CN116742008A - CuO-loaded Cu/Ag composite current collector for lithium metal battery cathode and preparation method thereof - Google Patents
CuO-loaded Cu/Ag composite current collector for lithium metal battery cathode and preparation method thereof Download PDFInfo
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- CN116742008A CN116742008A CN202310554118.8A CN202310554118A CN116742008A CN 116742008 A CN116742008 A CN 116742008A CN 202310554118 A CN202310554118 A CN 202310554118A CN 116742008 A CN116742008 A CN 116742008A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 157
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
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Classifications
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a CuO-loaded Cu/Ag composite current collector for a lithium metal battery cathode and preparation thereof; the composite current collector consists of spherical Cu/Ag alloy nano material with high lithium affinity and high conductivity and needle-wool-shaped CuO film layer uniformly loaded on the surface, and has a flexible micro-film structure on the macro-scale and a three-dimensional nano-porous structure on the micro-scale. The composite current collector is prepared by adopting a process of liquid phase reduction, slurry preparation, mechanical film coating and evaporation film forming, and the process is simple and feasible, safe and efficient, has controllable flow, is easy to amplify and has good application prospect.
Description
Technical Field
The invention belongs to the technical development field of lithium battery cathode materials, and particularly relates to a CuO-loaded Cu/Ag (CuO@Cu/Ag) 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, good safety, and the like. The lithium ion battery is most popular at present, and the energy density of the lithium ion battery basically reaches a theoretical value, and high-capacity charge and discharge cannot be realized due to the limitation of low theoretical specific capacity (372 mAh/g) of the negative electrode graphite material. The limited energy density of lithium ion batteries is not satisfactory for growing requirements of advanced energy storage devices. The metallic lithium is a well-known final solution for realizing the negative electrode of the lithium battery with high energy density due to the low oxidation-reduction potential (-3.04V) and the ultrahigh theoretical specific capacity of 3860 mAh/g. Therefore, the development of lithium metal batteries and related technologies is a key to breaking through the energy density technology bottleneck of lithium batteries.
During charge and discharge of the lithium metal battery, lithium metal deposition/stripping respectively occurs on the negative electrode. Due to the inherent physicochemical properties of lithium metal, lithium negative electrodes have many problems in the charge and discharge process: dendrites, corrosion of lithium, dead lithium, and volume expansion, etc. These problems will lead to serious capacity loss and safety problems of lithium metal batteries after long-term operation. The occurrence of the above problems is attributable to the non-uniform deposition of lithium. Therefore, inducing uniform deposition of lithium by modifying the negative electrode is one of the most effective means for improving the cycle reversibility and safety performance of the negative electrode of a lithium metal battery. The current collector in the negative electrode material directly influences lithium nucleation and growth, local current density and lithium ion flux as a substrate for lithium deposition stripping, and plays an electron transport function as a connector for connecting an external circuit with an active substance. Therefore, optimizing and modifying the current collector in the negative electrode is a key means for improving the battery performance.
At present, current collector modification means mainly comprise structural design and chemical modification of a current collector. The current collector structure design mainly comprises roughening, nanocrystallization and three-dimensional stereotactic of the current collector surface, but has the problems of complex process steps, low space utilization rate caused by lack of a lithium-philic site and the like. The chemical modification is mainly performed by performing lithiation modification on the material, and lithium nucleation and growth are induced by a conversion reaction or an alloying reaction, but the chemical modification has the defects of low volume capacity, difficult efficient continuous preparation and the like. In order to solve the problems of the single means, the negative electrode current collector is fully modified, and the combination of structural design and chemical modification to generate synergistic effect is a scientific and feasible scheme.
Disclosure of Invention
The invention provides a CuO@Cu/Ag composite current collector for a lithium metal battery cathode and a preparation method thereof; the method aims at providing a new reference for design and selection of the negative electrode current collector of the lithium metal battery.
The invention aims at realizing the following technical scheme:
in a first aspect, the invention relates to a CuO@Cu/Ag alloy nanomaterial, which consists of spherical Cu/Ag alloy nanoparticles with high conductivity and high lithium affinity, wherein the surfaces of the spherical Cu/Ag alloy nanoparticles are uniformly loaded with a needle-like CuO film layer with high lithium affinity. Wherein, the needle-shaped CuO axially grows to form a cluster structure, namely, a vertical cluster structure is formed.
As one embodiment, the microscopic particle size is 50 to 60nm. The CuO@Cu/Ag alloy nano material is spherical particles with the diameter of 50-60 nm, is Cu/Ag alloy nano particles with extremely high conductivity and high lithium philicity and uniformly loaded with a needle-shaped CuO film layer, and is formed by stacking and arranging regular spherical nano particles with needle-velvet surfaces. Specifically, the three-dimensional porous structure is formed because spherical nanoparticles are stacked with each other and the surfaces of the nanoparticles are loaded with needle-like CuO film layers, so that certain pores exist among the nanoparticles to form the three-dimensional structure.
As one embodiment, the surface of the Cu/Ag alloy nanoparticle is uniformly loaded with the acicular CuO film layer with high lithium affinity, and the CuO acicular structure is used as the outer film layer of the nanoparticle, so that the inter-particle gap is effectively increased, and the current collector has larger lithium storage space. The needle-shaped CuO grows axially to form a cluster structure, which provides a three-dimensional space for lithium deposition, and the vertical cluster structure can effectively inhibit the formation and growth of lithium dendrites through space limitation. Meanwhile, cuO can react with metal Li in a conversion way, has lower lithium deposition overpotential, has excellent lithium affinity and can induce uniform deposition of lithium. The Cu/Ag alloy nano particles with extremely high conductivity and lithium-philicity have the advantages that Cu provides the charge conduction function and structural stability of a composite structure, ag is used as the metal with the most excellent conductivity, the conductivity of the whole composite structure can be effectively improved, the Cu/Ag alloy nano particles have the extremely high lithium-philicity, and a lower lithium nucleation barrier can be provided through alloying reaction with metal Li, so that a smaller nucleation overpotential is generated. In the invention, cu and Ag form a solid solution alloy, and the Cu and Ag have electronic interaction, so that the Cu/Ag alloy nano particles have more excellent performance: the higher mechanical strength accommodates repeated deposition and stripping of lithium and the higher lithium affinity induces uniform deposition of lithium.
As an embodiment, the two metal components having excellent conductivity properties also ensure excellent conductivity of the alloy formed. The CuO@Cu/Ag alloy nano particles have excellent conductivity, lithium-philicity and mechanical properties. In the material component, cuO and metal Li are subjected to conversion reaction, ag and metal Li are subjected to alloying reaction, and two lithium-philic mechanisms are subjected to synergistic action, so that the nucleation overpotential reduction amplitude of Li during deposition is far greater than the effect of the independent action of the two mechanisms, and the deposition of metal Li is more uniform. When lithium metal is deposited in the upright needle-shaped CuO cluster, the deposition of metal lithium can occur at the bottom of the needle-shaped CuO cluster preferentially and is gradually accumulated from the bottom of the cluster structure to the outside, so that the full utilization of space is realized, the volume capacity of a current collector material is increased, and the lithium storage capacity of a negative electrode is increased.
As one embodiment, the CuO@Cu/Ag alloy nano particles are calculated by 10 parts by weight, wherein the CuO accounts for 4-6 parts, the Cu accounts for 3-4 parts and the Ag accounts for 1-2 parts. In order to ensure that the nano particles have excellent conductivity, lithium-philic property and mechanical strength, control the material cost and ensure the porosity of the current collector material, the above component proportions are selected for material synthesis. Wherein Cu provides stable electrical conductivity and structural stability of the composite structure. The needle-shaped CuO builds a three-dimensional structure, adjusts the porosity of the inventive current collector, and has lithium-philicity through conversion reaction. Ag increases the conductivity of the material, forms alloy with copper, generates electronic interaction, can induce uniform deposition of metallic lithium through alloying reaction, and generates synergistic effect with a conversion reaction lithium-philic mechanism of CuO. And the optimal solution of the comprehensive performance is realized by regulating and controlling the proportion of the three components. If the ratio of CuO in the three is too high, the conductivity of the material is weakened; when the Ag ratio is too high, the mechanical strength of the material is reduced; when the Cu ratio is too high, the lithium affinity of the material is lowered.
In a second aspect, the invention relates to a preparation method of a CuO@Cu/Ag alloy nanomaterial, which comprises the following steps:
s1-1, preparing liquid: weighing water-soluble cupric salt, water-soluble monovalent silver salt, organic metal chelating agent and reductive borohydride according to the proportion; then uniformly grinding and mixing water-soluble cupric salt and water-soluble monovalent silver salt, adding deionized water according to a certain concentration ratio so as to obtain the invented Cu-containing product 2+ And Ag + Is prepared for standby; dissolving organic metal chelating agent, morphology agent and reductive borohydride in OH according to a certain concentration ratio - The concentration is 0.8 to 1mol L -1 Preparing an alkaline borohydride solution containing an organic metal chelating agent and a surface morphology agent for later use;
s1-2, liquid phase reduction: the Cu-containing alloy is subjected to normal temperature and normal pressure 2+ And Ag + Is added dropwise to the said mixtureReacting an organic metal chelating agent with an alkaline borohydride solution of a surface morphology agent to prepare an aqueous solution dispersion system of CuO@Cu/Ag alloy nano material;
s1-3, high-speed centrifugation and freeze drying to obtain the CuO@Cu/Ag alloy nanomaterial.
