WO2020167725A1 - Électrodes ayant un additif d'électrode pour batteries haute performance et leurs applications - Google Patents

Électrodes ayant un additif d'électrode pour batteries haute performance et leurs applications Download PDF

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WO2020167725A1
WO2020167725A1 PCT/US2020/017611 US2020017611W WO2020167725A1 WO 2020167725 A1 WO2020167725 A1 WO 2020167725A1 US 2020017611 W US2020017611 W US 2020017611W WO 2020167725 A1 WO2020167725 A1 WO 2020167725A1
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lithium
electrode
mof
metal
uio
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PCT/US2020/017611
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Jianguo Xu
Yunfeng Lu
Li Shen
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Ford Cheer International Limited
The Regents Of The University Of California
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Priority to CN202080009832.3A priority Critical patent/CN113330608A/zh
Publication of WO2020167725A1 publication Critical patent/WO2020167725A1/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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
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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
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • 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
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates generally to batteries, and more particularly to electrodes having an electrode additive formed of metal-organic frameworks for high performance battery and applications of the same.
  • One aspect of the invention provides a general type of porous coordination solids, metal- organic framework (MOF), as electrode additives to improve thermal stability, rate and cycle performances of batteries.
  • MOF metal- organic framework
  • the incorporation of MOF additives into electrodes is fully compatible with current battery manufacturing process.
  • Activated MOF powders can serve as electrolyte modulator to enhance cationic transport and alleviate interfacial resistance by interacting liquid electrolyte with unsaturated open metal sites (OMS).
  • OMS unsaturated open metal sites
  • the flow-free liquid in solid configuration is realized by encapsulating liquid electrolyte into porous scaffold of MOF, which offers superior thermal stability.
  • the electrode includes an electrochemical active material, a conductive additive, a binder and an electrode additive.
  • the electrode additive comprises an MOF material defining a plurality of pores, where the MOF is a class of crystalline porous scaffolds constructed from metal cluster nodes and organic linkers.
  • the MOF material is activated under vacuum at a temperature for a period of time.
  • the MOF material comprises OMSs that are corresponding to unsaturated metal centers created by activating a pristine MOF material to remove guest molecules or partial ligands thereof.
  • the MOF material is adapted such that a diameter of the pores provides a desired size to allow molecules of a liquid electrolyte to enter, and to accommodate salt anions in the liquid electrolyte.
  • the MOF material comprises HKUST-1 having a formula of
  • CU 3 (BTC) 2 MIL-100-Al having a formula of Al 3 O(OH)(BTC) 2 , MIL-100-Cr having a formula of Cr 3 O(OH)(BTC)2, MI--100-Fe having a formula of Fe 3 O(OH)(BTC) 2 , UiO-66 having a formula of Zr 6 O 4 (OH) 4 (BDC) 6 , or UiO-67 having a formula of Zr 6 O 4 (OH) 4 (BPDC) 6 , wherein BTC is a benzene-1, 3, 5 -tricarboxylic acid, BDC is a benzene- 1,4-dicarboxylic acid, and BPDC is a biphenyl-4,4 '-dicarboxylic acid.
  • the MOF material comprises an zirconium-based MOF material with varied functional ligands comprising at least one of UiO-66 with the organic linkers of terephthalic acid; UiO-67 with the organic linkers of 4,4’-biphenyldicarboxylic acid; UiO-66- NH 2 with the organic linkers of 2-aminoterephthalic acid; UiO-66-NO 2 with the organic linkers of 2-nitroterephthalic acid; UiO-66-OH with the organic linkers of 2-hydroxyterephthalic acid; and UiO-66-Br with the organic linkers of 2-bromoterephthalic acid.
  • the MOF material further has surface defects for exposing more unsaturated metal centers to coordinate salt anions in the liquid electrolyte.
  • sites of the surface defects of the MOF material are tunable by changing at least one of a metal vs ligand ratio, a synthetic temperature and the organic linkers.
  • the electrode additive, the electrochemical active material, the conductive additive and the binder are mixed at a weight ratio in one or more solvents to form a slurry that is evenly casted on a current collector substrate, and the electrode is formed after the one or more solvents is evaporated.
