WO2020018790A1 - Structures revêtues de métal destinées à être utilisées en tant qu'électrodes pour batteries et leurs procédés de production - Google Patents

Structures revêtues de métal destinées à être utilisées en tant qu'électrodes pour batteries et leurs procédés de production Download PDF

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WO2020018790A1
WO2020018790A1 PCT/US2019/042405 US2019042405W WO2020018790A1 WO 2020018790 A1 WO2020018790 A1 WO 2020018790A1 US 2019042405 W US2019042405 W US 2019042405W WO 2020018790 A1 WO2020018790 A1 WO 2020018790A1
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metal
lithium
fabric
battery
copper
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PCT/US2019/042405
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Xin Li
David A. Weitz
Li-ya QI
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President And Fellows Of Harvard College
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
    • C23C18/2066—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/1648—Porous product
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
    • C23C18/1882—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/668—Composites of electroconductive material and synthetic resins
    • 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

Definitions

  • Lithium metal with its extremely high specific capacity (3,860 mA h g 1 ) and the lowest redox potential (-3.04 V versus the standard hydrogen electrode) has been long regarded as an ideal anode material.
  • the dendrite problem has largely limited its commercialization. hi Uncontrolled dendrite growth can penetrate the separator, causing short circuits and even catastrophic explosions. 4 Lithium dendrites were thought to originate from the inhomogeneity of the Li + concentration on the traditional anode surfaces and the drastic electrode dimensional change during cycling. Pi
  • Conductive micro/nanostructure frameworks have proved to be an effective method to ensure uniform Li deposition and to accommodate the Li volumetric expansion; 18 ⁇ these frameworks include the layered reduced graphene oxides, 13 ⁇ 4 121 nickel (Ni) foam 1131 and metal-coated sponges. 1141
  • the expensive and complex fabrication process may limit practical applications. Developing a simple, low-cost and versatile technique that can transform materials into 3D conductive frameworks remains a challenge in this field.
  • the invention features structures useful for electrodes or current collectors in a battery where the structure includes the formation of a layer of a metal coordinating polymer, e.g., polydopamine, on the surface of the structure and a layer of metal, e.g., copper, on the metal coordinating polymer, e.g., polydopamine, layer. Structures of the present invention may be incorporated into a battery as a current collector at an electrode of the battery, e.g., the anode.
  • a metal coordinating polymer e.g., polydopamine
  • the invention provides a method of coating a surface of a structure, the method including the steps of: a) forming a metal coordinating polymer, e.g., polydopamine layer, on the surface of the structure; and b) contacting the product of step a) with metal, e.g., copper, ions under conditions to form a layer of metal, e.g., copper, on the surface.
  • a metal coordinating polymer e.g., polydopamine layer
  • the structure includes metal, glass, polymer, paper, fabric, carbon, polyester, cotton or a composite thereof. In some embodiments, the structure includes natural or synthetic fibers. In particular embodiments, the structure includes a composite of polyester and cotton.
  • the structure is porous. In certain embodiments, the pores in the structure are randomly oriented. In certain embodiments, the pores in the structure are ordered.
  • any of step a) or step b) of the method occurs at room temperature. In some embodiments, any of step a) or step b) of the method occurs over a period of 1 -5 days, e.g., 1 day, 2, days, 3 days, 4 days, or 5 days.
  • the source of metal ions e.g., copper ions
  • is a metal salt e.g., copper salt.
  • the invention includes a battery having a) an anode including a current collector including a structure having a metal, e.g., copper, layer on a metal coordinating polymer, e.g., polydopamine, layer, where the current collector is in contact with lithium, sodium, or potassium ions; and b) a cathode comprising a redox active species.
  • a current collector including a structure having a metal, e.g., copper, layer on a metal coordinating polymer, e.g., polydopamine, layer, where the current collector is in contact with lithium, sodium, or potassium ions; and b) a cathode comprising a redox active species.
  • the structure includes metal, glass, polymer, paper, fabric, carbon, polyester, cotton or a composite thereof. In some embodiments, the structure includes natural or synthetic fibers. In particular embodiments, the structure includes a composite of polyester and cotton.
  • the structure is porous. In certain embodiments, the pores in the structure are randomly oriented. In certain embodiments, the pores in the structure are ordered.
  • the battery includes a separator between the anode and the cathode.
  • the current collector is in contact with lithium ions.
  • the battery is pressurized, as described herein.
  • the structure may include a fabric when the battery is pressurized.
  • Figures 1 A-1 E Fig. 1 A shows digital-camera photographs of 3D current collectors after different treatments.
  • Fig. 1 B is an SEM image of the pristine 3D current collector.
  • Fig. 1 C is an SEM image of a current collector after 500 °C annealing under N2 atmosphere for 2 hours.
  • Fig 1 D is an SEM image of a current collector after soaking in DEC solution.
  • Fig. 1 E is an SEM image of a current collector after cycling for 20 cycles.
  • Figures 2A-2D Schematic of converting a porous structure into a conductive 3D current collector.
  • Figs 2A and 2B show immersion of the glass fiber (GF) in the dopamine solution with the color change from light (Fig. 2A) to dark (Fig. 2B).
  • Fig. 2C shows the simple dip-coating of the polydopamine (PDA)-coated GF of Fig. 2B turned into a Cu coated 3D conductive framework.
