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WO2013003846A2 - Collecteurs de courant poreux à isolation de surface sous forme d'électrodes d'électrodéposition sans dendrite - Google Patents

Collecteurs de courant poreux à isolation de surface sous forme d'électrodes d'électrodéposition sans dendrite Download PDF

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Publication number
WO2013003846A2
WO2013003846A2 PCT/US2012/045257 US2012045257W WO2013003846A2 WO 2013003846 A2 WO2013003846 A2 WO 2013003846A2 US 2012045257 W US2012045257 W US 2012045257W WO 2013003846 A2 WO2013003846 A2 WO 2013003846A2
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WIPO (PCT)
Prior art keywords
lithium
current collector
metal
insulated
line
Prior art date
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PCT/US2012/045257
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English (en)
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WO2013003846A3 (fr
Inventor
Galen D. Stucky
Xiulei Ji
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The Regents Of The University Of California
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Publication of WO2013003846A2 publication Critical patent/WO2013003846A2/fr
Publication of WO2013003846A3 publication Critical patent/WO2013003846A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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

  • the present invention relates to spatially heterogeneous 3D current collectors and uses thereof.
  • a metallic lithium anode is energetically attractive in that it can theoretically provide a gravimetric capacity of 3861 mA-hg -1 , more than 10 times that of lithiated carbonaceous anodes (339 mA-hg "1 , for LiC6) at a very negative redox potential (- 3.04 V vs. Standard Hydrogen Electrode).
  • LBs Battery- vs. Standard Hydrogen Electrode
  • metallic lithium electrodes were eventually proven unsafe due to the uneven lithium electrodeposition and the growth of dendrites on the surface of a lithium anode.
  • the dendrites are associated with most of the failure mechanisms of LBs and can lead to a battery thermal runaway.
  • Substitution of metallic lithium with Li ions in insertion materials was an initial attempt to address the dendrite safety concern. This substitution came at the serious expense of energy density loss. This approach led to the tremendous success of lithium-ion batteries (LIBs) in powering portable electronics.
  • LIBs lithium-ion batteries
  • LIBs based on topotactic intercalation electrodes have approached the theoretical energy density for such devices.
  • substantially higher energy storage is required to strategically meet many demands including electrified transportation and load-leveling for intermittent renewable energy sources.
  • High energy Li-sulfur and Li-air batteries have been considered candidates to meet the above goals, but have met with difficulties.
  • Approaches other than intercalation chemistry are necessary to address the long-standing dendrite problem while retaining a high energy metallic form of a lithium electrode.
  • this application addresses, among other things, the dendrite formation problem for the lithium electrodes in rechargeable batteries.
  • the present invention comprises surface dendrite-free lithium deposition created by using spatially heterogeneous 3D current collectors.
  • the present invention confines lithium metal deposition inside the 3D current collectors.
  • the present invention employs, inter alia, controlling the conductive electrolyte-facing surface of the 3D current collectors to control or eliminate the dendrite growth, which provides favorable sites for lithium deposition while retarding dendrite growth and infiltrating the interior voids.
  • the present invention comprises introducing an anisotropic spatial heterogeneity in terms of conductivity for the 3D current collectors by insulating the electrolyte-facing surface while keeping the other parts conductive. This embodiment of the present invention reduces or prevents inter-electrode dendrite growth and forces lithium deposition inside the large voids.
  • an insulating layer is deposited by line-of-sight methods onto the electrolyte-facing surface of highly porous current collectors as lithium electrodeposition electrodes.
  • lithium electrodeposition with no electrons available from the insulating electrolyte facing surface, lithium ions from bulk electrolyte have to migrate deeper into the voids inside porous current collectors in order to be reduced.
  • the deposition process comprises essentially a lithium metal infiltration. With the porous volume of the current collector effectively utilized, the lithium plated current collectors or electrodes maintain a constant volume throughout the depositing/stripping cycles with no dendrites formed on the electrolyte-facing surface.
  • the solution for lithium dendrites herein is fundamentally distinct from state of the art technologies.
  • a line-of-sight surface insulated 3D current collector includes: a) a 3D current collector having an line-of-sight surface including openings, and non-line-of-sight surfaces accessible through the openings; and b) an insulating layer coating the line-of-sight surface, where the insulating layer allows access to the non-line-of-sight surfaces via the openings.
  • the 3D current collector can be, but is not limited to, carbon fiber paper, carbon fiber cloth, carbon nanotube cloth, carbon nanotube coated cellulose paper, graphene coated cellulose paper, 3D carbon nanotube structures, 3D graphene structures, macroporous porous carbon films wherein "macroporous” means pores sized over 50 nm, mesoporous porous carbon films wherein "mesoporous means pores sized between 2 nm to 50 nm, macroporous carbon monoliths, mesoporous carbon monoliths, 3D porous metallic structures made of metals including copper, aluminum, nickel, silver, gold, platinum, titanium, tantalum, iron, niobium, zirconium, chromium, molybdenum, zinc, vanadium, tungsten or beryllium, alloy s/intermetallics including stainless steel, copper alloys, cobalt alloys, nickel alloys, aluminum alloys or titanium alloys, 3D structures made of conducting ceramics including titanium carbides, vanadium
  • the insulating layer can be, but is not limited to, silicon oxide, graphene oxide, silicon carbide, hafnium oxide, zeolite, metal organic-ligand complexes, insulating organic materials including polyethylene oxides, polyethylene glycols, carbon hydrates, cellulose or biomass, metal sulfates, carbon nitride, non-metallic metal nitrides, metal phosphates, non-metallic metal phosphides, metal carbonates, non-metallic metal carbides, metal chlorates, metal fluorides, metal iodides, non- metallic metal arsenides, metal hydroxides, metal sulfides, metal bromides, metal selenides, metal borates, positive temperature coefficient thermistors (PTCT) including metal titanates, metal chromates, insulating ceramics, or other insulating polymeric materials.