  • the electrode additive comprises an activated UiO-66
  • the electrochemical active material comprises LiNi 0.33 Co 0.33 Mn 0.33 O 2 (NCM)
  • the conductive additive comprises acetylene black (CB)
  • the binder comprises polyvinylidene fluoride (PVDF)
  • the one or more solvents comprise N-Methyl-2-pyrrolidone (NMP), wherein the weight ratio of the activated UiO-66, NCM, CB and PVDF is 1.7 : 91.7 : 3.3 : 3.3.
  • the electrode additive comprises an activated UiO-66
  • the electrochemical active material comprises graphite or lithium titanate (Li 4 Ti 5 O 12 , LTO)
  • the conductive additive comprises CB
  • the binder comprises PVDF
  • the one or more solvents comprise NMP, wherein the weight ratio of the activated UiO-66, graphite/LTO, CB and PVDF is 5 : 87 : 5 : 2.
  • an electrochemical device comprising a positive electrode, a negative electrode, and a separator and an electrolyte disposed between the positive and negative electrodes.
  • the electrolyte is a non-aqueous liquid electrolyte comprising a metal salt dissolved in a non-aqueous solvent.
  • At least one of the positive and negative electrodes is the electrode as disclosed above, configured such that the activated MOF material is combined with and is soaked in the non-aqueous liquid electrolyte.
  • the non-aqueous solvent is adapted such that its polarity matches surface properties of the MOF material.
  • 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-l,3-oxazolidine-2-one, g-butyrolactone, 1,2-di-ethoxymethane,
  • tetrahydrofuran 2-methyltetrahydrofuran, 1,3-dioxolane, methyl acetate, ethyl acetate, nitromethane, 1,3-propane sultone, g-valerolactone, methyl isobutyryl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, diethyl oxalate, an ionic liquid, chain ether compounds including at least one of gamma butyrolactone, gamma valerolactone, 1,2-dimethoxy ethane and diethyl ether, and cyclic ether compounds including at least one of tetrahydrofuran, 2- methyltetrahydrofuran, 1,3-dioxolane and dioxane.
  • the metal salt is adapted to have anions with desired sizes to ensure that the metal salt infiltrates into at least some of the pores of the activated MOF material and then becomes immobilized therein to form ionic conducting channels.
  • the anions are bound to metal atoms of the MOF material and positioned within the pores of the MOF material.
  • 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
  • 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 tetrafluorob orate, lithium perchlorate, lithium tetrachloroaluminate, and lithium chloride.
  • LiTFSI lithium bis(trifluoromethlysulfonylimide)
  • LiTFSI lithium bis(trifluorosulfonylimide)
  • lithium trifluoromethanesulfonate lithium fluoroalkylsufonimides
  • lithium fluoroarylsufonimides lithium bis(o
  • the sodium salt comprises one or more of sodium
  • the magnesium salt comprises one or more of magnesium
  • Mg(ClO 4 ) 2 trifluoromethanesulfonate
  • Mg(PF 6 ) 2 trifluoromethanesulfonate
  • Mg(BF 4 ) 2 trifluoromethanesulfonate
  • Mg(TFSI) 2 magnesium(II) Bis(trifluoromethanesulfonyl)imide
  • Mg(FSI) 2 magnesium(II) Bis(fluorosulfonyl)imide
  • the zinc salt comprises one or more of zinc
  • the separator is either ionic conductive or non-conductive, and comprises one or more of poly-propylene (PP), poly-ethylene (PE), glass fiber (GF),
  • PP poly-propylene
  • PE poly-ethylene
  • GF glass fiber
  • PEO polyethylene oxide
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PAN polyacrylonitrile
  • PMMA polymethylmethacrylate
  • Ptetraethylene glycol diacrylate and copolymers of them
  • perovskite lithium lanthanum titanate Li 3x La(2/3- x) M (1/3)-2x TiO 3 (LLTO) with 0 ⁇ x ⁇ 0.16 and M Mg, Al, Mn or Ru
  • the electrochemical device is a lithium 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 Li Nio . xCoo .15 Al 0.05 O 2 or NCA, lithium vanadium oxide (L1V 2 O 5 ), and Li 2 MSiO 4 with M being composed of a ratio of Co, Fe, and/or Mn.
  • the negative electrode may be formed of lithium metal (Li), 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 (S1O 2 ), tin oxide (SnO 2 ), transition metal oxide (e.g., 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.
  • Li lithium metal
  • graphite 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 (S1O 2 ), tin oxide (SnO 2 ), transition metal oxide (e.g.
