CN114975847B - Composite metal negative electrode with sandwich structure and preparation method and application thereof - Google Patents

Composite metal negative electrode with sandwich structure and preparation method and application thereof Download PDF

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CN114975847B
CN114975847B CN202210804205.XA CN202210804205A CN114975847B CN 114975847 B CN114975847 B CN 114975847B CN 202210804205 A CN202210804205 A CN 202210804205A CN 114975847 B CN114975847 B CN 114975847B
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metal
current collector
fluorine
composite
sandwich structure
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CN114975847A (en
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陈月皎
王寒
陈立宝
于铧铭
李泉雨
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Central South University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a composite metal negative electrode with a sandwich structure, a preparation method and application thereof. The preparation method comprises the following steps: dipping one surface of a conductive current collector into fluorine-containing polymer sol to form a film, and carbonizing at a high temperature for later use; and enabling metal to enter the middle of the current collector and the carbonized film by an electrodeposition method to form the metal anode with a sandwich structure. The invention has the following functions by introducing fluorine doped amorphous carbon film as a protective layer: the electrolyte and the metal are effectively isolated; realizing ion homogenization distribution; the transmitted metal ion confinement can be deposited in a limited space under the film to inhibit the generation of metal dendrites. The composite metal negative electrode can be assembled with a conventional positive electrode, a diaphragm and electrolyte to form a secondary battery, can effectively improve the cycle life of the battery, and is applicable to secondary ion batteries such as zinc, lithium, sodium, potassium, aluminum, magnesium and the like.

Description

Composite metal negative electrode with sandwich structure and preparation method and application thereof
Technical Field
The invention relates to the technical field of metal battery preparation, in particular to a composite metal anode with a sandwich structure, and a preparation method, application and application thereof.
Background
Secondary batteries are important media for electric energy transfer, and are widely used in the fields of portable electronic products, electric automobiles and energy storage. In secondary batteries, active metal electrodes such as zinc, lithium, sodium and the like have the advantages of high theoretical specific capacity, low electrode potential and the like, and are often used as negative electrode materials of secondary batteries (such as zinc ion batteries, lithium ion batteries, sodium ion batteries and the like). However, in commercial applications, the direct use of metals such as zinc, lithium, sodium, etc. as the negative electrode is considered one of the technical difficulties in the art. The main reasons can be summarized as follows: (1) The metal electrode is easy to react irreversibly with the electrolyte to generate byproducts, so that the coulomb efficiency is reduced; (2) Uneven deposition/stripping of metal ions makes the metal surface extremely prone to dendrite and exfoliation, resulting in a battery that continually loses capacity and is extremely prone to shorting. Therefore, inhibiting the occurrence of side reactions and dendrite formation of the metal anode during the cycle is a key to promote the application and development of the metal secondary battery.
To address these challenges, various strategies have been proposed, including electrolyte modification, three-dimensional structural design, and interface modification. The interface modification not only can effectively prevent metal corrosion, but also is one of measures for regulating and controlling dendrite growth. At present, many methods focus on constructing an artificial protection layer on the surface of a metal negative electrode by physical or chemical means, such as a method of coating a coating to obtain a dendrite-free composite negative electrode, however, the methods depend on the use of a binder in transition, and the coating is often uneven and thick, so that the interface resistance of the electrode is increased and the energy density is reduced; for another example, some organic polymer films are used, and although no additional binder is needed, many organic matters are difficult to have high ionic conductivity, and cannot ensure efficient and rapid transmission of metal ions, and are not enough to resist dendrite growth. Therefore, development of an effective technology is urgently desired at present, which not only can effectively reduce direct contact between metal and electrolyte, but also can regulate and control rapid and uniform deposition behavior of metal ions to inhibit dendrite formation, thereby realizing a high-stability metal anode.
Disclosure of Invention
In order to solve the problems of dendrite formation and electrode corrosion of the metal negative electrode in charge-discharge cycles in the background technology, the invention provides a preparation method and application of a composite metal negative electrode with a sandwich structure, and the high-stability metal negative electrode is obtained by utilizing the electronic insulativity of a fluorine-doped amorphous carbon-based protective layer, the high ion conductivity caused by fluorine atom doping and better mechanical strength, realizing the efficient transmission of metal ions and uniformly depositing the metal ions below a film layer, and greatly inhibiting the generation of metal dendrites and side reactions.