  • PTCT positive temperature coefficient thermistors
  • the insulating layer material can be deposited onto the 3D current collector by a line-of-sight method, which can include, but is not limited to, printing, spray coating, electron beam deposition, ion beam deposition, sputtering, thermal evaporation, spin coating, stamping, or line-of-sight chemical vapor deposition.
  • a line-of-sight method can include, but is not limited to, printing, spray coating, electron beam deposition, ion beam deposition, sputtering, thermal evaporation, spin coating, stamping, or line-of-sight chemical vapor deposition.
  • an electrode including the line-of-sight surface insulated 3D current collector is provided.
  • electrodeposition can occur preferentially at the non-line-of-sight surfaces of the 3D current collector or electrode.
  • the electrode can include metallic lithium after electrodeposition.
  • a lithium metal rechargeable battery including the electrode is provided.
  • the lithium metal rechargeable battery includes lithium ion containing positive electrodes to provide lithium ions for the lithium electrodeposition on the spatially heterogeneous current collectors.
  • a battery can be a lithium metal rechargeable battery in certain embodiments.
  • One method is a way of preparing a line-of-sight insulated 3D current collector.
  • the method includes coating an insulating layer onto the line -of- sight surface of a 3D current collector, where the 3D current collector includes openings in the line-of-sight surface and non-line-of-sight surfaces accessible through the openings, and the insulating layer allows access to the non-line-of-sight surfaces via the openings.
  • Another method is a way of performing electrodeposition.
  • the method includes preferentially electrodepositing a metal at non-line-of-sight surfaces of a line-of-sight surface insulated 3D current collector.
  • the metal is lithium.
  • the metals can be sodium, potassium, magnesium, calcium, titanium, vanadium, silicon, tin, zinc, and aluminum.
  • the insulating layer can be coated onto a porous 3D current collector by a line-of-sight method, which can include, but is not limited to, printing, spray coating, electron beam deposition, ion beam deposition, sputtering, thermal evaporation, spin coating, stamping, or line-of- sight chemical vapor deposition.
  • the 3D current collector can be, but is not limited to, carbon fiber paper, carbon fiber cloth, carbon nanotube cloth, carbon nanotube coated cellulose paper, graphene coated cellulose paper, 3D carbon nanotube structures, 3D graphene structures, macroporous porous carbon films wherein "macroporous” means pores sized over 50 nm, mesoporous porous carbon films wherein "mesoporous means pores sized between 2 nm to 50 nm, macroporous carbon monoliths, mesoporous carbon monoliths, 3D porous metallic structures made of metals including copper, aluminum, nickel, silver, gold, platinum, titanium, tantalum, iron, niobium, zirconium, chromium, molybdenum, zinc, vanadium, tungsten or beryllium, alloy s/intermetallics including stainless steel, copper alloys, cobalt alloys, nickel alloys, aluminum alloys or titanium alloys, 3D structures made of conducting ceramics including titanium carbides, vanadium
  • poly(pyrrole)s PPY
  • poly(3,4-ethylenedioxythiophene) PEDOT
  • polythiophenes PT
  • poly(p-phenylene sulfide) PPS
  • the insulating layer can be, but is not limited to, silicon oxide, graphene oxide, silicon carbide, hafnium oxide, zeolite, metal organic ligand complexes, insulating organic materials including polyethylene oxides, polyethylene glycols, carbon hydrates, cellulose or biomass, metal sulfates, carbon nitride, non-metallic metal nitrides, metal phosphates, non-metallic metal phosphides, metal carbonates, non-metallic metal carbides, metal chlorates, metal fluorides, metal iodides, non- metallic metal arsenides, metal hydroxides, metal sulfides, metal bromides, metal selenides, metal borates, positive temperature coefficient thermistors (PTCT) including metal titanates, metal chromates, insulating ceramics, or other insulating polymeric materials.
  • PTCT positive temperature coefficient thermistors
  • a method of depositing metal on a porous substrate in accordance with one or more embodiments of the present invention comprises coating a first surface of the porous substrate with a layer, wherein the first surface remains porous to the metal to be deposited, placing the first surface with the layer facing an electrode, and depositing the metal on the substrate on a second surface of the substrate distinct from the first surface.
  • Such a method further optionally comprises the metal being lithium, the porous substrate being carbon fiber paper, the metal being electrodeposited on the substrate, the layer being silicon dioxide (Si02), silicon carbide (SiC), or SiC and silicon dioxide (Si02), the layer being deposited in a line-of-sight onto the first surface, the deposition of the metal having a reduced dendrite density compared to a porous substrate lacking the layer, and the layer being coated on the porous substrate using electron beam deposition.
