WO2019191787A2 - Électrolytes à l'état solide à canaux ioniques biomimétiques pour batteries et leurs procédés de fabrication - Google Patents

Électrolytes à l'état solide à canaux ioniques biomimétiques pour batteries et leurs procédés de fabrication Download PDF

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WO2019191787A2
WO2019191787A2 PCT/US2019/034104 US2019034104W WO2019191787A2 WO 2019191787 A2 WO2019191787 A2 WO 2019191787A2 US 2019034104 W US2019034104 W US 2019034104W WO 2019191787 A2 WO2019191787 A2 WO 2019191787A2
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lpc
electrolyte
metal
lithium
solid
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WO2019191787A3 (fr
WO2019191787A8 (fr
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Jianguo Xu
Yunfeng Lu
Li Shen
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Ford Cheer International Limited
The Regents Of The University Of California
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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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M10/056—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
    • 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

  • This present invention relates generally to batteries, and more particularly to solid electrolytes with biomimetic ionic channels and composite electrolyte membranes for batteries and methods of making the same.
  • Li- metal offers the highest capacity (3860 mA h g ') among anode materials for lithium-based batteries [1]
  • Adapting Li- metal anodes may substantially improve energy density, but has been hampered by its reactions with liquid electrolytes and instability of the resulted solid electrolyte interphase (SEI) layers [2].
  • SEI solid electrolyte interphase
  • Ceramic electrolytes generally exhibit ionic conductivity below KG 4 S cnr 1 , which may be improved by tuning their phase structure and composition [10].
  • their implementation has encountered critical challenges, such as unsatisfactory electrochemical stability, sensitivity to moisture and oxygen, poor interfacial contact with electrodes, and high grain boundary resistance [11-15].
  • critical challenges such as unsatisfactory electrochemical stability, sensitivity to moisture and oxygen, poor interfacial contact with electrodes, and high grain boundary resistance [11-15].
  • reducing interfacial resistance e.g., by depositing aluminum oxide on solid electrolytes using an atomic layer deposition technique
  • Polymeric electrolytes usually exhibit ionic conductivity on the order of KG 5 S enr 1 at room temperature.
  • enhanced ionic conductivity (up to 10 3 S enr 1 ) may be achieved by doping the electrolytes with extra liquid electrolyte or inorganic additives [17], the doping process generally decreases mechanical strength and the ability of the electrolytes to block dendrite growth.
  • One of the objectives is to provide a novel class of solid-state electrolytes with biomimetic ionic channels as ionic conductors for electrochemical devices, e.g., batteries.
  • this is achieved by complexing the anions of an electrolyte to the open metal sites (OMSs) of metal-organic frameworks (MOFs), which renders the MOF scaffolds into ionic- channel analogs with fast lithium-ion conductivity and low activation energy.
  • OMSs open metal sites
  • MOFs metal-organic frameworks
  • the solid-state electrolyte includes a composite
  • MOFs synthesized from an MOF material soaked in a liquid electrolyte, the MOFs being a class of crystalline porous solids constructed from metal cluster nodes and organic linkers.
  • the MOF material prior to soaking it into the a liquid electrolyte , is activated under vacuum at a temperature greater than 150 °C for a period of time, e.g., overnight, so that the activated MOF material comprises OMSs that are corresponding to unsaturated metal centers created by activating pristine MOFs to remove guest molecules or partial ligands thereof.
  • the MOF material comprises HKUST-l having a formula of
  • CU 3 (BTC)2 MIL- 100- Al having a formula of Al 3 0(0H)(BTC) 2 , MIL-lOO-Cr having a formula of Cr 3 0(0H)(BTC) 2 , MIL-lOO-Fe having a formula of Fe 3 0(0H)(BTC) 2 , UiO-66 having a formula of Zr 6 04(0H)4(BDC)6, or UiO-67 having a formula of Zr 6 04(0H)4(BPDC)6, wherein BTC is a benzene-l,3,5-tricarboxylic acid, BDC is a benzene- l,4-dicarboxylic acid, and BPDC is a biphenyl-4,4 '-dicarboxy lie acid.
  • BTC is a benzene-l,3,5-tricarboxylic acid
  • BDC is a benzene- l,4-dicarboxylic
  • the liquid electrolyte comprises one or more non-aqueous solvents and metal salts dissolved in the one or more non-aqueous solvents.
  • the one or more non- aqueous solvents are selected to match the surface properties of the MOF material.
  • the metal salts are selected to have anions with desired sizes, which depends, at least in part, upon the MOF material, wherein the anion sizes are selected to ensure that the salts to infiltrate into at least some of the pores of the MOFs, and become immobilized therein to form the ionic conducting channels.
  • the non-aqueous liquid electrolyte solvents comprise ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC), fluoroethylene carbonate (FEC), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), methylpropyl carbonate (MPC), butylmethyl carbonate (BMC), ethylpropyl carbonate (EPC), dipropyl carbonate (DPC), cyclopentanone, sulfolane, dimethyl sulfoxide, 3-methyl- l,3-oxazolidine-2-one, g-butyro lactone, l,2-di-ethoxymethane,
  • tetrahydrofuran 2-methyltetrahydrofuran, l,3-dioxolane, methyl acetate, ethyl acetate, nitromethane, 1, 3-propane sultone, g- valero lactone, methyl isobutyryl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, diethyl oxalate, an ionic liquid, chain ether compounds including at least one of gamma butyro lactone, gamma valero lactone, l,2-dimethoxyethane and diethyl ether, cyclic ether compounds including at least one of tetrahydrofuran, 2-methyltetrahydrofuran, l,3-dioxolane and dioxane, or a combination thereof.
  • the metal salts comprise one or more of a lithium (Li) salt, a sodium (Na) salt, a magnesium (Mg) salt, and a zinc (Zn) salt,
  • the liquid electrolyte comprises L1CIO4 and propylene carbonate, denoted as LPC.
  • the method for fabricating a solid-state electrolyte usable for ionic conductor for an electrochemical device includes: providing an MOF material, the MOFs being a class of crystalline porous solids constructed from metal cluster nodes and organic linkers; activating the MOF material under vacuum at a temperature greater than 150 °C for a period of time; soaking the activated MOF material in a liquid electrolyte to form a mixture; and filtrating the mixture and removing any excessive solvent to obtain the solid-state electrolyte in a free-flowing power form.
  • the period of time is more than 12 h.
  • the method of further comprises pressing the power into pellets.
  • the activated MOF material comprises OMSs that are corresponding to unsaturated metal centers created by activating pristine MOFs to remove guest molecules or partial ligands thereof.
  • the MOF material comprises HKUST-l having a formula of CU 3 (BTC)2, MIL- 100- Al having a formula of Al 3 0(0H)(BTC) 2 , MIL-lOO-Cr having a formula of Cr 3 0(0H)(BTC) 2 , MIL-lOO-Fe having a formula of Fe 3 0(0H)(BTC) 2 , UiO-66 having a formula of Zr 6 04(0H)4(BDC)6, or UiO-67 having a formula of Zr 6 04(0H)4(BPDC)6, wherein BTC is a benzene-l,3,5-tricarboxylic acid, BDC is a benzene- l,4-dicarboxylic acid, and BPDC is a biphenyl-4,4 '-dicarboxy lie acid.
  • BTC is a benzene-l,3,5-tricarboxylic acid
  • BDC is a
  • the liquid electrolyte comprises one or more non-aqueous solvents and metal salts dissolved in the one or more non-aqueous solvents, wherein the one or more non- aqueous solvents are selected to match the surface properties of the MOF material; and the metal salts are selected to have anions with desired sizes, which depends, at least in part, upon the MOF material, wherein the anion sizes are selected to ensure that the salts to infiltrate into at least some of the pores of the MOFs, and become immobilized therein to form the ionic conducting channels.