  • the electrochemical device is a sodium battery, a magnesium battery, or a zinc metal battery, where 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 TiSe2, MgFePO 4 F, MgCo 2 O 4 and V 2 O 5 for the magnesium battery, or one or more of g-MnO 2 , ZnMn 2 O 4 , and ZnMnO 2 for the zinc battery.
  • FIG. 1 A show an illustrative configuration of electrode structure and components of a reference electrode.
  • FIG. IB show an illustrative configuration of electrode structure and components according to embodiments of the invention.
  • FIG. 2A shows a topology structure of UiO-(66/67) serial MOFs, where the purple polyhedra 210 represent inorganic Zr 6 O 4 (OH) 4 clusters, the grey sticks 220 manifest organic linkers (BDC and BPDC for UiO-66 and UiO-67, respectively).
  • FIG. 2B shows schematic illustration for activation of UiO-(66/67) serial MOFs (purple: Zr, red: O, blue: H) according to embodiments of the invention.
  • OMSs are created by
  • FIG. 2C shows N 2 adsorption/desorption measurement of UiO-66 according to embodiments of the invention.
  • FIG. 2D shows image of scanning electron microscopy showing the microstructure of synthesized UiO-66 according to embodiments of the invention.
  • FIG. 2E shows X-ray powder diffraction pattern of synthesized and activated UiO-66 according to embodiments of the invention.
  • FIG. 3 A shows the cyclic voltammetry of an NCM cathode ( LiNi 0.33 Co 0.33 Mn 0.33 O 2 , a reference electrode, denoted as REF), where metallic Li was used as both reference and counter electrodes.
  • FIG. 3B shows the cyclic voltammetry of an NCM cathode with MOF additive (a high- performance electrode, abbreviated as HPE) at a variety of sweep rate according to embodiments of the invention, where metallic Li was used as both reference and counter electrodes.
  • MOF additive a high- performance electrode, abbreviated as HPE
  • FIG. 3C compares the Li + diffusion coefficient of the REF and HPE based on Randles- Selick equations according to embodiments of the invention.
  • FIG. 4 shows the long-term cycling performance comparison between the REF and HPE using NCM-NCM symmetric cell configurations according to embodiments of the invention.
  • FIGS. 5A-5D show the evolution comparison of electrochemical impedance spectroscopy (EIS) between the REF and HPE according to embodiments of the invention.
  • EIS electrochemical impedance spectroscopy
  • FIG. 6A shows the cycling performance comparison between the REF and HPE using graphite-graphite (C-C) symmetric cell configurations according to embodiments of the invention.
  • FIG. 6B shows the cycling performance comparison between the REF and HPE using Li 4 Ti 5 O 12 - Li 4 Ti 5 O 12 symmetric cell configurations according to embodiments of the invention.
  • FIGS. 7A-7C show the cycling performance comparisons between the REF and HPE using NCM-C full cell configurations at different rates according to embodiments of the invention.
  • FIG. 8 shows the cycling performance comparisons between the REF and HPE using NCM-C pouch cell 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 showed 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.
  • One aspect of the invention discloses a general type of porous coordination solids, metal- organic framework (MOF), as electrode additives to improve thermal stability, rate and cycle performances of batteries and an electrode having the electrode additive.
  • MOF additives include metal- organic framework (MOF) as electrode additives to improve thermal stability, rate and cycle performances of batteries and an electrode having the electrode additive.
  • MOF additives include metal- organic framework (MOF) as electrode additives to improve thermal stability, rate and cycle performances of batteries and an electrode having the electrode additive.
  • MOF additives into electrodes is fully compatible with current battery manufacturing process.
  • activated MOF powders serve as electrolyte modulator to enhance cationic transport and alleviate interfacial resistance by interacting liquid electrolyte with unsaturated open metal sites (OMS).
  • OMS unsaturated open metal sites
  • the flow-free liquid in solid configurations is realized by encapsulating liquid electrolyte into porous scaffold of MOF, which offers superior thermal stability.
  • the electrode includes an electrochemical active material, a conductive additive, a binder and an electrode additive.
  • the electrode additive comprises an MOF material defining a plurality of pores, where the MOF is a class of crystalline porous scaffolds constructed from metal cluster nodes and organic linkers.
  • the MOF material is activated under vacuum at a temperature for a period of time.