In order to achieve the above objective, the embodiment of the present invention provides a composite metal anode with a sandwich structure, which includes a current collector, an electrodeposited metal layer, and a fluorine doped amorphous carbon-based protective layer, wherein the current collector, the electrodeposited metal layer, and the fluorine doped amorphous carbon-based protective layer form a sandwich structure, the fluorine doped amorphous carbon-based protective layer is uniformly attached to the surface of the current collector, and the electrodeposited metal layer is in a sheet shape and parallel to the current collector.
Preferably, the fluorine doped amorphous carbon-based protective layer has a thickness of 4 to 6 μm and the electrodeposited metal layer has a thickness of 2 to 10 μm.
Preferably, the current collector is at least one of copper foil, nickel foil, titanium foil, stainless steel foil, carbon cloth, carbon paper, carbon nanotube film and graphene film, and the fluorine of the fluorine doped amorphous carbon-based protective layer is provided by at least one of polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, fluoroethylene/vinyl ether copolymer resin and polytrifluoroethylene.
Based on one general inventive concept, the invention also provides a preparation method of the composite metal anode with the sandwich structure, which comprises the following steps:
s1, immersing a current collector in fluorine-containing polymer viscous liquid to form a film, so as to obtain a composite current collector precursor;
s2, carbonizing the composite current collector precursor at high temperature to form an electrode precursor of the fluorine doped amorphous carbon base protective layer coated current collector;
and S3, depositing metal between the fluorine doped amorphous carbon-based protective layer of the electrode precursor and the current collector by an electrochemical deposition method to form the composite metal anode with the sandwich structure.
Preferably, the polar organic solvent is at least one of N-methyl pyrrolidone, dimethylformamide and dimethylacetamide.
Preferably, the step S1 specifically includes the following steps:
s1.1, alternately cleaning a current collector with deionized water and ethanol for 2-3 times, and drying for later use;
s1.2, mixing a fluorine-containing high polymer material with a polar organic solvent according to a proportion to obtain viscous liquid;
s1.3, dipping the current collector into fluorine-containing polymer viscous liquid, taking out and drying, and constructing a layer of film on the surface of the current collector to obtain the electrode precursor.
Preferably, in the step S1.2, the fluorine-containing polymer material and the polar organic solvent are mixed according to the mass volume ratio of 1:20-50, the polar organic solvent is at least one of N-methylpyrrolidone, dimethylformamide and dimethylacetamide, the dipping time in the step S1.3 is 3-5min, the drying temperature is 60 ℃, and the vacuum drying is carried out for 10-20 h.
Preferably, the S2 carbonization conditions are specifically:
and (3) placing the dried electrode precursor into a tube furnace, heating to 500-800 ℃ at a speed of 2 ℃/min under argon atmosphere, and then preserving heat for 2 hours to prepare the fluorine-doped amorphous carbon coated current collector electrode precursor.
Preferably, the step 3 electrochemical deposition is in particular at 0.25mA/cm 2 Is deposited at a current density of 1 to 5mAh/cm 2 The electrochemical deposition equipment adopts one of button cells and electrolytic tanks.
The invention also provides application of the composite metal anode with the sandwich structure, which is prepared by the method, and the composite metal anode with the sandwich structure is assembled into a symmetrical battery.
According to the common prior art, a positive electrode, a diaphragm and a metal negative electrode are assembled in a shell of the battery, electrolyte is injected into an inner cavity of the battery, and the metal negative electrode is a composite metal negative electrode with a sandwich structure prepared by the method.
Preferably, the composite metal negative electrode is composite zinc metal, the electrolyte is an aqueous electrolyte containing zinc salt, and the positive electrode is CNT/MnO 2 Or V 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the Or the composite metal cathode is composite lithium metal, and the electricityThe electrolyte is lithium salt-containing electrolyte, and the positive electrode is LFP or LTO; or the composite metal negative electrode is composite sodium metal, the electrolyte is an electrolyte containing sodium salt, and the positive electrode is sodium manganate or sodium iron phosphate.