  • the liquid electrolyte comprises LPC.
  • a composite electrolyte membrane usable for ionic conductor for an electrochemical device includes the solid-state electrolyte as disclosed above; and a binder mixed with the solid-state electrolyte.
  • a concentration of the binder is in a range of 5-20 wt.% of the composite electrolyte membrane.
  • the binder comprises poly-propylene (PP), poly-ethylene (PE), glass fiber (GF), polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyallylamine (PAH), polyurethane, polyacrylonitrile (PAN), polymethylmethacrylate (PMMA), polytetraethylene glycol diacrylate, or copolymers thereof.
  • an electrochemical device has the composite electrolyte membrane as disclosed above; a positive electrode; and a negative electrode, wherein the composite electrolyte membrane is disposed between the positive electrode and the negative electrode.
  • the electrochemical device is a lithium (Li) battery, a sodium (Na) battery, a magnesium (Mg) battery, or a zinc (Zn) battery.
  • the positive electrode of the Li battery includes at least one of L1C0O2 (LCO), LiNiMnCo0 2 (NMC), lithium iron phosphate (LiFePCL), lithium
  • LMFePCLF ironfluorophosphate
  • LPFePCLF spinel lithium manganese oxide
  • LiM CL lithium cobalt oxide
  • LiNio.5Mn1.5O4 lithium nickel cobalt aluminum oxide
  • LiV2O5 lithium vanadium oxide
  • Li 2 MSi0 4 wherein M is composed of any ratio of Co, Fe, and/or Mn, and a material that undergoes lithium insertion and deinsertion.
  • the negative electrode of the Li battery includes at least one of Li metal, graphite, hard or soft carbon, graphene, carbon nanotubes, titanium oxide, silicon (Si), tin (Sn), germanium (Ge), silicon monoxide (SiO), silicon oxide (S1O2), tin oxide (Sn0 2 ), transition metal oxide, and a material that undergoes intercalation, conversion or alloying reactions with lithium.
  • he positive electrode of the Na battery includes at least one of NaMnCL, NaFeP0 4 , and Na3V2(P0 4 )3.
  • the positive electrode of the Mg battery includes at least one of TiSc2, MgFeP0 4 F, MgCo 2 0 4 , and V2O5.
  • the positive electrode of the Zn battery includes at least one of g-Mh0 2 , ZnMn 2 0 4 , and Zn nC
  • the negative electrodes of the Na, Mg and Zn batteries include Na metal, Mg metal, and Zn metal, respectively.
  • FIGS. 1A-1D show schematic illustrations of the biomimetic ionic channels in MOFs, according to embodiments of this invention.
  • FIG. 1A shows a Na + -ions channel in biological systems with negatively charged glutamate ions [18].
  • FIG. 1B shows a structure of HKUST-l made from copper nodes (blue) and BTC ligands (black) with pore channels of about 1.1 nm.
  • FIG. 1C shows a schematic showing the formation of biomimetic ionic channels in HKUST-l with C10 4 anions bound to the OMSs and solvated Li + ions in the channels with high
  • FIG. 1D shows a schematic of biomimetic ionic channels in a MOF scaffold (dark gray) with bound C10 4 ions (cyan dots), enabling fast transport of solvated Li + ions (purple dots).
  • FIGS. 2A-2D show structure characterizations and lithium ion conductivity of
  • FIG. 2A shows a SEM image of HKUST-l particles (insets: photographs of pristine HKUST-l, activated HKUST-l, and LPC@HKUST-l electrolyte).
  • FIG. 2B shows XRD patterns of pristine HKUST-l, activated HKUST-l, and LPC@HKUST-l electrolyte.
  • FIG. 2C shows Nyquist plots of various
  • LPC@MOFs electrolytes at ambient temperature ⁇ : LPC@MIL-lOO-Al, o: LPC@MIL-l00-Fe, V: LPC@UiO-67, B: LPC@HKUST-l, O: LPC@MIL-l00-Cr, D: LPC@UiO-66.
  • FIG. 2D shows Arrhenius plots of various LPC@MOFs electrolytes and their calculated activation energies for lithium-ion conduction.
  • LiPONLi 3.5 P0 3 No .5 2) polymeric electrolytes (FiCl0 4 /PE0 with Ti0 2 additive [17], LiTFSI-PC in crosslinked Si0 2 -PE0 composites, and single ion polymer P(STFSILi)-PEO-P(STFSILi)), and 3) liquid-in-solid lithium-ion conductors, including liquid electrolyte @mesoporous silica, LiPF 6 - EC/DMC/DEC @ S i0 2 [30], LPC@organic porous solids, CB[6] 0.4LiClO 4 -3.4PC [31], Li alkoxide@MOFs, Mg 2 (dobdc) 0.35LiO 1 Pr 0.25LiBF 4 -EC DEC [23], and ionic liquid@MOFs, (EMIo . sLio . 2) TFSA@ZIF-67 [32]; and 4) liquid electrolyte, 1 M
  • FIGS. 3A-3D show spectroscopic investigation of FPC@MOFs electrolytes, according to embodiments of this invention.
  • FIG. 3 A shows Raman spectra of PC, FPC, PC@HKUST-l, and FPC@HKUST-l.
  • FIG. 3B shows FT-IR spectra of PC, FPC, PC@HKUST-l, and
  • FIG. 3C shows Raman spectra of PC @MOF-5 and FPC @MOF-5.
  • FIG. 3D shows comparisons of the activation energies of four FPC@MOFs electrolytes (FPC@HKUST- 1, FPC@UiO-66, FPC@UiO-67, and FPC@MOF-5) and two liquid-in-solid conductors ((LPC@CB[6] [31] and LPC@MCM-48) vs. their pore sizes, indicating the effect of pore size and OMS on their activation energy.
  • the pore size of LPC@UiO-66 and LPC@UiO-67 are averaged based the pore diameter of their bi-continuous pore channels.
  • FIGS. 4A-4J show electrochemical performance of LPC@MOF electrolyte and prototype lithium-based batteries, according to embodiments of this invention.
  • FIG. 4A shows a cyclic voltammetry (CV) comparison between LPC@UiO-67 pellet and LPC electrolytes.
  • FIG. 4B shows a flammability test of an LPC@UiO-67 electrolyte pellet.
  • FIG. 4C shows a photograph of an LPC@UiO-67/PTFE membrane (denoted as LPC@UM) next to a coin cell (inset shows a bent LPC@UM).
  • FIG. 4D shows SEM images of LPC@UM (top-left: cross-sectional view).
  • FIG. 4A shows a cyclic voltammetry (CV) comparison between LPC@UiO-67 pellet and LPC electrolytes.
  • FIG. 4B shows a flammability test of an LPC@UiO-67 electrolyte pellet.
  • FIG. 4C shows
  • FIG. 4E shows current-time profile for LilLPC@UMILi cell at 20 mV of polarization (inset: impedance spectra at initial and steady states).
  • FIG. 4F shows Li symmetric cell test comparison between LPC@UM and LPC at a current density of 0.125 mA cnr 2 (0.25 mAh cm 2 ).
  • FIG. 4H shows long-term cycling stability of prototype LiFcPOdLUTFOii batteries with LPC@UM electrolyte and LPC liquid electrolyte at 5 C (first two cycles at 1 C).
  • FIG. 41 shows DC miropolarization of LilLPC@UMILi cell from 2.5 to 50 uA cm 2 .