As one embodiment, the proportion of the ingredients in the step S1-1 is calculated by 10 parts of total weight, 2-3 parts of water-soluble cupric salt, 1-2 parts of water-soluble monovalent silver salt, 3-4 parts of organic metal chelating agent, 2-3 parts of reducing borohydride and 1-2 parts of surface topography agent. The main reason is to make the product: cuO, cu, ag, wherein the proportion of CuO is 4-6 parts, cu is 3-4 parts and Ag is 1-2 parts based on 10 parts of total weight. The purpose of adding excessive reducing agent sodium borohydride is to ensure Cu in the solution 2+ 、Ag + Is fully reduced. Organometallic chelating agent EDTA and Cu 2+ 、Ag + The coordination ratio of the two metal ions is 1:1, so that the dosage is approximately the same as that of the metal source salt.
As one embodiment, the alloy contains Cu 2+ And Ag + Cu in the uniform mixed solution of (2) 2+ The concentration is 0.2 to 1mol L -1 ，Ag + The concentration is 0.1 to 1mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the In the alkaline borohydride solution containing the organic metal chelating agent and the surface morphology agent, the concentration of the organic metal chelating agent is 0.2-2 mol L -1 ，BH 4 - The concentration of (C) is 0.1-1 mol L -1 The concentration of the surface morphology agent is 0.1 to 0.2mol L -1 . The larger mass concentration of the substance can ensure the concentration of activated molecules, and the probability of effective collision of molecules in unit time is increased, so that the efficient performance of the reaction is ensured.
In step S1-2, as one embodiment, the dropwise addition is carried out at a dropping speed of 30 to 100 drops per minute; the reaction is carried out under the condition of continuous stirring, and the reaction time is 10-60 min. The main reason for choosing the parameter is that the metal source solution is dropped into excessive reducing solvent containing organic metal chelating agent and surface morphology agent at uniform speed and small amount, thereby ensuring Cu 2+ 、Ag + Sufficient coordination with EDTA and oxygenThe chemical reduction reaction is fully performed. So that the product nano particles are mutually dispersed to obtain spherical nano particles with regular morphology and three-dimensional stacking in space.
In step S1-1, as an embodiment, the water-soluble divalent copper salt is copper nitrate, the water-soluble monovalent silver salt is silver nitrate, the organic metal chelating agent is ethylenediamine tetraacetic acid (EDTA), the reducing borohydride is sodium borohydride or potassium borohydride, and the morphology agent is Ethylenediamine (EDA). The water-soluble cupric salt and water-soluble monovalent silver salt in the preparation step of the CuO@Cu/Ag alloy nano particles are respectively selected as copper nitrate and silver nitrate, and the main reason is that the two selected nitrates are easily dissolved in water, and the same kind of impurity NO with stable properties is introduced 3 - The anions can reduce the impurity types in the system and avoid side reactions. The reducing borohydride is potassium borohydride, which has strong reducibility, water solubility, low toxicity and high safety compared with other reducing substances. In order to ensure the stability of the reducing agent potassium borohydride, the reaction is carried out in an alkaline environment. The reaction solution precursor is thus a potassium borohydride solution with a pH of approximately 14. The selected metal chelating agent is preferably ethylenediamine tetraacetic acid (EDTA) for binding metal ions Cu 2 + 、Ag + The metal ions are included in the chelating agent to prevent Cu 2+ 、Ag + With OH in solution - And combine to form a precipitate. The selected surface topography agent Ethylenediamine (EDA) prevents addition of atoms to specific crystal planes to induce anisotropic growth to produce a nanoscale one-dimensional needle-like structure.
As one embodiment, in the step S1-3, the rotation speed of the high-speed centrifugation is 5000-10000 r min -1 The method comprises the steps of carrying out a first treatment on the surface of the The freeze drying is carried out for 24-48 h under the conditions that the vacuum degree is minus 0.05-minus 0.1MPa and the temperature is minus 40-minus 60 ℃. The reason for choosing this parameter is that it is sufficiently cooled to maintain the regular spherical particle morphology of the material, preventing oxidation of the material.
In a third aspect, the invention relates to an application of a CuO@Cu/Ag alloy nanomaterial in preparing a lithium metal battery anode material or a lithium metal battery anode current collector. The CuO@Cu/Ag composite current collector and the lithium metal are directly compounded to manufacture the lithium metal battery cathode. Wherein, the compounding mode of the CuO@Cu/Ag composite current collector and the metal lithium is a mechanical rolling method, a melting method and an electrodeposition method, and preferably, the lithium attaching method of the CuO@Cu/Ag composite current collector is a mechanical rolling lithium attaching method.
In a fourth aspect, the invention relates to a CuO@Cu/Ag composite current collector, which consists of the CuO@Cu/Ag alloy nanomaterial, a conductive agent and a binder, and has a three-dimensional nano porous structure on a microscopic scale and a flexible micro thin film structure on a macroscopic scale. The current collector has a metal rigid structure connected with an external circuit and has the lithium metal cathode lithium storage function and the external circuit electron transmission function.
As one embodiment, the thickness of the CuO@Cu/Ag composite current collector is 10-20 μm.
In a fifth aspect, the present invention relates to a method for preparing a cuo@cu/Ag composite current collector, said method comprising the steps of:
s1, preparing slurry: uniformly dispersing the CuO@Cu/Ag alloy nano material, a binder and a conductive agent into a dispersing agent according to a certain mixing ratio to obtain a slurry dispersing system with uniform texture and proper viscosity;
s2, mechanical film coating: coating the prepared slurry on the surface of a substrate glass plate at a constant speed by using a mechanical scraper, wherein the thickness of the coating layer is 10-20 mu m, and obtaining a semi-solid slurry film with uniform texture;
s3, evaporating to form a film: evaporating and drying the semi-solid slurry film for 8-16 hours under the vacuum degree of minus 0.05 to minus 0.1MPa and the temperature of 60-100 ℃ to form a solid film, and stripping the flexible film on the surface of the substrate after film forming to obtain the CuO@Cu/Ag composite current collector. The current collector may be a lithium metal anode current collector with integrated structural function.
As one embodiment, the current collector is made by a "liquid phase reduction-slurry formulation-mechanical coating-evaporative film formation" process.
In step S1, the cuo@cu/Ag alloy nanomaterial, the binder, and the conductive agent are dispersed in a dispersant in an environment having a temperature of 18 to 28 ℃ and a humidity of 10 to 30%. The main purpose of this step of controlling the temperature and humidity is to easily obtain a slurry dispersion having a uniform texture and a proper viscosity under the experimental conditions of the temperature and humidity. Under the premise of preventing oxidation and water absorption of materials caused by higher temperature and humidity, experimental operation is performed under the most easily realized environmental conditions, so that the morphology and time cost of the materials are effectively controlled.
As one embodiment, the binder is an injection molding high polymer material, preferably polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC), polyacrylic acid (PAA) or polyvinyl alcohol (PVA), and is used for forming a micro-organic matter crosslinked network, so as to ensure uniformity and cohesiveness when the active substance (i.e., cuo@cu/Ag alloy nanoparticles) is pulped, and have a binding purpose on the active substance particles; the conductive agent is a conductive carbon material, preferably nano carbon black, and acts to increase the conductivity of the material.
As an embodiment, the main purpose of setting the thickness of the coating layer in the S2 step to 10-20 μm is to provide sufficient physical space for deposition of metallic lithium while controlling the thickness of the coating layer to obtain a thin and lightweight anode to manufacture a high energy density lithium metal battery.
In the step S1, the total weight is 10 parts, the CuO@Cu/Ag alloy nanomaterial accounts for 6-8 parts, the binder accounts for 1-2 parts, the conductive agent accounts for 1-2 parts, and the liquid-solid ratio of the dispersing agent is 3:1-5:1; wherein the dispersant is selected from N-methylpyrrolidone (NMP), isopropanol, ethanol or ethylene glycol.
As an embodiment, in the S4 step of the method for preparing a lithium metal negative electrode current collector with integrated structural function, the vacuum degree is set to 0.05-0.1 MPa, and the temperature is set to 60-100 ℃, so as to prevent the ratio of CuO, cu, ag from being changed due to oxidation of Cu in cuo@cu/Ag alloy nanoparticles.
Compared with the prior art, the invention has the following beneficial effects:
1) The CuO@Cu/Ag composite current collector provided by the invention has the characteristic of structural function integration, has excellent lithium affinity and excellent conductivity and mechanical strength, and meanwhile, spherical nano particles with needle-shaped surfaces are mutually connected to build a three-dimensional skeleton, and the three-dimensional skeleton does not need to be coated on a copper foil of a traditional current collector, so that the quality of a negative electrode is reduced, the characteristic of high specific capacity of the negative electrode is also realized, meanwhile, the high lithium affinity can induce uniform deposition of metallic lithium, and the formation of lithium dendrites is effectively avoided.
