WO2020192678A1 - Séparateurs composites à revêtement de structure métallo-organique (mof) pour dispositifs électrochimiques et leurs applications - Google Patents

Séparateurs composites à revêtement de structure métallo-organique (mof) pour dispositifs électrochimiques et leurs applications Download PDF

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WO2020192678A1
WO2020192678A1 PCT/CN2020/081053 CN2020081053W WO2020192678A1 WO 2020192678 A1 WO2020192678 A1 WO 2020192678A1 CN 2020081053 W CN2020081053 W CN 2020081053W WO 2020192678 A1 WO2020192678 A1 WO 2020192678A1
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lithium
mof
metal
separator
carbonate
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PCT/CN2020/081053
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English (en)
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Jimmy Wang
Li Shen
Feng Lu
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Ford Cheer International Limited
Xiongdi Fine Chemical Co. ltd
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Priority to CN202080010044.6A priority Critical patent/CN113574731A/zh
Publication of WO2020192678A1 publication Critical patent/WO2020192678A1/fr

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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • 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 invention relates generally to batteries, and more particularly, to metal-organic framework (MOF) -coated composite separators for electrochemical devices such as high safety, high-energy and high-power batteries, and application of the same.
  • MOF metal-organic framework
  • separators serve as the interlayers, which mediates the transport of ions and blocking the flow of electrons.
  • the structure and property of separators significantly impact the performance of batteries.
  • the commercial polyolefin-based separators are suffered from poor thermal stability, insufficient mechanical modulus to block lithium dendrites, and inability to improve the Li + transference number of the electrolytes, which cause safety hazards, limit the energy and power performance, and shorten the lifetime of the batteries.
  • Ceramic coatings which include ceramic particles such as ZrO 2 , Al 2 O 3 and SiO 2 particles within polymeric matrixes, e.g., disclosed in U.S. Patent No. 6,432,586, have been applied onto the polyolefin-based separators, which partially mitigate the aforementioned issues.
  • ceramic-coated separators exhibit improved thermal stability against thermal runaway, as well as improved ability to suppress the growth of lithium dendrites.
  • ceramic coatings cannot modulate the transport of the ions in electrolyte, rendering the batteries with a low Li + transference number ( ⁇ 0.4) . Accordingly, developing new functionalities on separators for efficient Li + conduction represents the promising pathway for advanced battery separators.
  • the Li + transference number which is defined as the ratio of Li + conductivity to overall ionic conductivity, plays as a critical role on governing electrochemical performances of batteries.
  • the low Li + transference number of commercial electrolytes in polyolefin-based separator ( ⁇ 0.4) gives rise to concentration polarization, deteriorated electrolyte-electrode interfaces, reduced energy efficiency, aggravated side reactions and intensive joule heating, which can shorten the cycling life especially under fast charging/discharging condition.
  • current polyolefin-based separators are not suitable for advanced batteries, such as lithium-metal batteries, high-power batteries with fast-charging capability.
  • This invention in one aspect, relates to a composite separator used for an electrochemical device comprising at least one metal-organic framework (MOF) composite layer; and at least one porous layer serving a mechanical support for the at least one MOF composite layer.
  • the at least one MOF composite layer comprises at least one metal-organic framework (MOF) material defining a plurality of pore channels and at least one polymer.
  • the at least one MOF material is a class of crystalline porous scaffolds constructed from metal clusters with organic ligands and is activated at a temperature for a period of time such that the at least one MOF material comprises unsaturated metal centers, open metal sites and/or structural defects that are able to complex with anions in electrolyte.
  • the at least one MOF composite layer is formed by coating of a mixture of the at least one MOF material with a polymer solution comprising the at least one polymer dissolved in at least one solvent on the at least one porous layer.
  • said coating includes dip coating, slot-die coating, blade coating, spin coating, or electrospinning.
  • the at least one porous layer has pores serving as liquid electrolyte hosts for conducting ions and is an electronic insulator for preventing short circuiting.
  • the at least one porous layer comprises one or more polymers including poly-propylene (PP) , poly-ethylene (PE) , glass fiber (GF) , cellulose, polyvinyl alcohol (PVA) , polyethylene oxide (PEO) , polyvinylidene fluoride (PVDF) , polytetrafluoroethylene (PTFE) , polyether ether ketone (PEEK) , polyimide (PI) , polyallylamine (PAH) , polyurethane, polyacrylonitrile (PAN) , polymethylmethacrylate (PMMA) , polytetraethylene glycol diacrylate, copolymers thereof, or their combinations.
  • PP poly-propylene
  • PE poly-ethylene
  • GF glass fiber
  • cellulose cellulose
  • PVA polyvinyl alcohol
  • PEO polyethylene oxide
  • PVDF polyvinylidene fluoride
  • PVDF polytetrafluoroethylene
  • PTFE polyether ether ketone
  • the at least one MOF composite layer comprises an amount of the MOF material in a range of about 5-99 wt%and an amount of the least one polymer in a range of about 1-95 wt%.
  • the at least one MOF material is activated by calcination, supercritical CO 2 , or other treatments.
  • the at least one MOF material has tunable ligand functionality and tunable pore sizes, where the tunable ligand functionality is negatively charged ligands by chemical modifications, and the tunable pore sizes is grafting of chemical groups in the ligands.
  • the organic ligands comprise benzene-1, 4-dicarboxylic acid (BDC) , benzene-1, 3, 5-tricarboxylic acid (BTC) , biphenyl-4, 4’ -dicarboxylic acid (BPDC) , or their derivatives
  • the metal clusters comprise magnesium (Mg) , Aluminium (Al) , Titanium (Ti) , Vanadium (V) , Chromium (Cr) , Manganese (Mn) , Iron (Fe) , Cobalt (Co) , Nickel (Ni) , Copper (Cu) , Zinc (Zn) , or Zirconium (Zr) .
