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WO2011072255A1 - Revêtement enrobant sur des matériaux électrodes nanostructurés pour applications tridimensionnelles - Google Patents

Revêtement enrobant sur des matériaux électrodes nanostructurés pour applications tridimensionnelles Download PDF

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Publication number
WO2011072255A1
WO2011072255A1 PCT/US2010/059946 US2010059946W WO2011072255A1 WO 2011072255 A1 WO2011072255 A1 WO 2011072255A1 US 2010059946 W US2010059946 W US 2010059946W WO 2011072255 A1 WO2011072255 A1 WO 2011072255A1
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nanowires
template
conformal
polymer
electrode
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Pulickel M. Ajayan
Fung Suong Ou
Manikoth M. Shajiumon
Sanketh R. Gowda
Arava L.M. Reddy
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William Marsh Rice University
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William Marsh Rice 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
    • H01M4/48—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
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0436—Small-sized flat cells or batteries for portable equipment
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
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    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
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    • 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
    • H01M4/664—Ceramic materials
    • H—ELECTRICITY
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    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • 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
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0472—Vertically superposed cells with vertically disposed plates
    • 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

Definitions

  • the present invention relates to conformal coating of a thin polymer electrolyte layer on nanostructured electrode materials for three-dimensional micro/nanobattery applications.
  • Nanostructured electrode materials due to their high surface area and superior electronic conductivity can be considered as potential candidates for the construction of 3D batteries.
  • the majority of the prior research efforts in 3D designs have been limited to the microstructured ( ⁇ 40um pore size) battery architecture.
  • [Golodnitsky 2006; Nathan 2005] Amongst the several methods available for synthesis of nanowire electrodes, template assisted synthesis has been shown to be a simple and versatile technique with excellent control over nanowire dimensions. [Hurst, S. J., et al., Angew. Chem. Int. Ed. 2006, 45, 2672-2692; Cheng, F., et al., Chem. Mater.
  • the present invention relates to three-dimensional batteries.
  • Planar lithium ion batteries used in the present day technology have a major drawback of slow lithium ion kinetics. To achieve faster lithium ion kinetics a large sacrifice in the mass loaded per unit area has to be made.
  • the three-dimensional nanostructured architecture developed in this invention improves Li ion kinetics in the cell and also allows for larger capacities per unit area. This is the first demonstration of coating thin polymer electrolyte layers in a conformal fashion around each individual anode nanowire and its subsequent use as an efficient 3D lithium ion battery. This thin layer of polymer gel electrolyte allows for fast lithium ion diffusion across the electrodes in contrast to the thicker and planar polymer films used in existing lithium ion battery technology.
  • the invention features a method that includes electrodepositing nanowires into pores of a template.
  • the nanowires are individual nanostructured electrodes.
  • the method further includes widening the pores of the template.
  • the method further includes that, after widening the pores of the template, infiltrating a polymer solution onto the template to obtain a polymer layer around the nanowires and yielding an anode-polymer electrolyte core-shell assembly.
  • Implementations of the invention can include one or more of the following features:
  • the method can further include operatively connecting a cathode to the anode- polymer electrolyte core-shell assembly to fabricate a three-dimensional battery.
  • the nanowires can include an anode material that is Ni-Sn, TiO 2 , MnO 2 , Fe304, V2O5, carbon nanotubes, Si, LiCoO 2/ LiFeP0 4 , or a combination thereof.
  • the nanowires can be intermetallic nanowires.
  • the intermetallic nanowires can be a combination of metallic elements that is Cu-Sb, Cu-Sn, Ti-Si, Al-Sb, Sn-Sb, Ni-Si, or a combination thereof.
  • the nanowires can be Ni-Sn nanowires.
  • the nanowires can include an oxide material.
  • the oxide material can be ⁇ nO 2 ,
  • the template can be an alumina template.
  • the step of infiltration can include a step of spin coating.
  • the step of widening the pores of the template can include using a solution of NaOH.