2) The invention realizes the synergistic effect of 1+1 & gt2 of two lithium-philic mechanisms, the conversion reaction of CuO and Li is carried out, the alloying effect of Ag and Li is carried out, both mechanisms can be used for inducing the uniform deposition of Li, and the CuO@Cu/Ag nano particles synthesized in the invention realize the two mechanisms simultaneously, and achieve the synergistic effect of 1+1 & gt2, thereby providing a certain thought and reference for the design of the negative electrode current collector material of the lithium metal battery.
3) The current collector preparation process provided by the invention is simple and convenient to operate, has low environmental requirement, can synthesize three-dimensional nano-scale spherical particles through the liquid phase reduction step, and prepares the current collector smear through an evaporation coating mode. The operation steps are simple and convenient, the operation time is short, the required experimental equipment is simple, the required environmental atmosphere requirement is low, the cost is easy to control, the actual operation is convenient, and the industrial application is expected to be realized.
4) 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.
5) Compared with a CuO@Ag core-shell structure, the CuO@Cu/Ag alloy nano material disclosed by the invention is externally coated by a needle velvet-shaped film to form a cluster-shaped three-dimensional lithium storage space, and meanwhile, the formation and growth of lithium dendrites can be inhibited through space confinement.
6) Compared with a CuO nano sheet@Ag nano rod structure, the CuO@Cu/Ag alloy nano material disclosed by the invention has the advantages that only gradient lithium affinity favorable for the sequential deposition of lithium from inside to outside exists from inside to outside, and the Cu nano sheet with higher conductivity is easy to cause the deposition of lithium from outside to inside, so that the maximization of space utilization rate is not favorable.
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 a flow chart of the preparation of a CuO@Cu/Ag composite current collector;
FIG. 2 is a digital photograph of a CuO@Cu/Ag composite current collector;
FIG. 3 is a TEM image of a CuO@Cu/Ag alloy nanomaterial;
FIG. 4 is an XRD pattern of a CuO@Cu/Ag alloy nanomaterial;
FIG. 5 is a STEM image of a CuO@Cu/Ag alloy nanomaterial and element distribution;
FIG. 6 is a HTEM image of a CuO@Cu/Ag alloy nanomaterial;
FIG. 7 is an SEM image and EDS analysis result of a CuO@Cu/Ag alloy nanomaterial;
FIG. 8 is a lithium deposition overpotential of a CuO@Cu/Ag composite current collector;
FIG. 9 is a graph of cycle coulombic efficiency of a half cell of a lithium metal battery of a CuO@Cu/Ag composite current collector;
FIG. 10 is a graph of the symmetric cell impedance of a lithium metal cell of a CuO@Cu/Ag composite current collector;
FIG. 11 is a graph of the cycling performance of a symmetric battery of a lithium metal battery of a CuO@Cu/Ag composite current collector;
FIG. 12 is a graph of the full cell performance of a lithium metal battery of a CuO@Cu/Ag composite current collector;
FIG. 13 is a surface-smooth nanoscale CuO@Cu/Ag alloy nanoparticle;
FIG. 14 is an SEM image and EDS analysis results of a CuO@Cu/Ag alloy nanomaterial.
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 CuO@Cu/Ag composite current collector is prepared by adopting a process of liquid phase reduction, slurry preparation, mechanical coating and evaporation film forming, and the specific preparation is shown in a flow chart (figure 1):
S1, liquid phase reduction: cu is contained under normal temperature and pressure 2+ And Ag + Dropwise adding the uniform mixed solution of (1) into an alkaline borohydride solution containing an organic metal chelating agent and a surface morphology agent, and washing, drying and grinding after the reaction is finished to obtain CuO@Cu/Ag alloy nano material powder.
The specific operation steps of the liquid phase reduction are as follows:
s1-1, preparing liquid: weighing cupric nitrate copper (Cu (NO) 3 ) 2 3H 2 O), monovalent silver salt silver nitrate (AgNO) 3 ) Organometal chelating agent ethylenediamine tetraacetic acid (EDTA), reducing agent potassium borohydride (KBH 4 ) Copper nitrate (Cu (NO 3 ) 2 3H 2 O) and silver nitrate (AgNO 3 ) Uniformly grinding and mixing, and adding deionized water to prepare Cu-containing alloy 2+ And Ag + For later use, so that Cu in the obtained solution 2+ The concentration is 0.8mol L -1 ，Ag + At a concentration of 0.4mol L -1 . EDTA, EDA and KBH 4 Dissolving in OH at a certain concentration ratio - At a concentration of 1mol L -1 Is prepared in potassium hydroxide alkaline solution, and EDTA concentration in the obtained solution is 1.5mol L -1 ，BH4 - Is 0.5mol L -1 EDA concentration of 0.1mol L -1 。
S1-2, liquid phase reduction: the Cu-containing alloy is subjected to normal temperature and normal pressure 2+ And Ag + Is added dropwise to basic KBH containing EDTA and EDA at a drop rate of 100 drops per minute 4 In the solution, stirring is continued for 60min, and an aqueous solution dispersion system with CuO@Cu/Ag alloy nano particles is prepared.
S1-3, freeze drying: at 10000r min -1 And (3) carrying out high-speed centrifugation at the rotating speed of (2) separating the CuO@Cu/Ag alloy nano particles from the aqueous solution, and freeze-drying for 24 hours under the conditions that the vacuum degree is-0.05 MPa and the temperature is-40 ℃ to obtain the CuO@Cu/Ag alloy nano particles.
S1-4, grinding and crushing: and taking a freeze-dried sample, grinding and crushing the sample by adopting an agate mortar until powder can pass through a 300-mesh sieve.
S2, preparing slurry: uniformly dispersing CuO@Cu/Ag alloy nano particles, a binder polyvinylidene fluoride (PVDF) and a conductive agent nano carbon black into a dispersing agent N-methylpyrrolidone (NMP) according to a mass ratio of 7:1:2 in an environment with a temperature of 25 ℃ and a humidity of 20%, wherein a liquid-solid ratio of the dispersing agent is 3:1, and grinding for 1h to obtain a slurry dispersion system with uniform texture and proper viscosity.
S3, mechanical film coating: and (3) taking a clean toughened glass plate, uniformly coating the prepared slurry on the surface of the glass plate by using a mechanical scraper, wherein the thickness of the coating layer is 15 mu m, and obtaining the semi-solid slurry film with uniform texture.
S4, evaporating to form a film: transferring the semi-solid slurry film into a vacuum oven, evaporating and drying for 10 hours under the conditions of the vacuum degree of-0.05 MPa and the temperature of 80 ℃ to form a solid film, and stripping the flexible film on the surface of the glass plate after film formation to obtain the CuO@Cu/Ag composite current collector material with integrated structure and function.
The CuO@Cu/Ag composite current collector material prepared under the condition has good macroscopic surface glossiness and high thickness consistency (figure 2). The prepared CuO@Cu/Ag alloy nanomaterial is microscopically presented as a porous lithium storage framework formed by three-dimensional stacking of spherical nanoparticles, the surface of a synthesized sphere is coated by a needle-like film, needle-like structures are distributed in a cluster shape, a three-dimensional multi-upright lithium storage space is formed on the surface of the sphere (figure 3), and the phase composition of the material is CuO, ag, cu (figures 4 and 5); wherein the main part of the spherical nano-particles is Cu/Ag alloy nano-particles, and the acicular structure film is CuO (figure 6). Based on 10 parts of total weight, in the CuO@Cu/Ag alloy nano-particles, 6 parts of CuO, 3 parts of Cu and 1 part of Ag are contained.
(FIG. 7)
The thickness of the metal lithium sheet with 1mm is 0.5mA/cm after the half cell is assembled 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 25mV (FIG. 8), and was 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle over 300 cycles remained 97% coulombic efficiency at the amount of metallic lithium deposition/stripping (fig. 9). 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, the anode is a CuO@Cu/Ag composite current collector, the cathode is a metal lithium sheet, and the addition amount of the electrolyte of the anode and the cathode is 40 mu l respectively. CuO@Cu/A is prepared by adopting a mechanical rolling method g composite current collector was combined with a metal lithium foil having a purity of 99.9% and a thickness of 25 μm to prepare a lithium metal battery negative electrode and assembled a symmetrical battery having a low battery resistance (fig. 10) and at 0.5mA/cm 2 And a current density of 0.5mAh/cm 2 The cycle life was over 1000 hours (fig. 11), about 500 cycles, at a metallic lithium deposition/stripping amount. 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 both CuO@Cu/Ag composite current collectors with lithium, and the addition amount of the electrolyte of the anode and the cathode is 40 mu l respectively. The CuO@Cu/Ag composite current collector is taken as a negative electrode, liCoO 2 A full cell was made for the positive electrode, and the capacity fade rate was 14% after 300 cycles at 1C rate (fig. 12). All batteries are assembled by adopting CR2016 button battery shell, and electrolyte adopts 1M LiPF 6 (EC: dec=1:1) electrolyte, separator was polypropylene (PP) separator, and the amount of electrolyte added to the positive and negative electrodes was 40 μl each.
Example 2
The CuO@Cu/Ag composite current collector is prepared by adopting a process of liquid phase reduction, slurry preparation, mechanical coating and evaporation film forming, and the specific preparation is shown in a flow chart (figure 1):
s1, liquid phase reduction: cu is contained under normal temperature and pressure 2+ And Ag + Dropwise adding the uniform mixed solution of (1) into an alkaline borohydride solution containing an organic metal chelating agent and a surface morphology agent, and washing, drying and grinding after the reaction is finished to obtain CuO@Cu/Ag alloy nano material powder.