  • the at least one MOF material comprises HKUST-1, MIL-100-Al, MIL-100-Cr, MIL-100-Fe, UiO-66, UiO-67, PCN series, MOF-808, MOF-505, MOF-74, or their combinations.
  • the at least one MOF material comprises a zirconium containing MOF (Zr-MOF) or zirconium terephthalate-based MOF having a general formula of Zr 6 ( ⁇ 3-O 4 ) ( ⁇ 3-OH 4 ) (-COO) 8 (OH) 4 (H 2 O) n , where n is an integer less than 10.
  • Zr-MOF zirconium containing MOF
  • zirconium terephthalate-based MOF having a general formula of Zr 6 ( ⁇ 3-O 4 ) ( ⁇ 3-OH 4 ) (-COO) 8 (OH) 4 (H 2 O) n , where n is an integer less than 10.
  • the at least one polymer comprises polyvinylidene fluoride (PVDF) , polytetrafluoroethylene (PTFE) , poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) , PVDF-tetrahydrofuran (PVDF-THF) , PVDF-chlorotrifluoroethylene (PVDF-CTFE) , poly (methyl methacrylate) (PMMA) , polyacrylonitrile (PAN) , and polyethyleneoxide (PEO) , copolymers thereof, or their combinations.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PVDF-HFP poly (vinylidene fluoride-co-hexafluoropropylene)
  • PVDF-THF poly (vinylidene fluoride-co-hexafluoropropylene)
  • PVDF-THF poly (viny
  • the at least one solvent comprises acetone, water, methanol, ethanol, acetic acid, dimethylformamide (DMF) , acetone, water, methanol, ethanol, acetic acid, dimethylformamide (DMF) , dimethylacetamide (DMAc) , N-Methyl-2-pyrrolidone (NMP) , tetrahydrofuran (THF) , or their combinations.
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • NMP N-Methyl-2-pyrrolidone
  • THF tetrahydrofuran
  • the invention in another aspect, relates to an electrochemical device, comprising a positive electrode, a negative electrode, an electrolyte disposed between the positive and negative electrodes, and a separator disposed in the electrolyte.
  • the electrolyte is an liquid electrolyte comprising a metal salt dissolved in a non-aqueous solvent.
  • the separator is the composite separator as disclosed.
  • the non-aqueous solvent comprises one or more of 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-1, 3-oxazolidine-2-one, ⁇ -butyrolactone, 1, 2-di-ethoxymethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, methyl acetate, ethyl acetate
  • anions in the liquid electrolytes are spontaneously adsorbed by the at least one MOF material and immobilized within the pore channels, thereby liberating metal ions and leading to the metal ions transport with a metal ion transference number higher than that of a separator without the at least one MOF material.
  • the metal ions transference number is a ratio of a metal ion conductivity to an ionic conductivity, where the ionic conductivity is a total value of the metal ion conductivity and anionic conductivity.
  • the metal ion transference number of the liquid electrolytes in the composite separator is in a range of about 0.5-1.
  • the metal salt comprises one or more of a lithium salt, a sodium salt, a magnesium salt, a zinc salt, and an aluminum salt.
  • the lithium salt comprises one or more of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium bis (trifluoromethlysulfonylimide) (LiTFSI) , lithium bis (trifluorosulfonylimide) , lithium trifluoromethanesulfonate, lithium fluoroalkylsufonimides, lithium fluoroarylsufonimides, lithium bis (oxalate borate) , lithium tris (trifluoromethylsulfonylimide) methide, lithium tetrafluoroborate, lithium perchlorate, lithium tetrachloroaluminate, and lithium chloride.
  • LiTFSI lithium bis (trifluoromethlysulfonylimide)
  • LiTFSI lithium bis (trifluorosulfonylimide)
  • lithium trifluoromethanesulfonate lithium fluoroalkylsufonimides
  • the sodium salt comprises one or more of sodium trifluoromethanesulfonate, NaClO 4 , NaPF 6 , NaBF 4 , NaTFSI (sodium (I) Bis (trifluoromethanesulfonyl) imide) , and NaFSI (sodium (I) Bis (fluorosulfonyl) imide) .
  • the magnesium salt comprises one or more of magnesium trifluoromethanesulfonate, Mg (ClO 4 ) 2 , Mg (PF 6 ) 2 , Mg (BF 4 ) 2 , Mg (TFSI) 2 (magnesium (II) Bis (trifluoromethanesulfonyl) imide) , and Mg (FSI) 2 (magnesium (II) Bis (fluorosulfonyl) imide) .
  • the zinc salt comprises one or more of zinc trifluoromethanesulfonate, Zn (ClO 4 ) 2 , Zn (PF 6 ) 2 , Zn (BF 4 ) 2 , Zn (TFSI) 2 (zinc (II) Bis (trifluoromethanesulfonyl) imide) , Zn (FSI) 2 (zinc (II) Bis (fluorosulfonyl) imide) .
  • the electrochemical device is a lithium battery, a sodium battery, a magnesium battery, or a zinc metal battery.