The scheme of the invention has the following beneficial effects:
(1) The above scheme of the invention provides a preparation method of a composite metal negative electrode with a sandwich structure, wherein the composite metal negative electrode can enable metal ions to be rapidly and stably transmitted to a space under a membrane for deposition through a fluorine doped amorphous carbon base protective layer with high ion conductivity and low electron conductivity on the surface of a current collector, inhibit dendrite formation, effectively isolate electrolyte from deposited metal, inhibit corrosion and reaction of the electrolyte on the metal, and realize long service life and stable work without dendrite of the composite metal negative electrode;
(2) The invention is not only suitable for preparing the composite zinc metal negative electrode of the zinc ion secondary battery, but also suitable for preparing the composite metal negative electrode of other secondary metal ion batteries, such as the composite negative electrodes of lithium, sodium, potassium, aluminum, magnesium and the like, and has wide applicability;
(3) According to the invention, the fluorine-containing organic gel is coated on the current collector and carbonized to obtain a layer of fluorine-doped densified carbon layer, the fluorine doping introduces defects in the carbon layer, and an ion transmission channel is provided, namely the carbon layer has electronic insulation and simultaneously enhances ion conductivity; wherein, no solid reaction or solid-phase diffusion occurs between the carbon layer and the current collector substrate, and the carbon layer and the current collector substrate are simple physical combination and do not undergo element transfer; the fluorine-doped carbon-based protective layer is an electronic insulating layer, and the deposition of metal on the upper layer is not caused;
(4) The current collector used in the invention can directly deposit metal to form a negative electrode as an active material without coating the active material to store the metal;
(5) The metal ions (for example, zinc ions) deposited on the negative electrode can pass through the carbon layer and are deposited between the carbon layer and the current collector substrate to form a sandwich structure; the protective layer is a solid material and has high mechanical property, and the upper insulating carbon layer can press the lower metal deposition to avoid dendrite occurrence and cause short circuit of the battery; in addition, the fluorine-doped carbon layer can induce the deposition orientation of metallic zinc, so that the metallic zinc is arranged below the fluorine-doped carbon layer and can be deposited in a way that the zinc (002) crystal face is parallel to the substrate orientation, and the growth of dendrites can be inhibited;
(6) The invention has the following functions by introducing fluorine doped amorphous carbon film as a protective layer: (a) The electrolyte and the metal are effectively isolated, and the metal is prevented from being corroded and reacted by the electrolyte; (b) Fluorine element with stronger electronegativity can act with metal ions to provide abundant nucleation sites for metal deposition, so that ion homogenization distribution is realized; (c) The fluorine doped amorphous carbon film has high ionic conductivity and low electronic conductivity, and can deposit the transmitted metal ion confinement in a limited space under the film to inhibit metal dendrite formation.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a copper-based current collector surface-coated with a fluorine-doped amorphous carbon-based protective layer obtained in example 1 of the present invention;
FIG. 2 is a cross-sectional SEM photograph of a composite metal zinc anode of a sandwich structure obtained in example 1 of the present invention;
FIG. 3 shows a symmetrical cell assembled by a composite zinc anode and an unprotected zinc anode in a sandwich structure obtained in example 1 and comparative example 1 of the present invention at a current density of 0.5mA/cm 2 And a capacity of 0.25mAh/cm 2 A time-voltage comparison graph for performing a cycle stability test;
FIG. 4 shows a composite metal zinc anode and unprotected zinc anode and V of the sandwich structure obtained in example 1 and comparative example 1 of the present invention 2 O 5 The full battery assembled by the positive electrode is subjected to a cycle number-discharge specific capacity/coulomb efficiency comparison chart of a charge-discharge cycle test under the current condition of 1A/g;
FIG. 5 shows a composite metal zinc anode and unprotected zinc anode and V of the sandwich structure obtained in example 1 and comparative example 1 of the present invention 2 O 5 The full battery assembled by the positive electrode is subjected to a cycle number-discharge specific capacity/coulomb efficiency comparison chart of a charge-discharge cycle test under the current condition of 3A/g;
FIG. 6 is XRD (left) and surface SEM pictures (right) of surface metallic zinc of the composite metallic zinc anode and unprotected zinc anode of the sandwich structure obtained in example 1 and comparative example 1 of the present invention;
FIG. 7 is a Tafil plot (left) and a linear sweep voltammogram (right) of the composite metallic zinc anode and unprotected zinc anode of the sandwich structure obtained in example 1 and comparative example 1 of the present invention;