  • the MOF material comprises OMSs that are corresponding to unsaturated metal centers created by activating a pristine MOF material to remove guest molecules or partial ligands thereof.
  • the MOF material is adapted such that a diameter of the pores provides a desired size to allow molecules of a liquid electrolyte to enter, and to accommodate salt anions in the liquid electrolyte.
  • the MOF material comprises HKUST-1 having a formula of
  • CU 3 (BTC) 2 MIL-lOO-Al having a formula of Al 3 O(OH)(BTC) 2 , MIL-100-Cr having a formula of Cr30(0H)(BTC)2, MIL-100-Fe having a formula of Fe30(0H)(BTC)2, UiO-66 having a formula of Zr 6 O 4 (OH) 4 (BDC) 6 , or UiO-67 having a formula of Zr 6 O 4 (OH) 4 (BPDC) 6 , wherein BTC is a benzene-1, 3, 5 -tricarboxylic acid, BDC is a benzene- 1,4-dicarboxylic acid, and BPDC is a biphenyl-4,4 '-dicarboxylic acid.
  • the MOF material comprises an zirconium-based MOF material with varied functional ligands comprising at least one of UiO-66 with the organic linkers of terephthalic acid; UiO-67 with the organic linkers of 4,4’-biphenyldicarboxylic acid; UiO-66- NH 2 with the organic linkers of 2-aminoterephthalic acid; U1O-66-NO 2 with the organic linkers of 2-nitroterephthalic acid; UiO-66-OH with the organic linkers of 2-hydroxyterephthalic acid; and UiO-66-Br with the organic linkers of 2-bromoterephthalic acid.
  • the MOF material further has surface defects for exposing more unsaturated metal centers to coordinate salt anions in the liquid electrolyte.
  • sites of the surface defects of the MOF material are tunable by changing at least one of a metal vs ligand ratio, a synthetic temperature and the organic linkers.
  • the electrode additive, the electrochemical active material, the conductive additive and the binder are mixed at a weight ratio in one or more solvents to form a slurry that is evenly casted on a current collector substrate, and the electrode is formed after the one or more solvents is evaporated.
  • the electrode additive comprises an activated UiO-66, the
  • electrochemical active material comprises LiNio . 33Coo . 33Mno . 33O2 (NCM)
  • the conductive additive comprises acetylene black (CB)
  • the binder comprises polyvinylidene fluoride (PVDF)
  • the one or more solvents comprise N-Methyl-2-pyrrolidone (NMP), wherein the weight ratio of the activated UiO-66, NCM, CB and PVDF is 1.7 : 91.7 : 3.3 : 3.3.
  • the electrode additive comprises an activated UiO-66, the
  • electrochemical active material comprises graphite or lithium titanate ( Li 4 Ti 5 O 12 , LTO), the conductive additive comprises CB, the binder comprises PVDF, and the one or more solvents comprise NMP, wherein the weight ratio of the activated UiO-66, graphite/LTO, CB and PVDF is 5 : 87 : 5 : 2.
  • the invention also provides an electrochemical device such as a battery comprising a cathode and an anode (i.e., two electrodes) as redox couples, and a separator and an electrolyte as an ionic conductor disposed between the two redox electrodes.
  • an electrochemical device such as a battery comprising a cathode and an anode (i.e., two electrodes) as redox couples, and a separator and an electrolyte as an ionic conductor disposed between the two redox electrodes.
  • FIGS. 1 A and IB show respectively two illustrative schemes for electrode configurations (alternatively, a cathode or an anode) 100 and 100’, each of which includes a current collector 110 and a composite electrode 120/120’ (in electrolyte 126) attached to the current collector 110.
  • the composite electrode 120/120’ is in electrolyte 126 and includes an electrochemical active material 122, a conductive additive 124 and a binder (not shown).
  • the adherence of the electrode 120/120’ on the current collector 110 is to ensure the continuous electron flow to outside circuit.
  • the electrochemical active material, the conductive additive and the binder are mixed and dispensed in appropriate solvents.
  • the resulting homogenous electrode slurry 120/120’ are evenly casted on a planar current collector substrate 110.
  • the solvents are evaporated by drying to create porous electrodes 120/120’.
  • the porous electrodes 120/120’ prepared from the slurry casted method guarantees the ionic transport 121, 123 and 125 by imbibing liquid electrolyte 126 into the porous voids.