  • the enlarged image of Fig. 2C shown in Fig. 2D illustrates the adherence of PDA and Cu films on the original structure.
  • Figures 3A-3E Characterization of dip-coating-treated GF frameworks.
  • Fig. 3A shows digital-camera images of original samples (upper), PDA coated samples (middle) and Cu coated samples (bottom).
  • Six different substrates from left to right are metal coin, polyester, polycarbonate, rice paper, glass fiber and nickel foam.
  • Fig. 3B shows XPS spectra of GF, PDA coated GF and Cu coated GF.
  • Figs. 3C-3E show pore size distributions of pristine GF (Fig 3C), PDA coated GF (Fig. 3D), and Cu coated GF (Fig. 3E) in SEM images.
  • Figure 4 Pore-size distributions of polycarbonate and its corresponding PDA coated and Cu coated structures.
  • Figure 5 High magnification SEM image of copper coated glass fiber, showing that copper is well coated on the fiber.
  • Figure 6 XPS characterization of polydopamine-coated and copper coated surfaces in the polycarbonate frameworks.
  • Figures 7A-7B 2D simulations performed on COMSOL Multiphysics using the“Tertiary Current Distribution, Nernst-Planck (tcdee)” module.
  • Fig. 7A shows the geometry of the simulation cell with the length expressed in meters.
  • the nuclei of Li (at the bottom of Fig. 7A) have a width of 1 .5pm and height of 2.75pm for the center one and 1 .75pm for the other four. Circles above the nuclei represent the 2D sections of the 3D copper wire network. For simplicity we assume the section is perpendicular to the wire direction.
  • Fig. 7B shown the cell configuration of the battery, with the top line standing for the cathode in a real battery, and the remaining surfaces in black are the anode.
  • Figures 9A-9F SEM images of the morphology of Li deposited on 2D and 3D current collectors with current density of 0.5 mA crrr 2 for a total of 1 mAh crrr 2 of Li.
  • Fig. 9A shows a top view SEM image of the 20th Li plating
  • Fig. 9C shows the 100th Li plating on pristine 2D planar current collector.
  • Fig 9B shows a top view SEM image of the 3D porous current collector at the 20th Li plating
  • Fig. 9D shows a top view SEM image of the 3D porous current collector at the 100th Li plating.
  • Fig. 9E shows a schematic of lithium plating on 2D copper.
  • Fig. 9F shows a schematic of lithium plating on a 3D framework.
  • Figures 10A-10B SEM images of the morphology after the deposited Li stripping out of the composites.
  • Figures 1 1 A-1 1 C Comparison of Coulombic efficiency (CE) of Li deposition on 2D planar and 3D porous current collectors after Li deposition/stripping at various current rates of 0.5 (Fig. 1 1 A), 1 .0 (Fig. 1 1 A), and 2.0 (Fig. 1 1 A) mA crrr 2 with the same area capacities of 1 mA h cm ⁇ 2 .
  • CE Coulombic efficiency
  • Figures 12A-12H SEM images of the morphology of Li deposited on 2D and 3D current collectors with current density of 1 and 2 mA crrr 2 for a total of 1 mAh crrr 2 of Li after 20 cycles.
  • Figs. 12A and 12C show top view SEM images of the 20th Li plating on 2D current collectors at 1 mA crrr 2 .
  • Figs. 12A and 12C show top view SEM images of the 20th Li plating on 2D current collectors at 1 mA crrr 2 .
  • FIGS. 12B and 12D show top view SEM images of the 20th Li plating on 3D frameworks at 1 mA crrr 2 .
  • Figures 12E and 12G are top view SEM images of the 20th Li plating on 2D current collectors at 2 mA crrr 2 .
  • Figures 12F and 12H are top view SEM images of the 20th Li plating on 3D frameworks at 2 mA crrr 2 .
  • Figures 13A-13D Voltage profiles in symmetric Li
  • Fig. 13C shows average voltage hysteresis of Li metal plating/stripping at 0.25 mA crrr 2 .
  • Fig. 13D shows cycling performances of an Li anode with 2D and 3D current collectors in a full cell with a LiFePCL cathode at 0.5 C.
  • Figures 14A-14B Fig. 14A shows an SEM image of the 50th Li stripping of the commercial Ni foam coated with Cu at current density of 0.5 mA crrr 2 for a total of 1 mAh crrr 2 of Li.
  • Fig. 14B shows an SEM image of the polycarbonate objects with too small pore size (100 to 200 nm) under the same test condition.
  • Figures 15A-15C Fig. 15A shows a schematic of 3D Cu-fabric current collector preparation by a two- step dip-coating method.
  • Fig. 15B and Fig. 15C show SEM images of prepared Cu-fabric (Fig. 15B) and an individual fiber of Cu-fabric (Fig. 1 5C).
  • Figure 16 The compressibility of the Cu-fabric. The extension is measured for ten layers of cloth. The initial thickness of each layer is 291 pm. After each step of compressing, pressure was released and re-applied onto the samples, which are denoted as specimen 1 -4. As shown in Fig. 16, the slope converges to the same value for each specimen.
  • Figures 17A-17B Schematics of lithium deposition during a lithium plating/stripping process on a 3D Cu-fabric (Fig. 17A) and 2D bare copper foil (Fig. 17B).
