US20210408549A9 - Lithium-sulfur and sodium-sulfur battery cathodes - Google Patents

Lithium-sulfur and sodium-sulfur battery cathodes Download PDF

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US20210408549A9
US20210408549A9 US17/051,764 US201917051764A US2021408549A9 US 20210408549 A9 US20210408549 A9 US 20210408549A9 US 201917051764 A US201917051764 A US 201917051764A US 2021408549 A9 US2021408549 A9 US 2021408549A9
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lithium
uio
organic framework
sulfur
defect
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Van Sara Thoi
Avery E. Baumann
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Johns Hopkins University
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    • H—ELECTRICITY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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    • 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
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the field of the invention relates generally to high capacity lithium-sulfur batteries and ambient temperature sodium sulfur batteries.
  • Li—S batteries have emerged as a promising contender to Li-ion batteries based on a high energy density of about 2600 Wh kg ⁇ 1 as compared to about 300 Wh ⁇ kg ⁇ 1 in typical Li-ion batteries. Furthermore, sulfur is an abundant and inexpensive raw material and can solve supply and cost issues associated LiCoO 2 cathodes in Li-ion batteries.
  • Li—S batteries comprise a cathode comprising sulfur, an anode comprising lithium, and an electrolyte.
  • polysulfides are reduced on the cathode surface, such as according to the following sequence:
  • polysulfides are formed at the cathode, such as according to the following sequence:
  • Li—S batteries the energy is derived from the oxidation of the Li anode to form Li + ions.
  • Li—S conversion chemistry promotes a high theoretical charge capacity of about 1680 mAh g ⁇ 1
  • challenges in Li—S devices that have hindered commercialization.
  • sulfur is a poor conductor of both ions and electrons, which attenuates the maximum capacity of the battery.
  • dissolution into the electrolyte of polysulfides from the sulfur cathode leads to a depletion of active sulfur and the formation of insoluble and insulating sulfide species on the surface of the anode and the cathode during repeated charge and discharge cycles. This phenomenon, termed the “polysulfide shuttle,” results in irreversible capacity loss and poor battery cycle life.
  • Li—S batteries To address problems associated with Li—S batteries, a variety of cathode materials have been studied to enhance conductivity and maximum charge capacity. For instance, Li 2 S has been demonstrated to improve Li ion conductivity and yield high sulfur utilization (defined as the amount of accessible sulfur for redox chemistry).
  • the Li-rich cathode provides existing Li + sites for promoting ion conduction. See, for instance: Z. Lin, et al., Lithium Superionic Sulfide Cathode for All - Solid Lithium - Sulfur Batteries , ACS Nano, 2013, 7, 2829-2833; and L.
  • Li 2 S cathodes still suffer from polysulfide leaching and high overpotentials.
  • attempts to incorporate solid-state lithium thiophosphate materials within the electrode to provide high ionic conductivity have proved to be impractical because of material instability. See, for instance, Z. Lin, et al., Lithium polysulfidophosphates: a family of lithium - conducting sulfur - rich compounds for lithium - sulfur batteries , Angew. Chem. Int. Ed. Engl., 2013, 52, 7460-3.
  • RT Na—S Ambient temperature sodium-sulfur batteries
  • RT Na—S batteries comprise a cathode comprising sulfur, an anode comprising sodium metal, and an electrolyte.
  • polysulfides are reduced on the cathode surface and during the battery charging cycle, polysulfides are formed at the cathode as follows:
  • a battery cathode comprises a plurality of defected metal organic framework moieties: (i) wherein each defected metal organic framework moiety independently comprises at least one defect selected from a structural defect and a compositional feature; and (ii) wherein each defect independently allows for capture of battery anode metal ions, incorporation of chemical anchor substituents for capture of polysulfides, or a combination thereof.
  • a lithium-sulfur battery comprises: (i) an anode comprising lithium; (ii) an electrolyte; and (iii) a cathode comprising sulfur and a plurality of defected metal organic framework moieties, (1) wherein each defected metal organic framework moiety independently comprises at least one defect selected from a structural defect and a compositional feature; and (2) wherein each defect independently allows for capture of battery anode metal ions or incorporation of chemical anchor substituents for capture of polysulfides.
  • a solid material having lithium conductivity comprises lithium and a plurality of defected metal organic framework moieties: (i) wherein each defected metal organic framework moiety independently comprises a defect selected from a metal coordination site, a compositional feature and a protic site; and (ii) wherein the lithium is bound to or captured by the defect.
  • a method of using a lithium-sulfur battery comprises providing a lithium-sulfur battery, said battery having a charge cycle and a discharge cycle.
  • the battery comprises (a) an anode comprising lithium, (b) an electrolyte, and (c) a cathode comprising sulfur and a plurality of defected metal organic framework moieties comprising at least one defect selected from a structural defect and a compositional feature wherein each defect independently allows for capture of lithium ions;
  • the discharge cycle comprises reducing elemental sulfur and/or lithium polysulfides to lithium sulfide at the cathode, wherein at least a portion of the lithium polysulfides is captured by the defected metal organic framework moieties;
  • the charge cycle comprises oxidizing lithium sulfide to lithium polysulfides and/or elemental sulfur at the cathode, wherein at least a portion of the lithium polysulfides in the oxidation
  • the lithium-sulfur battery comprises (a) an anode comprising lithium, (b) an electrolyte, and (c) a cathode comprising sulfur and a plurality of defected metal organic framework moieties comprising at least one defect selected from a chemical anchor substituent capable of functionalizing polysulfides thereto and a metal coordination site;
  • the discharge cycle comprises reducing elemental sulfur and/or lithium polysulfides to lithium sulfide at the cathode, wherein at least a portion of the polysulfides are captured by functionalization to the metal organic framework chemical anchor sites;
  • the charge cycle comprises oxidizing lithium sulfide to lithium polysulfides and/or elemental sulfur at the cathode, wherein at least a portion of the lithium polysulfides in the oxidation reaction is the lithium polysulfides captured in the discharge cycle.