  • FIG. 4J shows Li symmetric cell test comparison between LPC@UM and LPC at a current density of 0.125 mA cm 2 (0.25 mAh cm 2 ).
  • FIG. 5 shows N 2 adsorption/desorption isotherms of HKUST-l and LPC@HKUST-l electrolyte, according to embodiments of this invention.
  • FIG. 6 shows enlarged XRD patterns of as-prepared HKUST-l (black), activated
  • HKUST-l blue
  • LPC@HKUST-l red
  • the coordination status of guest molecules on Cu 11 metal sites is indicated by the 2Q peak at 5.8°, according to embodiments of this invention.
  • FIG. 7 shows a TGA curve of LPC@HKUST-l electrolyte in air, according to
  • LPC@HKUST-l is determined as Cu 3 (BTC) 2 (LiCl0 4 ) 2.
  • s(PC) x the remaining weight (26.1%) corresponds to a mixture of CuO and LiCl, and the value of x can be deduced from the following equation:
  • FIG. 8 shows SEM image of a pressed LPC@HKUST-l pellet used for the conductivity studies (inset of FIG. 4A: a photograph of an electrolyte pellet), according to embodiments of this invention.
  • FIG. 9A shows Nyquist plots of LPC@HKUST-l as a function of temperature, according to embodiments of this invention.
  • FIG. 9B shows N 2 adsorption/desorption isotherms of pyridine @HKUST-l, according to embodiments of this invention.
  • FIG. 9C shows Arrhenius plot of LPC@pyridine@HKUST-l (inset: Nyquist plot of LPC- pyridine@HKUST-l at room temperature), according to embodiments of this invention.
  • FIG. 10A shows a structure representation of two types of mesoporous cages in MIL- 100 serial MOFs, according to embodiments of this invention.
  • FIG. 10B shows an illustration of OMS evolution in a metal trimer unit of MIL- 100 serial MOFs (orange atoms Al/Cr/Fe, red atoms O, grey atoms C, green atoms anionic ligands), according to embodiments of this invention.
  • FIGS. 10C-10H show characterizations of synthesized MIL- 100 serial MOFs, according to embodiments of this invention.
  • FIG. 10C shows XRD patterns.
  • FIG. 10D shows N 2 adsorption/desorption isotherms. The analogous isotherms confirm the similar porous structure of the MIL- 100 serial MOFs. There is a large non- negligible N 2 adsorption at relative high pressure for MIL-lOO-Cr, which corresponds to large interparticular porosity and is expected to be eliminated during preparation of electrolyte pellet.
  • FIG. 10E shows FT-IR spectra together with the XRD patterns confirm the successful synthesis of isostructural MIL- 100 materials.
  • FIG. 10F shows a SEM image of MIL- 100- Al.
  • FIG. 10G shows a SEM image of MIL-lOO-Cr.
  • FIG. 10H shows a SEM image of MIL-lOO-Fe.
  • FIG. 11A shows a topology structure of UiO-(66/67) serial MOFs, the purple polyhedra represent inorganic Zr 6 0 4 (0H) 4 clusters, the grey sticks manifest organic linkers (BDC and BPDC for UiO-66 and UiO-67, respectively), according to embodiments of this invention.
  • FIG. 11B shows a schematic illustration for activation of UiO-(66/67) serial MOFs (purple: Zr, red: O, blue: H), according to embodiments of this invention.
  • OMSs are created by dehydration of Zr 6 04(0H)4 units.
  • FIGS. 11C-11E show characterizations of synthesized UiO-66, according to embodiments of this invention.
  • FIG. 11C shows XRD patterns. Insets show the crystal structures of the corresponding MOFs.
  • FIG. 11D shows N 2 adsorption/desorption measurements.
  • FIGS. 11E shows a SEM image.
  • FIGS. 11F-11H show characterizations of synthesized UiO-67, according to
  • FIG. 11F shows XRD patterns. Insets show the crystal structures of the corresponding MOFs.
  • FIG. 11G shows N 2 adsorption/desorption measurements.
  • FIG. 11H shows a SEM image.
  • FIG. 12A shows FT-IR spectra of pristine UiO-66, activated UiO-66 and LPC@UiO-66, according to embodiments of this invention.
  • FIG. 12B shows FT-IR spectra of pristine UiO-67, activated UiO-67 and LPC@UiO-67, according to embodiments of this invention.
  • FIG. 13 shows an Arrhenius plot of LPC liquid electrolyte and calculated activation energy for ionic conduction, according to embodiments of this invention.
  • FIG. 14A shows FT-IR spectra of PC and 1MLPC, according to embodiments of this invention.
  • FIG. 14B shows FT-IR spectra of PC @HKUST-l and LPC@HKUST-l, according to embodiments of this invention.
  • FIG. 15 shows FT-IR spectra of Cu(C10 4 ) 2 6H 2 0 and Cu(Cl0 4 ) 2 L;H 2 0, where 2 ⁇ r ⁇ 4, according to embodiments of this invention.
  • FIG. 16A shows cubic structure of MOF-5 (Zn 4 0(BDC) 3 ) in a ball-and-stick model (purple: Zn, red: oxygen, black: carbon), in which oxo-centered (m 4 -0) Zn 4 tetrahedra are interconnected through BDC to yield a highly porous framework with pore aperture of 8 A and pore diameter of 12 A [75, 76].
  • FIG. 16B shows N 2 adsorption/desorption isotherms of MOF-5, according to
  • the pristine MOF-5 exhibits higher BET surface area of 1810 m 2 g 1 and pore volume of 0.75 cm 3 g 1 compared with HKUST-l.
  • FIG. 16C shows a SEM image of MOF-5, according to embodiments of this invention.
  • FIG. 16D shows XRD patterns of simulated, pristine, activated, and LPC infiltrated MOF-5, according to embodiments of this invention.
  • the major crystal structure is unaltered, except for the change of a few peak intensities due to the presence of guest molecules [77].
  • FIG. 17 shows Arrhenius plots of LPC@CB[6] [78], LPC@MOF-5, and LPC@MCM- 48.
  • the plot of LPC@CB[6] is linearly fitted based on conductivity data reported in the reference, resulting in an activation energy different from the reported value.
  • FIGS. 18A-18B show synthesized MCM-48 mesoporous silica, according to
  • FIG. 18A shows N 2 adsorption/desorption isotherms.
  • FIG. 18B shows BJH pore size distribution.
  • MCM-48 was prepared according to a method reported in the literature [79].
  • FIG. 19A shows CVs of LPC@HKUST-l, according to embodiments of this invention.
  • FIG. 19B shows CVs of LPC@UiO-66, according to embodiments of this invention.
  • FIG. 20A shows a flammability test for a PP separator saturated with LPC, according to embodiments of this invention.
  • FIG. 20B shows a flammability test for an LPC@UiO-67 electrolyte pellet, according to embodiments of this invention.
  • FIGS. 21A-21E show Li symmetric cell comparison between LPC@UM electrolyte and LPC at (FIGS. 21A-21C) 0.25 mAh cm 2 (0.125 mA cm 2 , red: LPC@UM electrolyte, black: LPC), (FIG. 21D) 0.5 mAh cm 2 (0.25 mA cm 2 ), and (FIG. 21E) 1 mAh cm 2 (0.5 mA cm 2 ), according to embodiments of this invention.
  • FIG. 22A shows voltage-capacity curves of LPC liquid electrolyte in LiFeP0 4 ILi cells at various rates, according to embodiments of this invention.