  • FIG. 18A shows the Coulombic efficiency of lithium plating/striping on 3D Cu-fabric under different pressure.
  • Figs. 1 8B-1 8C show SEM images of the morphology of the lithium deposition after 20th plating under 0 degrees of pressure (Fig. 18B) and over 90 degrees of pressure (Fig. 1 8C).
  • Figs. 18D-18E show SEM images of the morphology of the lithium deposition after 10th plating on bare 2D copper (Fig. 1 8D) and 3D Cu-fabric (Fig. 18E). (Current density: 2mA/cm 2 , area capacity: 1 mAh/cm 2 ).
  • Figure 19 SEM image of the morphology of Celgard 2325 (polypropylene-polyethylene separator) in a Li
  • Figures 20A-20L Scanning electron microscopy images of the morphology of lithium deposition after 10 th , 50 th and 100 th plating on 3D Cu-fabric and 2D bare Cu.
  • Figs. 20A-20C show lithium deposition after the 10 th , 50 th and 100 th plating on 3D Cu-fabric.
  • Figs. 20D-20F show lithium deposition after the 10 th , 50 th and 100 th plating on 2D bare copper.
  • Figs. 20G-20I show lithium deposition after the 10 th , 50 th and 100 th plating on 3D Cu-fabric.
  • Figures 21 A-21 C SEM images of a cross-section view of the Cu-fabric after 1 0 th (Fig. 21 A), 50 th (Fig. 21 B), and 100 th (Fig. 21 C) plating. All experiments were performed at a current density of 2mA/cm 2 and an area capacity of 1 mAh/cm 2 .
  • Figures 22A-22D Modelling lithium deposition under external pressure.
  • Fig. 22A shows a schematic illustration of the model.
  • p ext and r s are external pressure and the surface tension pressure, respectively.
  • / is the total friction on the lithium exerted by each layer of cloth.
  • Fig. 22B shows an illustration of the suppression of Li trunk and more even distribution of Li observed in experiments.
  • Fig. 22C shows the maximum volume of lithium that can be stored in the fabric as a function of external pressure, with estimated compressibility b 1.5 x 10 _7 m/N, average gap size s 0 3 ⁇ 4 1 mth and friction / 3 ⁇ 4 300N/m.
  • the predicted optimal external pressure of 4.78 MPa is very close to the experimental value by a factor of only 2-3.
  • Fig. 22D shows a schematic illustration of the performance of structured current collector. Darker shade indicates larger lithium storage capacity inside the 3D Cu-fabric structure that has a high porosity.
  • Figures 23A-23C SEM images of Cu-fabric based on polyester (Fig. 23A) and silk (Fig. 23B). Fig.
  • 23C shows the Coulombic efficiency of lithium striping/plating on Cu-fabric based on polyester/silk and 2D bare Cu.
  • FIG. 24A shows an SEM image of the morphology after cycling 500 cycles.
  • Fig. 24B shows the CE under 2mA/cm 2 current density and 1 mAh/cm 2 area capacity.
  • Fig. 24C shows the CE under 1 mA/cm 2 current density and 2mAh/cm 2 area capacity.
  • Fig. 24D shows voltage-time profiles of the lithium stripping/plating process with 2mA/cm 2 current density and 1 mAh/cm 2 area capacity in Li
  • Figure 25 Coulombic efficiency of lithium striping/plating on Cu-fabric.
  • the electrolyte is
  • DME dimethoxyethane
  • DOL 1 ,3-dioxo!ane
  • the invention provides a structure for use as an electrode or current collector, e.g., an anode, in a battery.
  • the structures of the present invention are resistant to lithium dendrite formation, a common detrimental effect in traditional lithium ion batteries, due to their high porosity that allows lithium to deposit uniformly within the pores of the material, which also allows for volumetric changes in the lithium during electrical cycling.
  • the invention further provides methods of coating a surface of a structure using readily available and inexpensive reagents to form a 3D conductive framework.
  • PDA Polydopamine
  • a dip-coating method can turn virtually every porous material, ranging from metal to semiconductor to insulator, into an effective 3D current collector. This method includes cost effective compounds and operates under mild reaction conditions, making it highly competitive for scale up.
  • the 3D conductive architecture with large specific surface area can greatly reduce the ion flux density and provide enough sites for homogenous Li nuclei distribution and growth.
  • the porous scaffold also acts as a rigid host to accommodate the volume change of the Li metal.
  • this 3D current collector maintains an enhanced CE of 94% for 600 h at 0.5 mA crrr 2 and long-term cycling stability is demonstrated in full batteries (Li @ 3D GF-Cu
  • This facile and versatile strategy of metal coating makes a great step towards building an ideal scaffold for Li encapsulation and enormously broadens the choices of suitable 3D porous materials for hosting the Li metal. Batteries of the invention can be cycled for 1000 h or more.
  • a structure of the present invention includes a base material, a layer of metal coordinating polymer, e.g., polydopamine, in contact with the base material, and an outer layer of a metal, e.g., copper, in contact with the metal coordinating polymer, e.g., polydopamine, layer.
  • metal coordinating polymer e.g., polydopamine
  • Suitable materials for the base material include porous conducting, semiconducting, or insulating materials.