  • An insulated three-dimensional (3D) current collector in accordance with one or more embodiments of the present invention comprises a 3D current collector having a line-of-sight surface comprising openings, and non-line-of-sight surfaces accessible through the openings, and an insulating layer coating the line-of-sight surface, the insulating layer allowing access to the non-line-of-sight surfaces via the openings.
  • Such a current collector further optionally comprises lithium being deposited on the non-line-of-sight surfaces, the lithium being deposited on the non-line-of-sight surfaces electrolytically, the insulated 3D current collector being carbon fiber paper, the insulating layer being silicon dioxide (Si02), silicon carbide (SiC), or SiC and silicon dioxide (Si02), the insulating layer being deposited in a line-of-sight onto the line-of-sight surface, the deposition of the metal having a reduced dendrite density compared to a current collector lacking the insulating layer, and the insulating layer being coated on the insulated three-dimensional (3D) current collector using electron beam deposition.
  • preferentially means that electrodeposition of a metal occurs more at non-line-of-sight surfaces of a 3D current collector than at the coated line-of-sight surface of the 3D current collector.
  • Electrodes include electrodes, electrochemical cells and batteries involving, but not limited to, sodium, potassium, magnesium, calcium, titanium, vanadium, silicon, tin, zinc, and aluminum.
  • Figure 1 is a Schematic illustrating the experimental setup of the
  • Figure 2 is a Schematic showing the vial cell setup for the electrochemical characterization studies in accordance with one or more embodiments of the present invention.
  • FIGS. 3a-3f illustrate Scanning Electron Microscope (SEM) images and corresponding Energy Dispersive X-ray (EDX) maps of the Carbon fiber Paper (CP) samples in accordance with one or more embodiments of the present invention.
  • SEM Scanning Electron Microscope
  • EDX Energy Dispersive X-ray
  • Figures 4a-4d illustrate X-ray Photoelectron Spectroscopy (XPS) spectra of the SiC decorated carbon paper samples made in accordance with one or more embodiments of the present invention.
  • XPS X-ray Photoelectron Spectroscopy
  • Figures 5a-5d illustrate SEM images and corresponding EDX maps on SiC- CP samples made in accordance with one or more embodiments of the present invention.
  • Figure 6 is a panel of SEM images of cross-section areas of the lithium deposited CP and Si0 2 -CP samples made in accordance with one or more embodiments of the present invention
  • Figures 7a-7d illustrate SEM images of the cross-section area of the lithium plated SiC-CP samples made in accordance with one or more embodiments of the present invention.
  • Figure 8 illustrates the coulombic efficiency for the lithium
  • FIG. 9 illustrates lithium depositing/stripping profiles on SiC-CP-2 in accordance with one or more embodiments of the present invention.
  • Figures 10a- lOd illustrate the structures of pristine CP and spatially heterogeneous CP (SH-CP), and the different lithium deposition processes on them in accordance with one or more embodiments of the present invention.
  • Figures 11a and 1 lb illustrate characterizations of CP in accordance with one or more embodiments of the present invention.
  • Figure 11a illustrates a wide angle XRD pattern showing the highly graphitic nature of the carbon fibers
  • Figure l ib illustrates a representative SEM image exhibiting the scaffold morphology of the carbon fiber paper in accordance with one or more embodiments of the present invention.
  • Figures 12a-12d illustrates a SEM image and corresponding EDX maps of the non-Si0 2 side of the Si0 2 -CP in accordance with one or more embodiments of the present invention.
  • Figure 13 shows lithium deposition profiles of CP electrodes at 4 mA cm "2 for two hours in accordance with one or more embodiments of the present invention.
  • Figure 14 is a SEM image of the lithium deposited Si0 2 -CP from a wider view, zoomed out from the part in Figure 7a.
  • Figure 15 is a representative SEM image of the Si0 2 -CP after a lithium deposition for two hours at a current rate of 4 mA cm "2 in accordance with one or more embodiments of the present invention.
  • Figure 16 is a representative SEM image of Si0 2 -CP after a lithium deposition for six hours at a current rate of 4 mA cm "2 in accordance with one or more embodiments of the present invention.
  • Figure 17 illustrates a process chart according to one or more embodiments of the present invention.
  • the related art technologies on lithium metal electrodes have been mainly developed in terms of surface protection of lithium metal electrodes.
  • Various methods have been invented for "wrapping" the lithium metal electrodes with various lithium ion conducting layers/membranes.
  • the wrapping strategy has fundamental disadvantages.
  • a crack-free "wrapping" on the depositing/stripping lithium electrodes which go through large morphological changes repeatedly over 2000 cycles, remains to be a substantial challenge. This worries the battery manufactures and potential consumers. Alloying lithium with other metals induces certain chemical stability of lithium electrodes, but does not solve the dendrite problem or the volumetric change problem.
  • the present invention provides spatially heterogeneous three dimensional (3D) current collectors for lithium electrodeposition to address the dendrite problem.
  • Three dimension current collectors recently have attracted some attention due to the power density enhancement to some electrode materials.
  • the hurdle to infiltrate 3D current collectors by lithium electrodeposition is the conducting external surface which provides favorable sites for cathodic reactions.
  • the present invention introduces anisotropic spatial heterogeneity on to 3D current collectors in terms of conductivity for the lithium deposition.
  • heterogeneity is created by an insulating Si02 layer coated on only one side of carbon fiber papers (CP) by a line-of-sight electron-beam deposition method.