  • FIG. 22B shows voltage-capacity curves of LPC@UM electrolyte in LiFeP0 4 ILi cells at various rates, according to embodiments of this invention.
  • FIG. 23 shows tong-term cycling stability of prototype LiFeP0 4 ILi 4 Ti 5 0i 2 batteries with LPC@UM electrolyte and LPC liquid electrolyte at 5 C (first two cycles at 1 C), according to embodiments of this invention.
  • FIG. 24 shows performance of a Li symmetric cell using LPC@UM electrolyte at 0.5 mAh cm 2 (0.25 mA cm 2 ), according to embodiments of this invention.
  • first, second, third etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the invention.
  • relative terms such as“lower” or“bottom” and“upper” or“top,” may be used herein to describe one element’s relationship to another element as illustrated in the Figures. It will be understood that relative terms are intended to encompass different orientations of the device in addition to the orientation depicted in the Figures. For example, if the device in one of the figures is turned over, elements described as being on the“lower” side of other elements would then be oriented on“upper” sides of the other elements.
  • the exemplary term“lower” can therefore, encompasses both an orientation of“lower” and“upper,” depending of the particular orientation of the figure.
  • “around”,“about”,“approximately” or“substantially” shall generally mean within 20 percent, preferably within 10 percent, and more preferably within 5 percent of a given value or range. Numerical quantities given herein are approximate, meaning that the term“around”,“about”,“approximately” or“substantially” can be inferred if not expressly stated.
  • the phrase“at least one of A, B, and C” should be construed to mean a logical (A or B or C), using a non-exclusive logical OR.
  • the term “and/or” includes any and all combinations of one or more of the associated listed items.
  • nonaqueous liquid electrolytes enable ion transport between redox active electrodes.
  • the electrolyte chemistry involved here requires that polar solvents dissociate/dissolve the lithium salt which then allows facile ion transport via the fluidic medium.
  • the thermal instability of organic solvents poses daunting concerns about safety, particularly for large- scale applications and Li metal-based secondary batteries.
  • the bulky size of solvated Li + cations results in lower mobility relative to the anions. Consequently, during battery operation the effective current carried by the cations is mitigated by anion movement, leading to concentration polarization, battery life decay and inferior power output.
  • Solid-state electrolytes overcome some of these deficiencies and are considered to be a promising direction for developing next-generation batteries due to improved safety and transport properties.
  • One aspect of this invention discloses a novel class of solid-state (or pseudo solid-state) electrolytes with biomimetic ionic channels, inspired by ionic channels in biological systems. This is achieved by complexing the anions of an electrolyte to the open metal sites (OMSs) of metal-organic frameworks (MOFs), which renders the MOF scaffolds into ionic-channel analogs with fast lithium-ion conductivity and low activation energy.
  • OMSs open metal sites
  • MOFs metal-organic frameworks
  • the novel solid-state electrolytes are applicable to lithium-metal batteries.
  • FIG. 1A depicts a typical structure of Na + -ion channels, of which the key components are the oc-helix domains folded from glutamic-acid-rich peptide chains [19].
  • the carboxylic residues are deprotonated under the physiological environment (pH 7.4), forming negatively charged glutamate ions (-CH2CH2COO ) along the channels, which exclude anions (e.g., Cl ) while allow effective transport of cations [18].
  • the novel solid-state (or pseudo solid-state) electrolytes with biomimetic ionic channels are constructed using metal-organic frameworks (MOFs) as scaffolds.
  • MOFs metal-organic frameworks
  • HKUST-l one of the well investigated MOFs constructed from Cu (II) paddle wheels and benzene-l,3,5-tricarboxylate (BTC) ligands (linkers) [20].
  • HKUST-l possesses three-dimensional (3D) pore channels with a pore diameter of about 1.1 nm.
  • HKUST-l contains coordinated solvent molecules (e.g., water) along the channels.
  • liquid electrolyte e.g., L1CIO4 in propylene carbonate (PC)
  • anions e.g., Cl0 4
  • the anions are bound to metal atoms of the MOF such that the anions are positioned within the pores of the MOF. Similar to the glutamate-like ionic channels, such negatively charged MOFs channels allow effective transport of Li + ions with low activation energy, as shown in FIG. 1D.
  • Lithium electrolytes were also synthesized from an MOF, Mg 2 (dobdc), where dobdc is 1,4- dioxido-2,5-benzenedicarboxylate, by reacting Mg 2 (dobdc) with lithium isopropoxide and subsequent infiltration with L1BF4 in ethylene carbonate (EC) and diethyl carbonate (DEC), providing a lithium-ion conductivity of about 10 4 S cnr 1 [23, 24].
  • MOF metal oxide
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • MOF particles were mixed with an acrylate monomer to form composite membranes after polymerization, providing a lithium-ion conductivity below 10 ⁇ S cm -1 .
  • ionic channels were involved in Li + transport nor was there an indication that these MOF-related materials with ionic channels were able to serve as electrolytes in electrochemical devices.
  • the solid-state electrolyte includes a composite
  • MOFs synthesized from an MOF material soaked in a liquid electrolyte, the MOFs being a class of crystalline porous solids constructed from metal cluster nodes and organic linkers.
  • the MOF material prior to soaking it into the a liquid electrolyte , is activated under vacuum at a temperature greater than 150 °C for a period of time, e.g., overnight, so that the activated MOF material comprises OMSs that are corresponding to unsaturated metal centers created by activating pristine MOFs to remove guest molecules or partial ligands thereof.
  • the MOF material comprises HKUST-l having a formula of
  • CU 3 (BTC)2 MIL- 100- Al having a formula of Al 3 0(0H)(BTC) 2 , MIL-lOO-Cr having a formula of Cr 3 0(0H)(BTC) 2 , MIL-lOO-Fe having a formula of Fe 3 0(0H)(BTC) 2 , UiO-66 having a formula of Zr 6 04(0H)4(BDC)6, or UiO-67 having a formula of Zr 6 04(0H)4(BPDC)6, wherein BTC is a benzene-l,3,5-tricarboxylic acid, BDC is a benzene- l,4-dicarboxylic acid, and BPDC is a biphenyl-4,4 '-dicarboxy lie acid.
  • BTC is a benzene-l,3,5-tricarboxylic acid
  • BDC is a benzene- l,4-dicarboxylic
  • the liquid electrolyte comprises one or more non-aqueous solvents and metal salts dissolved in the one or more non-aqueous solvents.
  • the one or more non- aqueous solvents are selected to match the surface properties of the MOF material.
  • the metal salts are selected to have anions with desired sizes, which depends, at least in part, upon the MOF material, wherein the anion sizes are selected to ensure that the salts to infiltrate into at least some of the pores of the MOFs, and become immobilized therein to form the ionic conducting channels.
  • the non-aqueous liquid electrolyte solvents comprise ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC), fluoroethylene carbonate (FEC), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), methylpropyl carbonate (MPC), butylmethyl carbonate (BMC), ethylpropyl carbonate (EPC), dipropyl carbonate (DPC), cyclopentanone, sulfolane, dimethyl sulfoxide, 3-methyl- l,3-oxazolidine-2-one, g-butyro lactone, l,2-di-ethoxymethane,
  • tetrahydrofuran 2-methyltetrahydrofuran, l,3-dioxolane, methyl acetate, ethyl acetate, nitromethane, 1, 3-propane sultone, g- valero lactone, methyl isobutyryl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, diethyl oxalate, an ionic liquid, chain ether compounds including at least one of gamma butyro lactone, gamma valero lactone, l,2-dimethoxyethane and diethyl ether, cyclic ether compounds including at least one of tetrahydrofuran, 2-methyltetrahydrofuran, l,3-dioxolane and dioxane, or a combination thereof.