  • the positive electrode comprises one or more of LiCoO 2 (LCO) , LiNiMnCoO 2 (NMC) , lithium iron phosphate (LiFePO 4 ) , lithium iron fluorophosphate (Li 2 FePO 4 F) , an over-lithiated layer by layer cathode, spinel lithium manganese oxide (LiMn 2 O 4 ) , lithium cobalt oxide (LiCoO 2 ) , LiNi 0.5 Mn 1.5 O 4 , lithium nickel cobalt aluminum oxide including LiNi 0.8 Co 0.15 Al 0.05 O 2 or NCA, lithium vanadium oxide (LiV 2 O 5 ) , and Li 2 MSiO 4 with M being composed of a ratio of Co, Fe, and/or Mn; and the negative electrode comprises one or more of lithium metal (Li) , graphite, hard or soft carbon, graphene, carbon nanotubes, titanium oxide including at least one Li 4 Ti 5 O 12 and TiO 2 ,
  • the positive electrode comprises one or more of NaMnO 2 , NaFePO 4 and Na 3 V 2 (PO 4 ) 3 for the sodium battery, one or more of TiSe 2 , MgFePO 4 F, MgCo 2 O 4 and V 2 O 5 for the magnesium battery, or one or more of ⁇ MnO 2 , ZnMn 2 O 4 , and ZnMnO 2 for the zinc battery.
  • FIG. 1 shows schematic of a composite separator, according to embodiments of the invention.
  • FIG. 2 shows schematic of a metal-organic framework with open metal sites and respective ion conduction behaviors of lithium ions and anions, according to embodiments of the invention.
  • FIG. 3 shows schematic of a metal-organic framework chemically modified ligands and respective ion conduction behaviors of lithium ions and anions, according to embodiments of the invention.
  • FIG. 4 shows X-ray diffraction patterns of simulated zirconium terephthalate-based MOF (UiO-66) , as-synthesized UiO-66 and coated UiO-66 on polypropylene-based separator (support separator, denoted as PP) , according to embodiments of the invention.
  • FIG. 5 shows a thermogravimetric analysis curve of UiO-66 in air atmosphere, according to embodiments of the invention.
  • FIG. 6 shows a scanning electron microscopy image of a PP separator (asupport separator from Celgard Inc. ) .
  • FIG. 7 shows a scanning electron microscopy image of PP coated by UiO-66, according to embodiments of the invention
  • FIG. 8 shows measurements of the lithium ion transference number of the electrolyte in the support separator.
  • FIG. 9 shows measurements of the lithium ion transference number of the electrolyte in a composite separator with activated UiO-66, according to embodiments of the invention.
  • FIG. 10 shows measurements of the lithium ion transference number of the electrolyte in a composite separator with inactivated UiO-66.
  • FIG. 11 shows galvanostatic cycling of Li symmetric cells using an electrolyte saturated PP separator and a composite separator, according to embodiments of the invention.
  • FIG. 12 shows rate performances of full cells (LiNi 1/3 Co 1/3 Mn 1/3 O 2 as a cathode and graphite as an anode) using an electrolyte saturated support separator and a composite separator, according to embodiments of the invention.
  • FIG. 13 shows cycle performances of full cells (LiNi 1/3 Co 1/3 Mn 1/3 O 2 as a cathode and graphite as an anode) using an electrolyte saturated support separator and a composite separator, according to embodiments of the invention.
  • FIG. 14 shows the illustrative drawing of a zirconium-based MOF (UiO-66-NH 2 ) with chemical modification on ligands, according to embodiments of the invention.
  • FIG. 15 shows X-ray diffraction patterns of zirconium-based MOF (UiO-66-NH 2 ) during the respective chemical modification on ligands, according to embodiments of the invention.
  • FIG. 16 shows a scanning electron microscopy image of as-synthesized UiO-66-NH 2 , according to embodiments of the invention.
  • FIG. 17 shows a scanning electron microscopy image of a microporous layer (asupport separator from Celgard Inc. ) .
  • FIG. 18 shows a scanning electron microscopy image of a composite separator with modified UiO-66-NH 2 , according to embodiments of the invention.
  • FIG. 19 shows a scanning electron microscopy image of a composite separator with modified UiO-66-NH 2 , according to embodiments of the invention.
  • FIG. 20 shows measurements of the lithium ion transference number of the electrolyte in a composite separator with modified UiO-66-NH 2 , according to embodiments of the 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 can 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.
  • This invention in one aspect relates to a metal-organic frameworks (MOFs) -coated separator (composite separator) that can significantly improve the Li + transference number of commercial electrolytes (> 0.6) , where the MOFs are porous coordination solids periodically constructed by metal clusters and organic linkers, forming ordered porous scaffolds with various dimensions.
  • the MOFs disclosed herein contain unsaturated coordination sites, structural defects, or negatively charged moieties that can immobilize/repel the anion movement and facilitate cation (lithium ion) conduction.
  • the applications of MOFs-coated separators in batteries offers other multiple benefits, including, but are not limited to: alleviated concentration polarization, accelerated electrode reaction kinetics, reduced electrolyte decomposition, improved thermal stability, etc.
  • metal-organic frameworks in batteries have been reported.
  • an electrolyte membrane comprising metal-organic frameworks, polymers and electrolytes are discussed in U.S. Patent Nos. 9,105,940, and 10,347,939, where a crosslinking approach of preparing composite membrane is disclosed by covalently bonding metal-organic frameworks (e.g., carboxylic acid) with polymers (e.g., amine) .
  • metal-organic frameworks e.g., carboxylic acid
  • polymers e.g., amine
  • a solid polymer electrolyte comprising metal-organic frameworks, lithium salts and lithium-ion conducting polymers are disclosed in Chinese Patent Nos.
  • CN103474696B and CN106532112A where the benefit of adding claimed metal-organic frameworks into solid polymer electrolytes assemble the effect of conventional ceramic particles.