The specific operation steps of the liquid phase reduction are as follows:
s1-1, preparing liquid: weighing cupric nitrate, silver nitrate, organic metal chelating agent ethylenediamine tetraacetic acid (EDTA), and reducing agent potassium borohydride (KBH) 4 ) Copper nitrate (Cu (NO 3 ) 2 3H 2 O) and silver nitrate (AgNO 3 ) Uniformly grinding and mixing, and adding deionized water to prepare Cu-containing alloy 2+ And Ag + For later use, so that Cu in the obtained solution 2+ At a concentration of 1mol L -1 ，Ag + At a concentration of 0.5mol L -1 . EDTA, EDA and KBH 4 Dissolving in a certain concentration ratioSolution to OH - At a concentration of 1mol L -1 Is ready for use in an alkaline solution, the EDTA concentration in the resulting solution being 1.8mol L -1 ，BH4 - Is 0.8mol L -1 EDA concentration of 0.15mol L -1 。
S1-2, liquid phase reduction: the Cu-containing alloy is subjected to normal temperature and normal pressure 2+ And Ag + Is added dropwise to basic KBH containing EDTA and EDA at a drop rate of 100 drops per minute 4 In the solution, stirring is continued for 60min, and an aqueous solution dispersion system with CuO@Cu/Ag alloy nano particles is prepared.
S1-3, freeze drying: at 10000r min -1 And (3) carrying out high-speed centrifugation at the rotating speed of (2) separating the CuO@Cu/Ag alloy nano particles from the aqueous solution, and freeze-drying for 24 hours under the conditions that the vacuum degree is-0.05 MPa and the temperature is-60 ℃ to obtain the CuO@Cu/Ag alloy nano particles. The obtained CuO@Cu/Ag alloy nano particle comprises 5 parts of CuO, 3 parts of Cu and 2 parts of Ag by taking the total weight as 10 parts.
S1-4, grinding and crushing: and taking a freeze-dried sample, grinding and crushing the sample by adopting an agate mortar until powder can pass through a 300-mesh sieve.
S2, preparing slurry: uniformly dispersing CuO@Cu/Ag alloy nano particles, a binder polyvinylidene fluoride (PVDF) and a conductive agent nano carbon black into a dispersing agent N-methylpyrrolidone (NMP) according to a mass ratio of 8:1:1 in an environment with a temperature of 25 ℃ and a humidity of 20%, wherein a liquid-solid ratio of the dispersing agent is 4:1, and grinding for 1h to obtain a slurry dispersion system with uniform texture and proper viscosity.
S3, mechanical film coating: and (3) taking a clean toughened glass plate, uniformly coating the prepared slurry on the surface of the glass plate by using a mechanical scraper, wherein the thickness of the coating layer is 10 mu m, and obtaining the semi-solid slurry film with uniform texture.
S4, evaporating to form a film: transferring the semi-solid slurry film into a vacuum oven, evaporating and drying for 16 hours under the conditions of vacuum degree of-0.05 MPa and temperature of 60 ℃ to form a solid film, and stripping the flexible film on the surface of the glass plate after film formation to obtain the CuO@Cu/Ag composite current collector material with integrated structure and function.
Macroscopic body of the prepared current collector materialThe surface glossiness is better, the thickness consistency is high, the microscopic surface is a porous lithium storage framework formed by three-dimensional accumulation of spherical nano particles, the surface of the synthesized sphere is coated by needle-like films, and the needle-like structures are distributed in a cluster shape. CuO@Cu/Ag composite current collector and metal lithium sheet with purity of 99.9% and thickness of 1mm are assembled into half battery at 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 63mV, 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 90% at the amount of metallic lithium deposition/exfoliation. A lithium metal battery negative electrode having a low battery resistance and at 0.5mA/cm was fabricated by compounding a CuO@Cu/Ag composite current collector with a metal lithium foil having a purity of 99.9% and a thickness of 25 μm using a mechanical roll press method and assembling a symmetrical battery as in example 1 2 And a current density of 0.5mAh/cm 2 The cycle life of the lithium metal deposition/stripping amount is over 650h, about 325 turns. The CuO@Cu/Ag composite current collector is taken as a negative electrode, liCoO 2 A full cell was made for the positive electrode, and the capacity decay rate was 21.6% after 300 cycles at 1C magnification.
Example 3
The CuO@Cu/Ag composite current collector is prepared by adopting a process of liquid phase reduction, slurry preparation, mechanical coating and evaporation film forming, and the specific preparation is shown in a flow chart (figure 1):
S1, liquid phase reduction: cu is contained under normal temperature and pressure 2+ And Ag + Dropwise adding the uniform mixed solution of (1) into an alkaline borohydride solution containing an organic metal chelating agent and a surface morphology agent, and washing, drying and grinding after the reaction is finished to obtain CuO@Cu/Ag alloy nano material powder.
The specific operation steps of the liquid phase reduction are as follows:
s1-1, preparing liquid: weighing cupric nitrate copper (Cu (NO) 3 ) 2 3H 2 O), monovalent silver salt silver nitrate (AgNO) 3 ) Organometal chelating agent ethylenediamine tetraacetic acid (EDTA), reducing agent potassium borohydride (KBH 4 ) Subsequently Cu (NO 3 ) 2 3H 2 O and AgNO 3 Uniformly grinding and mixing, and adding deionized water to prepare Cu-containing alloy 2+ And Ag + Is uniformly mixed with (a)The solution is ready for use, so that Cu in the obtained solution 2+ The concentration is 0.6mol L -1 ，Ag + The concentration is 0.3mol L -1 . EDTA, EDA and KBH 4 Dissolving in OH at a certain concentration ratio - The concentration is 0.8mol L -1 Is ready for use in an alkaline solution, the EDTA concentration in the resulting solution being 1mol L -1 ，BH4 - Is 0.2mol L -1 EDA concentration of 0.18mol L -1 。
S1-2, liquid phase reduction: the Cu-containing alloy is subjected to normal temperature and normal pressure 2+ And Ag + Is added dropwise to basic KBH containing EDTA and EDA at a rate of 80 drops per minute 4 In the solution, stirring is continued for 45min, and an aqueous solution dispersion system with CuO@Cu/Ag alloy nano particles is prepared.
S1-3, freeze drying: at 10000r min -1 And (3) carrying out high-speed centrifugation at the rotating speed of (2) separating the CuO@Cu/Ag alloy nano particles from the aqueous solution, and freeze-drying for 24 hours under the conditions that the vacuum degree is-0.05 MPa and the temperature is-40 ℃. The obtained CuO@Cu/Ag alloy nano particle comprises 5 parts of CuO, 4 parts of Cu and 1 part of Ag by taking the total weight as 10 parts.
S1-4, grinding and crushing: and taking a freeze-dried sample, grinding and crushing the sample by adopting an agate mortar until powder can pass through a 300-mesh sieve.
S2, preparing slurry: uniformly dispersing CuO@Cu/Ag alloy nano particles, a binder polyvinylidene fluoride (PVDF) and a conductive agent nano carbon black into a dispersing agent N-methylpyrrolidone (NMP) according to a mass ratio of 7:1:2 in an environment with a temperature of 28 ℃ and a humidity of 15%, wherein a liquid-solid ratio of the dispersing agent is 5:1, and grinding for 1h to obtain a slurry dispersion system with uniform texture and proper viscosity.
S3, mechanical film coating: and (3) taking a clean toughened glass plate, and uniformly coating the prepared slurry on the surface of the glass plate by using a mechanical scraper, wherein the coating layer is 20 mu m, so as to obtain a semi-solid slurry film with uniform texture.
S4, evaporating to form a film: transferring the semi-solid slurry film into a vacuum oven, evaporating and drying for 10 hours under the conditions of the vacuum degree of-0.05 MPa and the temperature of 80 ℃ to form a solid film, and stripping the flexible film on the surface of the glass plate after film formation to obtain the CuO@Cu/Ag composite current collector material with integrated structure and function.
The prepared current collector material has good macroscopic surface glossiness and high thickness consistency, the microscopic surface is a porous lithium storage skeleton formed by three-dimensional accumulation of spherical nano particles, the surface of the synthesized sphere is coated by needle-shaped films, and the needle-shaped structures are distributed in a cluster shape. CuO@Cu/Ag composite current collector and metal lithium sheet with purity of 99.9% and thickness of 1mm are assembled into half battery at 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 57mV, and at 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle over 300 cycles of coulombic efficiency remained 91% at the amount of metallic lithium deposition/stripping. A lithium metal battery negative electrode having a low battery resistance and at 0.5mA/cm was fabricated by compounding a CuO@Cu/Ag composite current collector with a metal lithium foil having a purity of 99.9% and a thickness of 25 μm by a mechanical roll press method and assembling a symmetrical battery as in example 1 2 And a current density of 0.5mAh/cm 2 The cycle life was over 520 hours at a metallic lithium deposition/stripping amount of about 260 cycles. The CuO@Cu/Ag composite current collector is taken as a negative electrode, liCoO 2 A full cell was made for the positive electrode, and the capacity fade rate after 300 cycles at 1C was 21.9%.