  • the lithium-sulfur battery comprises (a) an anode comprising lithium, (b) an electrolyte, and (c) a cathode comprising sulfur and (I) a plurality of defected metal organic framework moieties comprising at least one defect selected from a structural defect and a compositional feature wherein each defect independently allows for capture of lithium ions and (II) and a plurality of defected metal organic framework moieties comprising at least one defect selected from a chemical anchor substituent capable of functionalizing polysulfides thereto and a metal coordination site; (2) the discharge cycle comprises reducing elemental sulfur and/or lithium polysulfides to lithium sulfide at the cathode wherein at least a portion of the lithium polysulfides are captured by functionalization to the metal organic framework chemical anchor sites; and (3) the charge cycle comprises oxidizing lithium sulfide to lithium polysulfides and/or elemental sulfur at the cathode wherein at least a portion of the lithium polysulf
  • an ambient temperature sodium-sulfur battery comprises: (i) an anode comprising sodium; (ii) an electrolyte; and (iii) a cathode comprising sulfur and a plurality of defected metal organic framework moieties, (1) wherein each defected metal organic framework moiety independently comprises at least one defect selected from a structural defect and a compositional feature, and (2) wherein each defect independently allows for capture of battery anode metal ions or incorporation of chemical anchor substituents for capture of polysulfides.
  • a solid material having sodium conductivity comprises sodium and a plurality of defected metal organic framework moieties: (i) wherein each defected metal organic framework moiety independently comprises a defect selected from a metal coordination site, a compositional feature and a protic site; and (ii) wherein the sodium is bound to or captured by the defect.
  • a method of using an ambient temperature sodium-sulfur battery comprises providing a sodium-sulfur battery, said battery having a charge cycle and a discharge cycle.
  • the battery comprises (a) an anode comprising sodium, (b) an electrolyte, and (c) a cathode comprising sulfur and a plurality of defected metal organic framework moieties comprising at least one defect selected from a structural defect and a compositional feature wherein each defect independently allows for capture of sodium ions;
  • the discharge cycle comprises reducing elemental sulfur and/or sodium polysulfides to sodium sulfide at the cathode, wherein at least a portion of the sodium polysulfides is captured by the defected metal organic framework moieties;
  • the charge cycle comprises oxidizing sodium sulfide to sodium polysulfides and/or elemental sulfur at the cathode, wherein at least a portion of the sodium polysulfides in the oxidation reaction
  • the sodium-sulfur battery comprises (a) an anode comprising sodium, (b) an electrolyte, and (c) a cathode comprising sulfur and a plurality of defected metal organic framework moieties comprising at least one defect selected from a chemical anchor substituent capable of functionalizing polysulfides thereto and a metal coordination site;
  • the discharge cycle comprises reducing elemental sulfur and/or sodium polysulfides to sodium sulfide at the cathode, wherein at least a portion of the polysulfides are captured by functionalization to the metal organic framework chemical anchor sites;
  • the charge cycle comprises oxidizing sodium sulfide to sodium polysulfides and/or elemental sulfur at the cathode, wherein at least a portion of the sodium polysulfides in the oxidation reaction is the sodium polysulfides captured in the discharge cycle.
  • the sodium-sulfur battery comprises (a) an anode comprising sodium, (b) an electrolyte, and (c) a cathode comprising sulfur and (I) a plurality of defected metal organic framework moieties comprising at least one defect selected from a structural defect and a compositional feature wherein each defect independently allows for capture of sodium ions and (II) and a plurality of defected metal organic framework moieties comprising at least one defect selected from a chemical anchor substituent capable of functionalizing polysulfides thereto and a metal coordination site; (2) the discharge cycle comprises reducing elemental sulfur and/or sodium polysulfides to sodium sulfide at the cathode wherein at least a portion of the sodium polysulfides are captured by functionalization to the metal organic framework chemical anchor sites; and (3) the charge cycle comprises oxidizing sodium sulfide to sodium polysulfides and/or elemental sulfur at the cathode wherein at least a portion of the sodium polysulf
  • FIG. 1 depicts one aspect of the present disclosure for introducing defective sites on UiO-66 metal organic frameworks and lithiating the defected metal organic framework.
  • FIG. 4A depicts the galvanostatic cycling results in specific capacity (mAh g ⁇ 1 ) versus cycle number for lithium-sulfur batteries of the present disclosure having a cathode comprising lithiated metal organic frameworks (LPS-UiO-66(50Benz) and LPS-Uio66(noMod)) versus a battery having a cathode comprising a non-lithiated metal organic framework (UiO-66(50Benz) and a battery comprising a sulfur-carbon composite cathode (S/C).
  • LPS-UiO-66(50Benz) and LPS-Uio66(noMod) versus a battery having a cathode comprising a non-lithiated metal organic framework (UiO-66(50Benz) and a battery comprising a sulfur-carbon composite cathode (S/C).
  • S/C sulfur-carbon composite cathode
  • FIG. 7 depicts solid-state 31 P Nuclear Magnetic Resonance (NMR) spectrum for a LPS-functionalized UiO-66 of the present disclosure ( FIG. 7A ) and a LPS-functionalized MOF-808 of the present disclosure ( FIG. 7B ).
  • NMR Nuclear Magnetic Resonance
  • FIG. 8 depicts an example of a coin cell battery.
  • the coin cell battery has a cathode comprising a defected metal organic framework of the present disclosure.
  • FIG. 9 depicts Powder X-ray diffraction (PXRD) results in counts versus position in 2° Theta for lithiated defected metal organic frameworks of the present disclosure (Li-UiO-66(noMod), Li-UiO-66(50Benz) and Li-UiO-66(12TFA)) and for a non-lithiated metal organic framework (UiO-66(50Benz)).
  • PXRD Powder X-ray diffraction
  • FIG. 11A depicts thermographic analysis (TGA) results in Weight Loss (%) versus Temperature (T) for a non-lithiated metal organic framework (UiO-66(50Benz)) and FIG. 11B depicts TGA results in Weight Loss (%) versus Temperature (T) for a lithiated metal organic framework of the present disclosure (Li-UiO-66(50Benz)).
  • FIG. 12 depicts atomic absorption spectroscopy (AAS) results of lithium incorporated into lithiated metal organic frameworks of the present disclosure (Li-UiO-66(MOD)) prepared under various lithiation synthetic conditions.
  • AAS atomic absorption spectroscopy
  • FIG. 13 depicts maximum discharge capacity (mAh g ⁇ 1 ) versus relative lithium content as measured by atomic absorption spectroscopy for various lithium-sulfur batteries of the present disclosure having cathodes comprising lithiated metal organic frameworks of the present disclosure (Li-UiO-66(50Benz) and Li-UiO-66(12TFA)), for a lithium-sulfur battery having a cathode comprising a lithiated non-modified metal organic framework (Li-UiO-66(noMod)), for lithium-sulfur batteries having cathodes comprising non-lithiated metal organic frameworks (UiO-66(50Benz)), and for a lithium-sulfur battery having a cathode comprising a metal organic framework lithiated at harsher chemical conditions (Li-UiO-66(50Benz)-80, Li-UiO-66(50Benz)-nBuLi).