FIG. 8 is a graph showing that the current density of a symmetrical cell assembled with a composite metal zinc anode of sandwich structure obtained in example 2 of the present invention was 0.5mA/cm 2 And a capacity of 0.25mAh/cm 2 A time-voltage comparison graph for performing a cycle stability test;
FIG. 9 is a graph showing that the current density of a symmetrical cell assembled with a composite metal zinc anode of sandwich structure obtained in example 3 of the present invention was 0.5mA/cm 2 And a capacity of 0.25mAh/cm 2 A time-voltage comparison graph for performing a cycle stability test;
FIG. 10 shows a symmetrical cell assembled from a composite zinc anode and an unprotected zinc anode in sandwich structure obtained in example 1 and comparative example 2 of the present invention at a current density of 1mA/cm 2 And a capacity of 1mAh/cm 2 Time-voltage contrast plot for the cycle stability test is performed below.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
In commercial applications, the following problems exist in directly adopting metals such as zinc, lithium, sodium and the like as a negative electrode: (1) The metal electrode is easy to react irreversibly with the electrolyte to generate byproducts, so that the coulomb efficiency is reduced; (2) Uneven deposition/stripping of metal ions makes the metal surface extremely prone to dendrite and exfoliation, resulting in a battery that continually loses capacity and is extremely prone to shorting. Therefore, inhibiting the occurrence of side reactions and dendrite formation of the metal anode during the cycle is a key to promote the application and development of the metal secondary battery. In order to solve these problems, various strategies such as electrolyte modification, three-dimensional structure design and interface modification have been proposed. The interface modification not only can effectively prevent metal corrosion, but also is one of measures for regulating and controlling dendrite growth. At present, many methods focus on constructing an artificial protection layer on the surface of a metal negative electrode by physical or chemical means, such as a method of coating a coating to obtain a dendrite-free composite negative electrode, however, the methods depend on the use of a binder in transition, and the coating is often uneven and thick, so that the interface resistance of the electrode is increased and the energy density is reduced; for another example, some organic polymer films are used, and although no additional binder is needed, many organic matters are difficult to have high ionic conductivity, and cannot ensure efficient and rapid transmission of metal ions, and are not enough to resist dendrite growth. Namely, the metal negative electrode has the problem of dendrite formation and electrode corrosion in charge and discharge cycles. Therefore, development of an effective technology is urgently desired at present, which not only can effectively reduce direct contact between metal and electrolyte, but also can regulate and control rapid and uniform deposition behavior of metal ions to inhibit dendrite formation, thereby realizing a high-stability metal anode.
In order to achieve the above purpose, the invention provides a composite metal anode with a sandwich structure, a preparation method and application thereof, and the composite metal anode utilizes the electronic insulation property of the fluorine doped amorphous carbon base protective layer, the high ion conductivity caused by fluorine atom doping and the better mechanical strength to realize the efficient transmission of metal ions and the uniform deposition below a film layer, thereby greatly inhibiting the generation of metal dendrites and the occurrence of side reactions and obtaining the high-stability metal anode.
Example 1
The sandwich structure metal cathode is prepared according to the following steps.
Firstly, preparing a copper sheet current collector wafer to be modified: taking a commercial three-dimensional reticular current collector with a certain size and thickness of 0.1mm, then punching the current collector into a wafer with the diameter of 14mm by a sheet punching machine, polishing the surface of the punched copper sheet current collector by using 2000-mesh sand paper to be rough, sequentially and alternately ultrasonically cleaning the polished copper sheet current collector by using deionized water and ethanol for 10 minutes, and then drying the copper sheet current collector in a drying oven at the temperature of 60 ℃ for later use.
2g of polyvinylidene fluoride is weighed and added into a beaker containing 40mL of N-methylpyrrolidone, and the mixture is stirred at 80 ℃ to be fully dissolved, and then cooled at room temperature to form gel for standby.
Immersing the prepared copper sheet current collector wafer in the gel for 3-5min, taking out, transferring to a vacuum oven, and drying at 60 ℃ for at least 8h to dry the surface of the copper sheet current collector wafer to form a film, thereby obtaining the modified copper sheet current collector precursor. And heating the modified copper sheet current collector precursor to 400 ℃ at a speed of 2 ℃/min in a tubular furnace under argon atmosphere, and then preserving heat for 2 hours, wherein the carbonization of the surface polymer protective layer precursor to black is observed, so that the fluorine-doped carbon-coated copper sheet current collector is successfully prepared. After that, the half cell was assembled at 0.25mA/cm 2 Deposition at current density of 5mAh/cm 2 To construct the composite metal zinc cathode with the sandwich structure.