  • the MOF additives 128 are added either into a cathode or an anode as an additional electrode component with no extra cost, as shown in FIG. IB.
  • the MOFs 128 within the electrode 120’ can spontaneously imbibe the liquid electrolyte 126 upon cell aging.
  • the resulting MOFs simultaneously serve as an electrolyte reservoir to withhold the liquid electrolyte 126 and act as a modulator to and tune ionic chemistry.
  • the safety issue is mitigated by confining the liquid electrolyte in porous solids; on the other hand, the OMS in the MOF promotes the cation transport by relatively immobilize the anions.
  • the role of the electrolyte modulator may be realized by spontaneously binding electrolyte anions, e.g., ClO-, BF -, PF 6 -, TFSI- (bis(trifluoromethane)sulfonimide), FSL (bis(fluorosulfonyl)imide), etc., to the open-metal sites of the MOF scaffolds.
  • electrolyte anions e.g., ClO-, BF -, PF 6 -, TFSI- (bis(trifluoromethane)sulfonimide), FSL (bis(fluorosulfonyl)imide), etc.
  • the binding constructs negatively charged channels in the pores of the MOF scaffold, which enable fast conduction of solvated ions, e.g., Li + , Na + , K + , Mg 2+ , Zn 2+ , Al 3+ , etc.
  • 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, but are not limited to, LiNiMnCoO 2 (NMC), lithium iron phosphate (LiFePO 4 ), lithium iron fluorophosphate (LhFePCLF), 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, etc.
  • lithium vanadium oxide 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.
  • Suitable negative electrodes include, but are not limited to, graphite, hard or soft carbon, graphene, carbon nanotubes, titanium oxide (Li 4 Ti 5 O 12 , T1O 2 ), silicon (Si), tin (Sn), Germanium (Ge), silicon monoxide (SiO), silicon oxide (S1O 2 ), tin oxide (SnO 2 ), transition metal oxide (e.g., 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.
  • other electrodes may be used for sodium, magnesium, or zinc metal batteries.
  • suitable negative electrodes for sodium, magnesium, or zinc metal batteries include, but are not limited to, sodium metal, magnesium metal, or zinc metal, respectively.
  • Suitable positive electrodes for sodium metal batteries include, but are not limited to, NaMnO 2 , NaFePCri, and Na 3 V 2 (PO4)3;
  • suitable positive electrodes for magnesium metal batteries include, but are not limited to, TiSe2, MgFePCriF, MgCo 2 O 4 , and V2O5 ;
  • suitable positive electrodes for zinc metal batteries include, but are not limited to, y-MnO 2 , ZnMmCri, and ZnMnO 2 .
  • MOFs are a class of crystalline materials constructed from metal centers and organic ligands, which have ordered nano-pores or nano-channels that are capable of hosting guest species. As described in detail below, the pores of the MOF are large enough to accommodate the metal salt. More particularly, the pores of the MOF are large enough to accommodate the binding of anions of a metal salt to the open metal backbone of the MOF, as well as solvated cations of the metal salt, such as, lithium ions and sodium ions.
  • An exemplary example of the MOFs, such as MIL-100(Al), is shown in FIG. 2A.
  • M 3+ is bonded to four oxygen atoms of bidendate dicarboxylate (BTC), and their linkage generates a hierarchical structure with mesoporous cages (25 and 29 A) that are accessible through microporous windows (6 and 9 A).
  • the corresponding terminals in octahedra are generally occupied by removable guest molecules.
  • Table 1 lists some exemplary MOF candidates that may be used as the channel scaffolds with pore size ranging from 1.1 nm to 2.9 nm, containing metal centers from the /2-block (A1 and In) and from the d-block (Cu, Fe, and Mn), as well as different ligands, e.g., benzene-1, 3,5- tricarboxylic acid (BTC), benzene-1, 4-dicarboxylic acid (BDC), and biphenyl -4, 4’ -dicarboxylic acid (BPDC).