  • the Si02 surface of the current collector facing the electrolyte acts as an insulating "roof, and the interior surface of the carbon fiber paper does the current collecting and provide a large accommodation capacity for lithium deposition without volume changes of the electrode.
  • lithium dendrites are prevented from forming on the insulting external surface of a lithium deposition electrode.
  • Figure 1 illustrates the experimental setup of the magnesiothermic reaction to convert Si0 2 -CP to SiC-CP in accordance with one or more embodiments of the present invention.
  • Si0 2 -CP was placed covering an alumina boat with the Si0 2 decorated side facing magnesium power located in the alumina boat.
  • the reaction experimental setup is schematically shown in Figure 1.
  • the Si0 2 decorated (or coated) side of the carbon paper directly faces hot magnesium vapor during the reaction.
  • magnesiothermic reactions are normally carried out at 650-700 °C.
  • the reaction was conducted at 800 °C for 2 hours with an excess of metallic magnesium source under an argon flow, although other temperatures, times, and pressures can be used without departing from the scope of the present invention.
  • the reacted carbon paper samples were soaked in 2M HC1 overnight in order to remove the formed MgO and possible Mg 2 Si.
  • the SiC decorated paper samples (also referred to as substrates herein) were soaked in 50% (weight) HF aqueous solution overnight to remove silicon.
  • Figure 2 illustrates a vial cell setup for the electrochemical studies in accordance with one or more embodiments of the present invention.
  • Electrochemical characterization studies were carried out in vial cells on an EC-lab VMP3 instrument at room temperature. Typically, only one side of the (Si0 2 -) CP electrode is allowed to expose to the electrolyte.
  • the transparent vial cells were deliberately used for the convenience of in situ visual inspection of the dendrite growth during deposition/stripping cycling, which cannot be readily realized with coin or Swagelok cells.
  • the cells were assembled in an argon-filled glove box.
  • the CP electrode loadings were typically ⁇ 5.8 mg (0.5 cm 2 ).
  • Lithium metal foils were used as a counter/reference electrode.
  • a 1.0 M solution of LiPF 6 in a mixture of EC/EMC (3:7, v/v) was used as the electrolyte.
  • the vial cell setup is schematically shown in Figure 2. The working and counter electrodes were soaked in the electrolyte without any pressure applied on them.
  • Si0 2 -CP SiC-CP
  • SiC-CP SiC-CP
  • the copper foil has the same dimensions as the carbon paper electrode, to avoid an electrolyte exposure on the non-Si0 2 (or non-SiC) side.
  • the copper surface opposite to the CP electrodes was shielded by spin coated and dried Na 2 Si0 3 solution.
  • the pristine CP electrode was assembled in the same manner. Voltage is applied between the carbon paper and the lithium foil electrode to allow for electrolytic migration and deposition of the lithium.
  • Other metals and substrates can be used without departing from the scope of the present invention.
  • the CP exhibits many desirable characteristics as a 3D current collector for lithium deposition, including limited surface area, large void volume, and good conductivity. According to N 2 sorption measurements, the CP used in the present invention exhibits a Brunauer-Emmett-Teller (BET) specific surface area of 5.3 m 2 g "1 and a Barrett- Joyner-Halenda (BJH) specific pore volume of 1.2 cm 3 g "1 . It is well known that the parasite reactions between deposited lithium and aprotic solvents/salt anions are inevitable, and they result in a loss of metallic lithium mass in the formation of the Solid Electrolyte Interface/Interphase (SEI) layer, which is typically several tens of nanometers thick.
  • SEI Solid Electrolyte Interface/Interphase
  • FIGS. 3a-3f illustrate Scanning Electron Microscope (SEM) images and corresponding Energy Dispersive X-ray (EDX) maps of the Carbon Paper (CP) samples in accordance with one or more embodiments of the present invention.
  • SEM Scanning Electron Microscope
  • EDX Energy Dispersive X-ray
  • Figures 11a and 1 lb illustrate characterizations of CP in accordance with one or more embodiments of the present invention.
  • Figure 11a illustrates A wide angle XRD pattern showing the highly graphitic nature of the carbon fibers
  • Figure 11 b illustrates a representative SEM image exhibiting the scaffold morphology of the carbon fiber paper in accordance with one or more embodiments of the present invention.
  • the CP demonstrates a scaffold structure, a smooth surface morphology, and the homogeneity of the Si0 2 deposition on the carbon fibers in accordance with one or more embodiments of the present invention.
  • FIGS. 3 a and 3b illustrate SEM images of the CP in accordance with one or more embodiments of the present invention
  • FIGS. 3 c and 3d illustrate SEM images of the Si0 2 -CP in accordance with one or more embodiments of the present invention.
  • FIGS. 3e and 3f illustrate corresponding silicon and carbon EDX maps of the Si0 2 - CP in accordance with one or more embodiments of the present invention.
  • Figures 12a-12d illustrates a SEM image and corresponding EDX maps of the non-Si0 2 side of the Si0 2 -CP in accordance with one or more embodiments of the present invention.
  • Si02 crystals (99.99%) were electron-beam evaporated by an instrument of Airco Temescal (Model CV-8) onto the CP substrates.
  • CP (Model: 2050 A) was purchased from Fuel Cell Store, Inc.
  • Powder X-ray diffraction (XRD) patterns were collected on a Scintag PADX diffractometer with Cu Ka radiation (45 kV, 35 mA).