Example 4
The CuO@Cu/Ag composite current collector is prepared by adopting a process of liquid phase reduction, slurry preparation, mechanical coating and evaporation film forming, and the specific preparation is shown in a flow chart (figure 1):
S1, liquid phase reduction: cu is contained under normal temperature and pressure 2+ And Ag + Dropwise adding the uniform mixed solution of (1) into an alkaline borohydride solution containing an organic metal chelating agent and a surface morphology agent, and washing, drying and grinding after the reaction is finished to obtain CuO@Cu/Ag alloy nano material powder.
The specific operation steps of the liquid phase reduction are as follows:
s1-1, preparing liquid: weighing cupric nitrate copper (Cu (NO) 3 ) 2 3H 2 O), monovalent silver salt silver nitrate (AgNO) 3 ) Organometal chelating agent ethylenediamine tetraacetic acid (EDTA), reducing agent potassium borohydride (KBH 4 ) Subsequently Cu (NO 3 ) 2 3H 2 O and AgNO 3 Uniformly grinding and mixing, and adding deionized water to prepare Cu-containing alloy 2+ And Ag + For later use, so that Cu in the obtained solution 2+ At a concentration of 0.4mol L -1 ，Ag + At a concentration of 0.2mol L -1 . EDTA, EDA and KBH 4 Dissolving in OH at a certain concentration ratio - The concentration is 0.8mol L -1 Is ready for use in an alkaline solution, the EDTA concentration in the resulting solution being 0.8mol L -1 ，BH4 - Is 0.2mol L -1 EDA concentration of 0.2mol L -1 。
S1-2, liquid phase reduction: the Cu-containing alloy is subjected to normal temperature and normal pressure 2+ And Ag + Is added dropwise to basic KBH containing EDTA and EDA at a drop rate of 100 drops per minute 4 In the solution, stirring is continued for 60min, and an aqueous solution dispersion system with CuO@Cu/Ag alloy nano particles is prepared.
S1-3, freeze drying: at 8000r min -1 And (3) carrying out high-speed centrifugation at the rotating speed of (2) separating the CuO@Cu/Ag alloy nano particles from the aqueous solution, and freeze-drying for 24 hours under the conditions that the vacuum degree is-0.05 MPa and the temperature is-40 ℃. The obtained CuO@Cu/Ag alloy nano particle comprises 5 parts of CuO, 3 parts of Cu and 2 parts of Ag by taking the total weight as 10 parts.
S1-4, grinding and crushing: and taking a freeze-dried sample, grinding and crushing the sample by adopting an agate mortar until powder can pass through a 300-mesh sieve.
S2, preparing slurry: uniformly dispersing CuO@Cu/Ag alloy nano particles, a binder polyvinylidene fluoride (PVDF) and a conductive agent nano carbon black into a dispersing agent N-methylpyrrolidone (NMP) according to a mass ratio of 6:1:3 in an environment with a temperature of 18 ℃ and a humidity of 30%, and grinding for 1h to obtain a slurry dispersion system with uniform texture and proper viscosity, wherein the liquid-solid ratio of the dispersing agent is 3:1.
S3, mechanical film coating: and (3) taking a clean toughened glass plate, and uniformly coating the prepared slurry on the surface of the glass plate by using a mechanical scraper, wherein the coating layer is 15 mu m, so as to obtain the semi-solid slurry film with uniform texture.
S4, evaporating to form a film: transferring the semi-solid slurry film into a vacuum oven, evaporating and drying for 10 hours under the conditions of the vacuum degree of-0.05 MPa and the temperature of 80 ℃ to form a solid film, and stripping the flexible film on the surface of the glass plate after film formation to obtain the CuO@Cu/Ag composite current collector material with integrated structure and function.
The prepared current collector material has good macroscopic surface glossiness and high thickness consistency, the microscopic surface is a porous lithium storage skeleton formed by three-dimensional accumulation of spherical nano particles, the surface of the synthesized sphere is coated by needle-shaped films, and the needle-shaped structures are distributed in a cluster shape. CuO@Cu/Ag composite current collector and metal lithium sheet with purity of 99.9% and thickness of 1mm are assembled into half battery at 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 58mV, and at 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle over 300 cycles of coulombic efficiency remained 89% with the amount of metallic lithium deposition/stripping. A lithium metal battery negative electrode having a low battery resistance and at 0.5mA/cm was fabricated by compounding a CuO@Cu/Ag composite current collector with a metal lithium foil having a purity of 99.9% and a thickness of 25 μm by a mechanical roll press method and assembling a symmetrical battery as in example 1 2 And a current density of 0.5mAh/cm 2 The cycle life is over 670 hours, about 335 cycles, at a metallic lithium deposition/stripping amount. The CuO@Cu/Ag composite current collector is taken as a negative electrode, liCoO 2 A full cell was made for the positive electrode, and the capacity decay rate was 23.4% after 300 cycles at 1C magnification.
Example 5
The CuO@Cu/Ag composite current collector is prepared by adopting a process of liquid phase reduction, slurry preparation, mechanical coating and evaporation film forming, and the specific preparation is shown in a flow chart (figure 1):
S1, liquid phase reduction: cu is contained under normal temperature and pressure 2+ And Ag + Dropwise adding the uniform mixed solution of (1) into an alkaline borohydride solution containing an organic metal chelating agent and a surface morphology agent, and washing, drying and grinding after the reaction is finished to obtain CuO@Cu/Ag alloy nano material powder.
The specific operation steps of the liquid phase reduction are as follows:
s1-1, preparing liquid: weighing cupric nitrate copper (Cu (NO) 3 ) 2 3H 2 O) monovalent silver salt silver nitrate(AgNO 3 ) Organometal chelating agent ethylenediamine tetraacetic acid (EDTA), reducing agent potassium borohydride (KBH 4 ) Subsequently Cu (NO 3 ) 2 3H 2 O and AgNO 3 Uniformly grinding and mixing, and adding deionized water to prepare Cu-containing alloy 2+ And Ag + For later use, so that Cu in the obtained solution 2+ At a concentration of 0.2mol L -1 ，Ag + At a concentration of 0.1mol L -1 . EDTA, EDA and KBH 4 Dissolving in OH at a certain concentration ratio - The concentration is 0.8mol L -1 Is ready for use in an alkaline solution, the EDTA concentration in the resulting solution being 0.4mol L -1 ，BH4 - Is 0.1mol L -1 EDA concentration of 0.15mol L -1 。
S1-2, liquid phase reduction: the Cu-containing alloy is subjected to normal temperature and normal pressure 2+ And Ag + Is added dropwise to basic KBH containing EDTA and EDA at a drop rate of 100 drops per minute 4 In the solution, stirring is continued for 60min, and an aqueous solution dispersion system with CuO@Cu/Ag alloy nano particles is prepared.
S1-3, freeze drying: at 10000r min -1 And (3) carrying out high-speed centrifugation at the rotating speed of (2) separating the CuO@Cu/Ag alloy nano particles from the aqueous solution, and freeze-drying for 24 hours under the conditions that the vacuum degree is-0.05 MPa and the temperature is-40 ℃ to obtain the CuO@Cu/Ag alloy nano particles. The obtained CuO@Cu/Ag alloy nano particle comprises 5 parts of CuO, 3 parts of Cu and 2 parts of Ag by taking the total weight as 10 parts.
S1-4, grinding and crushing: and taking a freeze-dried sample, grinding and crushing the sample by adopting an agate mortar until powder can pass through a 300-mesh sieve.
S2, preparing slurry: uniformly dispersing CuO@Cu/Ag alloy nano particles, a binder polyvinylidene fluoride (PVDF) and a conductive agent nano carbon black into a dispersing agent N-methylpyrrolidone (NMP) according to a mass ratio of 7:2:1 in an environment with a temperature of 25 ℃ and a humidity of 20%, and grinding for 1h to obtain a slurry dispersion system with uniform texture and proper viscosity, wherein the liquid-solid ratio of the dispersing agent is 4:1.
S3, mechanical film coating: and (3) taking a clean toughened glass plate, and uniformly coating the prepared slurry on the surface of the glass plate by using a mechanical scraper, wherein the coating layer is 10 mu m, so as to obtain the semi-solid slurry film with uniform texture.
S4, evaporating to form a film: transferring the semi-solid slurry film into a vacuum oven, evaporating and drying for 16 hours under the conditions of the vacuum degree of-0.1 MPa and the temperature of 80 ℃ to form a solid film, and stripping the flexible film on the surface of the glass plate after film formation to obtain the CuO@Cu/Ag composite current collector material with integrated structure and function.
The prepared current collector material has good macroscopic surface glossiness and high thickness consistency, the microscopic surface is a porous lithium storage skeleton formed by three-dimensional accumulation of spherical nano particles, the surface of the synthesized sphere is coated by needle-shaped films, and the needle-shaped structures are distributed in a cluster shape. CuO@Cu/Ag composite current collector and metal lithium sheet with purity of 99.9% and thickness of 1mm are assembled into half battery at 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 58mV, and at 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle over 300 cycles of coulombic efficiency remained 89.6% with the amount of metallic lithium deposition/stripping. A lithium metal battery negative electrode having a low battery resistance and at 0.5mA/cm was fabricated by compounding a CuO@Cu/Ag composite current collector with a metal lithium foil having a purity of 99.9% and a thickness of 25 μm by a mechanical roll press method and assembling a symmetrical battery as in example 1 2 And a current density of 0.5mAh/cm 2 The cycle life was over 490 hours, about 245 cycles at the amount of metallic lithium deposited/stripped. The CuO@Cu/Ag composite current collector is taken as a negative electrode, liCoO 2 A full cell was made for the positive electrode, which had a capacity fade rate of 24.6% after 300 cycles at 1C rate.