  • the polymer solution can include a polymer that is polymethylmethacralate, polyethylene oxide, polyvinyldiflouride, polyacrylonitrile, or a combination thereof.
  • the polymer solution can include polymethylmethacralate in acetonitrile.
  • the method can further include soaking the polymer layer around the nanowires in LiPF 6 .
  • the LiPF 6 can be LiPF 6 in solution, such as 1M LiPF 6 in solution.
  • the solution can be a solution of ethylene carbonate and dimethyl carbonate, such as a 1:1 solution of ethylene carbonate and dimethyl carbonate.
  • the cathode can include a cathode material that is LiCoO 2 or lithium foil.
  • the polymer layer around the nanowires can have a uniform thickness.
  • the polymer layer around the nanowires can have a thickness between about 20 and about 100 nm.
  • the polymer layer around the nanowires can have a thickness between about 20 and about 30 nm.
  • the invention features is an assembly fabricated by any of the methods described above.
  • the invention features an assembly fabricated by any of the methods described above.
  • the invention features a nanostructured battery fabricated by any of the methods described above.
  • the invention features a nanostructured battery that includes an anode-polymer electrolyte core shell assembly and a cathode operatively connected to the anode-polymer electrolyte core shell assembly.
  • the anode-polymer electrolyte core shell assembly includes a template having pores, nanowires in the pores of the template, and a polymer layer around the nanowires.
  • Implementations of the invention can include one or more of the following features:
  • the nanostructure battery can be a three-dimensional nanostructured battery.
  • FIGS. 1A-1B show the textural and elemental characterization of Ni-Sn nanowires grown by electrodeposition that can be used in embodiments of the present invention.
  • FIG. 1A is an SEM image showing uniform diameter of the Ni-Sn nanowires obtained after dissolving the AAO template.
  • FIG. IB is an EDX spectra of Ni-Sn nanowire confirming the presence of elements Ni and Sn.
  • FIG. 2 shows X-ray diffraction patterns of the Ni-Sn obtained in the Ni-Sn nanowires grown.
  • FIGS. 3A-3B shows the fabrication of nanostructured conformal Ni-Sn/PMMA hybrid assembly.
  • FIG. 3A is a schematic showing the fabrication of the novel nanostructured conformal configuration of the electrode/separator assembly.
  • FIG. 3B. is a TE image of the conformal configuration showing the conformal PMMA layer (—25 nm) around a ⁇ 3 ⁇ long segment of a Ni-Sn nanowire.
  • FIG. 4 is a TEM image of a lOum long PMMA coated Ni-Sn nanowire.
  • FIGS. 5A-5C shows the fabrication of nanostructured Ni-Sn/PMMA hybrid assembly.
  • FIG. 5A is a schematic showing the fabrication of the nanostructured ID and 3D configuration of the electrode/separator assembly.
  • FIG. 5B is a TEM image of the 3D configuration showing the conformal PMMA layer ( ⁇ 25 nm) around the Ni-Sn nanowire.
  • FIG. 5C is a TEM image of the ID configuration showing the planar heterojunction between the Ni- Sn and PMMA segments.
  • FIGS. 6A-6C show the electrochemical performance of a Ni-Sn/PMMA assembly in planar (2D) and conformal (3D) configurations, galvanostatically cycled in Li-half cells.
  • FIG. 1A is a schematic showing the fabrication of the nanostructured ID and 3D configuration of the electrode/separator assembly.
  • FIG. 5B is a TEM image of the 3D configuration showing the conformal PMMA layer ( ⁇ 25 nm) around the Ni-Sn
  • FIG. 6A is a graph showing the variation in voltage versus the capacity per footprint area for the planar Ni-Sn/PMMA electrode/electrolyte configuration cycled at a rate of 0.12 mA/cm 2 between 1.5 V and 0.02 V versus Li/Li + using PMMA separator soaked in 1M solution of LiPF 6 in 1 : 1 (v/v) mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) as the electrolyte.