  • Scanning electron microscopy (SEM) images were acquired on a FEI XL40 Sirion FEG digital scanning electron microscope.
  • the electrodes taken from the vial cells were washed by dry tetrahydrofuran (THF) in an argon-filled glove box to remove the residual electrolytes and later on dried under vacuum at room temperature. Nitrogen sorption isotherms were measured at -196 °C on a Micromeritics Tristars 3000 analyzer. Before measurements, the samples were degassed on a vacuum line at 150 °C overnight.
  • Figure 12a illustrates an illustrative SEM image which confirms a line-of- sight deposition of Si0 2 achieved on the CP by electron beam deposition.
  • Other methods of deposition of Si02 or other materials, onto CP or other equivalent structures, can be used without departing from the scope of the present invention.
  • Figures 12b-12d are corresponding EDX maps showing the energy dispersion for silicon, carbon, and a background element (titanium is shown), respectively.
  • the Si0 2 e-beam evaporation coating was used in accordance with one or more embodiments of the present invention to selectively insulate the line-of-sight (also the electrolyte-facing surface) of the 3D current collector.
  • the line-of-sight process is confirmed in our case by the fact that the silicon energy dispersive X-ray (EDX) map on the non-Si0 2 side of the carbon paper displayed very weak signals close to the background noise (see Figures 12b-12d).
  • the CP After the Si0 2 deposition, the CP turns from gray to a dark-brown color.
  • the SEM image and the corresponding silicon EDX map reveal the homogeneity of the Si0 2 coating as shown in Figures 3c and 3e.
  • the present invention shows that the surface of the carbon fibers when the present invention is applied stays smooth with a pinhole-free Si0 2 deposition as shown in Figure 3d. This indicates impermeability to lithium ions from the electrolyte during lithium deposition. Silicon Carbide Formation on Carbon Paper
  • Figures 4a-4d illustrate X-ray Photoelectron Spectroscopy (XPS) spectra of the SiC decorated carbon paper samples made in accordance with one or more embodiments of the present invention.
  • the present invention formed a SiC coating on the carbon fibers as well, in order to resist the potential HF etching in the electrolytes. It is challenging to form SiC coating on the CP by conventional methods due to its high formation temperatures. Magnesiothermic reactions have been applied in converting a nanoporous silica film into a silicon film.
  • the present invention used a
  • the deconvo luted carbon [Is] signal exhibits the characteristic peak assigned to SiC at 282.5 eV.
  • the Si [2p] signal can be assigned to metallic silicon at 99.0 eV and SiC at 100.1 eV,
  • Figure 4c illustrates a C [Is] signal of SiC-CP-2 deconvo luted into
  • Figure 4d illustrates a Si [2p] signal of SiC-CP-2 centered at 100.1 eV without any contribution from metallic silicon.
  • Figures 5a-5d illustrate SEM images and corresponding EDX maps on SiC-
  • SiC-CP- 1 The CP sample after the magnesiothermic reaction and HF etching is referred to as SiC-CP- 1.
  • Figures 5a and 5b are SEM images that reveal the rough surface morphology of SiC-CP, in contrast to that of the pristine (uncoated or un-decorated) CP and the Si0 2 -CP shown in Figures 3a-3f.
  • Figure 5b is an enlarged image of the inset shown in Figure 5 a.
  • the corresponding silicon EDX map remains intense and homogeneous on the surface of CP as shown in Figure 5c.
  • the roughness is not continuous, indicating an incomplete coverage of SiC on the carbon fiber surface.
  • the Si0 2 coating and magnesiothermic conversion were repeated once upon the SiC-CP-1, although this process could be repeated more than once without departing from the scope of the present invention.
  • the obtained sample is referred to as SiC-CP-2.
  • the line-of- sight surface morphology of SiC-CP-2 is now completely roughened, suggestive of a much better SiC coverage on the designated area of CP.
  • SiC-CP-2 XPS was used to characterize HF etched SiC-CP-2.
  • the minor C [Is] component at 282.5 assigned to the SiC phase from SiC-CP-1 turns into a major component in the C [Is] signal from SiC-CP-2, which confirms a better SiC coverage of SiC-CP-2 than Si-CP- 1.
  • SiC-CP-2 displays a Si [2p] signal centered at 100.1 eV that can be assigned to the SiC phase, without any contribution from metallic silicon.
  • Figure 13 illustrates lithium deposition profiles of CP electrodes at 4 mA cm " 2 for two hours in accordance with one or more embodiments of the present invention.
  • Si0 2 -CP current collector line 1302 are shown.
  • the present invention carried out lithium depositing on pristine CP, Si0 2 -CP,
  • SiC-CP-1 and SiC-CP-2 as working electrodes.
  • the present invention minimized the lithium intercalation reactions into the CP samples and focused on the lithium depositing behavior.
  • a high current density of ⁇ 4 mA cm “2 (330 mA g _1 cp , based on 0.012 g cm "2 for CP) was applied between the working electrode and a lithium counter/reference electrode during the depositing process.
  • This current density represents one of the highest values reported for lithium deposition studies, compared to current densities of less than 1 mA cm "2 in most previous studies.
  • the deposition process was carried out for two hours, and the deposition capacity was set to be 28.8 C cm "2 (or 660 mA-h g _1 cp ).