Fig. 1 is a sectional scanning electron micrograph of the fluorine-doped carbon-coated copper sheet current collector prepared in example 1, and it can be seen that the obtained fluorine-doped carbon-based protective layer is uniformly attached to the surface of the copper sheet current collector, and the thickness is about 6 μm.
The cross-sectional scanning electron microscope photograph of the obtained sandwich structure composite metal zinc cathode is shown in fig. 2, and it can be seen that a layer of metal zinc with the thickness of about 2 μm is deposited between the copper sheet current collector and the fluorine-doped carbon-based protective layer. Because the conductivity of the copper sheet electrical current collector is significantly better than that of the fluorine doped carbon based protective layer, zinc ions will tend to preferentially deposit onto the underlying metal copper sheet current collector, and once zinc ions deposit onto the copper sheet through the carbon based protective layer, the electrolyte will be inhibited from corroding zinc metal while also greatly inhibiting dendrite growth.
Example 2
The parallel test was performed similarly to example 1, in which the mass of polyvinylidene fluoride was 1.6g, and the other preparation methods were exactly the same as example 1, to obtain a sandwich-structured composite metal zinc anode.
Example 3
Similar parallel experiments are carried out in the embodiment similar to the embodiment 1 and the embodiment 2, wherein the mass of polyvinylidene fluoride is 2.7g, and other preparation methods are completely the same as the embodiment 1, so that the composite metal zinc anode with the sandwich structure is obtained.
Comparative example 1
The difference from example 1 is that: the copper sheet current collector is not provided with a fluorine doped carbon-based protective layer, and then the current collector is coated with a fluorine doped carbon-based protective layer at 0.25mA/cm 2 Is deposited at a current density of 5mAh/cm 2 The metal zinc of (2) is coated on the surface of the copper sheet current collector to form an unprotected zinc cathode.
Comparative example 2
The difference from example 1 is that: the polyvinylidene fluoride used was changed to polyvinyl alcohol, and fluorine atom doping was excluded, and the other preparation methods were exactly the same as in example 1 to obtain a zinc anode without a carbon-based protective layer doped.
Performance test:
the metallic zinc anode obtained in example 1 and comparative example 1 was assembled into a button-type symmetrical battery at 0.5mA/cm 2 And (3) carrying out charge-discharge cycle test under the current density, and testing the cycle life and the battery stability. FIG. 3 shows the cycle life and polarization voltage during the cycle, after 10 hours, the overpotential of the unprotected zinc anode was 21.7mV, whereas the sandwich structure composite metal zinc anode was only 14.6mV; after 360 hours, the unprotected zinc cathode appears obvious short circuit phenomenon. The overpotential of the sandwich structure composite metal zinc anode symmetrical battery can still be kept at 19.8mV after 2200 hours, which shows that the fluorine doped carbon-based protective layer has the effect of stabilizing the deposition/dissolution reaction of Zn, and can remarkably improve the cycle performance of the symmetrical battery. The metallic zinc anode obtained in example 1 and comparative example 1 was combined with V 2 O 5 The positive electrode sheet was assembled into a full cell for electrochemical performance test, and as shown in fig. 4, the charge and discharge test was performed at a current density of 1A/g, and the capacity retention rate was 90% when it was cycled for 1000 cycles. The metallic zinc anode obtained in example 1 and comparative example 1 was combined with V 2 O 5 The positive electrode sheet was assembled into a full cell for electrochemical performance test, and as shown in fig. 5, the capacity retention rate was 60% or more when the charge and discharge test was performed at a current density of 3A/g and 2500 cycles.
The surface scanning electron microscope observation of the metallic zinc on the metallic zinc cathodes obtained in example 1 and comparative example 1 shows that the modified metallic zinc is deposited in a flaky morphology parallel to the substrate, while the metallic zinc on the unprotected metallic zinc cathode shows a disordered vertically grown dendrite morphology, as shown on the right of fig. 6. The XRD characterization of the metallic zinc on the metallic zinc negative electrode obtained in example 1 and comparative example 1 was further performed, and as shown in the left side of fig. 6, it can be seen that the metallic zinc on the metallic zinc negative electrode after modification is mainly oriented with the (002) crystal plane, while the metallic zinc on the metallic zinc negative electrode without protection is mainly oriented with the (010) crystal plane.