  • FIG. 15A depicts rate capability in relative capacity (mAh g ⁇ 1 ) versus cycle number at low to moderate charge rates of from C/10 to 2 C for a lithium-sulfur battery of the present disclosure having a cathode comprising lithiated metal organic frameworks (Li-UiO-66(50Benz)) versus a battery having a cathode comprising a non-lithiated metal organic framework (UiO-66(50Benz)).
  • Li-UiO-66(50Benz) lithiated metal organic frameworks
  • UiO-66(50Benz) non-lithiated metal organic framework
  • 16B depicts the compiled galvanostatic cycling results for the capacity at 100 ⁇ cycles (mAh g ⁇ 1 ) versus lithium weight percent, where increased Li wt. % correlates with increased LPS incorporation, for lithium-sulfur batteries of the present disclosure having a cathode comprising lithiated metal organic frameworks (LPS-UiO-66(50Benz); LPS-UiO-66(noMod); 2 ⁇ LPS MOF-808; 1 ⁇ LPS MOF-808; and 0.7 ⁇ LPS MOF-808) versus batteries having a cathode comprising a non-lithiated metal organic framework (UiO-66(50Benz) and MOF-808) and a battery comprising a S/C composite cathode.
  • LPS-UiO-66(50Benz) LPS-UiO-66(noMod
  • 2 ⁇ LPS MOF-808 1 ⁇ LPS MOF-808
  • 0.7 ⁇ LPS MOF-808 0.7 ⁇ LPS MOF
  • FIG. 17A depicts rate capability in specific capacity (mAh g ⁇ 1 ) versus cycle number at low to moderate charge rates of from C/10 to 2 C for a lithium-sulfur battery of the present disclosure having a cathode comprising lithiated metal organic frameworks (LPS-UiO-66(50Benz)) versus a battery having a cathode comprising a non-lithiated metal organic framework (UiO-66(50Benz)) and a battery comprising a S/C composite cathode.
  • LPS-UiO-66(50Benz) lithiated metal organic frameworks
  • UiO-66(50Benz) non-lithiated metal organic framework
  • FIG. 17B depicts rate capability in specific capacity (mAh g ⁇ 1 ) versus cycle number at moderate to high charge rates of from C/2 to 4 C for a lithium-sulfur battery of the present disclosure having a cathode comprising lithiated metal organic frameworks (LPS-UiO-66(50Benz)) versus a battery having a cathode comprising a non-lithiated metal organic framework (UiO-66(50Benz)) and a battery comprising a S/C composite cathode.
  • LPS-UiO-66(50Benz) lithiated metal organic frameworks
  • UiO-66(50Benz) non-lithiated metal organic framework
  • FIG. 18 at the bottom three lines in the graph and the left axis, depict extended galvanic cycling profiles in specific capacity (mAh g ⁇ 1 ) versus cycle number at 1 C for lithium-sulfur batteries of the present disclosure having a cathode comprising lithiated metal organic frameworks (LPS-UiO-66(50Benz) and LPS-UiO-66(noMod)) versus a battery having a cathode comprising a S/C composite cathode.
  • LPS-UiO-66(50Benz) and LPS-UiO-66(noMod) lithiated metal organic frameworks
  • FIG. 19 depicts the NMR spectrum of Li 5 P 2 S 6 N material of the present disclosure.
  • FIG. 20 depicts the IR spectrum of Li 5 P 2 S 6 N material of the present disclosure.
  • Li—S batteries and RT Na—S batteries comprising defected material organic framework (MOF) moieties provide for improved absolute capacity and improved capacity retention as compared to Li—S batteries and RT Na—S batteries known in the art.
  • high capacity Li—S battery cathodes comprising lithiated MOFs provide for extended Li—S cycling.
  • high capacity RT Na—S battery cathodes comprising sodiated MOFs provide for extended RT Na—S cycling.
  • MOFs that are derivatized with chemical anchors provide for capture and/or encapsulation of polysulfides resulting in Li—S performance improvements through reduction of dissolution of polysulfides in the electrolyte and concomitant loss of reactive sulfur.
  • MOFs that are derivatized with the chemical anchors provide for capture and/or encapsulation of polysulfides resulting in RT Na—S performance improvements through reduction of dissolution of polysulfides in the electrolyte and concomitant loss of reactive sulfur.
  • Li—S and RT Na—S batteries of the present disclosure achieve an order of magnitude in energy density compared to current Li-ion and RT Na—S technologies while providing for improved battery cycle life and capacity retention as compared to current Li—S and RT Na—S technologies.
  • Li—S batteries of the present disclosure have an absolute capacity of at least 800 mA h g ⁇ 1 , at least 900 mAh g ⁇ 1 , at least 1000 mAh g ⁇ 1 , at least 1100 mAh g ⁇ 1 , at least 1200 mAh g ⁇ 1 , at least 1300 mAh g ⁇ 1 , for instance 1320 mAh g ⁇ 1 .
  • Li—S batteries of the present disclosure further have an absolute capacity of at least 800 mAh g ⁇ 1 , at least 900 mAh g ⁇ 1 , at least 1000 mAh g ⁇ 1 , at least 1100 mAh g ⁇ 1 , or at least 1200 mAh g ⁇ 1 , after 20 charge-discharge cycles. In some aspects, Li—S batteries of the present disclosure have a capacity retention of at least 60%, at least 65%, at least 70%, at least 75% or at least 80% after 20 charge-discharge cycles.
  • a “metal node” refers to a cluster comprising two or more metal ions connected by bridging oxide and/or hydroxide ligands. Such nodes may be referred to as a secondary binding unit (SBU).
  • SBU secondary binding unit
  • a non-limiting example of a metal node is hexa-zirconium oxo-hydroxo.
  • MOF metal organic framework
  • MOF structure may be characterized as a porous framework having voids and may be further characterized by surface area.
  • an “organic ligand” or “organic linker” refers to a molecule or combination of molecules comprising at least one C—H bond and which is/are capable of binding to at least two metal nodes.
  • defects refer to sites capable of capture/encapsulation of metal ions (e.g., Li t ) and/or polysulfides.
  • Defects may be a structural defect such as a dislocation, local defect or large scale defect, where the defect results in one or more MOF voids or vacancies.
  • Other defects may be compositional features such as metal coordination sites, protic sites (e.g., —OH and —OH 2 ) for functionalization, chemical anchors, and substituents functionalized on the organic linker. See, for instance: Z. Fang, et al., Defect Engineered Metal - Organic Frameworks , Agnew. Chem. Int. Ed.