Example 6
The CuO@Cu/Ag composite current collector is prepared by adopting a process of liquid phase reduction, slurry preparation, mechanical coating and evaporation film forming, and the specific preparation is shown in a flow chart (figure 1):
S1, liquid phase reduction: cu is contained under normal temperature and pressure 2+ And Ag + Dropwise adding the uniform mixed solution of (1) into an alkaline borohydride solution containing an organic metal chelating agent and a surface morphology agent, and washing, drying and grinding after the reaction is finished to obtain CuO@Cu/Ag alloy nano material powder.
The specific operation steps of the liquid phase reduction are as follows:
s1-1, preparing liquid: weighing cupric nitrate copper (Cu (NO) 3 ) 2 3H 2 O), monovalent silver salt silver nitrate (AgNO) 3 ) Organometal chelating agent ethylenediamine tetraacetic acid (EDTA), reducing agent potassium borohydride (KBH 4 ) Subsequently Cu (NO 3 ) 2 3H 2 O and AgNO 3 Uniformly grinding and mixing, and adding deionized water to prepare Cu-containing alloy 2+ And Ag + For later use, so that Cu in the obtained solution 2+ The concentration is 0.8mol L -1 ，Ag + At a concentration of 0.4mol L -1 . EDTA, EDA and KBH 4 Dissolving in OH at a certain concentration ratio - At a concentration of 1mol L -1 Is ready for use in an alkaline solution, the EDTA concentration in the resulting solution being 1.5mol L -1 ，BH4 - Is 0.5mol L -1 EDA concentration of 0.1mol L -1 。
S1-2, liquid phase reduction: the Cu-containing alloy is subjected to normal temperature and normal pressure 2+ And Ag + Is added dropwise to basic KBH containing EDTA and EDA at a drop rate of 100 drops per minute 4 In the solution, stirring is continued for 60min, and an aqueous solution dispersion system with CuO@Cu/Ag alloy nano particles is prepared.
S1-3, freeze drying: at 10000r min -1 And (3) carrying out high-speed centrifugation at the rotating speed of (2) separating the CuO@Cu/Ag alloy nano particles from the aqueous solution, and freeze-drying for 24 hours under the conditions that the vacuum degree is-0.05 MPa and the temperature is-40 ℃ to obtain the CuO@Cu/Ag alloy nano particles. The obtained CuO@Cu/Ag alloy nano particle comprises 5 parts of CuO, 3 parts of Cu and 2 parts of Ag by taking the total weight as 10 parts.
S1-4, grinding and crushing: and taking a freeze-dried sample, grinding and crushing the sample by adopting an agate mortar until powder can pass through a 300-mesh sieve.
S2, preparing slurry: uniformly dispersing CuO@Cu/Ag alloy nano particles, a binder polyvinylidene fluoride (PVDF) and a conductive agent nano carbon black into a dispersing agent N-methylpyrrolidone (NMP) according to a mass ratio of 7:1:2 in an environment with a temperature of 25 ℃ and a humidity of 20%, wherein a liquid-solid ratio of the dispersing agent is 5:1, and grinding for 1h to obtain a slurry dispersion system with uniform texture and proper viscosity.
S3, mechanical film coating: and (3) taking a clean toughened glass plate, and uniformly coating the prepared slurry on the surface of the glass plate by using a mechanical scraper, wherein the coating layer is 15 mu m, so as to obtain the semi-solid slurry film with uniform texture.
S4, evaporating to form a film: transferring the semi-solid slurry film into a vacuum oven, evaporating and drying for 10 hours under the conditions of the vacuum degree of-0.05 MPa and the temperature of 80 ℃ to form a solid film, and stripping the flexible film on the surface of the glass plate after film formation to obtain the CuO@Cu/Ag composite current collector material with integrated structure and function.
The prepared current collector material has good macroscopic surface glossiness and high thickness consistency, the microscopic surface is a porous lithium storage skeleton formed by three-dimensional accumulation of spherical nano particles, the surface of the synthesized sphere is coated by needle-shaped films, and the needle-shaped structures are distributed in a cluster shape. CuO@Cu/Ag composite current collector and metal lithium sheet with purity of 99.9% and thickness of 1mm are assembled into half battery at 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 68mV, and was at 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle over 300 cycles of coulombic efficiency remained 87% at the amount of metallic lithium deposition/stripping. The CuO@Cu/Ag composite current collector and the metallic lithium are compounded to prepare the lithium metal battery cathode by adopting an electrodeposition method, and the 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 0.5mA/cm 2 And a current density of 0.5mAh/cm 2 The cycle life is over 580h at a metal lithium deposition/stripping amount of about 290 turns. The CuO@Cu/Ag composite current collector is taken as a negative electrode, liCoO 2 A full cell was made for the positive electrode, and the capacity fade rate after 300 cycles at 1C was 22.5%.
Example 7
The CuO@Cu/Ag composite current collector is prepared by adopting a process of liquid phase reduction, slurry preparation, mechanical coating and evaporation film forming, and the specific preparation is shown in a flow chart (figure 1):
s1, liquid phase reduction: at normal temperatureCu is contained under normal pressure 2+ And Ag + Dropwise adding the uniform mixed solution of (1) into an alkaline borohydride solution containing an organic metal chelating agent and a surface morphology agent, and washing, drying and grinding after the reaction is finished to obtain CuO@Cu/Ag alloy nano material powder.
The specific operation steps of the liquid phase reduction are as follows:
s1-1, preparing liquid: weighing cupric nitrate copper (Cu (NO) 3 ) 2 3H 2 O), monovalent silver salt silver nitrate (AgNO) 3 ) Organometal chelating agent ethylenediamine tetraacetic acid (EDTA), reducing agent potassium borohydride (KBH 4 ) Subsequently Cu (NO 3 ) 2 3H 2 O and AgNO 3 Uniformly grinding and mixing, and adding deionized water to prepare Cu-containing alloy 2+ And Ag + For later use, so that Cu in the obtained solution 2+ The concentration is 1.0mol L -1 ，Ag + At a concentration of 0.5mol L -1 . EDTA, EDA and KBH 4 Dissolving in OH at a certain concentration ratio - At a concentration of 1mol L -1 Is ready for use in an alkaline solution, the EDTA concentration in the resulting solution being 1.8mol L -1 ，BH4 - Is 0.5mol L -1 EDA concentration of 0.1mol L -1 。
S1-2, liquid phase reduction: the Cu-containing alloy is subjected to normal temperature and normal pressure 2+ And Ag + Is added dropwise to basic KBH containing EDTA and EDA at a drop rate of 100 drops per minute 4 In the solution, stirring is continued for 60min, and an aqueous solution dispersion system with CuO@Cu/Ag alloy nano particles is prepared.
S1-3, freeze drying: at 10000r min -1 And (3) carrying out high-speed centrifugation at the rotating speed of (2) separating the CuO@Cu/Ag alloy nano particles from the aqueous solution, and freeze-drying for 24 hours under the conditions that the vacuum degree is-0.05 MPa and the temperature is-40 ℃ to obtain the CuO@Cu/Ag alloy nano particles. The obtained CuO@Cu/Ag alloy nano particle comprises 5 parts of CuO, 4 parts of Cu and 1 part of Ag by taking the total weight as 10 parts.
S1-4, grinding and crushing: and taking a freeze-dried sample, grinding and crushing the sample by adopting an agate mortar until powder can pass through a 300-mesh sieve.
S2, preparing slurry: uniformly dispersing CuO@Cu/Ag alloy nano particles, a binder polyvinylidene fluoride (PVDF) and a conductive agent nano carbon black into a dispersing agent N-methylpyrrolidone (NMP) according to a mass ratio of 8:1:1 in an environment with a temperature of 25 ℃ and a humidity of 20%, wherein a liquid-solid ratio of the dispersing agent is 5:1, and grinding for 1h to obtain a slurry dispersion system with uniform texture and proper viscosity.
S3, mechanical film coating: and (3) taking a clean toughened glass plate, and uniformly coating the prepared slurry on the surface of the glass plate by using a mechanical scraper, wherein the coating layer is 10 mu m, so as to obtain the semi-solid slurry film with uniform texture.
S4, evaporating to form a film: transferring the semi-solid slurry film into a vacuum oven, evaporating and drying for 12 hours under the conditions of the vacuum degree of-0.05 MPa and the temperature of 80 ℃ to form a solid film, and stripping the flexible film on the surface of the glass plate after film formation to obtain the CuO@Cu/Ag composite current collector material with integrated structure and function.