  • the metal salts comprise one or more of a lithium (Li) salt, a sodium (Na) salt, a magnesium (Mg) salt, and a zinc (Zn) salt,
  • the liquid electrolyte comprises LiCl0 4 and propylene carbonate, denoted as LPC.
  • the method for fabricating a solid-state electrolyte usable for ionic conductor for an electrochemical device includes: providing an MOF material, the MOFs being a class of crystalline porous solids constructed from metal cluster nodes and organic linkers; activating the MOF material under vacuum at a temperature greater than 150 °C for a period of time; soaking the activated MOF material in a liquid electrolyte to form a mixture; and filtrating the mixture and removing any excessive solvent to obtain the solid-state electrolyte in a free-flowing power form.
  • the period of time is more than 12 h.
  • the method of further comprises pressing the power into pellets.
  • the activated MOF material comprises OMSs that are corresponding to unsaturated metal centers created by activating pristine MOFs to remove guest molecules or partial ligands thereof.
  • the MOF material comprises HKUST-l having a formula of
  • CU 3 (BTC) 2 MIL- 100- Al having a formula of Al 3 0(0H)(BTC) 2 , MIL-lOO-Cr having a formula of Cr 3 0(0H)(BTC) 2 , MIL-lOO-Fe having a formula of Fe 3 0(0H)(BTC) 2 , UiO-66 having a formula of Zr 6 04(0H)4(BDC)6, or UiO-67 having a formula of Zr 6 04(0H)4(BPDC)6, wherein BTC is a benzene-l,3,5-tricarboxylic acid, BDC is a benzene- l,4-dicarboxylic acid, and BPDC is a biphenyl-4,4 '-dicarboxy lie acid.
  • the liquid electrolyte comprises one or more non-aqueous solvents and metal salts dissolved in the one or more non-aqueous solvents, wherein the one or more non- aqueous solvents are selected to match the surface properties of the MOF material; and the metal salts are selected to have anions with desired sizes, which depends, at least in part, upon the MOF material, wherein the anion sizes are selected to ensure that the salts to infiltrate into at least some of the pores of the MOFs, and become immobilized therein to form the ionic conducting channels.
  • the liquid electrolyte comprises LPC.
  • a composite electrolyte membrane usable for ionic conductor for an electrochemical device includes the solid-state electrolyte as disclosed above; and a binder mixed with the solid-state electrolyte.
  • a concentration of the binder is in a range of 5-20 wt.% of the composite electrolyte membrane.
  • the binder comprises poly-propylene (PP), poly-ethylene (PE), glass fiber (GF), polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyallylamine (PAH), polyurethane, polyacrylonitrile (PAN), polymethylmethacrylate (PMMA), polytetraethylene glycol diacrylate, or copolymers thereof.
  • an electrochemical device has the composite electrolyte membrane as disclosed above; a positive electrode; and a negative electrode, wherein the composite electrolyte membrane is disposed between the positive electrode and the negative electrode.
  • the electrochemical device is a lithium (Li) battery, a sodium (Na) battery, a magnesium (Mg) battery, or a zinc (Zn) battery.
  • the positive electrode of the Li battery includes at least one of L1C0O2 (LCO), LiNiMnCo0 2 (NMC), lithium iron phosphate (LiFePCL), lithium
  • ironfluorophosphate Li 2 FeP0 4 F
  • an over-lithiated layer by layer cathode spinel lithium manganese oxide (LiMn 2 0 4 ), lithium cobalt oxide (LiCo0 2 ), LiNio . 5Mn1 . 5O4, lithium nickel cobalt aluminum oxide, lithium vanadium oxide (LiV 2 0 5 ), Li 2 MSi0 4 wherein M is composed of any ratio of Co, Fe, and/or Mn, and a material that undergoes lithium insertion and deinsertion.
  • the negative electrode of the Li battery includes at least one of Li metal, graphite, hard or soft carbon, graphene, carbon nanotubes, titanium oxide, silicon (Si), tin (Sn), germanium (Ge), silicon monoxide (SiO), silicon oxide (Si0 2 ), tin oxide (Sn0 2 ), transition metal oxide, and a material that undergoes intercalation, conversion or alloying reactions with lithium.
  • he positive electrode of the Na battery includes at least one of NaMn0 2 , NaFeP0 4 , and Na 3 V 2 (P0 4 ) 3 .
  • the positive electrode of the Mg battery includes at least one of TiSe 2 , MgFeP0 4 F, MgCo 2 0 4 , and V 2 0 5 .
  • the positive electrode of the Zn battery includes at least one of g-Mh0 2 , ZnMn 2 0 4 , and ZnMn0 2 .
  • the negative electrodes of the Na, Mg and Zn batteries include Na metal, Mg metal, and Zn metal, respectively.
  • Metal organic frameworks are a class of crystalline porous solids constructed from metal cluster nodes and organic linkers.
  • the synthetic procedures of MOF typically involve hydrothermal method, as-prepared MOF pore channels are usually occupied by guest species (e.g. solvent molecules, like water or dimethylformamide). The removal of solvent species by activation creates vacant spaces to accommodate guest binary electrolyte.
  • guest species e.g. solvent molecules, like water or dimethylformamide.
  • the removal of solvent species by activation creates vacant spaces to accommodate guest binary electrolyte.
  • the colossal candidates of MOF are of particular interest due to their various metal centers, ligand derivatives and corresponding topology. Exemplary examples of synthesis of MOFs are described as follows.
  • HKUST-l was synthesized according to a modified microwave- assisted method [66].
  • BTC benzene-l,3,5-tricarboxylic acid
  • II copper
  • nitrate trihydrate 0.42 g of benzene-l,3,5-tricarboxylic acid (BTC) and 0.88 g of copper (II) nitrate trihydrate were dissolved in 24 mL solution of ethanol and water (volume ratio of 1:1). After continuous stirring for 20 min, the sample was transferred to a microwave reactor (Ultrawave, Milestone Inc.). The solution was heated at 800 W under nitrogen with a ramp rate of 10 °C per min before being held at 140 °C for lh. The product was collected by centrifugation and washed for further use.
  • Isostructural MIL-l00-(Al, Cr, Fe) MOFs were synthesized according to a modified microwave-assisted method [67].
  • MIL- 100- Al 1.43 g of aluminum nitrate nonahydrate and 1.21 g of trimethyltrimesate were dispersed in 20 mL of water, followed by the addition of 4 mL of nitric acid (4 M). The mixture was transferred to the microwave reactor, heated at 1500 W to 240 °C in 6 min, and held for 1 min.
  • MIL-lOO-Cr For MIL-lOO-Cr, 2.4 g of chromium nitrate nonahydrate and 0.84 g of BTC were dispersed in 30 mL of water, followed by the addition of 5 mL of nitric acid (4 M). The mixture was heated in the microwave reactor at 1500 W to 200 °C in 10 min, and held for 5 min.
  • MIL-lOO-Fe 2.43 g of iron (III) nitrate nonahydrate and 0.84 g of BTC were dispersed in 30 mL of water. The mixture was heated in the microwave reactor at 1500 W to 130 °C in 2 min 30 s, and held for 5 min. After the reactions, all of the samples were collected by centrifugation and washed several times for further use.
  • UiO-(66/67) UiO-(66/67).
  • UiO-66 and UiO-67 were prepared according to a reported method [68].
  • 1.23 g of BDC ligand and 1.25 g of ZrCL were dissolved in 100 mL of N,N-dimethylformamide (DMF) and 50/10 mL of DMF.