  • At least 50%, at least 75% or at least 90% by number of MOF moieties in a plurality of MOF moieties comprise at least one defect.
  • a defect in a solid material structure may be a local defect (or point defect), a large-scale defect, or a dislocation.
  • Point defects are generally of atomic size and may result from: the occupancy (replacement) of one or more sites in a lattice structure or a metal organic framework by an impurity (e.g., an atom or an ion) where such replacement atoms are termed extrinsic defects; a void (vacancy) due to the absence of an atom where voids are termed as an intrinsic defect; or the presence of an extra atom or extra ion at one or more lattice structure sites where no atom would normally appear, where such extra atoms are termed as an intrinsic defect.
  • an impurity e.g., an atom or an ion
  • Dislocations are irregularities in within a solid material structure and result from the change in the regular ordering of atoms along a line, termed a dislocation line.
  • a large-scale structural defect (or volume defect or a bulk defect) is generally a three-dimensional aggregate of atoms or voids large enough to affect the three dimensional (macroscopic) structure of a solid material as may be reflected in one or more solid material properties, such as structure mechanical strength, porosity, cracking, and the formation of separate small regions of homogenous and heterogeneous material (e.g., due to atom clustering).
  • MOF refers to a MOF wherein one or more of the backbone atoms of the organic linkers carries a pendant functional group, a MOF functionalized with a chemical anchor (such as Li 3 PS 4 ).
  • Metal-organic MOFs are tunable materials with the ability to incorporate functionalities through the selection of organic linkers and metal ion precursors.
  • the high porosity of MOFs provides the ability to host and stabilize reactive sulfide species and metal ions (e.g., lithium ions), while the associated structural integrity and long-range order provides a convenient handle for the detection of intermediates using molecular spectroscopy and single-crystal and powder diffraction techniques.
  • Sodium-sulfur batteries are known in the art. See, for instance and without limitation: K. Kumar, et al., Progress and prospects of sodium sulfur batteries: A review , Solid State Ionics 312 (2107) 8-16; A. Douglas, et al., Ultrafine Iron Pyrite ( FeS 2 ) Nanocrystals Improve Sodium - Sulfur and Lithium - Sulfur Conversion Reactions for Efficient Batteries , ACS Nano, Vol. 9, No. 11, 11156-11165, 2015; and A. Abouimrane, A New Class of Lithium and Sodium Rechargeable Batteries Based on Selenium and Selenium - Sulfur as a Positive Electrode , J. Am. Chem.
  • the metal for the MOF is suitably any metal, such as for instance and without limitation, a transition metal that provides for defected MOF suitable for capture/encapsulation of metal ions and polysulfide.
  • the metal is selected from zirconium, hafnium, cerium, copper, zinc, titanium, iron, vanadium, molybdenum, niobium, and chromium, and combinations thereof.
  • the metal is selected from a combination of at least two of zirconium, hafnium, cerium, copper, zinc, titanium, iron, vanadium, molybdenum, niobium, and chromium.
  • the metal is zirconium.
  • the MOFs are Zr-based.
  • a Zr-MOF species is UiO-66.
  • MOF-808 Another example of such as Zr-MOF species is MOF-808.
  • the MOF is a porous Zr-based MOF, and the MOF is incorporated with lithium atoms fur use as a Li-rich MOF/S cathode for Li—S batteries.
  • Typical zirconium MOF node structures consist of a hexanuclear Zr cluster connected by bridging oxide and hydroxide ligands.
  • the SBU may be formed in the presence of carboxylic acids, resulting in the generic formula of Zr 6 ( ⁇ 3 -O) 4 ( ⁇ 3 -OH) 4 (RCOO) 12 .
  • 1,4-benzenedicarboxylic acid serves as a ditopic linker forming and connecting the SBUs of the MOF where all carboxylic acid sites are occupied.
  • H 2 BDC 1,4-benzenedicarboxylic acid
  • Defected UiO-66 exhibits higher BET surface area than pristine MOF (i.e., non-defected MOF) as characterized by a surface are increase of at least 5%, at least 10%, at least 15%, at least 20% or at least 25% and contain open Zr sites where an aqua and hydroxo ligand occupy the missing-linker site. These defected sites are reactive and can be further functionalized using other carboxylates or phosphates. See: G. C. Shearer, et al., Chem. Mater., 2016, 28, 7190-7193; G. C. Shearer, et al., Chem. Mater., 2016, 28, 3749-3761; S.
  • the introduction of missing linker defects introduces additional protons that can be swapped for Li + and create additional Li + storage sites.
  • Such a deprotonating method differs from prior art methods (such as disclosed by R. Ameloot, et al., Ionic Conductivity in the Metal - Organic Framework UiO -66 by Dehydration and Insertion of Lithium tert - Butoxide , Chem.—A Eur. J., 2013, 19, 5533-5536, incorporated by reference herein in its entirety) for dehydration of the Zr nodes in order to increase Li + ionic conductivity and sulfur utilization.
  • the node structure of Zr-MOFs features six metal atoms connected by bridging hydroxo, oxo, and carboxylate ligands. In a fully coordinated node, twelve carboxylates bridge each Zr atom to its neighboring atom and prevent interaction with guest species. If a portion of the nodal carboxylate ligands are removed, open sites become available to bind guest molecules, providing synthetic handles for the advanced functionalization of the metal node (see, e.g., FIG. 3 ). Certain Zr-MOFs are capable of supporting these open sites, either through the inherent crystal structure (for example, and without limitation, MOF-808) or by introducing defects using a modulated synthetic approach (for example, and without limitation, UiO-66).
  • BTC 1,3,5-benzenetricarboxylate
  • the formate (HCOO) sites can be removed under HCl activation and functionalized with other carboxylic acids and chemical anchors, such as thiophosphates.
  • Synthesis of MOF-808 has been reported. See: H. Furukawa, et al., Water Adsorption in Porous Metal - Organic Frameworks and Related Materials , J. Am. Chem. Soc.
  • Non-defected MOF-808 comprises at least six more potential aqua/hydroxyl terminal sites per Zr cluster as compared to the parent UiO-66 MOF (non-defected). It is believed that introduction of additional defects to MOF-808 may be done using synthetic methods described herein.
  • the organic linker is not narrowly limited and may suitably be any organic linker conventionally used in MOF production.
  • Suitable organic linkers generally comprise at least two functional groups selected from carboxylic acid, boronic acid, amine, nitro, anhydride, hydroxyl, and combinations thereof.
  • Organic linkers having two, three or four functional groups are within the scope of the present disclosure.