  • FIG. 6B is a graph showing the variation in voltage versus capacity per footprint area for the conformal Ni-Sn/PMMA electrode/electrolyte configuration cycled at a rate of 0.12mA/cm 2 between 1.5 V and 0.02 V versus Li/Li + using PMMA separator soaked in 1M solution of LiPF 6 in 1 : 1 (v/v) mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) as the electrolyte.
  • FIG. 6C is a graph comparing the cycling behavior of the planar configuration (curve 603) and conformal configuration (curve 604). The conformal configuration showed a reversible capacity of 0.26 mAh/cm 2 after 30 cycles of charge/discharge which was two orders of magnitude greater than the capacity delivered by the planar design.
  • FIGS. 7A-7B show rate capability and capacity retention of conformal Ni- Sn/PMMA assembly.
  • FIG. 7A is a graph comparing the rate capability of the planar and conformal configuration.
  • Curve 701 shown by the circles
  • curve 702 shown by the squares
  • Curve 703 shown by the circles
  • curve 704 shown by the squares
  • FIG. 7B is a graph comparing the cycling behavior of Ni-Sn/PMMA core/shell nanowire with different lengths of the Ni-Sn nanowire (10 um of curve 705 and 6 um of curve 706). Reversible capacities of ⁇ 0.4mAh/cm 2 (10 um Ni-Sn) and ⁇ 0.2 mAh/cm 2 (6 um Ni-Sn) were observed after 15 cycles of charge/discharge. [0041] FIG.
  • Ni-Sn nanowire height—10 ⁇ charge-discharge profiles for conformal Ni-Sn/PMMA configuration (Ni-Sn nanowire height—10 ⁇ ) cycled at a rate of 0.3 mA/cm 2 between 1.5 V and 0.02 V using PMMA separator soaked in 1M solution of LiPFe in 1 :1 (v/v) mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC).
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • FIG. 9 shows charge-discharge profiles for conformal Ni-Sn/PMMA configuration (Ni-Sn nanowire height ⁇ 6 ⁇ ) cycled at a rate of 0.12 mA cm 2 between 1.5 V and 0.02 V using PMMA separator soaked in 1M solution of LiPF 6 in 1 :1 (v/v) mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC).
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • FIG. 10 is a graph showing the electrochemical performance of conformally coated (PMMA) Ni-Sn nano wires and uncoated Ni-Sn nanowires.
  • Curve 1001 shown by the circles
  • curve 1002 shown by the squares
  • Curve 1001 correspond to the cycling characteristics of the uncoated Ni-Sn nanowires and 3D PMMA coated Ni-Sn nanowires (nanowire length—12 urn) cycled at 0.3 mA cm 2 (3C) respectively.
  • the PMMA coating soaked in 1M solution of LiPF 6 in 1 : 1 (v/v) mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) served as the separator/electrolyte unit for conformal PMMA coated Ni-Sn nanowires whereas an external glass microfiber separator in 1 M solution of LiPF 6 in 1 : 1 (v/v) mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) was used as a separator for the uncoated Ni-Sn nanowires.
  • a schematic of the uncoated Ni-Sn nanowires 1003 and PMMA coated Ni-Sn nanowires 1004 is shown in the inset.
  • FIGS. 11 A-l ID are TEM images of a PMMA coated Ni-Sn nanowire.
  • FIG. 12 is a graph comparing the cycling characteristics of the PMMA coated Ni-Sn nanowires with home-made Ni-Sn powder with conductive additive and binder cycled at 0.5C rate between 1.5 and 0.02 V.
  • FIGS. 13A-13B illustrate the electrochemical performance of Ni-Sn/PMMA conformal assembly tested in a full Li-ion Cell.
  • FIG. 13A is a schematic of full Li-ion cell.
  • FIG. 13B shows charge-discharge profiles for Ni-Sn/PMMA gel/ L1C0O 2 configuration (Ni-Sn nanowire length ⁇ 10 ⁇ ) cycled at a rate of 0.05 mA/cm 2 between 2.7 V and 3.95 V using PMMA separator soaked in liquid electrolyte of 1M solution of L1PF 6 in 1 : 1 (v/v) mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC).