  • the claimed benefits of adding metal-organic frameworks in solid polymer electrolytes include: reduced polymer crystallinity, improved Li + conductivity, enhanced mechanical and thermal stability.
  • a solid lithium-ion electrolyte comprising metal-organic frameworks is disclosed in U.S. Patent No. 9,525,190, where a post-synthesis approach by grafting alkoxide on metal-organic frameworks is disclosed.
  • the metal center in claimed metal-organic frameworks is capped with a lithium compound (lithium alkoxide) , followed by soaking in a typical electrolyte.
  • a polyolefin-based separator coated with particles of metal-organic frameworks (NH 2 -MIL-125 (Ti) ) , a titanium terephthalate-based framework, is disclosed for the application of stabilizing lithium-metal anode (Chemical Science, 2017, 8, 4285) .
  • the benefit of incorporating MOFs is a homogenous electrodeposition of lithium ions via the interactions between the –NH 2 groups (in ligands) and Li + ions.
  • Zirconium-based MOFs (UiO-66-NH 2 ) particles with cationic centers are synthesized by chemically modifying the amine groups in the ligands (Energy Storage Materials (2019) ) .
  • Such modified positively charged particles are then incorporated within a polymeric electrolyte, which leads to improved lithium ion transference number through the interactions between the cationic centers and anions; and MOFs-based separators are disclosed in application of lithium-sulphur batteries (Nature Energy 1.7 (2016) : 16094, ACS Energy Letters 2.10 (2017) : 2362-2367) .
  • the claimed benefit is a mitigated shuttling of dissolved polysulfides by blocking their transport through the microporous apertures of the MOFs.
  • Other claimed benefit reports the strong chemisorption of poylsulfides in MOFs-carbon nanotube composite separators (Energy Storage Materials 14 (2016) : 383-391 and Nature Communications 8 (2017) : 14628) .
  • the metal-organic frameworks described herein contain open metal sites (OMSs) , the OMSs can be understood as coordinately unsaturated metal sites, exposed metal sites and the like.
  • OMSs open metal sites
  • the MOFs with the OMSs interact directly with commercially available liquid electrolytes (e.g., LiPF 6 -based electrolytes) , where OMSs can spontaneously bound anions (e.g., PF 6 - ) in electrolytes, forming negatively charged ion channels and facilitating translocation of lithium ions.
  • the separators coated by MOFs with the OMSs effectively enhance the Li + transference number or Li + conductivity of the electrolytes, in comparison with commercial polyolefin-based separators.
  • the metal-organic frameworks described herein may also be modified with negatively charged moieties to exclude/repel the anion movements and allow the effective transport of cations, mimicking the ionic channels that commonly exist in biological systems.
  • the composite separator used for an electrochemical device includes at least one MOF composite layer; and at least one porous layer serving a mechanical support for the at least one MOF composite layer.
  • the at least one MOF composite layer comprises at least one metal-organic framework (MOF) material defining a plurality of pore channels and at least one polymer.
  • the at least one MOF material is a class of crystalline porous scaffolds constructed from metal clusters with organic ligands and is activated at a temperature for a period of time such that the at least one MOF material comprises unsaturated metal centers, open metal sites and/or structural defects that are able to complex with anions in electrolyte.
  • the at least one MOF material is activated by calcination, supercritical CO 2 , or other treatments.
  • the at least one MOF composite layer is formed by coating of a mixture of the at least one MOF material with a polymer solution comprising the at least one polymer dissolved in at least one solvent on the at least one porous layer.
  • said coating includes dip coating, slot-die coating, blade coating, spin coating, or electrospinning.
  • the at least one porous layer has pores serving as liquid electrolyte hosts for conducting ions and is an electronic insulator for preventing short circuiting.
  • the at least one porous layer comprises one or more polymers including poly-propylene (PP) , poly-ethylene (PE) , glass fiber (GF) , cellulose, polyvinyl alcohol (PVA) , polyethylene oxide (PEO) , polyvinylidene fluoride (PVDF) , polytetrafluoroethylene (PTFE) , polyether ether ketone (PEEK) , polyimide (PI) , polyallylamine (PAH) , polyurethane, polyacrylonitrile (PAN) , polymethylmethacrylate (PMMA) , polytetraethylene glycol diacrylate, copolymers thereof, or their combinations.
  • PP poly-propylene
  • PE poly-ethylene
  • GF glass fiber
  • cellulose cellulose
  • PVA polyvinyl alcohol
  • PEO polyethylene oxide
  • the at least one MOF composite layer comprises an amount of the MOF material in a range of about 5-99 wt%and an amount of the least one polymer in a range of about 1-95 wt%.
  • the at least one MOF material has tunable ligand functionality and tunable pore sizes, where the tunable ligand functionality is negatively charged ligands by chemical modifications, and the tunable pore sizes is grafting of chemical groups in the ligands.
  • the organic ligands comprise benzene-1, 4-dicarboxylic acid (BDC) , benzene-1, 3, 5-tricarboxylic acid (BTC) , biphenyl-4, 4’ -dicarboxylic acid (BPDC) , or their derivatives
  • the metal clusters comprise magnesium (Mg) , Aluminium (Al) , Titanium (Ti) , Vanadium (V) , Chromium (Cr) , Manganese (Mn) , Iron (Fe) , Cobalt (Co) , Nickel (Ni) , Copper (Cu) , Zinc (Zn) , or Zirconium (Zr) .
  • the at least one MOF material comprises HKUST-1, MIL-100-Al, MIL-100-Cr, MIL-100-Fe, UiO-66, UiO-67, PCN series, MOF-808, MOF-505, MOF-74, or their combinations.