The electrokinetic polarization curves of the metallic zinc cathodes obtained in example 1 and comparative example 1 were measured, and as shown in the right side of fig. 7, the fluorine-doped carbon-based protective layer-modified sandwich-structure composite metallic zinc cathode obtained in example 1 significantly reduced the corrosion current. And then the hydrogen evolution capacity is measured by a linear voltammetry, as shown in the left side of fig. 7, the fluorine-doped carbon-based protective layer modified sandwich structure composite metal zinc anode has better hydrogen evolution inhibition effect.
The electrochemical performance test was carried out by assembling the modified zinc metal anodes obtained in examples 2 and 3 into a symmetrical battery, and the results are shown in fig. 8 and 9, and it is found that the cycle duration was similar to 2000 hours under the same test conditions, and the modified zinc metal anodes have excellent cycle performance similar to the results in example 1.
The electrochemical performance test was performed by assembling the modified zinc metal anodes obtained in example 1 and comparative example 2 into a symmetrical battery, respectively, and as shown in fig. 10, the electrochemical performance of the symmetrical battery of the modified zinc metal anode prepared in comparative example 2 was significantly reduced due to the lack of induction effect caused by doping of fluorine atoms with high zinc affinity, and the zinc ion conductivity of the carbon-based film layer was significantly reduced.
The scheme of the invention has the following beneficial effects:
(1) The preparation method of the composite metal negative electrode with the sandwich structure provided by the scheme of the invention can enable metal ions to be quickly and stably transmitted to a space under a membrane for deposition through the fluorine doped amorphous carbon base protective layer with high ion conductivity and low electron conductivity on the surface of the current collector, inhibit dendrite formation, effectively isolate electrolyte from deposited metal, inhibit corrosion and reaction of the electrolyte on the metal, and realize long service life and stable work without dendrite of the composite metal negative electrode.
(2) The invention is not only suitable for preparing the composite zinc metal negative electrode of the zinc ion secondary battery, but also suitable for preparing the composite metal negative electrode of other secondary metal ion batteries, such as the composite negative electrodes of lithium, sodium, potassium, aluminum, magnesium and the like, and has wide applicability.
(3) According to the invention, the fluorine-containing organic gel is coated on the current collector and carbonized to obtain a layer of fluorine-doped densified carbon layer, the fluorine doping introduces defects in the carbon layer, and an ion transmission channel is provided, namely the carbon layer has electronic insulation and simultaneously enhances ion conductivity; wherein, no solid reaction or solid-phase diffusion occurs between the carbon layer and the current collector substrate, and the carbon layer and the current collector substrate are simple physical combination and do not undergo element transfer; the fluorine doped carbon based protective layer is an electronic insulating layer and does not cause deposition of metal on the upper layer.
(4) The current collector used in the present invention can directly deposit metal to form the anode as an active material without coating the active material to store the metal.
(5) The metal ions (for example, zinc ions) deposited on the negative electrode can pass through the carbon layer and are deposited between the carbon layer and the current collector substrate to form a sandwich structure; the protective layer is a solid material and has high mechanical property, and the upper insulating carbon layer can press the lower metal deposition to avoid dendrite occurrence and cause short circuit of the battery; in addition, the fluorine-doped carbon layer can induce the deposition orientation of metallic zinc, so that the metallic zinc is arranged below the fluorine-doped carbon layer and can be deposited in a way that the zinc (002) crystal face is parallel to the substrate orientation, and the growth of dendrites can be inhibited.
(6) The invention has the following functions by introducing fluorine doped amorphous carbon film as a protective layer: (a) The electrolyte and the metal are effectively isolated, and the metal is prevented from being corroded and reacted by the electrolyte; (b) Fluorine element with stronger electronegativity can act with metal ions to provide abundant nucleation sites for metal deposition, so that ion homogenization distribution is realized; (c) The fluorine doped amorphous carbon film has high ionic conductivity and low electronic conductivity, and can deposit the transmitted metal ion confinement in a limited space under the film to inhibit metal dendrite formation.
The above embodiments are only for illustrating the technical solution of the present invention, and it should be understood by those skilled in the art that although the present invention has been described in detail with reference to the above embodiments: modifications and equivalents may be made thereto without departing from the spirit and scope of the invention, which is intended to be encompassed by the claims.