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • the present invention includes a template assisted technique to fabricate nanoarchitectured conformal electrode/electrolyte assembly that is and can be useful in Li-ion micro/nanobattery systems.
  • Thin conformal layer of PMMA deposited around Ni-Sn nanowire electrode provide the separator functionality to the assembly and serve as the gel electrolyte when soaked with liquid electrolyte.
  • the conformal configuration of the present invention has showed excellent electrochemical performance with two orders of magnitude improvement in the reversible discharge capacities, compared to its planar counterpart. High rate capability over extended cycling resulting from the nanoarchitectured conformal electrode-electrolyte assembly has also been demonstrated.
  • the PMMA coating has been observed to stay intact around the Ni- Sn nanowires over extended cycling at high current rates and has shown to improve the cycling characteristics of the bare nanowires. It is believed that the present invention could easily be extended to deposit other active electrode materials and polymer separators (such as T1O 2 , MnO 2 , Fe 3 0 4 , V 2 0 5 , carbon nanotubes, Si, LiCoO 2 , LiFeP0 4 ) which could lead to the development of even further efficient nanoscale Li ion batteries.
  • the conformal configuration of the PMMA coated electrode of the present invention is an important step towards realizing the true 3D nanostructured battery where the anode, electrolyte and cathode are all conformally integrated into the single nanowire assembly.
  • the present invention includes the fabrication of a conformal layer of uniform thickness (such as around 20 nm to around 30 nm thick) of Polymethylmethacralate (PMMA) (separator/gel electrolyte) around individual nanostructured electrode (Ni-Sn intermetallic nanowire) using a hard template assisted polymer infiltration technique (such as drop coating).
  • PMMA Polymethylmethacralate
  • nanostructured electrode Ni-Sn intermetallic nanowire
  • a hard template assisted polymer infiltration technique such as drop coating.
  • the nanostructured conformal configuration of the gel electrolyte has led to improved rate capabilities and discharge capacities of the electrode per footprint area (footprint area: overall device area) compared to its planar (stacked layers as used in bulk technologies) counterpart.
  • Such a fabrication process is advantageous because it is relatively inexpensive, as compared to other fabrication techniques and also is readily adaptable in large scale production.
  • Such fabrication process is also capable of uniformly coating over a relatively large length of a nanowire.
  • Embodiments of the present invention have been produced for coated Ni- Sn nanowires uniformly coated over a length of around 12 ⁇ m.
  • the core-shell anode-electrolyte array was fabricated using alumina templates. The two layers were grown using a combination of electrodeposition and solution wetting techniques. A variety of anode materials were fabricated by electrodeposition in alumina templates followed by a pore widening step. The space around individual anode nanowires was filled by polymer layer using a solution wetting technique. Vertically aligned arrays of core- shell anode-electrolyte nanowires were obtained and characterized by electron microscopy techniques. The three-dimensional nanostructured assembly for the anode and electrolyte was electrochemically characterized by cyclic voltammetry and charge discharge analysis in vacuum tight Swagelok cells. Full cells were constructed using known cathode materials (LiCoO 2 , V2O5) and electrochemically characterized against the novel 3D anode-separator nanocomposites.
  • the invention can include the following steps:
  • Ni-Sn nanowires are electrodeposited into the pores of a WHATMAN alumina template.
  • a dilute solution of NaOH is used to partially widen the pores of the alumina template from (A).
  • a solution of polymethylmethacralate in acetonitrile is prepared in an argon filled glove box.
  • the solution from (C) is spin coated onto the alumina template from (B) to obtain a thin polymer layer around the anode.
  • the polymer layer is soaked in a 1 M LiPF 6 in 1 : 1 solution of ethylene carbonate and dimethyl carbonate.
  • the full and half cell were assembled against L1C0O2 and Lithium foil respectively in an Argon filled glove box.
  • Electrochemical performance of the cells from (F) were studied using cyclic voltammetry and galvanostatic charge discharge analysis.