  • the at least one MOF material comprises a zirconium containing MOF (Zr-MOF) or zirconium terephthalate-based MOF having a general formula of Zr 6 ( ⁇ 3-O 4 ) ( ⁇ 3-OH 4 ) (-COO) 8 (OH) 4 (H 2 O) n , where n is an integer less than 10.
  • Zr-MOF zirconium containing MOF
  • zirconium terephthalate-based MOF having a general formula of Zr 6 ( ⁇ 3-O 4 ) ( ⁇ 3-OH 4 ) (-COO) 8 (OH) 4 (H 2 O) n , where n is an integer less than 10.
  • the at least one polymer comprises polyvinylidene fluoride (PVDF) , polytetrafluoroethylene (PTFE) , poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) , PVDF-tetrahydrofuran (PVDF-THF) , PVDF-chlorotrifluoroethylene (PVDF-CTFE) , poly (methyl methacrylate) (PMMA) , polyacrylonitrile (PAN) , and polyethyleneoxide (PEO) , copolymers thereof, or their combinations.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PVDF-HFP poly (vinylidene fluoride-co-hexafluoropropylene)
  • PVDF-THF PVDF-tetrahydrofuran
  • PVDF-CTFE PVDF-chlorotrifluoroethylene
  • PMMA methyl
  • the at least one solvent comprises acetone, water, methanol, ethanol, acetic acid, dimethylformamide (DMF) , acetone, water, methanol, ethanol, acetic acid, dimethylformamide (DMF) , dimethylacetamide (DMAc) , N-Methyl-2-pyrrolidone (NMP) , tetrahydrofuran (THF) , or their combinations.
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • NMP N-Methyl-2-pyrrolidone
  • THF tetrahydrofuran
  • the invention in another aspect, relates to an electrochemical device, comprising a positive electrode, a negative electrode, an electrolyte disposed between the positive and negative electrodes, and a separator disposed in the electrolyte.
  • the electrolyte is an liquid electrolyte comprising a metal salt dissolved in a non-aqueous solvent.
  • the separator is the composite separator as disclosed.
  • the non-aqueous solvent comprises one or more of 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-1, 3-oxazolidine-2-one, ⁇ -butyrolactone, 1, 2-di-ethoxymethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, methyl acetate, ethyl a
  • anions in the liquid electrolytes are spontaneously adsorbed by the at least one MOF material and immobilized within the pore channels, thereby liberating metal ions and leading to the metal ions transport with a metal ion transference number higher than that of a separator without the at least one MOF material.
  • the metal ions transference number is a ratio of a metal ion conductivity to an ionic conductivity.
  • the ionic conductivity is a total value of the metal ion conductivity and anionic conductivity.
  • the metal ion transference number of the liquid electrolytes in the composite separator is in a range of about 0.5-1.
  • the metal salt comprises one or more of a lithium salt, a sodium salt, a magnesium salt, a zinc salt, and an aluminum salt.
  • the lithium salt comprises one or more of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium bis (trifluoromethlysulfonylimide) (LiTFSI) , lithium bis (trifluorosulfonylimide) , lithium trifluoromethanesulfonate, lithium fluoroalkylsufonimides, lithium fluoroarylsufonimides, lithium bis (oxalate borate) , lithium tris (trifluoromethylsulfonylimide) methide, lithium tetrafluoroborate, lithium perchlorate, lithium tetrachloroaluminate, and lithium chloride.
  • LiTFSI lithium bis (trifluoromethlysulfonylimide)
  • LiTFSI lithium bis (trifluorosulfonylimide)
  • lithium trifluoromethanesulfonate lithium fluoroalkylsufonimides
  • the sodium salt comprises one or more of sodium trifluoromethanesulfonate, NaClO 4 , NaPF 6 , NaBF 4 , NaTFSI (sodium (I) Bis (trifluoromethanesulfonyl) imide) , and NaFSI (sodium (I) Bis (fluorosulfonyl) imide) .
  • the magnesium salt comprises one or more of magnesium trifluoromethanesulfonate, Mg (ClO 4 ) 2 , Mg (PF 6 ) 2 , Mg (BF 4 ) 2 , Mg (TFSI) 2 (magnesium (II) Bis (trifluoromethanesulfonyl) imide) , and Mg (FSI) 2 (magnesium (II) Bis (fluorosulfonyl) imide) .
  • the zinc salt comprises one or more of zinc trifluoromethanesulfonate, Zn (ClO 4 ) 2 , Zn (PF 6 ) 2 , Zn (BF 4 ) 2 , Zn (TFSI) 2 (zinc (II) Bis (trifluoromethanesulfonyl) imide) , Zn (FSI) 2 (zinc (II) Bis (fluorosulfonyl) imide) .
  • the electrochemical device is a lithium battery, a sodium battery, a magnesium battery, or a zinc metal battery.
  • the positive electrode comprises one or more of LiCoO 2 (LCO) , LiNiMnCoO 2 (NMC) , lithium iron phosphate (LiFePO 4 ) , lithium iron fluorophosphate (Li 2 FePO 4 F) , an over-lithiated layer by layer cathode, spinel lithium manganese oxide (LiMn 2 O 4 ) , lithium cobalt oxide (LiCoO 2 ) , LiNi 0.5 Mn 1.5 O 4 , lithium nickel cobalt aluminum oxide including LiNi 0.8 Co 0.15 Al 0.05 O 2 or NCA, lithium vanadium oxide (LiV 2 O 5 ) , and Li 2 MSiO 4 with M being composed of a ratio of Co, Fe, and/or Mn; and the negative electrode comprises one or more of lithium metal (Li) , graphite, hard or soft carbon, graphene, carbon nanotubes, titanium oxide including at least one Li 4 Ti 5 O 12 and TiO 2
  • the positive electrode comprises one or more of NaMnO 2 , NaFePO 4 and Na 3 V 2 (PO 4 ) 3 for the sodium battery, one or more of TiSe 2 , MgFePO 4 F, MgCo 2 O 4 and V 2 O 5 for the magnesium battery, or one or more of ⁇ MnO 2 , ZnMn 2 O 4 , and ZnMnO 2 for the zinc battery.
