium by mechanical roll method as in example 1 and assembling a symmetrical battery having a low battery resistance at 1mA/cm 2 And a current density of 2mAh/cm 2 The cycle life was over 140h at a metallic lithium deposition/stripping level of about 70 turns.
Comparative example 1
Preparation of copper current collector material by treating a copper-micrometer foil with an acid etching process, subjecting the copper-micrometer foil to an acid etching treatment at room temperature by immersing the copper current collector in H made of HCl + And (3) treating the copper current collector in acid etching liquid with the concentration of 1mol/L for 10min to obtain the acid etching copper current collector with the surface having a micro rough network topology structure.
The microscopic surface of the copper current collector prepared under the condition has a microscopic rough network topology structure (figure 11), and the copper current collector is assembled with a metal lithium sheet with the purity of 99.9 percent and the thickness of 1mm into a half cell at 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 152mV, and at 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle of more than 45 cycles of coulombic efficiency remains 98% at the amount of metallic lithium deposition/stripping. A lithium metal battery negative electrode was fabricated by compounding Sn@Cu composite current collector with metallic lithium by mechanical roll method as in example 1 and assembling a symmetrical battery having a medium battery resistance at 1mA/cm 2 And a current density of 2mAh/cm 2 The cycle life was over 50 hours, about 25 cycles, at the amount of metallic lithium deposited/stripped.
Comparative example 2
Preparation of copper Current collector Material by treating a copper-micron foil with an "acid etching-laser ablation" Process, the copper-micron foil is first acid etched at room temperature by soaking the copper Current collector in H configured with HCl + Acid etching solution with 1mol/LAnd (3) treating for 10min to obtain the acid etched copper current collector with the surface having the micro rough network topology structure. And then carrying out laser ablation treatment on the washed and dried acid etched copper foil under the conditions that the laser ablation parameter is 1064nm, the pulse duration is 50ns, the repetition frequency is 20kHz, the spot diameter is 5 mu m, the lens focal length is 182mm and the distance between adjacent laser scanning lines is 10 mu m, so as to obtain the laser ablated copper current collector with the microcosmic surface having a regular arranged gully-like structure.
The microscopic surface of the copper current collector prepared under the condition is of a regular gully-shaped structure (figure 12), the copper current collector and a metal lithium sheet with the purity of 99.9 percent and the thickness of 1mm are assembled into a half cell at 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) is 180mV and at 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle of more than 40 cycles of coulombic efficiency still maintains 98% at the amount of metallic lithium deposition/stripping. A lithium metal battery negative electrode was fabricated by compounding Sn@Cu composite current collector with metallic lithium by mechanical roll method as in example 1 and assembling a symmetrical battery having a medium battery resistance at 1mA/cm 2 And a current density of 2mAh/cm 2 The cycle life is over 40 hours, about 20 cycles, at the amount of metallic lithium deposited/stripped.
Comparative example 3
The method comprises the steps of adopting a laser ablation process to treat a micro copper foil to prepare a Sn@Cu composite current collector material, carrying out laser ablation treatment on the micro copper foil under the conditions that laser ablation parameters are 1064nm of laser wavelength, pulse duration is 50ns, repetition frequency is 20kHz, light spot diameter is 5 mu m, lens focal length is 182mm and distance between adjacent laser scanning lines is 10 mu m, and obtaining the double-etched copper current collector with a micro surface having a regular arranged gully-like structure and a disordered coarse mesh topological structure.
The microscopic surface of the copper current collector prepared under the condition has a regular arranged gully-like structure and a disordered coarse net-like topological structure (figure 13), the copper current collector and a metal lithium sheet with the purity of 99.9 percent and the thickness of 1mm are assembled into a half cell and then are arranged at 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 120mV, and was 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle of over 80 cycles of coulombic efficiency remains 98% at the amount of metallic lithium deposition/stripping. As in example 1, a Sn@Cu composite current collector was composited with metallic lithium by mechanical rolling to produce a lithium metal battery negative electrode and a symmetrical battery having a medium battery resistance at 1mA/cm was assembled 2 And a current density of 2mAh/cm 2 The cycle life is over 80 hours, about 40 cycles at the amount of metallic lithium deposition/stripping.
Comparative example 4
Preparing Sn@Cu composite current collector material by adopting chemical tinning process to treat micro copper foil, soaking the micro copper foil in tin sulfate and thiourea to prepare the composite current collector material with pH value of 0 and Sn at room temperature 2+ And (3) in chemical tinning solution with the concentration of 20g/L and the thiourea concentration of 50g/L, carrying out slow stirring soaking treatment for 5min at room temperature, and washing and drying to obtain the Sn@Cu composite current collector.
The Sn@Cu composite current collector prepared under the condition has a bright metal tin layer on the surface, the microscopic surface is in a flat state, the current collector and a metal lithium sheet with the purity of 99.9 percent and the thickness of 1mm are assembled into a half battery, and then the half battery is assembled at 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 100mV, and was 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle of over 60 cycles of coulombic efficiency remains 98% at the amount of metallic lithium deposition/stripping. As in example 1, a Sn@Cu composite current collector was composited with metallic lithium by mechanical rolling to produce a lithium metal battery negative electrode and a symmetrical battery having a medium battery resistance at 1mA/cm was assembled 2 And a current density of 2mAh/cm 2 The cycle life is over 100 hours, about 50 cycles, at a metallic lithium deposition/stripping amount.