  • the pores in the structure may be randomly ordered or may have an ordered pattern. Exemplary pore sizes range from 100 nm to 100 pm, e.g., 100 nm to 10 pm, 400 nm to 100 pm, 400 nm to 10 pm, 400 nm to 1 pm, 750 nm to 10 pm, or 750 nm to 1 pm.
  • useful materials for the base material include, but are not limited to, metals, e.g.
  • a base material for a structure of the invention may be a fabric blend, e.g., 80% polyester and 20% cotton.
  • the fabric includes fibers, e.g., synthetic fibers, having diameters from 10 nm to 100 pm, e.g., 1 0 nm to 100 nm, 10 nm to 500 nm, 10 nm to 1 pm, 10 nm to 50 pm, 100 nm to 1 pm, 100 nm to 10 pm, 100 nm to 100 pm, 500 nm to 1 pm, 500 nm to 10 pm, 500 nm to 100 pm, 1 pm to 50 pm, or 1 pm to 100 pm.
  • fibers e.g., synthetic fibers, having diameters from 10 nm to 100 pm, e.g., 1 0 nm to 100 nm, 10 nm to 500 nm, 10 nm to 1 pm, 10 nm to 50 pm, 100 nm to 1 pm, 100 nm to 10 pm, 100 nm to 100 pm, 500 nm to 1 pm, 500 nm to 10 pm, 500 nm to 100 pm, 1 pm to
  • the metal of the outer layer of structure may be transition metal, e.g., Ni, Co, Fe, Mn, Rh, Pt, Cu, Mo, W, or a combination thereof.
  • An exemplary metal is copper.
  • the metal, e.g., copper may be uniformly coated on the metal coordinating polymer, e.g., polydopamine, layer.
  • Suitable metal coordinating polymers include polydopamine.
  • polydopamine includes unmodified polydopamine and derivatized polydopamine.
  • dopamine may be derivatized according to formula:
  • Specific derivatives include 3,4-dihydroxy-L-phenylalanine, norepinephrine, 6-nitrodopamine, 2- bromo-N-[2-(3,4-dihydroxyphenyl)ethyl]-2-methyl propenamide, and 5-hydroxydopamine.
  • Other polymers may be formed from nitrogen-free phenols and polyphenols. Examples include hydrocaffeic acid, alkylcatechol, thiol-terminated catechols, gallol, pyrogallol, tannic acid, epigallocatechin gallate (EGCG), epicatechin gallate (ECG), and epigallocatechin (EGC).
  • Metal coordinating polymers also include proteins such as Mfp-3 and -5. Other metal coordinating polymers are known in the art.
  • Structures of the present invention may be used to form an electrode, e.g., an anode, or a portion of an electrode, such as a current collector, of a battery.
  • An exemplary battery of the invention includes a cathode comprising a redox active species, a separator, an electrolyte, and an anode comprising a current collector.
  • the current collector is in contact with ions in the electrolyte.
  • the separator is between the cathode and the anode.
  • Exemplary materials for separators are nonwoven fibers (cotton, nylon, polyesters, glass), polymer films
  • polyethylene polyethylene, polypropylene, poly (tetrafluoroethylene), polyvinyl chloride), ceramics, and naturally occurring substances (rubber, asbestos, cellulose).
  • the battery may be under pressure, e.g., when the structure includes a fabric, e.g., 80%
  • polyester/20% cotton polyester/20% cotton.
  • the application of a pressure to a softer fabric structure allows for the retention of an increased lithium content while modifying the lithium deposition to allow for the formation of a smooth surface without sharp nuclei to form dendrites that may damage the battery separator.
  • Increasing the lithium content of the structure and smoothness of the surface increases Columbic efficiency and electrical, e.g., cycling, performance.
  • the pressure applied to the structure in a battery may be from 0.1 MPa to 20 MPa, e.g., 0.1 MPa to 15 MPa, 0.1 MPa to 5 MPa, 0.1 MPa to 3 MPa, 0.1 MPa to 1 , MPa, 0.4 MPa to 10 MPa, 0.4 MPa to 5 MPa, 0.4 MPa to 3 MPa, 0.4 MPa to 1 MPa, 0.7 MPa to 5 MPa, 0.7 MPa to 3 MPa, 0.7 MPa to 1 MPa, 1 MPa to 3 MPa, 1 MPa to 5 MPa, 1 MPa to 10 MPa, or 1 MPa to 15 MPa.
  • the structures of the invention may be used as an anode of a battery.
  • Cathodes for batteries of the present invention include a redox active species.
  • Examples include LiFeP04, UC0O2, UMn204, L MnOs, LiMn02, LiFe02, LiFesOs, UFes04, and lithium nickel manganese cobalt oxide. Others are known in the art.
  • the cathode includes LiFeP04, PVDF, and carbon black
  • the anode includes a structure of the invention that has been lithiated.
  • Suitable electrolytes for batteries include alkali metal, e.g., lithium, sodium, or potassium, salts dissolved in an appropriate solvent.
  • concentration of the alkali metal salt in the electrolyte may be from about 1 M to about 9M, e.g., from about 1 M to about 4M, from about 2M to about 5M, from about 3M to about 6M, from about 4M to about 7M, from about 5M to about 8M, or from about 6M to about 9M, e.g., about 1 M, about 2M, about 3M, about 4M, about 5M, about 6M, about 7M, about 8M, or about 9M.