  • the composite separator comprises a composite layer 1 containing particles of metal-organic frameworks (MOFs) and a porous support separator layer 2.
  • the support separator layer 2 is commercially available separators, which contain pores serving as liquid electrolyte host for conducting ions.
  • the support separator layer 2 is an electronic insulator for preventing short circuiting.
  • the composite layer 1 as a functional layer includes the particles of MOFs 3 and a polymer matrix 4, where the MOFs serve as functional moieties tuning electrolyte properties and the polymer serves as either binder or mechanical matrix for adhering MOFs on the support separator layer 2.
  • the support separator layer 2 includes, but is not limited to, poly-propylene (PP) , poly-ethylene (PE) , glass fiber (GF) , cellulose, polyvinyl alcohol (PVA) , polyethylene oxide (PEO) , polyvinylidene fluoride (PVDF) , polytetrafluoroethylene (PTFE) , Polyether ether ketone (PEEK) , polyimide (PI) , polyallylamine (PAH) , polyurethane, polyacrylonitrile (PAN) , polymethylmethacrylate (PMMA) , polytetraethylene glycol diacrylate, copolymers thereof or their combinations.
  • PP poly-propylene
  • PE poly-ethylene
  • GF glass fiber
  • cellulose cellulose
  • PVA polyvinyl alcohol
  • PEO polyethylene oxide
  • PVDF polyvinylidene fluoride
  • PVDF polytetrafluoroethylene
  • PTFE polytetrafluoroethylene
  • the MOFs 3 a class of crystalline porous scaffolds constructed from metal cluster nodes and organic ligands and represent a class of porous coordination solids with versatile structural and functional turnabilities.
  • the particles of the MOFs 3 are constructed by periodically bridging inorganic metal clusters with organic ligands (linkers) , forming pore windows 5 generally below 2 nanometres, yet mesoporous MOFs can be prepared by isoreticular expansion of organic ligands.
  • Suitable ligands are preferably, but are not limited to, benzene-1, 4-dicarboxylic acid (BDC) , benzene-1, 3, 5-tricarboxylic acid (BTC) and their derivatives.
  • Suitable metal clusters include, but are not limited to, magnesium (Mg) , Aluminium (Al) , Titanium (Ti) , Vanadium (V) , Chromium (Cr) , Manganese (Mn) , Iron (Fe) , Cobalt (Co) , Nickel (Ni) , Copper (Cu) , Zinc (Zn) , Zirconium (Zr) , or the like.
  • Table 1 Selected MOFs for high-performance composite separators
  • Table 1 shows MOFs examples, including their typical formulas, ligand structures and approximate pore sizes.
  • M 3+ is bonded to four oxygen atoms of bidendate dicarboxylate (BTC) , and their linkage generates a hierarchical structure with mesoporous cages (25 and ) that are accessible through microporous windows (6 and ) .
  • the corresponding terminals in octahedra are generally occupied by removable guest molecules.
  • BDC 4-dicarboxylate
  • the Zr 6 -octahedrons are alternatively coordinated by ⁇ 3 -O, ⁇ 3 -OH and O atoms from BDC, where ⁇ 3 -OH can undergo dehydroxylation to form a distorted Zr 6 O 6 node (seven-coordinated Zr) upon thermal activation.
  • BPDC biphenyl-4, 4’ -dicarboxylate
  • Both UiO-66 and UiO-67 contain two types of pore size, small tetrahedral pore and large octahedral pore.
  • Other ligands derivatives are exemplified in Table 2.
  • MOFs are synthesized in the presence of a solvent (e.g., water) and the ligands, both of which coordinate with the MOF’s metal centers.
  • a solvent e.g., water
  • Removal of the solvent molecules breaks the solvent coordination from the MOFs, resulting in MOF scaffolds with unsaturated metal centers.
  • the conditions for solvent molecule removal include a temperature ranging from about 200°C to about 220°C at a pressure of about 30 mTorr. This temperature range is suitable for removing any solvent, although it is to be understood that high boiling point solvent may require longer evacuation times than low boiling point solvents.
  • the powder form an MOF material is degassed or activated under vacuum at a high/elevated temperature (e.g., from about 200°C to about 220°C) to remove absorbed water molecules.
  • a high/elevated temperature e.g., from about 200°C to about 220°C
  • Other solvent molecule removal methods can also be used to practice the invention.
  • Polymer matrix 4 includes, for example, but are not limited to, polyvinylidene fluoride (PVDF) , polytetrafluoroethylene (PTFE) , poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) , PVDF-tetrahydrofuran (PVDF-THF) , PVDF-chlorotrifluoroethylene (PVDF-CTFE) , poly (methyl methacrylate) (PMMA) , polyacrylonitrile (PAN) , and polyethyleneoxide (PEO) .
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PVDF-HFP poly (vinylidene fluoride-co-hexafluoropropylene)
  • PVDF-THF PVDF-tetrahydrofuran
  • PVDF-CTFE PVDF-chlorotrifluoroethylene
  • PMMA methyl meth
  • the MOF particles 3 are blended with the polymer matrix 4, and the resulting mixture is composite with the support separator layer 2.