Comparative example 5
Preparation of Sn@Cu composite current collector material by treating micro copper foil with 'acid etching-chemical tinning process', immersing micro copper foil in H prepared from HCl + And (3) treating the mixture in acid etching solution with the concentration of 1mol/L for 10min, then treating the mixture by adopting chemical tinning solution in the same way as in the example 1, and washing and drying the mixture to obtain the Sn@Cu composite current collector.
The Sn@Cu composite current collector prepared under the condition has bright metallic tin on the surfaceThe layer has a micro surface with a slight bulge on the whole and flat part, the current collector and a metal lithium sheet with the purity of 99.9 percent and the thickness of 1mm are assembled into a half cell at 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 98mV and was 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle of over 70 cycles of coulombic efficiency remains 98% at the amount of metallic lithium deposition/stripping. A lithium metal battery negative electrode was fabricated by compounding Sn@Cu composite current collector with metallic lithium by mechanical roll method as in example 1 and assembling a symmetrical battery having a medium battery resistance at 1mA/cm 2 And a current density of 2mAh/cm 2 The cycle life is over 120 hours, about 60 cycles, at the amount of metallic lithium deposited/stripped.
Specific examples and comparative examples of the present invention are described above. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (10)
1. The Sn@Cu composite current collector is characterized in that a smooth and bright metal tin layer is arranged on the macroscopic surface of the Sn@Cu current collector, the microscopic surface is an orderly gully-shaped rough surface and uniformly distributed with hilly micro-nano tin metal sites in an unordered way, and the metal tin layer is formed by closely stacking 100-500 nm prismatic micro-nano tin metal particles and has the thickness of 0.1-5 mu m.
2. The sn@cu composite current collector of claim 1, wherein the sn@cu current collector is comprised of a surface micro-nano metallic tin layer having high lithium affinity properties, a tin-copper alloy transition layer having strong electron interactions between atoms, and a metallic inner copper backbone layer having high electron conductivity properties, wherein the layers are intimately connected in an atomic intercalated composite state.
3. The sn@cu composite current collector of claim 1, wherein the overall morphology of the prismatic micro-nano tin metal particles is random spheres, and the surfaces of the spheres have sharp prismatic structures.
4. The sn@cu composite current collector of claim 1, wherein the sn@cu composite current collector is prepared by an "acid etch-laser ablation-complex redox tin plating" process.
5. A method for preparing the sn@cu composite current collector according to claim 1, comprising:
s1, acid etching: performing acid etching treatment on the copper current collector at room temperature, and soaking the copper current collector into acid etching solution with a certain concentration and treating for a certain time to obtain an acid etched copper current collector with a micro rough network topology structure on the surface;
s2, laser ablation: carrying out laser ablation treatment on the washed and dried acid etched copper current collector to obtain a double-etched copper current collector with a microscopic surface having a regular arranged gully-shaped structure and a disordered distributed rough network-shaped topological structure;
s3, complex redox tinning: and immersing the double-etched copper current collector in normal-temperature chemical tin plating solution at room temperature for complex redox tin plating treatment, washing and drying the current collector after a certain time to obtain the Sn@Cu composite current collector with the microcosmic surface being an ordered gully-shaped rough surface and uniformly and irregularly distributed hilly micro-nano tin metal sites.
6. The method for producing a sn@cu composite current collector according to claim 5, wherein in step S1, the copper current collector comprises a strip, plate, bar, wire, tube, or other structural copper material having a copper element on the surface.
7. The method for producing a Sn@Cu composite current collector according to claim 5, wherein in step S1, H of said acid etching solution + The concentration is 0.1-1 mol/L, wherein the acid etching solution comprises HNO 3 、HCl、H 2 SO 4 The acid etching treatment time is5-30 min; the mesh size of the micro rough mesh topological structure is 1-10 mu m.
8. The method for preparing a Sn@Cu composite current collector according to claim 5, wherein in the step S2, the laser ablation adopts a laser wavelength of 1000-1500 nm, a pulse duration of 30-100 ns, a repetition frequency of 10-30 kHz, a spot diameter of 5-10 μm, a lens focal length of 150-200 mm, and an adjacent laser scanning line spacing of 10-20 μm; the spacing between the gully-shaped structures regularly distributed on the surface is 10-20 mu m.
9. The method for preparing a Sn@Cu composite current collector according to claim 5, wherein in the step S3, main raw materials of the normal-temperature chemical tinning solution are divalent metal tin salt, thiourea and deionized water, the divalent metal tin salt comprises at least one of stannous chloride dihydrate and stannous sulfate, the pH of the chemical tinning solution is 0-5, and Sn 2+ The concentration is 10-100 g/L, the thiourea concentration is 10-100 g/L, and the treatment time is 0.5-30 min.
10. Use of the sn@cu composite current collector according to claim 1 for manufacturing a lithium metal battery negative electrode by directly compositing the sn@cu composite current collector with metal lithium.
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2022
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