  • the present invention illustrates one of the largest quantity of lithium deposition compared to previous dendrite -related studies, including those with protection layers in the related art.
  • the deposition on Si0 2 -CP was also done for six hours to approach the limit of the accommodation capacity.
  • the potentials of both CP and Si0 2 -CP electrodes rapidly dropped below 0.0 V vs. Li + /Li, indicating that metallic lithium deposition on the carbon fiber surface had started.
  • Lithium intercalation into carbon is thermodynamically favorable; however, at potentials below 0.0 V vs. Li /Li, lithium plating on carbon surface is kinetically more facile. This leads to the fact that lithium-ion batteries on electric vehicles have to be charged for hours to prevent lithium plating.
  • the deposition and stripping current density was set to be 2 mA cm “2 (or 165 mA g _1 C p), and lithium of 14.4 C cm “2 (or 330 mA g _1 cp) was deposited.
  • the cut-off potential was set to be 3.0 V versus Li + /Li for lithium stripping.
  • Figure 8 illustrates the coulombic efficiency for the lithium
  • Figure 8 reveals the superior disposition performance of the methods and apparatuses of the present invention.
  • Figure 8 is an image of the vial cell containing SiC-CP-2 working electrode and lithium foil counter electrode, taken after 15 cycles, showing the dendrite-free surface of SiC-CP-2 current collector and mossy lithium phase formed around the lithium counter electrode. Note that the low coulombic efficiency in the first cycle is due to SEI formation on the carbon surface, which is widely observed for carbon electrodes in the first discharge/charge cycle.
  • SiC-CP-2 displays a very stable lithium stripping/deposition efficiency of -94% starting with the second cycle. This is one of the highest lithium-cycling efficiencies reported for aprotic organic electrolytes. It is worth stressing that the high efficiency is achieved at a current rate of 2 mA cm “2 and a deep lithium deposition of 14.4 C cm “2 in a carbonate based organic electrolyte, in contrast to previously reported lower efficiencies of around 70%> to 90%> typically obtained by using current rates less than 1 mA cm “2 , a lithium deposition less than 2 C cm “2 , and certain surface protection methods in favorable organic electrolytes. Note that the internal surface area of a 3D current collector is much larger than its footprint area, which is a significant advantage than 2D ones. This could be an important factor that leads to the high coulombic efficiency.
  • the lithium cycling efficiency is strongly influenced by the morphology of the deposited lithium.
  • the high cycling efficiency obtained here corroborates the ex-situ SEM observation that deposited lithium is closely packed in the voids of the 3D current collectors. This clearly illustrates the superiority of the lithium deposition into 3D current collectors as in the present invention that is facilitated by a spatially heterogeneous structure.
  • the lithium counter electrode was covered by isolated mossy lithium
  • the SiC-CP-2 current collector retained a dendrite-free surface.
  • Figure 9 illustrates lithium depositing/stripping profiles on SiC-CP-2 in accordance with one or more embodiments of the present invention.
  • Figure 9 shows the first 15 deposition/stripping cycle profiles plotted on voltage versus time, at a current density of 2 mA cm “2 and a lithium deposition of 14.4 C cm “2 (330 mA-h g " 1 caAon paper ).
  • a lithium cycling efficiency of up to 99.2% can be achieved with ionic liquid based or polymer based electrolytes in the related art.
  • these high efficiencies were obtained at lower current densities and lower lithium deposition rates than those of the present invention.
  • the morphology of the deposited lithium is still highly dendritic.
  • the present invention does not suffer from these infirmities of the related art.
  • Figures 6a-6f illustrate SEM images of cross-section areas of the lithium deposited CP and Si0 2 -CP samples made in accordance with one or more
  • Figure 6a is representative SEM image of lithium deposited on pristine CP.
  • Figure 6b is an enlarged image of the inset of Figure 6a.
  • Figure 6c is representative SEM image showing the surface morphology of the lithium deposited CP and existence of formed dendrites.
  • Figure 6d illustrates a representative SEM image of the lithium deposited Si0 2 -CP made in accordance with one or more embodiments of the present invention.
  • Figures 6e and 6f are enlarged images of inset a and inset ⁇ of Figure 6d. All the images here were taken with the paper specimen stage tilted by 45°. Note that the dendrites readily apparent in Figures 6a-6c are not present in figures 6d-6f.
  • Figures 7a-7d illustrate SEM images of the cross-section area of the lithium plated SiC-CP samples made in accordance with one or more embodiments of the present invention.
  • Figure 7a is an overview image of the cross-section area of SiC-CP-1.
  • Figure 7b is an enlarged image of inset a shown in Figure 7a.
  • Figure 7c is an enlarged image of inset ⁇ of Figure 7a.
  • Figure 7d is a representative SEM image of carbon fibers in the line-of-sight surface of lithium deposited SiC-CP-2. All the images were taken with the paper specimen stage tilted by 45°.
  • the deposited electrodes were examined ex-situ by SEM in order to investigate the "geographical" distribution of the deposited lithium metal.
  • the SEM specimen stage was tilted by 45° in order to show both the cross-section and the adjacent face area of the lithium metal deposited CP electrodes.
  • the cross-section of lithium metal deposited CP electrode displays a uniform morphology of carbon fibers as shown in Figures 6a and 6b. It is evident that lithium metal deposition did not infiltrate the voids of pristine CP.