  • polymer layers of thickness between around 20 to 100 nm were well suited.
  • the thickness of the polymer layer achieved may be limited by the interpore distances of the commercial WHATMAN alumina templates used for this embodiment. Thicker polymer layers can be achieved using lab-grown alumina templates with larger interpore distances which in turn allows for larger widening of pores.
  • various anode materials can be engineered to build the novel three-dimensional core shell nanowires.
  • Cathode materials with different rate of lithium ion diffusion can also be used to construct full cells against the anode-polymer electrolyte core-shell assembly.
  • Ni-Sn intermetallic nanowires Owing to its high specific capacity, low cost and easy fabrication, Ni-Sn intermetallic nanowires have been chosen as the exemplar electrode material for embodiments of the present invention.
  • Other intermetallic nanowires can be utilized as the electrode material in other embodiments of the present invention.
  • Such other intermetallic nanowires include nanowires such as one of the following combinations of metallic elements: Cu-Sb, Cu-Sn, Ti-Si, Al-Sb, Sn-Sb, or Ni-Si; or a combination thereof.
  • the nanowires can also be an oxide material, such as ⁇ 2, T1O2, V2O5, Fe304, CuO, CoO, or a combination thereof.
  • Ni-Sn nanowires were grown inside pores of an anodized alumina template using a galvanostatic electrodeposition method.
  • Alumina templates such as ANODISC 13 from WHATMAN
  • a thin (200 tun) copper layer was sputtered onto the branched side of the alumina template that served as the electrical contact for the electrodeposition of nanowires.
  • An aqueous solution of 0.2M CUSO 4 and 0.1M H 3 BO 3 was prepared for the electrodeposition of Copper nanorod current collectors.
  • a 20 mL aqueous solution of 0.075M NiCl 2 , 0.175M SnCl 2 , 0.5M K 4 P 2 O 7 , 0.125M Glycine and 5mL L -1 NH 4 OH was prepared for the electrodeposition of Ni-Sn nanowires.
  • the electrodepositions were carried out in a three electrode cell consisting of a Pt counter electrode, Ag AgCl reference electrode and the Au-coated alumina template working electrode using an AUTOLAB PGSTAT 302N potentiostat/galvanostat.
  • a short copper nanorod current collector segment was grown potentiostatically at -0.7V for 90s.
  • FIGS. 1A-1B Morphological and structural characterization of the Ni-Sn nanowires is shown in FIGS. 1A-1B and 2.
  • FIG. 1 A is an SEM image showing uniform diameter of the Ni-Sn nanowires obtained after dissolving the AAO template.
  • FIG. IB is an EDX spectra of Ni-Sn nanowire confirming the presence of elements Ni and Sn.
  • FIG. 2 shows X-ray diffraction patterns of the Ni-Sn obtained in the Ni-Sn nanowires grown.
  • a copper foil (Nimrod Hall Copper foil company) of thickness 0.025 mm was used as the substrate for electrodeposition of the planar Ni-Sn film.
  • the same Ni-Sn electrolyte solution as used for the nanowire growth was used to grow planar films on the copper foil current collector.
  • the copper foil was cleaned thoroughly with DI water before electrodeposition.
  • planar Ni-Sn bulk film was grown on the copper foil to obtain films of same thickness.
  • FIG. 3A is a schematic showing the fabrication of the novel nanostructured conformal configuration of the electrode/separator assembly.
  • a gold-back coated template 302 can be utilized. Nanowires are electrodeposited into pores of the template 302 as shown in assembly 303. The nanowires can function as individual nanostructured electrodes. The pores are then widened, as shown in assembly 304. A polymer is then infiltrated, such as by drop coating a polymer solution onto the assembly 304 to obtain a polymer layer around the nanowires and yielding a nanostructured conformal hybrid assembly 305.
  • Thickness of PMMA layer can be controlled by tuning the alumina pore- widening step.
  • an entire nanowire was visualized at 24 continuous segments by TEM to confirm the conformal nature of the coating along the length of the nanowire.