  • the functional groups are selected from carboxylate and hydroxyl, and a combination thereof.
  • each functional group is carboxyl.
  • the organic linker may comprise a linear or branched C 1-20 alkyl group, a C 3-12 cycloalkyl group, an aromatic moiety, and combinations thereof.
  • the alkyl group is a C 1-6 alkyl.
  • the cycloalkyl group is a C 4-6 cycloalkyl.
  • the aromatic moiety can comprise from 1 to 6 rings.
  • the rings may optionally be present in a spirocycle or fused configuration.
  • the aromatic moiety comprises one or two rings, such as benzyl, naphthyl, pyridyl or bipyridyl.
  • the alkyl, cycloalkyl and aromatic moieties may optionally comprise one or more heteroatoms selected from N, O, S, and Si.
  • suitable organic linker compounds include: BTC; oxalic acid; ethyloxalic acid; fumaric acid; 1,3,5-benzene tribenzoic acid (BTB); 1,3,5-benzene tribenzoic acid; benzene tribiphenylcarboxylic acid (BBC); 5,15-bis (4-carboxyphenyl) zinc (II) porphyrin (BCPP); 1,4-benzene dicarboxylic acid (H 2 BDC); 2-amino-1,4-benzene dicarboxylic acid (R3-BDC or H2N BDC); 1,2,4,5-benzene tetracarboxylic acid; 2-nitro-1,4-benzene dicarboxylic acid; 1,1′-azo-diphenyl 4,4′-dicarboxylic acid; cyclobutyl-1,4-benzene dicarboxylic acid (R6-BDC); 1,2,4-benzene tricarboxylic acid; 2,6-naphthal
  • the organic linker compounds are selected from H 2 BDC, 2-amino-1,4-benzene dicarboxylic acid, 1,2,4-benzene tricarboxylic acid, 1,2,4,5-benzene tetracarboxylic acid and 2-nitro-1,4-benzene dicarboxylic acid or mixtures thereof.
  • the organic linker compound is H 2 BDC.
  • a mixture of two or more of the above-mentioned linkers may be used to introduce one or more functional groups.
  • aminobenzoic acid may be used to provide free amine groups or by using a shorter linker such as oxalic acid.
  • the electrolyte is not narrowly limited, and suitable electrolytes are known in the art. Solid and liquid electrolytes are within the scope of the present disclosure. See, for instance: J. Scheers, et al., A review of electrolytes for lithium - sulfur batteries, Journal of Power Sources, 2014, 255(1), 204-218; X. Yu, et al., Electrode - Electrolyte Interfaces in Lithium - Sulfur Batteries with Liquid or Inorganic Solid Electrolytes , Acc. Chem. Res., 2017, 50(11), 2653-2660; and X.
  • the electrolytes may suitably comprise ether mixtures, dimethylsulfoxide, and dimethylformamide.
  • An example of one such electrolyte is Li bis(trifluoromethane sulfonimide) (LiTFSI) dissolved in a mixture of dimethoxyethane and dioxalane.
  • defected UiO-66 samples may be synthesized using the modulated synthesis approach developed by Lillerud et al,. using competing monocarboxylic acids that are then incorporated into the MOF structure (See G. Shearer, et al., Functionalizing the Defects: Postsynthetic Ligand Exchange in the Metal Organic Framework UIO -66, Chem. Mater. 2016, 28, 7190-7193 and G. C. Shearer, et al., Defect Engineering: Tuning the Porosity and Composition of the Metal - Organic Framework UiO -66 via Modulated Synthesis , Chem.
  • the competing carboxylic acid can then be swapped with an aqua and hydroxyl ligand to create an open site on the UiO-66 Zr 6 -cluster for further binding or functionalization.
  • modulating strength e.g. pKa, binding constants
  • molar ratio of the modulator to the multi-topic carboxylic acid linker used in synthesis a series of MOFs with controllable defect concentrations may be obtained.
  • An increase in missing linker sites correlates to an increased number of labile protons by introducing H 2 O— and HO— groups that can be quantified by potentiometric acid-base titration. See M. R. R.
  • lithiated defected UiO-66 exemplified by Li-UiO-66(50Benz) in FIG. 14 , provided for enhanced Li—S capacity retention as compared to parent UiO-66.
  • lithiated defected UiO-66 provided for a maximum Li—S battery capacity of about 900 mAh g ⁇ 1 (about 1390 Wh kg ⁇ 1 ) and it is believed that the use of MOFs with lithiated defect sites used as a host for polysulfides improves Li—S cyclability and provides for a specific energy density closer to the theoretical limit.
  • the degree of lithium incorporation can be controlled by, for instance, (i) the concentration of defect sites, (ii) the strength of the base (pKa ⁇ 30), and (iii) the temperature used for synthesis ( ⁇ 77 to 200° C.).
  • the pK a values of the UiO-66 ⁇ 3 -OH, —OH 2 , and —OH are 3.52, 6.79, and 8.30, respectively. See R. C.
  • the strong base is an organolithium base such as N-butyllithium.
  • the base is an amine, a hydroxide, or an alkoxide such as pyridine, trimethylamine (TEA), or sodium methoxide.
  • the polar solvent may be selected from N-methylpyrrolidone, tetrahydrofuran, ethyl acetate, acetone, methanol, ethanol, dimethylformamide (DMF) acetonitrile, dimethyl sulfoxide and propylene carbonate.
  • the solvent is DMF.
  • the lithium source may come from an organolithium base or a lithium salt such as, but not limited to, LiNO 3 .
  • the lithiation procedure may suitably have a reaction time of at least one hour, at least 4 hours, at least 8 hours, at least 16 hours or at least 24 hours, such as for instance 24 hours.
  • Li reservoirs in the MOFs will promote encapsulation of polysulfides through favorable electrostatic interactions.
  • Li-rich cathodes based on the success of using Li-rich cathodes, it is believed that the amount of lithium in the cathode may favorably influence polysulfide encapsulation and Li—S battery performance.
  • the reduction of neutral sulfur (S 8 ) to shorter chain lithium polysulfides requires the diffusion of charge-balancing Li + ions to reach high sulfur utilization in a Li—S battery (see FIG. 2 ).
  • Increasing the Li content would not only further promote Li ion conduction, but also provide favorable electrostatic interactions to stabilize the charged polysulfides and prevent their dissolution.
  • Li content is not easily tunable in conventional solid-state materials as it may ultimately impact the lattice energy and lead to other structural changes.
  • lithium-defected MOFs are provided that promote metal conduction and electrostatic interactions with polysulfides.
  • Li—S cathodes comprise such lithium-defected MOFs.