The prepared current collector material has good macroscopic surface glossiness and high thickness consistency, the microscopic surface is a porous lithium storage skeleton formed by three-dimensional accumulation of spherical nano particles, the surface of the synthesized sphere is coated by needle-shaped films, and the needle-shaped structures are distributed in a cluster shape. CuO@Cu/Ag composite current collector and metal lithium sheet with purity of 99.9% and thickness of 1mm are assembled into half battery at 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 78mV, 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 90.5% at the amount of metallic lithium deposition/stripping. And compounding the CuO@Cu/Ag 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 0.5mA/cm 2 And a current density of 0.5mAh/cm 2 The cycle life is 460h, about 230 cycles, at the amount of metallic lithium deposition/stripping. The CuO@Cu/Ag composite current collector is taken as a negative electrode, liCoO 2 A full cell was made for the positive electrode, and the capacity decay rate was 20.5% after 300 cycles at 1C magnification.
Example 8
The CuO@Cu/Ag composite current collector is prepared by adopting a process of liquid phase reduction, slurry preparation, mechanical coating and evaporation film forming, and the specific preparation is shown in a flow chart (figure 1):
s1, liquid phase reduction: cu is contained under normal temperature and pressure 2+ And Ag + Dropwise adding the uniform mixed solution of (1) into an alkaline borohydride solution containing an organic metal chelating agent and a surface morphology agent, and washing, drying and grinding after the reaction is finished to obtain CuO@Cu/Ag alloy nano material powder.
The specific operation steps of the liquid phase reduction are as follows:
s1-1, preparing liquid: weighing cupric nitrate copper (Cu (NO) 3 ) 2 3H 2 O), monovalent silver salt silver nitrate (AgNO) 3 ) Organometal chelating agent ethylenediamine tetraacetic acid (EDTA), reducing agent potassium borohydride (KBH 4 ) Subsequently Cu (NO 3 ) 2 3H 2 O and AgNO 3 Uniformly grinding and mixing, and adding deionized water to prepare Cu-containing alloy 2+ And Ag + For later use, so that Cu in the obtained solution 2+ The concentration is 1.0mol L -1 ，Ag + At a concentration of 0.5mol L -1 . EDTA, EDA and KBH 4 Dissolving in OH at a certain concentration ratio - At a concentration of 1mol L -1 Is ready for use in an alkaline solution, the EDTA concentration in the resulting solution being 1.8mol L -1 ，BH4 - Is 0.5mol L -1 EDA concentration of 0.1mol L -1 。
S1-2, liquid phase reduction: the Cu-containing alloy is subjected to normal temperature and normal pressure 2+ And Ag + Is added dropwise to basic KBH containing EDTA and EDA at a drop rate of 100 drops per minute 4 In the solution, stirring is continued for 60min, and an aqueous solution dispersion system with CuO@Cu/Ag alloy nano particles is prepared.
S1-3, freeze drying: at 10000r min -1 And (3) carrying out high-speed centrifugation at the rotating speed of (2) separating the CuO@Cu/Ag alloy nano particles from the aqueous solution, and freeze-drying for 24 hours under the conditions that the vacuum degree is-0.05 MPa and the temperature is-40 ℃ to obtain the CuO@Cu/Ag alloy nano particles. The obtained CuO@Cu/Ag alloy nano particles are used for preparingThe total weight is 10 parts, 6 parts of CuO, 3 parts of Cu and 1 part of Ag.
S1-4, grinding and crushing: and taking a freeze-dried sample, grinding and crushing the sample by adopting an agate mortar until powder can pass through a 300-mesh sieve.
S2, preparing slurry: uniformly dispersing CuO@Cu/Ag alloy nano particles, a binder polyvinylidene fluoride (PVDF) and a conductive agent nano carbon black into a dispersing agent N-methylpyrrolidone (NMP) according to a mass ratio of 7:1:2 in an environment with a temperature of 25 ℃ and a humidity of 20%, wherein a liquid-solid ratio of the dispersing agent is 3:1, and grinding for 1h to obtain a slurry dispersion system with uniform texture and proper viscosity.
S3, mechanical film coating: and (3) taking a clean toughened glass plate, and uniformly coating the prepared slurry on the surface of the glass plate by using a mechanical scraper, wherein the coating layer is 10 mu m, so as to obtain the semi-solid slurry film with uniform texture.
S4, evaporating to form a film: transferring the semi-solid slurry film into a vacuum oven, evaporating and drying for 12 hours under the conditions of the vacuum degree of-0.05 MPa and the temperature of 80 ℃ to form a solid film, and stripping the flexible film on the surface of the glass plate after film formation to obtain the CuO@Cu/Ag composite current collector material with integrated structure and function.
The prepared current collector material has good macroscopic surface glossiness and high thickness consistency, the microscopic surface is a porous lithium storage skeleton formed by three-dimensional accumulation of spherical nano particles, the surface of the synthesized sphere is coated by needle-shaped films, and the needle-shaped structures are distributed in a cluster shape. CuO@Cu/Ag composite current collector and metal lithium sheet with purity of 99.9% and thickness of 1mm are assembled into half battery at 0.5mA/cm 2 The overpotential of the surface electrodeposited metallic lithium at the current density of (2) was 56mV, and at 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle over 300 cycles of coulombic efficiency remains 90% at the amount of metallic lithium deposition/stripping. And compounding the CuO@Cu/Ag 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 0.5mA/cm 2 And a current density of 0.5mAh/cm 2 The cycle life is over 570h, about 285 cycles at lithium metal deposition/stripping levels. The CuO@Cu/Ag composite current collector is taken as a negative electrode, liCoO 2 A full cell was made for the positive electrode, and the capacity fade rate after 300 cycles at 1C was 22.3%.
Comparative example 1
The preparation of CuO@Cu/Ag alloy nanoparticles by the "liquid-liquid phase reduction-freeze drying" process is basically the same as that of example 1, and Cu is contained at normal temperature and pressure 2+ And Ag + Dropwise addition of EDTA EDA-free basic KBH 4 In solution, wherein Cu 2+ The concentration is 0.8mol L -1 ，Ag + At a concentration of 0.4mol L -1 ，OH - At a concentration of 1mol L -1 EDTA concentration of 1.5mol L -1 ，BH4 - Is 0.5mol L -1 Continuously stirring to prepare an aqueous solution dispersion system with CuO@Cu/Ag alloy nano particles, and carrying out high-speed centrifugation and freeze drying to prepare the CuO@Cu/Ag alloy nano particles.
The CuO@Cu/Ag alloy nanoparticle prepared under the condition has a smooth surface and a nanoscale regular spherical structure, as shown in figure 13. Based on 10 parts of total weight, in the CuO@Cu/Ag alloy nano particles, 5 parts of CuO, 3 parts of Cu and 2 parts of Ag are contained. The synthesized nanoparticles were mixed with a binder (PVDF) and a conductive agent (nano carbon black) at a mass ratio of 7:1:2, uniformly dispersed in a dispersant NMP to prepare a slurry, and a current collector was prepared by mechanical coating and evaporation to form a film (same as in example 1).
The current collector and the 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 79mV, and at 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle over 300 cycles of coulombic efficiency remained 82% at the amount of metallic lithium deposition/stripping. A lithium metal battery negative electrode was fabricated by compounding a CuO@Cu/Ag composite current collector with metallic lithium using a mechanical roll press method as in example 1 and assembling a symmetrical battery having a medium battery resistance at 0.5mA/cm 2 And a current density of 0.5mAh/cm 2 The cycle life is over 290h, about 145 cycles at lithium metal deposition/stripping levels. To be used forThe CuO@Cu/Ag composite current collector is taken as a negative electrode, liCoO 2 A full cell was made for the positive electrode, which had a capacity fade rate of 38% after 300 cycles at 1C rate.
Comparative example 2
The preparation of CuO@Cu/Ag alloy nanoparticles by liquid phase reduction-freeze drying process is basically the same as that of example 1, and Cu is contained at normal temperature and normal pressure 2+ And Ag + Dropwise addition of the aqueous solution to an alkaline glucose solution containing EDTA, EDA, wherein Cu 2+ The concentration of Ag is 0.8mol L-1 + At a concentration of 0.4mol L -1 ，OH - At a concentration of 1mol L -1 EDTA concentration of 1.5mol L -1 Glucose concentration of 0.5mol L -1 EDA concentration of 0.1mol L -1 . Continuously stirring to prepare an aqueous solution dispersion system with CuO@Cu/Ag alloy nano particles, and carrying out high-speed centrifugation and freeze drying to prepare the CuO@Cu/Ag alloy nano particles.
The surface of the CuO@Cu/Ag alloy nano particle prepared under the condition is covered with a needle-shaped CuO film layer, the interior of the CuO@Cu/Ag alloy nano particle is provided with nano-scale spherical particles, and in the CuO@Cu/Ag alloy nano particle, 8 parts of CuO, 1 part of Cu and 1 part of Ag are calculated by 10 parts of the total weight, as shown in figure 14. The synthesized nanoparticles were mixed with a binder (PVDF) and a conductive agent (nano carbon black) at a mass ratio of 7:1:2, uniformly dispersed in a dispersant NMP to prepare a slurry, and a current collector was prepared by mechanical coating and evaporation to form a film (same as in example 1).
The current collector and the 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 96mV and at 0.5mA/cm 2 And a current density of 1mAh/cm 2 The half cell cycle over 300 cycles of coulombic efficiency maintained 78% at the amount of metallic lithium deposition/stripping. The same mechanical roll method as in example 1 was used to compound CuO@Cu/Ag composite current collector with metallic lithium to prepare a lithium metal battery negative electrode and assemble a symmetrical battery having a large battery resistance at 0.5mA/cm 2 And a current density of 0.5mAh/cm 2 The cycle life was over 140h at a metallic lithium deposition/stripping level of about 70 turns. The CuO@Cu/Ag composite current collector is taken as a negative electrode, liCoO 2 A full cell was made for the positive electrode, and the capacity fade rate was 34% after 300 cycles at 1C rate.