  • DMF N,N-dimethylformamide
  • UiO-67 was prepared in a similar procedure with different reagents, in which 1.35 g of BPDC ligand and 1 g of ZrCL were dissolved in 150 mL of DMF and 75/7.5 mL of DMF/HC1 (37 wt% HC1, concentrated) mixture, respectively.
  • MOF-5 was prepared by a room temperature synthesis [69]. In a typical synthesis, 17 g of zinc acetate dihydrate (Zn(0Ac) 2* H 2 0) and 5.1 g of BDC were dissolved in 500 mL of DMF and 400/8.5 mL of DMF/triethylamine mixture, respectively. Upon addition of the metal salt solution into the ligand solution, white precipitate forms immediately. After continuous stirring for 2.5 h, the precipitate was centrifuged and washed by DMF Solvent change was carried out by immersing DMF- washed samples in chloroform (CHCL) and renewing the solvent once a day for one week. The resulting product was evacuated overnight and stored in a moisture-free environment for further use.
  • CHCL chloroform
  • MOFs solid-state electrolytes.
  • MOFs including HKUST-l, UiO- (66/67), MIL-l00-(Al/Cr/Fe), and MOF-5 were synthesized according to the reported literature and characterized by various techniques.
  • the MOF samples were activated under vacuum at 200 °C (350 °C for MIL- 100- Al and UiO-(66/67)) over night, subsequently soaked in the LiCl0 4 -PC (LPC) electrolyte, collected by vacuum filtration, and pressed into pellets with a diameter of 13 mm at 300 MPa. The surface of the pellets was wiped with tissue paper prior to further electrochemical tests.
  • LPC LiCl0 4 -PC
  • LPC@UiO-67/PTFE membrane electrolytes were pressed at 200 MPa to extrude any excessive liquid electrolyte and wiped with tissue paper.
  • XRD Rigaku powder X-ray diffractometer
  • Infrared spectra experiments were performed in a transmission mode on a Jasco 420 Fourier transform infrared (FT-IR) spectrophotometer.
  • Thermogravimetric analysis (TGA) was carried out in air atmosphere by a ramping rate of 5 °C min 1 .
  • Copper and lithium ratio was determined by inductively coupled plasma atomic emission spectrometer (ICP-AES, Shimadzu, ICPE-2000) using standard copper and lithium solutions from Sigma- Aldrich.
  • FIG. 2A presents a scanning electron microscope (SEM) image of the as-synthesized HKUST-l, which shows an average particle size of tens of micrometers and light blue color due to its water-coordinated copper centers. Removing the coordinated water (activation process) turns the color to dark purple, which then becomes dark cyan after soaking with a LiCl0 4 -PC solution (LPC), implying the emergence of unsaturated sites and re-coordination of the unsaturated sites with C10 4 ions, respectively (insets of FIG. 2A).
  • LPC LiCl0 4 -PC solution
  • the LPC-soaked HKUST-l (denoted as LPC@HKUST-l) was collected after filtration and removal of any excessive solvent, showing a free-flowing power form.
  • HKUST-l exhibits a typical microporous structure with a surface area of about 1150 cm 2 g 1 and a pore volume of about 0.5 cm 3 g ⁇ both of which decrease to near zero in
  • the crystalline structure of the HKUST-l is well retained after the activation process and soaking with LPC as confirmed by the x-ray diffraction (XRD) patterns shown in FIG. 2B.
  • the (111) peak disappears after the activation process and reappears after incorporating with LPC, which are consistent with removal of the coordinated water molecules, as shown in FIG. 6 [26] and binding of the OMSs with C10 4 ions, respectively.
  • the composition of LPC@HKUST-l was estimated by inductively coupled plasma atomic emission spectroscopy (ICP-AES) and thermogravimetric analysis (TGA). ICP-AES gives a Li/Cu molar ratio of about 0.94, which is consistent with our hypothesis that each C10 4 ion binds to an OMS (Cu center). Compared with the reported electrolyte based on
  • LPC@HKUST-l Mg 2 (dobdc), which possesses a Li/Mg molar ratio of about 0.3 [23]
  • concentration of Li + ions in LPC@HKUST-l is three-fold higher, which is important to provide high ionic conductivity.
  • the content of PC within LPC@HKUST-l is estimated by TGA, which gives a formula of LPC @HKUST- 1 as Cu 3 (BTC) 2 (LiCl0 4 ) 2.8 (PC) 4.6 (see details in FIG. 7).
  • LPC@HKUST-l powder was then pressed into dense pellets (inset of FIG. 8A) and sandwiched between two stainless steel plates in coin cells to measure the ionic conductivity.
  • FIGS. 8A-8C the pellets are free of notable cracks or interparticle voids as examined by SEM.
  • the ionic conductivity of LPC@HKUST-l was then measured by electrochemical impedance spectroscopy (EIS).
  • FIG. 9A shows the Nyquist plots of the LPC@HKUST-l pellets at various temperatures. Each plot includes a semi-circle in the high- frequency region and a spike in the low-frequency region, which correspond to the impedance from the bulk/grain boundary and blocking electrode, respectively [28]. Ionic resistance of the electrolytes was determined based on the intersect points of the semi-circles and the spikes.
  • the conductivity of LPC@HKUST-l at room temperature is determined as about 0.38 mS cm 1 , which is approximately one magnitude lower than that of liquid LPC, yet sufficiently high for device applications (FIG. 9B).
  • activated HKUST-l was pro-soaked with pyridine, a complex agent that strongly binds to the OMSs. After removing any excess pyridine, the pyridine-treated HKUST-l
  • pyridine@HKUST-l exhibit intra-particle void (pore volume about 0.05 cm 3 g 1 ), indicating an intra-particle void fraction of less than 5% assuming the density of the pyridine-treated HKUST- 1 is about lg/cc (FIG. 9C).
  • the pydridine@HKUST-l was then infiltrated with LPC, and pressed into pellets (denoted as LPC@ pyridine@HKUST-l) using the same procedure for ionic conductivity measurement. In this design [29], the conduction of lithium ions through the ionic channels is inhibited while that through the intra-particular LPC is retained.
  • this approach is generalized to synthesize a novel family of solid-state electrolytes using MOFs with different metal centers, organic linkers, and crystalline structures (see Table 1 for a list of selected MOFs), which are denoted as
  • M 3+ is bonded to four oxygen atoms of bidendatedicarboxylate (BTC), and their linkage generates a hierarchical structure with mesoporous cages (25 and 29 A) that are accessible through microporous windows (6 and 9 A).
  • the corresponding terminals in octahedra are generally occupied by removable guest molecules.
  • BDC l,4-dicarboxylate
  • the Zr 6 -octahedrons are alternatively coordinated by m 3 -0, m 3 -OH and O atoms from BDC, where m 3 -OH could undergo dehydration to form a distorted Zr 6 0 6 node (seven-coordinated Zr) upon thermal activation.
  • UiO-67 has the same topology as UiO-66 with expanded pore channels due to the larger linker size of BPDC
  • UiO-66 and UiO-67 contain two types of pore size, small tetrahedral pore and large octahedral pore.
  • the Nyquist plots of the LPC@MOFs electrolytes at ambient temperature are displayed in FIG. 2C, and their conductivities are summarized in Table 2.
  • two series of isostructural MOFs were selected to study the effect of OMS and pore size on ionic conductivity.
  • the electrolyte based on MIL- 100- Al exhibits the highest ionic conductivity of over 1 mS cnr 1 at room temperature, which is in the same order of magnitude as commercial gel electrolytes [34].