  • An exemplary alkali metal salt for use in an electrolyte is LiTFSI (lithium
  • LiPF6 LiAsF6, L1BF4, UCF 3 SG 3 , or LiCIC .
  • Suitable solvents include polar aprotic solvents, e.g., carbonates (such as diethyl carbonate, ethylene carbonate, and mixtures thereof), dimethoxyethane, dioxolane, and mixtures thereof.
  • Solvents for the electrolyte may include other solutes, e.g., acids (e.g., HCI) or bases (e.g., NaOH or KOH) salts (e.g., KCI or UNO3), or alcohols (e.g., methyl, ethyl, or propyl) or other co-solvents to increase the solubility of a particular component in the electrolyte or to stabilize the interface on the anode or cathode side.
  • acids e.g., HCI
  • bases e.g., NaOH or KOH
  • alcohols e.g., methyl, ethyl, or propyl
  • the invention features methods of coating a surface of a structure.
  • the method involves forming a metal coordinating polymer, e.g., polydopamine, layer on the surface of the structure and then contacting the metal coordinating polymer, e.g., polydopamine, layer with metal, e.g., copper, ions under conditions to form a layer of metal, e.g., copper, on the surface.
  • a metal coordinating polymer e.g., polydopamine
  • dopamine may be dissolved into a solution using a suitable solvent, such as a buffer, e.g., 10 mM Tris-HCI, at an appropriate concentration.
  • a suitable solvent such as a buffer, e.g., 10 mM Tris-HCI
  • the structure to be coated may be heated using methods known in the art, e.g., in air, under vacuum, or in the presence of an inert gas, e.g., N2, to compact the pores of the structure.
  • the dopamine layer may be formed on the surface of the structure by immersing the structure into the solution of dopamine for an appropriate length of time.
  • the thickness of the polydopamine coating on the structure is dependent on the length of time the structure is in contact with the dopamine solution.
  • the formation of a suitable layer of dopamine on the structure may take from 1 to 5 days, e.g., 1 day, 2 days, 3, days, 4 days, or 5 days.
  • the polydopamine-coated structure may be placed into contact with, e.g., immersed in, a source of copper ions, such as a solution comprising a copper salt, e.g., CuC .
  • a source of copper ions such as a solution comprising a copper salt, e.g., CuC .
  • a solution of copper ions may include other components, such as acids, e.g., H3BO3, bases, e.g., NaOH, chelators, e.g.,
  • ethylenediaminetetraacetic acid or reducing agents, e.g., dimethylamine-borane (DMAB).
  • DMAB dimethylamine-borane
  • Formation of a copper layer on the polydopamine layer of the structure may occur at conditions suitable to allow this process to occur over a longer time scale, e.g., room temperature and pressure, to ensure the formation of a uniform layer of copper on the polydopamine layer of the structure.
  • the formation of a suitable layer of copper on the polydopamine layer of the structure may take from 1 to 5 days, e.g., 1 day, 2 days, 3, days, 4 days, or 5 days.
  • PDA Polydopamine
  • dopamine is a small-molecule with both catechol and amine functionalities, and is a simple mimic of the blue mussel ( Mytilus edulis) foot protein.
  • the protein is rich in 3,4-dihydroxy-L-phenylalanine (DOPA) and lysine amino acids and performs an important role in the mussels’ adhesive ability.
  • DOPA 3,4-dihydroxy-L-phenylalanine
  • Dopamine may participate in reactions of bulk solidification and form strong covalent and noncovalent interactions with substrates.
  • the glass fiber substrate was heated in air at 500°C for 2 h before use. After dipping the substrates into the aqueous dopamine solution, dark brown color was observed over time.
  • the thickness of the PDA coating is a function of the immersion process and can be reached up to 50nm after 24 hours. [15al As a result, the immersion process was continued for 24 hours to ensure the formation of the polydopamine coating on substrates.
  • the as-immersed substrates were washed with distilled water and dried at 60 °C.
  • Electrode metallization an aqueous solution of 50 mM CuCL, 0.1 M H3BO3, 50 mM
  • ethylenediaminetetraacetic acid (EDTA) was prepared, followed by a pH adjusting process with 1 M NaOH until the pH is 7. Before dipping the PDA coated substrates into the solution, 0.1 M
  • FIGS 1 A-1 E The mechanical robustness of the as-prepared electrodes is shown in Figures 1 A-1 E.
  • the samples were treated by 500 °C annealing for 2h, soaking in DEC for 2h, and cycling for 20 times, respectively. Then we compared the digital-camera images and SEM images among original sample and treated samples.
  • Figure 1 A shows that no geometrical or copper color change was observed after annealing, soaking or cycling, indicating the strong mechanical robustness of the coated copper on the fiber.
  • the SEM images in Figures 1 B-1 E show that the porous inner structure of samples stays the same after treatments.
  • Electrochemistry All batteries were carefully prepared in the glove box with a Swagelok cell configuration. 3D copper electrode and 2D copper foil were assembled and tested with lithium metal as the anode and Celgard 2500 (polypropylene) as the separator. Batteries were cycled at different current densities ranging from 0.5 mA/cm 2 to 1 .5 mA/cm 2 with a capacity of 1 mAh/cm 2 . Lithium was first deposited on the copper electrode for 1 mAh/cm 2 and then charged to 0.5 V to delithiate from the copper electrode.