  • the defected MOFs are Zr-MOFs.
  • Lithiated-MOFs provide for high-capacity sulfur cathodes and extended Li—S cycling. A scheme for lithiating defected Zr-MOFs is depicted in FIG. 1 .
  • lithium-defected MOFs are provided that incorporate chemical anchor functional groups for covalent anchoring of polysulfides.
  • Li—S cathodes comprise such lithium-defected MOFs.
  • suitable chemical anchors for polysulfides include: thiophosphates, such as [P x O y S z ] a ⁇ where x is 1-3, y is 0-9, z is 1-10, and a is 3-6; thiogermanates, such as [Ge x O y S z ] a ⁇ where x is 1-3, y is 0-9, z is 1-10, and a is 3-6; and thioarsenates, such as [As x O y S z ] a ⁇ where x is 1-3, y is 0-9, z is 1-10, and a is 3-6.
  • FIG. 3 depicts introducing —OH and —H 2 O protic defect sites to linked Zr-UiO-66 MOF clusters, deprotonizing the active sites, and lithiating the deprotonated defective MOF active sites thereby generating Li-UiO-66(MOD) (where UiO-66(MOD) refers to defected UiO-66 synthesized with modulators (MOD), such as benzoic acid and TFA).
  • modulators such as benzoic acid and TFA
  • chemical anchor functional groups for covalent anchoring of polysulfides are thiophosphates of the general formula M r P n S o and M r P n S o X q .
  • M is Li or Na.
  • X is a non-sulfur atom such a N, O or a halide.
  • r is 2 to 9, n is 1 to 3, o is 1 to 8, and q is 1 to 4.
  • suitable anchors include Li 5 P 2 S 6 N, Li 3 PS 3 O, and Li 2 PS 3 Cl.
  • Such lithiated thiophosphate chemical anchors are referred to as LPSN, LPSO, or LPSX.
  • Li—S cathodes comprise both lithium-defected MOFs that promote metal conduction and electrostatic interactions with polysulfides as described herein and lithium-defected MOFs that incorporate chemical anchor functional groups for covalent anchoring of polysulfides as described herein.
  • Li—S battery performance may be demonstrated by galvanostatic cycling studies.
  • One metric of battery performance in Li—S batteries is maximum charge capacity that is a reflection of the ability of the battery to store charge and is directly related to the total energy density.
  • the additional Li sites promote the reduction of polysulfides and enhance the maximum charge capacity.
  • the cycle life metric is measured by the relative capacity after extended galvanostatic cycling. The rate of capacity decay provides insights on the ability of the MOFs to retain polysulfides during the discharge cycles.
  • the obtained solids were collected by centrifuge and washed in 150 mL of fresh DMF overnight. The solids were again collected and washed with DMF in this manner 2 ⁇ more times for 4 h. After washing, the MOF powders were dried overnight at 60° C.
  • HCl activation was used in accordance with previous modulated synthesis of UiO-66. See G. Shearer, et al., Chem. Mater. 2016, 28, 7190-7193.
  • a DMF-HCl solution was prepared using a ratio of 600:25 of DMF to 8M HCl (v/v). For every 2 g of UiO-66-MOD obtained, 600 mL of this solution was used for the HCl activation process.
  • the HCl activation process may be scaled up or down accordingly.
  • Li-UiO-66(noMod) was also synthesized and activated using the same procedure except no modulators were added in the initial UiO-66 synthesis.
  • a lithium incorporation solution was prepared by dissolving 82 mg LiNO 3 (70 mmol) in 10.5 mL DMF. Once dissolved, 6.3 mL of triethylamine (TEA, 45 mmol) was added to the solution as the base for deprotonation. This solution was then added to a 20 mL scintillation vial containing about 150 mg HCl-Activated UiO-66(MOD) followed by shaking to mix. The mixture was allowed to react (e.g. at room temperature or in an oven set to 60 or 80° C. for 24 h). After 24 hours the solution was decanted and replaced with 20 mL of acetone.
  • TEA triethylamine
  • the solids were collected by centrifuge, washed with 20 mL acetone, and allowed to soak in a new acetone solution overnight. The solids were washed four more times with acetone, and after one of the additional washes the solids were soaked overnight in acetone. Following the acetone washes, the solvent was switched to DCM and the above wash process was repeated. After the last DCM wash, the solvent was removed and the Li-UiO-66(MOD) solid was allowed to dry in air. Samples were stored in a desiccator until further use or characterization.
  • n-butyl lithium was used as the base instead of TEA.
  • As-synthesized UiO-66(50Benz) was solvent-exchanged from DMF to acetone and then to DCM using the washing procedure described above.
  • 150 mg of MOF was then placed into a 25 mL round bottom flask fitted with a Schlenk adapter and purged under flowing nitrogen.
  • 7 mL of a 1.6 M n-butyl lithium solution in hexane was slowly added to the flask under flowing nitrogen and held for 24 h. The solution was removed and the collected MOF was washed several times with 10 mL pentane followed by soaking and solvent exchange using distilled tetrahydrofuran.
  • FIGS. 9 and 10 both show the lithiated MOFs remain structurally intact with high crystallinity.
  • FIG. 9 and 10 both show the lithiated MOFs remain structurally intact with high crystallinity.
  • FIG. 9 shows that, for TEA-treated MOFs and based on PXRD, the lithiated MOF structure remains intact with crystallinity as compared to HCl-activated UiO-66(50Benz).
  • the asterisks in FIG. 10 shows that UiO-Li has characteristic MOF carbonyl stretches thereby indicating that the structure is preserved.
  • a slight shift in the Zr—O peak (denoted by o) indicates that supporting node deprotonation occurs.
  • Li-UiO-66(50Benz) and non-lithiated UiO-66(50Benz) were further evaluated by scanning electron microscopy (JEOL JSM IT100) and showed no deterioration of the octahedral crystals or a change in particle size between Li-UiO-66(50Benz) and UiO-66(50Benz).
  • thermographic analysis TGA, TA Instruments SDT Q600 under flowing Ar at a heating rate of 5.0° C. min ⁇ 1 ).
  • TGA plots depicted in FIGS. 11A and 11B show the characteristic thermal stability of the Li-MOF remains unchanged as compared to MOF.
  • Li-UiO-66(50Benz) and UiO-66(50Benz) were further evaluated by nitrogen adsorption techniques (Micromeritics ASAP2020Plus).
  • Li-UiO-66(50Benz) provided a BET surface area of 450.6 m 2 /g and UiO-66(50Benz) provided a BET surface area of 1520.8 m 2 g ⁇ 1 .