  • both UiO- 66 and UiO-67 are obtained by bridging the Zr 6 0 4 (0H) 4 cornerstones with BDC or BPDC linkers, possessing the same topology structure and OMS, but with different pore size.
  • the Zr 6 0 4 (0H) 4 units undergo dehydration and the resulting Zin,O d clusters (seven-coordinated Zr) possess unsaturated open Zr 4+ sites (FIG. 11B).
  • the UiO- 66 exhibits bicontinous porous channels with a pore diameter of about 0.75 nm and about 1.2 nm, respectively; while UiO-67 shows a similar porous structure with a larger pore diameter of about 1.2 nm and about 2.3 nm, respectively (Table 1, FIGS. 11A-11H) [36].
  • LPC@UiO-67 exhibits a higher ionic conductivity (about 0.65 mS cm 4 vs. about 0.18 mS cm 4 ).
  • the higher conductivity observed for UiO-67 is attributed by its larger pore channels that allow more effective solvation of the lithium ions with less confinement effect (FIGS. 12A-12B and Table 2).
  • electrolytes exhibit temperature-dependent conductivities with a typical Arrhenius- like behavior.
  • the activation energies measured are in the range of about 0.12-0.21 eV (FIG. 2D), which are slightly higher than that of LPC liquid electrolyte (0.10 eV, see FIG. 13) possibly due to confinement of the ions within the channels.
  • the conduction of lithium ions in LPC@UiO-67 shows a lower activation energy than that of LPC@UiO-66 (0.12 eV vs. 0.21 eV) due to its larger pore size, as listed in Table 3.
  • the activation energies of these MOFs electrolytes are among the lowest activation energies reported for solid-state electrolytes, including the well-established ceramic electrolytes (e.g., LiioGeP 2 Si2 (0.25 eV) [11], glassy L12S-P2S5 (0.19 eV) [37], and garnet Li 7 La 3 Zr 2 0i 2 (0.3-0.4 eV) [38]) and polymeric electrolytes (e.g., LiCKVPEO with T1O2 additive (0.2-0.22 eV) [39]).
  • ceramic electrolytes e.g., LiioGeP 2 Si2 (0.25 eV) [11
  • glassy L12S-P2S5 (0.19 eV) [37]
  • polymeric electrolytes e.g., LiCKVPEO with T1O2 additive (0.2-0.22 eV
  • FIG. 2E shows further comparisons of the ionic conductivity of LPC@UiO-67
  • the conductivity of these electrolytes surpasses most polymeric electrolytes e.g., LiCKVPEO with T1O2 additive and PEO-based single ion polymer [40]
  • ceramic electrolytes e.g., garnet LbLasZW [38], and LiPONLL . sPOsNo . s [41]
  • liquid-in- solid lithium-ion conductors e.g., LPC@organic porous solids [31], Li alkoxide@MOFs [23], and ionic liquid@MOFs [32]).
  • LPC@MOFs electrolytes With a conductivity higher than 10 4 S cm 4 and an activation energy below 0.21 eV, such LPC@MOFs electrolytes can be classified as a new class of superionic solid-state electrolytes [42].
  • Table 3 Major peak assignments for pristine/activated UiO-(66/67) and LPC@UiO-(66/67) electrolytes.
  • UiO-66 and UiO-67 show similar trends in following aspects.
  • Zr-p 3 -0 vibrations are either broadened or red shifted, signifying the symmetry recovery of Zr clusters due to introduced guest molecules.
  • (2) Activation causes the red shift of asymmetric components of (COO) in BDC linkers. After complexing with LPC, those shifts are partially recovered.
  • FIG. 3A shows the Raman spectra of PC, LPC, HKUST-l soaked with PC (denoted as
  • PC@HKUST-l PC@HKUST-l
  • LPC@HKUST-l show the featured peaks of HKUST-l associated with the BTC ligands at 746 cnr 1 , 832 cnr 1 and 1010 cnr 1 , which agree well with the literature (see detailed assignments in Table 4) [43, 44].
  • the peak ascribed the Cu-0 (carboxylate oxygen atom from the ligands) vibration shifts from 496 cnr 1 to 499 cnr 1 .
  • the Raman spectra related to PC provide further insights into the interactions between the MOFs and LPC.
  • LPC shows a broadened carbonyl stretching peak at 708 cnr 1 due to its solvation with Li + ions [46, 47].
  • the emerging peaks at 931 cnr 1 and 937 cnr 1 represent the vi symmetric vibrational stretch of ClOr and ClOr paired with Li + , respectively [48]. Since the carbonyl stretching is sensitive to the surrounding environment, the Raman shift of stretching increases from 708 cnr 1 for PC to 712 cnr 1 for PC@HKUST-l, indicating their interaction with the MOFs scaffolds.
  • the perchlorate group has a built-in spectroscopic handle that enables determination of the complexation state when coordinated to the Cu metal centers.
  • the original T d symmetry of perchlorate is reduced to C 3v and then C 2v for monodentate and bidentate perchlorate, respectively (see Table 5).
  • the peaks associated with free C10 4 at 931 cnr 1 and Li + -C10 4 ion-pairs at 937 cm 1 disappear in LPC@HKUST-l, and a new peak appearing at 940 cm 1 indicates the coordination of ClOr to the OMS [46, 48-52].
  • FIG. 3B shows the FT-IR spectra for PC, LPC, PC@HKUST-l, and LPC@HKUST-l (see full spectra in FIG. 15).
  • LPC shows a sharp peak at 626 cnr 1 , which arises from the symmetric vibration of the C10 4 ions.
  • LPC@HKUST-l exhibits two distinct C10 4 peaks at 635 cnr 1 and 627 cnr 1 due to its interaction with the OMS.
  • LPC@HKUST-l, LPC@MOF-5 shows inferior ambient ionic conductivity of 0.13 mS cnr 1 (FIGS. 18A-18B).
  • FIG. 3C shows further comparisons of the Raman spectra of PC@MOF-5 and LPC@MOF-5, where the stretching at 934 cnr 1 in LPC@MOF-5 indicates ion pairing between ClOr and Li + . This observation confirms the essential role of OMSs, which coordinate with anions to form negatively charged ionic-channel analogs.
  • FIG. 3D shows further comparisons of the activation energies of four LPC@MOFs electrolytes (LPC@HKUST-l, LPC@UiO-66, LPC@UiO-67, and LPC@MOF-5) and two liquid-in-solid electrolytes (LPC@CB[6] [31] and LPC@MCM-48).
  • LPC@HKUST-l LPC@UiO-66
  • LPC@UiO-67 LPC@UiO-67
  • LPC@MOF-5 two liquid-in-solid electrolytes
  • LPC@CB[6], LPC@UiO-66, LPC@HKUST-l, and LPC@MOF-5 are in a similar range.
  • LPC@MOF-5 pore size of 1.2 nm
  • LPC@CB[6] [31] pore size of 0.75 nm
  • LPC@UiO-67 pore size of 2.3 nm with OMSs
  • mesoporous silican LPC@MCM-48 pore size of 2.5 nm without OMS
  • LPC@MCM-48 exhibits a notably higher activation energy (about 0.27 eV) than LPC@UiO-67 (about 0.12 eV) (FIGS. 19A-19B).
  • the activation energy of the electrolytes with OMSs LPC@UiO-66, LPC@HKUST-l, and
  • LPC@UiO-67 decreases with increasing pore size.
  • the activation energy of the electrolytes without OMS decreases with increasing pore size. Therefore, it is reasonable to conclude that OMSs and large pore facilitate the transport of lithium ions with low activation energy.