Claims (10)

1. A composite metal negative electrode with a sandwich structure is characterized in that: the structure comprises a current collector, an electrodeposited metal layer and a fluorine-doped amorphous carbon base protective layer, wherein the current collector, the electrodeposited metal layer and the fluorine-doped amorphous carbon base protective layer form a sandwich structure, the fluorine-doped amorphous carbon base protective layer is uniformly attached to the surface of the current collector, and the electrodeposited metal layer is in a sheet shape and parallel to the current collector.
2. The composite metal negative electrode with a sandwich structure according to claim 1, wherein: the thickness of the fluorine doped amorphous carbon base protective layer is 4-6 mu m, and the thickness of the electrodeposited metal layer is 2-10 mu m.
3. A composite metal anode with a sandwich structure according to claim 1 or 2, characterized in that: the current collector is at least one of copper foil, nickel foil, titanium foil, stainless steel foil, carbon cloth, carbon paper, carbon nanotube film and graphene film, and fluorine of the fluorine-doped amorphous carbon-based protective layer is provided by at least one of polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, fluoroethylene/vinyl ether copolymer resin and polytrifluoroethylene.
4. A method for preparing a composite metal anode having a sandwich structure according to any one of claims 1 to 3, comprising the steps of:
s1, dissolving a fluorine-containing high polymer material into a polar organic solvent to prepare a viscous liquid, and immersing a current collector into the viscous liquid to form a film so as to obtain a composite current collector precursor;
s2, carbonizing the composite current collector precursor at a high temperature to obtain an electrode precursor of the fluorine-doped amorphous carbon layer coated current collector;
s3, slicing the electrode precursor, then loading the sliced electrode precursor into a battery, and depositing metal between the fluorine-doped amorphous carbon layer and the current collector through electrochemical deposition to obtain the composite metal anode with the sandwich structure.
5. The method for preparing a composite metal anode with a sandwich structure according to claim 4, wherein the step S1 specifically comprises the following steps:
s1.1, alternately cleaning a current collector with deionized water and ethanol for 2-3 times, and drying for later use;
s1.2, mixing a fluorine-containing high polymer material with a polar organic solvent according to a proportion to obtain viscous liquid;
s1.3, immersing the current collector in the viscous liquid, taking out and drying, and constructing a layer of film on the surface of the current collector to obtain the composite current collector precursor.
6. The preparation method of claim 5, wherein in the step S1.2, the fluorine-containing polymer material and the polar organic solvent are mixed according to a mass volume ratio of 1:20-50, the polar organic solvent is at least one of N-methylpyrrolidone, dimethylbenzamide and dimethylacetamide, the dipping time in the step S1.3 is 3-5min, the drying temperature is 60 ℃, and the vacuum drying is carried out for 10-20 h.
7. The method for preparing the composite metal anode with the sandwich structure according to claim 4, wherein the method comprises the following steps: the specific step of the S2 is that the dried composite current collector precursor is placed in a tube furnace, and is heated to 500-800 ℃ at a speed of 2 ℃/min under the argon atmosphere, and then is preserved for 2 hours, so that the fluorine doped amorphous carbon layer coated current collector electrode precursor is prepared.
8. The method according to claim 4, wherein the electrochemical deposition in S3 comprises the specific steps of at least 0.25mA/cm 2 Is deposited at a current density of 1 to 5mAh/cm 2 The electrochemical deposition equipment adopts one of button cells and electrolytic tanks.
9. A secondary battery comprising a casing, a positive electrode, a separator, a metal negative electrode and an electrolyte, characterized in that: the metal negative electrode is a composite metal negative electrode with a sandwich structure obtained by the preparation method of any one of claims 1 to 3 or any one of claims 4 to 8.
10. The secondary battery according to claim 9, wherein: the composite metal cathode is composite zinc metal, the electrolyte is a water-based electrolyte containing zinc salt, and the anode is CNT/MnO 2 Or V 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the Or the composite metal negative electrode is composite lithium metal, the electrolyte is organic electrolyte containing lithium salt, and the positive electrode is LFP or LTO; or the composite metal negative electrode is composite sodium metal, the electrolyte is an electrolyte containing sodium salt, and the positive electrode is sodium manganate or sodium iron phosphate.
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