Comparative example 3
The preparation of CuO@Cu/Ag alloy nanoparticles by liquid phase reduction-freeze drying process is basically the same as that of example 1, and Cu is contained at normal temperature and normal pressure 2+ And Ag + Is added dropwise to an alkaline KBH containing EDTA and EDA 4 In solution, wherein Cu 2+ The concentration is 0.8mol L -1 ，Ag + At a concentration of 0.4mol L -1 ，OH - At a concentration of 1mol L -1 EDTA concentration of 1.5mol L -1 ，BH4 - Is 0.5mol L -1 EDA concentration of 0.1mol L -1 Continuously stirring to prepare an aqueous solution dispersion system with CuO@Cu/Ag alloy nano particles, and carrying out high-speed centrifugation and freeze drying to prepare the CuO@Cu/Ag alloy nano particles.
The surface of the CuO@Cu/Ag alloy nano particle prepared under the condition is covered with a needle-shaped CuO film layer, and the interior of the CuO@Cu/Ag alloy nano particle is provided with nano-scale spherical particles. Based on 10 parts of total weight, in the CuO@Cu/Ag alloy nano particles, 5 parts of CuO, 3 parts of Cu and 2 parts of Ag are contained. The synthesized nanoparticles were mixed with a binder (PVDF) and a conductive agent (nano carbon black) at a mass ratio of 5:3:2, uniformly dispersed in a dispersant NMP to prepare a slurry, and a current collector was prepared by mechanical coating and evaporation to form a film (basically the same as in example 1). After evaporation to form a film, the current collector cannot peel off the glass plate to form a film.
Comparative example 4
The preparation of CuO@Cu/Ag alloy nanoparticles by liquid phase reduction-freeze drying process is basically the same as that of example 1, and Cu is contained at normal temperature and normal pressure 2+ And Ag + Is added dropwise to an alkaline KBH containing EDTA and EDA 4 In solution, wherein Cu 2+ At a concentration of 0.1mol L -1 ，Ag + The concentration is 0.05mol L -1 ，OH - At a concentration of 0.5mol L -1 EDTA concentration of 0.5mol L -1 ，BH4 - Is 0.2mol L -1 EDA concentration of 0.1mol L -1 Continuously stirring to obtain an aqueous solution dispersion system with CuO@Cu/Ag alloy nano particlesAnd (3) carrying out high-speed centrifugation and freeze drying to obtain the CuO@Cu/Ag alloy nano particles.
The surface of the CuO@Cu/Ag alloy nano particle prepared under the condition is covered with a needle-shaped CuO film layer, and the interior of the CuO@Cu/Ag alloy nano particle is provided with nano-scale spherical particles. Based on 10 parts of total weight, in the CuO@Cu/Ag alloy nano particles, 7 parts of CuO, 2 parts of Cu and 1 part of Ag are contained. The synthesized nanoparticles were mixed with a binder (PVDF) and a conductive agent (nano carbon black) at a mass ratio of 7:1:2, uniformly dispersed in a dispersant NMP to prepare a slurry, and a current collector was prepared by mechanical coating and evaporation to form a film (same as in example 1).
The current collector and the 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 89mV, 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 75% at the amount of metallic lithium deposition/stripping. A lithium metal battery negative electrode was fabricated by compounding a CuO@Cu/Ag composite current collector with metallic lithium using a mechanical roll press method as in example 1 and assembling a symmetrical battery having a medium battery resistance at 0.5mA/cm 2 And a current density of 0.5mAh/cm 2 The cycle life is over 120 hours, about 60 cycles, at the amount of metallic lithium deposited/stripped. The CuO@Cu/Ag composite current collector is taken as a negative electrode, liCoO 2 A full cell was made for the positive electrode, and the capacity decay rate was 30% after 300 cycles at 1C magnification.
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. A CuO@Cu/Ag alloy nano material consists of spherical Cu/Ag alloy nano particles with needle-wool-shaped CuO film layers loaded on the surfaces.
2. The cuo@cu/Ag alloy nanomaterial of claim 1, wherein the microscopic particle size is 50 to 60nm. Based on 10 parts of the total weight, in the CuO@Cu/Ag alloy nanomaterial, 4-6 parts of CuO, 3-4 parts of Cu and 1-2 parts of Ag are contained.
3. A method for preparing the cuo@cu/Ag alloy nanomaterial according to claim 1, comprising the steps of:
s1-1, preparing liquid: weighing water-soluble cupric salt, water-soluble monovalent silver salt, organic metal chelating agent and reductive borohydride according to the proportion; then uniformly grinding and mixing water-soluble cupric salt and water-soluble monovalent silver salt, adding deionized water according to a certain concentration ratio so as to obtain the invented Cu-containing product 2+ And Ag + Is prepared for standby; dissolving organic metal chelating agent, morphology agent and reductive borohydride in OH according to a certain concentration ratio - The concentration is 0.8 to 1mol L -1 Preparing an alkaline borohydride solution containing an organic metal chelating agent and a surface morphology agent for later use;
s1-2, liquid phase reduction: the Cu-containing alloy is subjected to normal temperature and normal pressure 2+ And Ag + Dropwise adding the uniform mixed solution of the metal chelating agent and the surface morphology agent into the alkaline borohydride solution containing the metal chelating agent and the surface morphology agent, and reacting to obtain an aqueous solution dispersion system of the CuO@Cu/Ag alloy nano material;
s1-3, high-speed centrifugation and freeze drying to obtain the CuO@Cu/Ag alloy nanomaterial.
4. The method for producing a CuO@Cu/Ag alloy nanomaterial according to claim 3, characterized by comprising Cu 2+ And Ag + Cu in the uniform mixed solution of (2) 2+ The concentration is 0.2 to 1mol L -1 ，Ag + The concentration is 0.1 to 1mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the In the alkaline borohydride solution containing the organic metal chelating agent and the surface morphology agent, the concentration of the organic metal chelating agent is 0.2-2 mol L -1 ，BH 4 - The concentration of (C) is 0.1-1 mol L -1 The concentration of the surface morphology agent is 0.1 to 0.2mol L -1 。
5. The method for preparing cuo@cu/Ag alloy nanomaterial according to claim 3, wherein in step S1-1, the water-soluble divalent copper salt is copper nitrate, the water-soluble monovalent silver salt is silver nitrate, the organic metal chelating agent is ethylenediamine tetraacetic acid EDTA, the reducing borohydride is sodium borohydride or potassium borohydride, and the morphology agent is ethylenediamine EDA.
6. The method for preparing CuO@Cu/Ag alloy nanomaterial according to claim 3, wherein in step S1-3, the high-speed centrifugation is performed at a rotation speed of 5000-10000 r min -1 The method comprises the steps of carrying out a first treatment on the surface of the The freeze drying is carried out for 24-48 h under the conditions that the vacuum degree is minus 0.05-minus 0.1MPa and the temperature is minus 40-minus 60 ℃.
7. Use of the cuo@cu/Ag alloy nanomaterial according to claim 1 in the preparation of a lithium metal battery negative electrode material or a lithium metal battery negative electrode current collector.
8. A cuo@cu/Ag composite current collector, wherein the current collector consists of the cuo@cu/Ag alloy nanomaterial, a conductive agent and a binder according to claim 1, and has a three-dimensional nano porous structure on a microscopic scale and a flexible micro thin film structure on a macroscopic scale.
9. The cuo@cu/Ag composite current collector according to claim 8, wherein the thickness of the cuo@cu/Ag composite current collector is 10 to 20 μm; the current collector is prepared by a method comprising the following steps:
s1, preparing slurry: uniformly dispersing the CuO@Cu/Ag alloy nano material, a binder and a conductive agent into a dispersing agent according to a certain mixing ratio to obtain a slurry dispersion system;
s2, mechanical film coating: coating the prepared slurry on the surface, wherein the thickness of the coating layer is 10-20 mu m, and obtaining a semi-solid slurry film;
s3, evaporating to form a film: evaporating and drying the semi-solid slurry film for 8-16 hours under the vacuum degree of minus 0.05 to minus 0.1MPa and the temperature of 60-100 ℃ to form a solid film, and stripping the flexible film on the surface of the substrate after film forming to obtain the CuO@Cu/Ag composite current collector.
10. The CuO@Cu/Ag composite current collector according to claim 8, wherein in the step S1, based on 10 parts by weight of the total, 6-8 parts by weight of CuO@Cu/Ag alloy nanomaterial, 1-2 parts by weight of binder, 1-2 parts by weight of conductive agent and 3:1-5:1 of dispersing agent; wherein the dispersing agent is selected from N-methyl pyrrolidone NMP, isopropanol, ethanol or glycol; the binder is an injection molding high polymer material and is selected from polyvinylidene fluoride PVDF, sodium carboxymethylcellulose CMC, polyacrylic acid PAA or polyvinyl alcohol PVA; the conductive agent is conductive carbon material and is selected from nano carbon black.
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