  • a pre-lithiation process was first conducted using lithium metal as the anode. The lithium metal was then replaced by a new copper electrode. The batteries were charged and discharged for 1 h at current density of 1 mA/cm 2 .
  • a LiFePC cathode was prepared by coating an active material (80 wt%), carbon black (10 wt%), and PVDF (10 wt%) solution (in NMP) on an Al foil and then dried under vacuum. The pre-lithiated 3D copper are cycled with LiFePC as a counter electrode at 0.5 C.
  • the procedure to obtain the 3D porous Cu foil is schematically presented in Figure 2 and illustrated using different original materials in Figure 3A.
  • the preparation process first involved the immersion of the substrates in an aqueous dopamine solution and then dipping polydopamine coated objects into CuCl2 solutions. After the first immersion step of 24 hours the colors of all the samples, including a metal coin, polyester, polycarbonate, paper, glass fiber and nickel foam, changed toward brown, which clearly demonstrated that an adherent polymer film was deposited on the object surface (Figure 3A). Further evidence for dopamine polymerization was found by X-ray-photoelectron-spectroscopy (XPS) measurements.
  • XPS X-ray-photoelectron-spectroscopy
  • the characteristic XPS substrate signals for unmodified GF such as silicon (-100 eV) were highly suppressed after polydopamine coating. Instead, nitrogen (-399.5 eV) in PDA was clearly observed, as shown in Figure 3B.
  • Scanning electron microscopy (SEM) images showed that before and after coating with PDA, the pore-size distributions were almost identical, as shown in Figures 3C-3E; this suggested that the PDA coating has little influence on the pore-size distributions of the substrates.
  • the preserved porous nature was confirmed by quantitative analysis of the porosity measurement. As shown in Figure 4, the PDA coating does not alter the porosity of the substrates for the specific battery application of interest here.
  • the stabilization of the electrode dimension is highly beneficial in lithium metal anodes.
  • small dendritic Li grows from bare planar electrodes to promote further dendrite growth.
  • drastic volume expansion during continuous cycling can easily destroy the SEI layer, which in turn results in the inhomogeneous concentration of Li + flux to further accelerate the Li dendrite growth and the rapid consumption of the electrolyte.
  • the design of the 3D conductive frameworks with large internal surface area can effectively reduce the current density and provide enough space to accommodate the Li deposition and alleviate the drastic volume change of Li metal during battery cycling.
  • the interconnecting conductive inner-structure can effectively regulate the electronic and ionic transportation and distribution properties. As shown in Figures 7A-7B and 8A-8F, distinct“hot spot” regions with high local current densities are observed among the top regions of Li metal nuclei.
  • Figures 7A-7B show 2D simulations performed using COMSOL
  • the 3D copper network has a diameter distribution around 1 pm.
  • the diameters of the large and small circles are chosen as 1 pm and 0.6pm, and the positions of these circles are randomly chosen. Note that the observed phenomena remain largely unchanged for different directions and sizes of the 3D copper wire.
  • the deposition of Li to the 3D copper network has a limited thickness. These unconstrained hot spots will eventually grow into the Li dendrites. In contrast, the hot spots are effectively prevented with the introduction of the 3D conductive structure due to the more homogeneous distribution of the electric fields. Hence, a more uniform Li deposition should improve the lifespan of Li-metal anodes.
  • planar copper and the 3D conductive frameworks based on five different materials are used here as the counter electrodes, respectively, to observe the anode morphologies.
  • a standard carbonate electrolyte (1 M LiPF6 in ethylene carbonate (ECydiethyl carbonate (DEC)) was used without other additives.
  • electrolyte it shows more intrinsic improvement related to the 3D structure, since the SEI layers formed are dominated by Li alkyl carbonate (ROCO2U) in carbonate electrolyte and are usually too fragile to prevent the Li dendrite formation.
  • ROCO2U Li alkyl carbonate
  • the initial plated Li on the 3D framework has a high surface area and it tends to react with electrolyte more than the plated Li on the 2D Cu foil.
  • the CE of planar Cu electrode is lower than 3D GF-Cu, which may be related to the formation of dendritic lithium metal and the cracking of SEI.
  • 3D GF-Cu 3D GF-Cu
  • the differences between two samples are even more obvious ( Figure 1 1 B, 1 1 C).
  • SEM images of the Li deposited 2D and 3D current collectors at a high current density are shown in Figures 12A-12H, the extremely high current density of Li deposited 2D and 3D current collectors at a high current density are shown in Figures 12A-12H, the extremely
  • 3D framework can be directly seen from the high rate lithium plating. A much more even distribution of lithium metal was observed in the 3D current collector than the 2D counterpart, while dendritic Li appeared on the 2D planar after high current density cycling. In the 3D framework, lithium metal was hosted by the copper coated fiber, which prevented the formation of dendritic lithium particles. In contrast, the accumulation of extremely inhomogeneous lithium deposition can be observed from the 2D copper foil after lithium plating.
  • the voltage profiles of Li-plating-stripping process were also investigated for all the samples.
  • the voltage hysteresis is defined as the difference between the voltages of lithiation and delithiation performances, which is mainly influenced by the current density and interfacial properties.