  • Figure 6c reveals a representative area on the CP surface with large lithium metal dendrites over 20 ⁇ in size and small lithium metal crystals homogeneously distributed.
  • the pristine CP electrode functions essentially as a two-dimensional current collector.
  • the voids near the bottom of the Si0 2 -CP were well infiltrated by lithium metal deposition.
  • the surface morphology of the Si0 2 decorated area near the cross-section remains very smooth and free of deposited lithium crystallites or dendrites, as shown in Figure 6f. This indicates that the Si0 2 coating is impermeable to lithium ions and has successfully created an insulating roof for the 3D current collector.
  • Figure 14 is a SEM image of the lithium deposited Si0 2 -CP from a wider view, zoomed out from the part in Figure 7a.
  • a zoom-out view under SEM confirms that the surface of deposited Si0 2 - CP is completely free of lithium dendrites and that the voids near the top surface are also free of lithium infiltration as shown in Figure 14.
  • the lithium metal deposition into the Si0 2 -CP fills up the voids from the non-silica to the silica side, which is facilitated by the conducting copper foil support on the non-Si0 2 surface of the electrode and, more importantly, by the anisotropic structure of the current collector.
  • the surface is free of dendrites and the voids near the top surface are free of lithium infiltration.
  • the image was taken with the paper specimen stage tilted by 45°.
  • Figure 15 is a representative SEM image of the Si0 2 -CP after a lithium deposition for two hours at a current rate of 4 mA cm "2 in accordance with one or more embodiments of the present invention.
  • lithium deposition occurs on the conducting carbon surface which is oppositely oriented towards the Si0 2 coated electrode surface.
  • the top part of the carbon fiber coated with a Si0 2 layer is free of lithium deposition, and the bottom part without Si0 2 is covered with lithium deposition.
  • the image was taken with the paper specimen stage tilted by 45°.
  • Figure 16 is a representative SEM image of Si0 2 -CP after a lithium deposition for six hours at a current rate of 4 mA cm "2 in accordance with one or more embodiments of the present invention.
  • the deposited lithium provided a capacity of 71.3 C cm “2 (or 1980 mA-h g _1 C p), which is near (79%) 90 C cm “2 (2500 mA-h g _1 C p), the theoretical accommodation capacity calculated based on the specific pore volume and lithium metal density.
  • Further deposition on a fully infiltrated 3D current collector may result in the dendrite growth on the filled paper top surface. Therefore, it is important to prevent an over- infiltration during the deposition cycle in practical scenarios.
  • the spatially controlled lithium deposition resembles in some degree the single-crystal growth of calcium carbonate in the assembly process that generates the abalone cell. Compared to the deposition on pristine CP, the surface Si0 2 coating effectively realizes the proposed function of a spatially heterogeneous structure.
  • Figures 10a- lOd illustrate the structures of pristine CP and spatially
  • heterogeneous CP (SH-CP)
  • the different lithium deposition processes on them in accordance with one or more embodiments of the present invention.
  • Figure 10a illustrates pristine CP.
  • Figure 10b illustrates SH-CP, where anisotropic spatial heterogeneity is achieved after a line-of-sight deposition of Si0 2 onto the carbon fibers. Areas 2 indicate a Si0 2 or SiC coating, and black areas 4 represent uncovered conducting carbon surface.
  • Figure 10c illustrates the situation of lithium deposition on CP, mostly on the line-of-sight surface, as shown by spheres 6, which represent the lithium atoms.
  • Figure 6d illustrates lithium
  • Lithium electrodeposition does not take place on the insulating line-of-sight surface, but is driven by the electric field towards voids of the current collector.
  • insulating/conducting properties of the CP can be obtained after the Si0 2 electron- beam deposition.
  • the same spatial heterogeneity can be maintained by converting Si0 2 into SiC atop the carbon paper surface.
  • This anisotropic spatial heterogeneity is essential in order to achieve surface dendrite-free lithium deposition on the Si0 2 -CP or SiC-CP current collectors, as schematically shown in Figure lOd.
  • the electrode With the large porous volume of the current collector effectively utilized by lithium deposition, the electrode maintains a constant volume upon deposition.
  • due to the scaffold-like structure of the carbon paper disintegration of deposited lithium cannot occur inside the paper in the presence of nearby 3D electric contacts at a high depositing rate.
  • the stable lithium cycling efficiency of 94% achieved in SiC-CP-2 in a carbonate based organic electrolyte further demonstrates the superiority of the anisotropic spatial heterogeneity of the 3D current collector.
  • Figure 17 illustrates a process chart according to one or more embodiments of the present invention.
  • Box 1700 illustrates coating a first surface of the porous substrate with a layer, wherein the first surface remains porous to the metal to be deposited.
  • Box 1702 illustrates placing the first surface with the layer facing an electrode.
  • Box 1704 illustrates depositing the metal on the substrate on a second surface of the substrate distinct from the first surface.
  • the teachings of the present invention address the dendrite formation problem in a fundamentally new concept via rationally designed current collectors with heterogeneous properties.
  • 3D architectures such as carbon cloth, carbon nanotube infiltrated papers and those made with copper, aluminum or conducting ceramics should show similar performances and are contemplated within the scope of the present invention.
  • Other systems with metallic electrodes, e.g. sodium, magnesium, calcium, aluminum or zinc batteries may be benefited from this method as well, and are also contemplated within the scope of the present invention.