  • High magnification images at two different segments of the nanowire shows the Ni-Sn PMMA interface.
  • FIG. 5A a schematic showing the fabrication of the novel nanostructured conformal configuration of the electrode/separator assembly similar to that shown in FIG. 3, except that it further illustrates performing the polymer infiltration step directly assembly 303 (i.e., not including the pore widening step).
  • sequential filling of PMMA in the Ni-Sn nanowire grown template results in the fabrication of ID assembly, while spin-coating of PMMA layer onto the pore widened alumina template results in 3D conformal configuration.
  • FIG. 5B is a TEM image of the 3D configuration (i.e., the "conformal configuration") showing the conformal PMMA layer (—25 nm) around the Ni-Sn nanowire. Similar to as shown in FIG 3B, the high resolution image (inset 502) of FIG. 5B shows a good interface between the thin PMMA layer around the Ni-Sn nanowire. A schematic of a single 3D Ni-Sn/PMMA nanowire assembly 503 is also shown. Again, the thickness of PMMA layer can be controlled by tuning the alumina pore-widening step. FIG.
  • FIG. 5C is a TEM image of the ID configuration (i.e., "multisegmented configuration") showing the planar heterojunction between the Ni-Sn and PMMA segments.
  • a schematic of a single multisegmented Ni-Sn/PMMA nanowire FIG. 5C is a TEM image of the 1 D configuration showing the planar heterojunction between the Ni-Sn and PMMA segments. Schematic of a single multisegmented Ni-Sn/PMMA nanowire 504 is also shown.
  • Ni-Sn/PMMA electrode-electrolyte assemblies with planar (i.e., 2D) and conformal (i.e., 3D) nanostructured configurations were tested for their electrochemical performance in Li half cells by Galvanostatic charge/discharge cycling between 1.5 V and 0.02 V versus Li/Li + , with Ni-Sn as the working electrode.
  • Conformal PMMA layer soaked in liquid electrolyte solution formed the gel electrolyte and separator.
  • nanowires of height 10 ⁇ were electrodeposited in the AAO templates and for the planar configuration a film of same thickness was electrodeposited on a copper foil.
  • the planar and conformal Ni-Sn/PMMA nanostructures were fabricated as follows: After the growth of the Ni-Sn (electrode) nanowires and bulk film, the PMMA based polymer electrolyte/separator was coated onto the electrode. A 2 wt% solution of PMMA in acetonitrile was prepared inside an Argon filled glove box. The PMMA electrolyte was coated onto the Ni-Sn nanowires to obtain two different electrode-electrolyte designs. A thin film of PMMA was coated onto the planar Ni-Sn bulk film by spin coating to obtain the 2D electrode-electrolyte architecture.
  • the Ni-Sn grown AAO template was typically first treated with 0.1 M NaOH for 40 minutes to widen the pores of the template. After the pore widening process the PMMA was drop coated onto the alumina template. After the coating process the template surface was wiped off the excess liquid using a clean tissue paper and dried in vacuum at 25°C for lh. A thin film of PMMA was allowed on top of the template to ensure electrical insulation between the two electrodes.
  • the structure of the conformal configuration was analyzed by Transmission electron microscopy (FEI Quanta 400 ESEM FEG, JEOL 21 OOF). The template was dissolved completely in 3M NaOH to release individual nanowires prior to the electron microscopy characterization.
  • the electrochemical performance of the Ni-Sn/PMMA core-shell nanowires was tested by galvanostatic charge/discharge measurements.
  • an electrochemical test cell was assembled in a Swagelok-type cell inside an Argon-filled glovebox using the Ni-Sn PMMA (planar and conformal configurations) electrode/separator unit as the working and lithium metal foil as the counter/reference electrode.
  • the cathode was made of LiCoO 2 (SIGMA ALDRICH), carbon black and PVDF binder in the weight ratio of 85: 10: 5.