  • Figure 13A shows the stable deposition/stripping behaviors of 3D GF-Cu with the nearly constant hysteresis of 40 mV.
  • LiFeP04 full battery tests were performed (Figure 13D) using bare Li metal and 3D GF-Cu @ Li at 0.5 C.
  • the slight capacity increase in the first few cycles is due to the activation process of the LiFeP04 materials.
  • the 3D GF-Cu @ Li cells exhibited an improved cycling stability, which retained 91 % of their initial discharge capacity after 200 cycles with the stable CE of 99.5%.
  • the bare Li metal showed more evident capacity fading, which only delivered 81 % of initial discharge capacity at 200th cycle.
  • polyether, polycarbonate objects with pore sizes that are too small act much like the planar 2D current collectors, since most of the deposited Li metal was found on the surface ( Figure 14B). Additionally, excellent mechanical stability is also necessary to construct an ideal 3D current collector. Consequently, rice paper substrates present an average CE over 90% over 100 cycles at 0.5 mA cm 2 , but drops below 70 % after 50 cycles at higher rates such as 1 and 2 mA cm 2 . Strong conductive 3D current collectors derived from the matrixes with proper pore structures of glass fiber, PC or PETE with pore size range from 400 nm to 1 pm achieved better cycling performance.
  • Copper coated 3D soft fabric (Cu-fabric) current collectors were developed to show superior battery performance under an optimized mechanical stress for the lithium metal anode application.
  • the role of the external pressure can be evaluated by cycling performance and scanning electron microscopy (SEM) imaging. By modelling the dynamics of the lithium deposition, it was found that there exists an optimal external pressure for the cloth to hold the largest amount of lithium inside the pores. Such design principle is directly applied to and confirmed by the experiments.
  • the framework of the current collector is collected from lab clothing, which is both low cost and scalable.
  • the composition of the clothing fabric is 80% polyester and 20% cotton.
  • Cu-fabric was prepared by a two-step dip-coating method, shown in Figure 15A t 30 31 !, that is low cost and has no extreme requirements for chemicals, experimental conditions or facilities.
  • PDA polydopamine
  • the Cu-fabric was rinsed by distilled water for three times and then dried at 90°C.
  • the morphology of Cu-fabric was characterized by SEM.
  • the mechanical properties of the Cu fabric were measured by a materials testing machine (Instron, USA).
  • the 3D conductive fabric can modify the lithium deposition to a smooth surface without sharp nuclei, and shows a superior cycling performance of 500 cycles (1000 h working hours).
  • LiPFe 1 M hexafluorophosphate
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • Each clothing fiber was covered by a thin copper layer, and the interweaved structure was observed.
  • the gray arrows in Figure 15C show the Cu layer and clothing fiber inside separately.
  • the fiber is around 10 pm diameter and the distance between fibers is less than 2pm.
  • the elastic modulus of the interweaved fabric was measured to show an estimated compressibility around 1.5 x 10 -7 N/m as shown in Figure 16.
  • the Cu-fabric framework thus serves as a container and a soft cushion that regulates the lithium deposition.
  • a 3D Cu-fabric is optimized for use in a battery system. The deposited lithium is mostly pressed into the soft Cu-fabric and shows some flat bulks on the surface (Figure 17).
  • the deposited lithium is distributed uniformly on Cu fabric during the plating/striping process, leaving a wave-shaped surface.
  • the dendrite grows quickly on the 2D Cu foil and penetrates through the Celgard separator.
  • the assembled Li-Cu battery also shows a stable cycling performance at high current density and area capacity.
  • the symmetric battery based on lithium deposited on Cu-fabric shows more stable performance compared to that with Li deposited on 2D Cu (Li@2D bare Cu).
  • Cu batteries were assembled in a Swagelok cell configuration to evaluate the electrochemical performance of the 2D/3D current collectors.
  • the use of a Swagelok cell contributes to a denser lithium deposition due to the pressure inside the cell. Moreover, the reaction between deposited lithium and electrolyte will be depressed to increase the Coulombic efficiency, which represents the ratio between the amount of stripped and plated lithium every cycle.
  • 3D Cu-fabric is more sensitive to pressure, since it is a soft substrate with special microstructure. In order to choose an optimal pressure for battery test, different external pressure was applied on the battery by screwing the Swagelok cell tightly until 0, 90 and 180 degrees (Figure 18A).
  • Cu batteries were assembled to run for 10/50/100 cycles at 2 mA/cm 2 current density with
  • the 3D Cu-fabric provided a soft substrate to regulate the shape of the deposited lithium and a large storage space for deposited lithium.
  • V 0 is the original volume of the pores under no pressure.
  • V pore is proportional to s 2 .
  • V ln cioth kN s 2 (k 1), assuming the friction / is also a constant, we can write the equilibrium formula for V ln cloth ,
  • the porosity of the cloth without pressure is 10% and the thickness and area are 200 pm and 1 cm 2 , under optimal pressure, the porous volume decreases to about 1 /e.
  • the total volume inside the cloth is
  • Cu batteries were also applied to test the long-cycle electrochemical performance of 3D Cu-fabric electrode. Lithium was deposited to the 3D/2D current collector, then the battery cycled by charging to a cut-off voltage at 0.5V and discharging at 1 mA/cm 2 or 2mA/cm 2 .