  • an insulated 3D current collector in accordance with one or more embodiments of the present invention can comprise carbon fiber paper, carbon fiber cloth, carbon nanotube cloth, carbon nanotube coated cellulose paper, graphene coated cellulose paper, 3D carbon nanotube structures, 3D graphene structures, macroporous porous carbon films wherein "macroporous” means pores sized over 50 nm, mesoporous porous carbon films wherein "mesoporous means pores sized between 2 nm to 50 nm, macroporous carbon monoliths, mesoporous carbon monoliths, 3D porous metallic structures made of metals including copper, aluminum, nickel, silver, gold, platinum, titanium, tantalum, iron, niobium, zirconium, chromium, molybdenum, zinc, vanadium, tungsten or beryllium, alloy s/intermetallics including stainless steel, copper alloys, cobalt alloys, nickel alloys, aluminum alloys or titanium
  • poly(pyrrole)s PPY
  • poly(3,4-ethylenedioxythiophene) PEDOT
  • polythiophenes PT
  • poly(p-phenylene sulfide) PPS
  • the 3D current collector of one or more embodiments of the present invention can comprise a layer that is insulating or non-insulating, and, where insulating, can comprise silicon oxide, graphene oxide, silicon carbide, hafnium oxide, zeolite, metal organic-ligand complexes, insulating organic materials including polyethylene oxides, polyethylene glycols, carbon hydrates, cellulose or biomass, metal sulfates, carbon nitride, non-metallic metal nitrides, metal phosphates, non- metallic metal phosphides, metal carbonates, non-metallic metal carbides, metal chlorates, metal fluorides, metal iodides, nonmetallic metal arsenides, metal hydroxides, metal sulfides, metal bromides, metal selenides, metal borates, positive temperature coefficient thermistors (PTCT) including metal titanates, metal chromates, insulating ceramics, or other insulating polymeric materials, and can be applied or deposited by a line-
  • a method of preparing an insulated 3D current collector in accordance with one or more embodiments of the present invention comprises coating an insulating layer onto an line-of-sight surface of a 3D current collector, wherein the 3D current collector comprises openings in the line-of-sight surface and non-line-of-sight surfaces accessible through the openings, and the insulating layer allows access to the non-line-of-sight surfaces via the openings.
  • a method of electrodeposition in accordance with one or more embodiments of the present invention comprises preferentially electrodepositing a metal at non-line-of- sight surfaces of an insulated 3D current collector.
  • Such methods further optionally comprise the insulated 3D current collector comprises a 3D current collector having a line-of-sight surface comprising openings, the non-line-of-sight surfaces being accessible through the openings, and an insulating layer coating the line-of-sight surface, the insulating layer allowing access to the non- line-of-sight surfaces via the openings, where the line-of-sight surface is coated by a line-of-sight method, and the line-of-sight method is printing, spray coating, electron beam deposition, ion beam deposition, sputtering, thermal evaporation, spin coating, stamping, or line-of-sight chemical vapor deposition.
  • Such methods further optionally comprise the insulating layer being silicon oxide, graphene oxide, silicon carbide, hafnium oxide, lithium phosphorous oxynitride (LIPON), zeolite, metal organic-ligand complexes, insulating organic materials including polyethylene oxides, polyethylene glycols, carbon hydrates, cellulose or biomass, metal sulfates, carbon nitride, non-metallic metal nitrides, metal phosphates, non-metallic metal phosphides, metal carbonates, non-metallic metal carbides, metal chlorates, metal fluorides, metal iodides, nonmetallic metal arsenides, metal hydroxides, metal sulfides, metal bromides, metal selenides, metal borates, positive temperature coefficient thermistors (PTCT) including metal titanates, metal chromates, insulating ceramics, or other insulating polymeric materials, and further optionally comprise the 3D current collector being carbon fiber paper, carbon cloth, carbon nanotube coated paper, graph

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Abstract

La présente invention concerne un dispositif, un appareil et un procédé qui comprennent un collecteur de courant 3D à isolation de surface en visibilité directe. Le collecteur de courant 3D à isolation de surface en visibilité directe comporte un collecteur de courant 3D ayant une surface en visibilité directe dotée d'ouvertures, ainsi que des surfaces sans visibilité directe accessibles par le biais des ouvertures, et il présente une couche isolante qui recouvre la surface en visibilité directe, ladite couche isolante permettant d'accéder aux surfaces sans visibilité directe par l'intermédiaire des ouvertures. Le collecteur de courant 3D isolé peut être utilisé dans des électrodes, des cellules électrochimiques et des batteries rechargeables où l'électrodéposition d'un métal se produit lors du processus de charge. La présente invention se rapporte à des procédés de fabrication du collecteur de courant 3D isolé ainsi qu'à des procédés d'électrodéposition utilisant ledit collecteur de courant 3D isolé.
PCT/US2012/045257 2011-06-30 2012-07-02 Collecteurs de courant poreux à isolation de surface sous forme d'électrodes d'électrodéposition sans dendrite WO2013003846A2 (fr)

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JP2020501305A (ja) * 2016-12-06 2020-01-16 ナショナル インスティテュート オブ フォレスト サイエンスＮａｔｉｏｎａｌ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｆｏｒｅｓｔ Ｓｃｉｅｎｃｅ 紙集電体、その製造方法およびこれを含む電気化学素子
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