  • the conduction of lithium ions in the MOFs electrolytes is attributed to the biomimetic ionic channels, which are constructed through spontaneous complexing of electrolyte anions to the OMSs within the MOFs channels filled with solvent molecules.
  • Complexing of anions with OMSs creates ionic channels with a negatively charged surface, of which the Debye screening length is comparable to or exceeds the pore sizes of most MOFs.
  • Such complexing structure weakens the interactions between Li + cations and the anions, enabling fast conduction of Li + ions through the channels. Stronger interactions between the OMSs and the anions, and larger pore sizes lead to electrolytes with higher ionic conductivity and lower activation energy.
  • Ionic conductivity was measured using electrochemical impedance spectroscopy (EIS) after placing the pellets between two stainless steel blocking contacts in a 2032-type coin cell.
  • EIS electrochemical impedance spectroscopy
  • the conductivity of LPC liquid electrolyte was collected by saturating a glass fiber membrane (Whatman, GF-C) with LPC. The frequency range was from 10 6 to 1 Hz, and alternating- current (AC) amplitude was 100 mV.
  • LPC@FTiO-67/PTFE electrolyte membranes were used to assemble symmetric cells, LiFePCFILi cells, and LiFePQ LFTFOii cells.
  • Lithium symmetric cells were assembled by sandwiching LPC@UM electrolyte between two pieces of lithium foil in a coin-cell; a single drop (about 6 ul) of electrolyte was delivered to the electrolyte/electrode interface.
  • the Li stripping/plating tests were performed using the symmetric cells by charging and discharging for a periodic 2 h each at current densities of 0.125, 0.25 and 0.5 mA cm 2 .
  • Lithium ion transference number (tn + ) was measured by combining an AC impedance measurement and a potentio static polarization measurement using Li/electrolyte/Li cells.
  • an AC impedance test (10 6 to 1 Hz, 20 mV amplitude) was performed to obtain the initial bulk resistance (R b °) and the interfacial resistance (R mt °).
  • the symmetric cell was then subjected to a constant DC voltage (V, 20 mV), during which the initial current (Io) was monitored until reaching the steady- state current (I ss ).
  • lithium metal batteries were fabricated by assembling a LiFePCL cathode and a Li chip into a CR2032 coin cell.
  • the cathode electrodes were prepared by homogenously blending LiFeP0 4 , acetylene black, and PVdF with a ratio of 7:2: 1 in NMP The resulting slurry was uniformly coated on a conductive carbon-coated Al foil and dried in a vacuum oven at 70 °C for 24 h.
  • the cathodes and as-prepared LPC@UM electrolyte were pressed together at 200 Mpa to minimize interface resistance, and one drop (about 6 uL) of electrolyte was added to ensure permeation into the electrode matrix.
  • cycling tests were carried out at 0.2, 0.5, 1, and 2 C for five cycles each and at 1 C for subsequent cycles at ambient temperature (electrochemical window: 2.4-4 V vs. Li/Li + ).
  • Li4Ti 5 O l2 electrodes were prepared by the same procedure as that of LiFeP0 4 .
  • the weight ratio between LiFeP0 4 and Li 4 Ti 5 0i 2 is one.
  • FIG. 4A shows the cyclic voltammetry (CV) of a cell, which contains a lithium metal counter electrode, an LPC@UiO-67electrolyte pellet, and a stainless steel (SS) working electrode (LilLPC@UiO-67ISS).
  • the cell was tested using a scan rate of 0.5 mV s 1 at a potential range from -0.2 to 5 V vs. Li/Li + .
  • Liquid LPC and PP separator were used to assemble the reference cells.
  • the cathodic sweep below 1 V vs. Li/Li + , the current associated with the irreversible reduction of C10 4 and PC is less pronounced in
  • LPC@UiO-67/PTFE electrolyte membrane is denoted as LPC@UM (FIG. 4C).
  • FIG. 4D cross-sectional and in-plane SEM images of the UiO- 67/PTFE membrane explicitly show the formation of PTFE polymer fibers that tightly thread the MOF particles into a robust and dense structure with a thickness of about 70-100 pm.
  • Li + cations are heavily solvated (approximately four solvent molecules per Li + ion) [27] in conventional liquid carbonate electrolytes, resulting in relatively free anions and ion- pairings.
  • the lu + of the LPC@UM electrolyte measured by the classical Bruce potentio static polarization method [63] (FIG. 4E) yields a high value of about 0.65. Although the value deviates from unity due to possible decomposition of PC on the surface of the membrane [64], such a lu + number is much higher than the typical value of about 0.2-0.4 observed in liquid LPC electrolyte [65].
  • FIG. 41 shows the DC (direct current) stepped current cycling from 2.5 to 50 uA cm 2 , the potential increased linearly with current, the corresponding resistance (about 175-200 W cm 2 ) based on Ohm’s law is in good agreement with ac impedance. Even at higher current density (0.125 and 0.25 mA cm 2 in 2 hour segments) (FIGS.
  • Li stripping and plating experiments were conducted using LilLPC@UMILi symmetric cells under 0.125 mA cm 2 and 2 h per cycle.
  • the cell with an LPC@UM electrolyte exhibits regular stepwise voltage curves during galvanostatic polarization up to 1200 h (well- maintained below 30 mV), suggesting exceptional stability.
  • the cell with a commercial separator and liquid LPC electrolyte shows higher overpotential fluctuating from 50 mV up to 180 mV and irregular curves (see zoom-in curves in FIGS. 21A-21C), which could be ascribed to high interfacial resistance and unstable SEI formation.
  • Li-metal batteries with LiFeP0 4 cathodes and Li anodes Li-metal batteries with LiFeP0 4 cathodes and Li anodes
  • LiFeP0 4 ILi LiFeP0 4 ILi batteries assembled with LPC@UM electrolyte or liquid electrolyte were initially evaluated at rates from 0.2 to 2 C and cycled at 1 C afterward. At 0.2 C, the cell with LPC@UM electrolyte exhibits a high specific capacity of 146 mAh g 1 , in contrast to only 123 mAh g 1 obtained from the cell with LPC liquid electrolyte. A well-defined potential plateau up to 2 C can be observed (FIG.
  • the invention discloses, among other things, design and synthesis of MOFs-based electrolytes with biomimetic ionic channels for fast and effective transport of lithium ions are demonstrated.
  • the approach results in six new superionic conductors, the best of which exhibits an ambient conductivity surpassing 10 3 S cnr 1 , activation energies below 0.21 eV, electrochemical stability up to 4.5 V vs. Li/Li + , enhanced Li + transference number, and low flammability.
  • These features endow Li-based batteries with superior rate performance and cycling stability.
  • Croce F Appetecchi GB, Persi L, Scrosati B. Nanocomposite polymer electrolytes for lithium batteries. Nature 1998, 394(6692): 456-458.
  • Electrolytes Nanoconfining Liquids within the Hollow Structures. Nano Letters 2015, 15(5): 3398-3402.

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Abstract

Un aspect de l'invention concerne une nouvelle classe d'électrolytes à l'état solide à canaux ioniques biomimétiques en tant que conducteurs ioniques pour des dispositifs électrochimiques, par exemple des batteries. Ceci est obtenu par complexation des anions d'un électrolyte avec les sites métalliques ouverts de réseaux organométalliques (MOF), ce qui transforme les échafaudages MOF en analogues de canaux ioniques avec une conductivité lithium-ion rapide et une faible énergie d'activation.
PCT/US2019/034104 2018-03-30 2019-05-28 Électrolytes à l'état solide à canaux ioniques biomimétiques pour batteries et leurs procédés de fabrication WO2019191787A2 (fr)

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