  • the BET data show increasing surface area as a function of defect concentration.
  • the experimental data therefore show that the lithiation method does not degrade the UiO-66 structure, and the advantageous properties of high crystallinity, thermal stability, and high surface area are preserved.
  • the defect site concentration plays a role in lithium storage capability. Since an increased number of defect sites results in more acidic protons, the most defected samples will undergo H + /Li + exchange readily and have a higher lithium content. Based on experimental evidence, it has been shown that the lithium content in Li-UiO-66(noMod), Li-UiO-66(12TFA), and Li-UiO-66(50Benz) increases as a function of defect concentration as quantified by Li and Zr atomic absorption spectroscopy (AAS, Perkin Elmer AAnalyst 100 system and Perkin Elmer Intesitron hollow cathode lamps). As depicted in FIG.
  • AAS Perkin Elmer AAnalyst 100 system and Perkin Elmer Intesitron hollow cathode lamps.
  • Li-UiO66(50Benz)-80 leads to an increase in molar Li concentration by 1.3 and 1.7 ⁇ , respectively (see FIG. 12 and Table 2).
  • the use of the stronger base, n-butyllithium (Li-UiO-66(50Benz)-nBuLi), at room temperature also enhanced the molar Li content by 1.8 ⁇ compared to the analogous room-temperature lithiation using TEA.
  • the highly lithiated MOFs achieved via these alternate routes maintain their structural integrity and crystallinity (See FIGS. 9, 10, 11A and 11B ).
  • Li-UiO-66(noMod) Li-UiO-66(12TFA) 7.8 Li-UiO-66(50Benz) 10.4 Li-UiO-66(50Benz)-no base 0.6 Li-UiO-66(50Benz)-acid 0.0 Li-UiO-66(50Benz)-pyridine 1.1
  • UiO-66(noMod) and MOF-808 were further evaluated for number of open sites and surface area. The number of open sites was determined by potentiometric acid-base titration according to the following method. First, the activated MOF powders were washed with acetone (5 ⁇ 20 mL over 24 h) and evacuated at 150° C. for 2 h to remove protic solvents from within the MOF. The evacuated flask was then charged with nitrogen and approximately 40 mg of powder was placed into a beaker.
  • the derivative curve (dpH/dV, where V is the volume of 0.05 M NaOH solution) was used to determine the equivalence points (EP) to quantify the number of missing linkers for UiO-66 and MOF-808 samples, following previously reported procedures.
  • the surface area was determined by The BrunauerEmmett Teller (BET) method was applied to obtain a surface area from the N2 adsorption isotherms. Nitrogen adsorption isotherms (Micromeritics ASAP 2020) used to calculate BET surface areas were collected on samples that had been thoroughly degassed by heat and vacuum at 60° C. for 1 h, followed by holding at 150° C. for 2 h. The results are reported in Table 4 below. It has been discovered that the number of open sites may be used to systematically regulate the incorporation of guest molecules at the Zr-node.
  • a cathode slurry was prepared using a 30 wt. % MOF, 45 wt. % S, 15 wt. % Super-P carbon (99+%, Alfa Aesar), and 10 wt. % poly(vinylidene fluoride) (PVDF) solid mixture in N-methyl-2-pyrrolidinone (NMP).
  • MOF was ground with a mortar and pestle and mixed with sulfur.
  • the MOF and sulfur mixture were admixed with PVDF and Super-P carbon.
  • a small stainless steel ball was added to the admixture and the solids were thoroughly mixed using a vortexer for 5 minutes.
  • a slurry was prepared by adding NMP to the admixture and homogenizing on the vortexer for at least 30 min.
  • the amount of NMP was measured by weight and in some aspects may be 4 ⁇ the total mass of the solid mixture.
  • more NMP was added as needed in order to achieve desired slurry consistency for forming a homogeneous film after drying.
  • the slurry was cast onto pre-weighed 12.7 mm carbon paper discs and dried overnight in an 80° C. oven to form the cathodes. The 12.7 mm cathodes were weighed again to determine the sulfur loading and stored in an Ar-filled glovebox until use.
  • CR 2032-type coin cells were constructed in an Ar-filled glovebox using a pre-weighed cathode, a polished metallic Li anode, two Celgard separators, two stainless steel spacers and spring (TOB New Energy).
  • An example of a coin cell is shown in FIG. 8 .
  • the electrolyte was composed of 1 M bis-(trifluoromethanesulfonyl)imide lithium (LiTFSI) in a mixed solution of 1,2-dimethoxyethane (DME, 99+%) and 1,3-dioxolane (DOL, 99.5%) (1:1, v/v) with an added 2 wt. % lithium nitrate salt (LiNO 3 , 99%).
  • the amount of electrolyte added to each coin cell assembly was based on the mass of S on the cathode with a ratio of 60 ⁇ l, per mg S.
  • Example 5 Performance of Li—S Batteries Having a Cathode Comprising Lithiated Defected MOFs
  • cathodes containing a composite of Li-UiO-66(MOD) and Sulfur/Carbon were constructed to examine the effect of varying lithium content on Li—S performance.
  • FIG. 13 shows that Li-MOFs obtained from harsh reaction conditions result in degradation and minimized maximum capacity.
  • the Li-UiO-66(50Benz) cells which contains the highest Li content of the cells evaluated and depicted in FIG.
  • FIG. 14 shows a significant increase in average maximum (absolute) capacity up to 1272 mAh g ⁇ 1 compared to the parent UiO-66(50Benz) at 918 mAh without lithiation.
  • FIG. 14 further shows Coulombic efficiency of the lithiated and non-lithiated MOFs are close to 100% during extended cycling.
  • FIGS. 15A and 15B further show that Li-UiO-66(50Benz) has better capacity retention than UiO-66(50Benz) as the C-rate was varied from C/10 to 2 C and from C/2 to 4 C.
  • the galvanostatic charge-discharge rate (C-rate) reflects the ability of the cell to transport ions and cycle effectively.
  • the cell containing Li-UiO-66-(50Benz) is able to maintain a stable capacity, only dropping 4% over 30 ⁇ cycles at the high rate of 4 C. Conversely, the nonlithiated UiO-66(50Benz) cell suffers significantly worse capacity fade of 12% over the same cycling experiment.
  • LPS-MOF composite cathodes yield significantly higher maximum capacities than the analogous MOF electrodes, averaging 1193 mAh g ⁇ 1 , 1172 mAh g ⁇ 1 , and 891 mAh for LPS-UiO-66(50Benz), LPS-UiO-66(noMod), and UiO-66, respectively (see also FIG. 16A ).