  • the Coulombic efficiency is the main parameter we considered to evaluate the cycling stability. When CE decreases quickly or shows large fluctuations, it usually means that lithium dendrite have grown large enough to penetrate through the separator.
  • the Coulombic efficiencies of lithium stripping/plating process on 2D/3D current collector were shown in Figures 24A-24C.
  • the CE of 3D Cu-fabric electrode maintains over 90% stability for 500 cycles, 10OOh at 1 mA/cm 2 current density and 1 mAh/cm 2 area capacity.
  • the CE of 2D bare Cu electrode dropped to be less than 80% quickly after about 60 cycles. It is clear that the 3D Cu-fabric shows a much longer cycle life.
  • the battery after 500 cycles was disassembled and characterized the surface morphology of the 3D Cu-fabric. No obvious nucleation existed on the electrode surface and the shape of the fiber was still maintained.
  • the 3D Cu-fabric regulated the lithium deposition into the fiber and reduced the damage to the separator.
  • the soft Cu-fabric structure was proved to be a versatile method, applicable to various materials for improving the safety of lithium metal anode.
  • an ether-based electrolyte was chosen, and CE comes to over 95% with stable cycling over 300 cycles.
  • Li@Cu symmetric batteries were also used for testing the stability of electrodes (Figure 24D). The lithium was firstly deposited to the 2D/3D Cu current collector and then collected to assemble symmetric batteries. The batteries were cycled at a high current density of 2mA/cm 2 , and
  • Li@3D Cu-fabric battery 0.1 V
  • Li@2D bare Cu battery -0.2V
  • 3D Cu-fabric electrode shows great promise to achieve a more stable lithium deposition on the anode at higher current density ( Figure 25).
  • Examples 5-7 we developed and demonstrated a soft 3D Cu-fabric current collector which achieved superior long-cycle performance with the commercial carbonate electrolyte. Combining the experimental and simulation results, we suggested an optimal external pressure to the battery assemble. The lithium deposition was regulated and squeezed into the Cu-fabric during cycling. The 3D Cu-fabric surface maintained smoothness without obvious dendrite growth after cycling.
  • 3D Cu-fabric Simulations were also performed to reveal the mechanism of suppressing lithium dendrite growth by 3D Cu-fabric. A principle for 3D-structured current collector design was also obtained.
  • the 3D Cu fabric described herein is prepared from readily available clothing fibers using a scalable dip-coating method, which increases applicability for large-scale industrial production due to the low cost and straightforward processing.

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Abstract

L'invention concerne de nouveaux procédés de revêtement d'une structure dans une couche conductrice. Les procédés comprennent les étapes consistant à revêtir une structure avec une couche de polymère de coordination métallique, par exemple, la polydopamine, puis à revêtir la couche avec une couche de métal, par exemple du cuivre. Le procédé peut être utilisé sur des matériaux poreux facilement disponibles et économiques, tels que des fibres de verre et des tissus mélangés, à l'aide de réactifs économiques dans des conditions de réaction douce. L'invention concerne en outre des batteries utilisant des structures de l'invention en tant que collecteur de courant. Les batteries au lithium utilisant les structures de l'invention en tant que collecteurs de courant ne présentent pas de croissance de dendrites de lithium et présentent d'excellentes performances de batterie sur de longues périodes de cycle.
PCT/US2019/042405 2018-07-18 2019-07-18 Structures revêtues de métal destinées à être utilisées en tant qu'électrodes pour batteries et leurs procédés de production WO2020018790A1 (fr)

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CN111799445A (zh) * 2020-08-24 2020-10-20 中南大学 一种锂金属阳极及其制备和应用
CN112724737A (zh) * 2021-01-14 2021-04-30 中山大学 一种多巴胺墨水及其用于制备微纳图案的方法和应用
CN113224313A (zh) * 2021-04-30 2021-08-06 北京化工大学 一种金属有机膦框架玻璃修饰的金属负极集流体及其制备方法
WO2022226862A1 (fr) * 2021-04-29 2022-11-03 The Hong Kong Polytechnic University Collecteur de courant pour batterie et procédé de fabrication associé
CN115852679A (zh) * 2022-09-08 2023-03-28 西南科技大学 蚕丝织物铁活化法实现铜-镍双层化学镀

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111799445A (zh) * 2020-08-24 2020-10-20 中南大学 一种锂金属阳极及其制备和应用
CN112724737A (zh) * 2021-01-14 2021-04-30 中山大学 一种多巴胺墨水及其用于制备微纳图案的方法和应用
CN112724737B (zh) * 2021-01-14 2022-02-22 中山大学 一种多巴胺墨水及其用于制备微纳图案的方法和应用
WO2022226862A1 (fr) * 2021-04-29 2022-11-03 The Hong Kong Polytechnic University Collecteur de courant pour batterie et procédé de fabrication associé
CN113224313A (zh) * 2021-04-30 2021-08-06 北京化工大学 一种金属有机膦框架玻璃修饰的金属负极集流体及其制备方法
CN113224313B (zh) * 2021-04-30 2022-12-27 北京化工大学 一种金属有机膦框架玻璃修饰的金属负极集流体及其制备方法
CN115852679A (zh) * 2022-09-08 2023-03-28 西南科技大学 蚕丝织物铁活化法实现铜-镍双层化学镀

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