  • the slurry was prepared by mixing the above mixture of LiCoO 2 , carbon black and PVDF in Dimethylformamide thoroughly, followed by casting onto an Aluminium foil (Alfa Aesar, thickness of 0.1 mm).
  • the coated cathode was dried in a vacuum oven at 120°C for 24 hours.
  • the conformal nanostructured Ni-Sn/PMMA array was used as anode/separator unit against the L1C0O 2 cathode.
  • the PMMA film was soaked in 1 M solution of LiPFi in 1 :1 (v/v) mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) for 1 hour prior to assembly of each of the electrochemical cells.
  • FIGS. 6A-6B The potential versus capacity curves for the two electrode-electrolyte configurations (shown in FIGS. 6A-6B) at a current rate of 0.12 mA/cm 2 show typical Li insertion/extraction behavior of tin based intermetallic anodes.
  • Inset 601 in FIG. 6A is a schematic of the planar configuration with the arrows indicating direction of Li ion transport. Li ion transport in these configurations has been schematically illustrated in the respective plots.
  • Inset 602 in FIG. 6B is a schematic of the core-shell morphology of individual nanowires in the conformal configuration with the radial direction of Li ion transport.)
  • FIG. 6C is a graph comparing the cycling behavior of the planar configuration (curve 603) and conformal configuration (curve 604).
  • the thin film based planar configuration showed a reversible capacity of ⁇ 0.002 mAh cm 2 respectively after 10 cycles of charge/discharge, whereas the conformal configuration was able to retain a reversible capacity of ⁇ 0.26 mAh/cm 2 even after 30 cycles of charge/discharge.
  • the novel conformal nanostructured electrode-electrolyte configuration showed an improvement in the reversible capacity by two orders of magnitude. Moving to the third dimension with a conformal nanowire based configuration has resulted in geometrical area gain and an associated electrode volume gain. This leads to shorter transport path for Li ion diffusion between the electrodes.
  • Ni-Sn/PMMA gel electrolyte
  • electrode length of ⁇ 10 urn were galvanostatically cycled in a Li half cell at different current rates of 0.12 mA/cm 2 (0.5C) and 0.3 mA/cm 2 (3C) (curves 701 and 702 in FIG. 7A, respectively)
  • C-rate is defined as the rate at which the nominal capacity of the electrode material is achieved: 1C— 1 hour to discharge the nominal capacity of the cell.
  • a planar electrode-electrolyte assembly with same electrode height (thickness) is also tested for comparison (curves 703 and 704 in FIG. 7A, respectively).
  • Pore density in commercial Alumina template taken to be ⁇ 1E9 pores/cm 2
  • Thickness (Height of nanowire) 10 ⁇
  • Diameter of nanowire 200 nm
  • FIG. 11 A is a TEM image of a PMMA coated Ni-Sn nanowire before cycling (electron diffraction shown in the inset 1101).
  • FIG. 11B is a TEM image after 15 cycles of charge/discharge (electron diffraction shown in the inset 1102).
  • FIGS. 11C-11D are, respectively, TEM images of low and high magnification images after 60 cycles of charge/discharge. Pin hole free PMMA layers intact around individual Ni-Sn nanowires even after extended cycling.
  • FIG. 12 is a graph comparing such cycling characteristics of the PMMA coated Ni-Sn nanowires with home-made Ni-Sn powder with conductive additive and binder cycled at 0.5C rate between 1.5 and 0.02 V. Reversible capacity of ⁇ 200 mAh/g and ⁇ 102mAh/g were observed for the PMMA coated Ni-Sn nanowires and the Ni-Sn powder respectively.
  • Ni-Sn powder was synthesized by electrodepositing (current density 6mA cm 2 ) Ni-Sn nanowires in commercial ANODISC alumina templates and completely dissolving the alumina template in 3M NaOH. The Ni-Sn powder obtained was cleaned several times using deionized water). The results indicated that the PMMA coated Ni-Sn nanowires show an improvement in capacity retained at current rate ⁇ 0.5C.