  • the LPS-UiO-66(50Benz) and LPS-UiO-66(noMod) composite cathodes have average specific capacities of 835 mAh g ⁇ 1 and 767 mAh g ⁇ 1 , compared to only 560 mAh g ⁇ 1 for the UiO-66(50Benz) composites ( FIGS. 4A and 16B ).
  • MOF-808 has more open sites than UiO-66, enhancing its ability to bind additional equivalents of thiophosphate. Based on the LPS-UiO-66 results, it is believed, without being bound to any particular theory, that both the maximum capacity and the capacity retention increase with increasing LPS concentration.
  • Composite cathodes of LPS-MOF-808 samples synthesized using 0.7, 1.0, and 2.0 LPS equivalents per Zr were assembled into cells and cycled galvanostatically using the same procedure as the LPS-UiO-66 samples ( FIGS. 4B and 16B ). The compiled results in FIG.
  • 16A exhibit a clear trend in maximum capacity delivery, with an average improvement over MOF-808 cells of 70 mAh g ⁇ 1 , 130 mAh g ⁇ 1 , and 300 mAh g ⁇ 1 for 0.7 ⁇ , 1.0 ⁇ and 2.0 ⁇ -LPS-MOF-808 samples, respectively.
  • Increased capacity is again attributed to the increased Li and LPS content within the functionalized MOF.
  • the capacity retention resembles that of LPS-UiO-66, with 0.7 ⁇ -, 1.0 ⁇ - and 2.0 ⁇ -LPS-MOF-808 cells delivering capacities of 800 mAh whereas the cells containing MOF-808 average less than 700 mAh g ⁇ 1 .
  • all cells constructed with LPS-MOF additives exhibit higher capacity retention when compared to sulfur-carbon composite cathodes (45 wt % S/C) ( FIGS. 4A, 4B, 16A and 16B ).
  • LPS-MOF composite cells The performance of LPS-MOF composite cells was evaluated under more arduous cycling conditions.
  • the LPS-UiO-66(50Benz) composite cell exhibits higher capacities compared to UiO-66(50Benz) at all C-rates ( FIGS. 17A and 17B ).
  • the LPS-UiO-66(50Benz) cell when returned to a lower C-rate of C/10, the LPS-UiO-66(50Benz) cell surprisingly recovered and maintained a capacity of 1040 mAh g ⁇ 1 , identical to the capacity after its first 5 cycles at C/10.
  • UiO-66(50Benz) and 45 wt % S/C cells do not fully recover capacity and continue to undergo capacity fade, losing nearly 200 mAh g ⁇ 1 in just 15 cycles.
  • LPS-UiO-66(50Benz) This superior ability of LPS-UiO-66(50Benz) to recover capacity is apparent even after the cells have been abused by continual cycling at charge rates up to 4 C and prolonged storage in the discharged state.
  • the LPS-UiO-66(50Benz) cell provides a capacity of 940 mAh g ⁇ 1
  • the UiO-66(50Benz) cell can only reach 250 mAh g ⁇ 1
  • the 45 wt % S/C cell irreversibly decays to zero capacity.
  • Cells constructed with LPS-MOF composite cathodes also show improved capacity delivery and retention in long-term cycling experiments at a C-rate of 1 C ( FIG. 18 ).
  • FIG. 18 FIG.
  • LPS-UiO-66(50Benz) and LPS-UiO-66(noMod) composite cathodes were surprisingly found to deliver 375 mAh g ⁇ 1 and 300 mAh g ⁇ 1 after 600 cycles, respectively, whereas the 45 wt % S/C cell is unable to retain even 100 mAh g ⁇ 1 .
  • the thiophosphate precursor, Li 3 PS 4 was synthesized by mixing 200 mg P 2 S 5 (0.9 mmol) with 122 mg Li 2 S (2.7 mmol) in a 20 mL scintillation vial in an Ar filled glovebox. To these solids, 5 mL distilled THF was added and stirred at room temperature in the glovebox for 24 h. A yellow solution and white powder are obtained after allowing the reaction mixture to settle. The yellow solution was removed and the solid was washed with sequentially with THF until the yellow color was no longer observed. Additional THF was used to suspend the powder and transfer the product to a 50 mL recovery flask fitted with a Schlenk adapter.
  • Phosphate moieties may be incorporated into UiO-66(MOD) moieties by solvent-assisted ligand incorporation where the activated MOF was soaked in a solution of the desired phosphate or phosphonate compound.
  • solvent was selected in order to preserve the thiophosphate species which is sensitive to oxidation.
  • the amount of Li 3 PS 4 used to prepare a LPS-precursor solution varied for different MOF loadings. For all UiO-66 MOFs, the same mass ratio of 3:1 (UiO-66:Li 3 PS 4 ) was used.
  • This ratio was chosen as it lies between the molar amount of PS 4 3 ⁇ subunits needed to fully occupy missing-linker open sites if the molar mass of UiO-66 used is of the highly defected “reo”-phase or of the parent, non-defected, structure. In either the defected or the non-defected structure calculation, a value of 3 open sites per mole of MOF is used to overestimate the amount of Li 3 PS 4 needed.
  • the calculated mass of Li 3 PS 4 was placed into a flask in an Ar-filled glovebox and capped with a rubber septum.
  • the LPS-precursor solution was prepared using a dry triethylamine-methanol solution mixed in a 1:4 (v:v) ratio.
  • the Li 3 PS 4 salt was dissolved under inert atmosphere using this solution, to form an approximate Li 3 PS 4 molarity of ⁇ 50 mM.
  • the LPS-precursor solution was then injected into the flasks containing the activated MOF under inert atmosphere at room temperature.
  • the Flasks were sealed, swirled, and then left undisturbed for 24 h.
  • the color of the MOF-powder remained unchanged in this loading procedure.
  • FIG. 5A depicts infrared (IR) spectroscopy results in transmittance (%) versus wavenumber (cm ⁇ 1 ) for the LPS-functionalized UiO-66(50Benz) and for the parent non-defected MOF (UiO-66)
  • FIG. 5B depicts infrared (IR) spectroscopy results in transmittance (%) versus wavenumber (cm ⁇ 1 ) for the LPS-functionalized MOF-808 and for the parent non-defected MOF (MOF-808).
  • LPS MOF-808 prepared 4.2 moles of Li 3 PS 4 per mole of MOF-808 would be termed 0.7 ⁇ LPS MOF-808 and LPS MOF-808 prepared 12 moles of Li 3 PS 4 per mole of MOF-808 would be termed 2 ⁇ LPS MOF-808.

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