  • the composite separator can be prepared by methods of, but is not limited to, coating, lamination, extrusion and electrospinning. Suitable examples of coating include, but are not limited to, dip coating, slot-die coating, blade coating and spin coating.
  • the structure of the composite separator is not limited in the form of single layer-by-layer structure as shown in FIG. 1.
  • the stacking sequence and number of layers 1 and 2 can be of any combinations.
  • the MOFs layer 1 can be present on the surface of the support separator layer 2 or can be coated on the surface of pores in the support separator layer 2.
  • the MOFs layer 1 can fill up or interpenetrate with the support separator layer 2.
  • the liquid electrolyte solvent (s) include 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-1, 3-oxazolidine-2-one, ⁇ -butyrolactone, 1, 2-di-ethoxymethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, methyl acetate, ethyl acetate
  • examples of suitable lithium salts include lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium bis (trifluoromethlysulfonylimide) (LiTFSI) , lithium bis (trifluorosulfonylimide) , lithium trifluoromethanesulfonate, lithium fluoroalkylsufonimides, lithium fluoroarylsufonimides, lithium bis (oxalate borate) , lithium tris (trifluoromethylsulfonylimide) methide, lithium tetrafluoroborate, lithium perchlorate, lithium tetrachloroaluminate, lithium chloride, or combinations thereof.
  • LiTFSI lithium bis (trifluoromethlysulfonylimide)
  • LiTFSI lithium bis (trifluorosulfonylimide)
  • lithium trifluoromethanesulfonate lithium fluoroalkylsufonimides, lithium
  • the open metal sites (OMSs) 6 in the MOF skeleton are defined as the unsaturated coordination sites from metal centers, which can be derived from eliminations of coordinated solvents or ligands on metal sites by thermal treatments (or thermal activation) .
  • the unsaturated metal sites can bound anionic species 7 in electrolyte, affording highly mobile lithium ions 8 through MOF pore channels.
  • FIG. 3 another functionality of a MOF particle in composite separator and electrolyte is shown according to one embodiment of the invention.
  • the negatively charged MOF 9 enabled by modified ligands repel the movement of anions 10, thus affording highly mobile lithium ions 11 and improved lithium ion transference number.
  • the advantages of presented ion conduction behaviors in the MOF pore channels include, but are not limited to, (1) high lithium ion transference number; (2) alleviated concentration polarization; (3) improved reaction kinetics; (4) affinitive electrode-electrolyte interfaces; (5) suppressed dendritic lithium formation; (6) enhanced power density; (7) superior durability at high rate; and (8) improved thermal stability.
  • the positive electrode may be formed of LiCoO 2 (LCO) and the negative electrode may be formed of lithium metal (Li) .
  • suitable positive electrodes include LiNiMnCoO 2 (NMC) , lithium iron phosphate (LiFePO 4 ) , lithium iron fluorophosphate (Li 2 FePO 4 F) , an over-lithiated layer by layer cathode, spinel lithium manganese oxide (LiMn 2 O 4 ) , lithium cobalt oxide (LiCoO 2 ) , LiNi 0.5 Mn 1.5 O 4 , lithium nickel cobalt aluminum oxide (e.g., LiNi 0.8 Co 0.15 Al 0.05 O 2 or NCA) , lithium vanadium oxide (LiV 2 O 5 ) , Li 2 MSiO 4 (M is composed of any ratio of Co, Fe, and/or Mn) , or any other suitable material that can sufficiently undergo lithium insertion and deinsertion.
  • NMC LiNiMnCoO 2
  • Suitable negative electrodes include graphite, hard or soft carbon, graphene, carbon nanotubes, titanium oxide (Li 4 Ti 5 O 12 , TiO 2 ) , silicon (Si) , tin (Sn) , Germanium (Ge) , silicon monoxide (SiO) , silicon oxide (SiO 2 ) , tin oxide (SnO 2 ) , transition metal oxide (Fe 2 O 3 , Fe 3 O 4 , Co 3 O 4 , Mn x O y , etc) , or any other suitable material that can undergo intercalation, conversion or alloying reactions with lithium.
  • a polymer matrix solution is prepared by dissolving about 1.4 g of PVDF-HFP in about 20 mL acetone at about 50 °C.
  • the MOF is exemplified by UiO-66, which is synthesized by dissolving ZrOCl 2 ⁇ 8H 2 O and BDC in N, N-dimethylformamide and subsequent hydrothermal treatment (about 120 °C for about 24 hours) in autoclaves.
  • the as-synthesized UiO-66 particles are thermally activated at about 350 °C under dynamic vacuum for 2 about 4 h.
  • the crystal structure of as-synthesized and activated UiO-66 (on support separator) particles are consistent with simulated UiO-66 structure as confirmed by x-ray powder diffraction.
  • the thermogravimetric analysis of UiO-66 confirms the high thermal stability of MOF, which does not decompose up to about 500 °C in air atmosphere.
  • FIG. 6 the images of scanning electron microscopy of pristine polypropylene microporous separators are shown. The unmodified separator exhibits a porous morphology with pore size of about 30 nm.
  • FIG. 7 shows the composite separator, where the surface of separator is coated with a particulate layer containing UiO-66 particles and PVDF-HFP polymer matrix.
  • a conventional potentiostatic approach is used to evaluate Li + transference number of electrolytes in pristine support separator and modified composite separator by activated UiO-66, which are displayed in FIGS. 8 and 9, respectively.