  • the improved rate capability of the conformal electrode/electrolyte configuration could be due to the direct contact of the nanowires to the current collector substrate and the thinner PMMA separator layer which is lacking in the conventionally (randomly oriented with conductive additive and binder on stainless steel substrate with thick glass microfiber separator) prepared Ni-Sn nanowire electrodes.
  • FIG. 13A is a schematic of full Li-ion cell 1301 constructed using the conformal Ni-Sn/PMMA (anode/electrolyte) assembly 1302 with LiCoO 2 cathode 1303. A thin layer of excess PMMA 1304, coated on top of the assembly serves as the separator.
  • FIG. 13B shows charge-discharge profiles for Ni-Sn/PMMA gel/ LiCoO 2 configuration (Ni-Sn nanowire length ⁇ 10 um) cycled at a rate of 0.05 mA/cm 2 between 2.7 V and 3.95 V using PMMA separator soaked in liquid electrolyte of 1M solution of LiPF 6 in 1 :1 (v/v) mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC). Cycling characteristics of full cell showing a reversible discharge capacity of around 0.15 mAh/cm 2 over 10 cycles of charge/discharge is shown in the inset 1305. An optimized cell assembly with a balanced electrode choice would result in improved cycling performances.

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Abstract

La présente invention concerne un procédé de fabrication pour un revêtement enrobant d'une couche d'électrolyte polymère mince sur des matériaux électrodes nanostructurés pour des applications tridimensionnelles de micro/nanobatterie, des compositions associées, et des dispositifs qui incorporent lesdites compositions. Dans des modes de réalisation, des revêtements enrobants (tels qu'une épaisseur uniforme d'environ 20 à 30 nanomètres) de couches d'électrolyte de polymère de polyméthacrylate de méthyle (PMMA) autour de nanofils individuels de Ni-Sn ont été utilisés en tant qu'anodes pour une batterie au Li-ion. Cette configuration présentait une capacité de décharge élevée et une excellente rétention de capacité même à des taux élevés durant un cyclage prolongé, permettant une augmentation graduée de capacité de surface avec l'épaisseur d'électrode. Il a été démontré que de telles architectures conformes d'anode-électrolyte à nanoéchelle sont un système efficace de batterie au Li-ion.
PCT/US2010/059946 2009-12-10 2010-12-10 Revêtement enrobant sur des matériaux électrodes nanostructurés pour applications tridimensionnelles Ceased WO2011072255A1 (fr)

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CN103066283A (zh) * 2013-01-15 2013-04-24 上海大学 一种制备三维有序大孔结构磷酸锰锂材料的方法
WO2014028853A1 (fr) * 2012-08-16 2014-02-20 The Regents Of The University Of California Micro-batteries 3d à base d'électrolyte à couches minces
US10381651B2 (en) 2014-02-21 2019-08-13 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Device and method of manufacturing high-aspect ratio structures
CN112436151A (zh) * 2020-11-13 2021-03-02 昆明理工大学 一种锂硫电池集流体的制备方法
CN113140452A (zh) * 2021-04-21 2021-07-20 北海惠科光电技术有限公司 氧化铟锡纳米线及其制备方法和薄膜晶体管

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WO2014028853A1 (fr) * 2012-08-16 2014-02-20 The Regents Of The University Of California Micro-batteries 3d à base d'électrolyte à couches minces
CN103066283A (zh) * 2013-01-15 2013-04-24 上海大学 一种制备三维有序大孔结构磷酸锰锂材料的方法
US10381651B2 (en) 2014-02-21 2019-08-13 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Device and method of manufacturing high-aspect ratio structures
CN112436151A (zh) * 2020-11-13 2021-03-02 昆明理工大学 一种锂硫电池集流体的制备方法
CN112436151B (zh) * 2020-11-13 2023-02-03 昆明理工大学 一种锂硫电池集流体的制备方法
CN113140452A (zh) * 2021-04-21 2021-07-20 北海惠科光电技术有限公司 氧化铟锡纳米线及其制备方法和薄膜晶体管

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