  • the Li + transference number of the electrolyte in composite separator is about 68%higher than the value derived from pristine separator (about 0.62 vs. about 0.37) , demonstrating the role of UiO-66 on improving lithium ion conduction.
  • the significance of open metal sites in UiO-66 is highlighted in this example.
  • a composite separator is prepared by UiO-66 without activation in a similar manner, the resulting Li + transference number of the electrolyte in a modified composite separator by inactivated UiO-66 is presented in FIG. 10, the obtained value of about 0.43 is close to the about 0.37 from pristine unmodified separator, further proving the importance of open metal sites Zr (IV) on immobilizing anions in pore channels of MOF.
  • the electrochemical stability of the electrolyte-imbibed composite separator against high-energy lithium metal is evaluated in Li symmetric cell at about 0.5 mA cm -2 .
  • the voltage of cell using composite separator exhibit stable and small voltage at about 50 mV
  • the cell with pristine PP separator shows escalating voltage with cycling up to about 400 h.
  • the electrochemical performances of pristine separator and composite separator (with aforementioned UiO-66 coating) in prototype batteries are shown in FIGS. 12 and 13.
  • full cells including LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM) cathode, graphite anode and electrolyte of about 1M LiPF 6 in ethylene carbonate and diethyl carbonate are used for device evaluation.
  • the areal loading of active materials is comparable to the commercial benchmarks, where the NCM loading is about 20 mg cm -2 and graphite is about 10 mg cm -2 .
  • the cell with composite separator retains 76 %of its original capacity at 0.1C, comparing with about 62 %for the cell with pristine separator at the same condition.
  • the long-term cycle stability of full cells is evaluated at 1C (initial 5 cycles at 0.2C)
  • the cell with composite separator shows higher capacity retention of about 76%after about 350 cycles than about 45%for the cell with pristine separator.
  • UiO-66-NH 2 (denoted as UN) is synthesized based on a published literature (Chem. Commun. 2013, 49, 9449–9451. ) .
  • the anionic functionalization of UN is shown, where the ligands (2-aminoterephthalic acid) are sulfonated (denoted as UN-SH) and lithiated (UN-SLi) to yield anionic grafted groups repelling the translocation of anions across the separator membrane.
  • As-synthesized UN particles are mixed with excess 1, 3-propanesultone in CHCl 3 . After being stirred at about 45 °C for 12h, the bright yellow solids are collected through the centrifuge. The solids are washed by CHCl 3 three times then dried at about 80°C to obtain SO 3 H-functionalized UN. Lithiation of UN-SH is carried out by neutralizing the UN-SH with dilute LiOH aqueous solution. The final UN-SLi was collected by filtering, washed by water and ethanol for three times each, and dried at about 80 °C. Before being used for batteries, the powder was further dried at about 120 °C under vacuum condition for activation. The crystal structure of UN, UN-SH, UN-SLi are examined by x-ray diffraction (FIG. 15) , all of which are indexable to simulated pattern of UiO-66-NH 2 .
  • FOG. 15 x-ray diffraction
  • the coating of UN-SLi on microporous propylene separator (denoted as PP, Celgard 2325) is conducted by using PVDF-HFP polymer matrix. About 0.4 g PVDF-HFP and 0.6 g UN-SLi are dispersed in 10mL acetone. After stirring at about 60 °C for about 12 h, PP membrane is dipped coated with the mixture and dried in the air. Repeat for three times. After the coating process, the membrane is dried under about 90 °C in vacuum before use.
  • Other suitable solvents to dissolve the polymer matrix may be used, for example, co-solvents of ethylene carbonate and dimethyl carbonate (denoted as EC/DMC) .
  • FIGS. 16-19 Typical scanning electron spectroscopy images of UN, PP, PP coated with UN-SLi by acetone, and PP coated with UN-SLi by EC/DMC are shown in FIGS. 16-19, respectively.
  • Commercial electrolyte about 1M LiPF 6 in ethylene carbonate and diethyl carbonate, from BASF is used to evaluate the ion conduction behaviors in the composite separator. Referring to FIG. 20, the Li + transference number of the electrolyte in (UN-SLi) -coated PP is about 0.74, indicating that the anionic MOF in composite separator can repel and immobilize the movement of anions while facilitate the conduction of lithium ions.
  • the above disclosed exemplary examples clearly indicate the invention, among other things, achieves at least the following improvements to the lithium batteries: improved lithium transference number; improved overall lithium ion conductivity; reduced interfacial resistance between electrolyte and electrode (cathode or anode) ; enhanced electrode reaction kinetics; improved electrochemical window of the lithium ion electrolyte; improved power output; improved cycled life; improved thermal stability.

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Abstract

L'invention porte sur un séparateur composite et un dispositif électrochimique tel qu'une batterie avec le séparateur composite. Le séparateur composite comprend au moins une couche composite de structure métallo-organique (MOF), et au moins une couche poreuse servant de support mécanique pour la ou les couches composites de MOF. La ou les couches composites de MOF comprennent au moins un matériau de MOF définissant une pluralité de canaux de pores et au moins un polymère. Le au moins un matériau MOF est une classe d'échafaudages poreux cristallins construits à partir d'amas métalliques avec des ligands organiques et est activé à une température pendant une période de temps telle que le au moins un matériau MOF comprend des centres métalliques insaturés, des sites métalliques ouverts et / ou défauts structurels capables de se complexer avec des anions dans l'électrolyte.
PCT/CN2020/081053 2019-03-25 2020-03-25 Séparateurs composites à revêtement de structure métallo-organique (mof) pour dispositifs électrochimiques et leurs applications WO2020192678A1 (fr)

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