  • BTC 3,5- tricarboxylic acid
  • BDC 4-dicarboxylic acid
  • BPDC biphenyl -4, 4’ -dicarboxylic acid
  • MOF materials may also be selected, based on having suitable pore size, pore volume, metal centers, and good compatibility to the liquid electrolyte that is used to form the ionic channels. Since the liquid electrolyte to be infiltrated into the MOFs, MOF structures can be selected and modified easily, and different MOF structures can be designed to meet certain requirements of different rechargeable batteries by changing and modifying the liquid electrolyte. In one example, the MOF structure may be initially selected such that a diameter of the pores provides a large enough size to allow molecules of the liquid electrolyte to enter, and to accommodate the anions of the salt in the liquid electrolyte.
  • MOF material selection may also be based on the stability of the MOFs in the battery electrochemical environment.
  • the judicious selection of the metal centers and organic linkers (ligands) affords the synthesis of over 20,000 MOFs with designable
  • MOFs with mesopore structures may be synthesized by using a large ligand.
  • MOFs with a mesopore structure is the UiO-67.
  • MOFs with more surface functional groups for coordinating liquid electrolytes may also be used.
  • suitable MOF materials include, but are not limited to, Mil-100 serial MOFs, where pore topology is small while metal center varies. It should be appreciated that any MOF may be used in the examples disclosed herein and to practice the invention.
  • UiO-66 stands for Zirconium MOF with perfect stoichiometry of [Zr 6 O 4 OH 4 ][C 6 H 4 (COO) 2 ] 6.
  • the synthetic route is hydrothermal reactions between ZrCl 4 with terephthalic acid (BDC) in a polar (hydrophilic) aprotic solvent of dimethylformamide (DMF).
  • BDC terephthalic acid
  • DMF dimethylformamide
  • Zr 4+ is gradually hydrolyzed to form a six-center octahedral metal cluster with the assistance from basicity of DMF. Capping the faces of metal cluster octahedron are eight oxygen, of which four a protonated to balance the charge.
  • Another isostructural material UiO-67 can be obtained by replacing the terephthalic acid (BDC) with longer linker of 4,4’ -biphenyl di carboxylic acid (BPDC). The consequent pore size expands from 7.5 and 12 ⁇ to 12 and 16 A, respectively.
  • MOFs are synthesized with linker possessing functional groups such as amines, halogens, hydroxyls or nitros, as enclosed in Table 2.
  • linker possessing functional groups such as amines, halogens, hydroxyls or nitros, as enclosed in Table 2.
  • the vast diversity of functional side groups introduces desirable properties for the MOFs as solid electrolyte, like higher ionic conductivity, higher transference number and superior stability against reactive alkali metals. For instance, electron donor/acceptor properties of side groups would impact the acidity of benzene carboxylate, thus shifting the charge balance of overall metal organic framework and resulting anion adsorption capability.
  • the synthesized MOFs undergo a pre-treatment step: activation.
  • the 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. Removal of the solvent molecules (or dehydration of capping hydroxyl groups, e.g., as shown in FIG. 2B) at an elevated temperature under vacuum breaks the solvent coordination from the MOFs, resulting in MOF scaffolds with unsaturated metal centers.
  • a solvent e.g., water
  • the activation process is illustrated in FIG. 2B, UiO-66 is obtained by bridging
  • BDC 1,4-dicarboxylate
  • the Zr 6 -octahedrons are alternatively coordinated by m3-O, m3-OH and O atoms from BDC, where m3-OH can undergo dehydration to form a distorted Zr 6 O 6 node (seven-coordinated Zr) upon thermal activation.
  • the Zr 6 O 4 (OH) 4 units undergo dehydration and the resulting Zr 6 O 6 clusters (seven-coordinated Zr) possess unsaturated open Zr 4+ sites.
  • the conditions of thermal activation for coordinating molecule removal vary by different MOFs, which depend on the synthetic conditions and thermal stability of MOFs.
  • the powder form an MOF material may be degassed or activated under vacuum at a high/elevated temperature (e.g., abouu 350°C) to remove coordinated water molecules.
  • a high/elevated temperature e.g., abouu 350°C
  • other methods for removing coordinating molecule including supercritical drying, solvent exchange, lyophilization, etc., may also be used to practice the invention.
  • the surface defects of the MOF materials are similar to pores in that they expose more unsaturated metal centers to coordinate salt anions. Therefore, the pores inside of the MOF materials, as well as the defects resulting from the packing of the MOF materials, can become ion transportation channels.
  • metal vs ligand ratio, synthetic temperature, hydrochloric acid as well as incorporation of mono/di-carboxylic acid are manipulated to tune the MOF defects sites.
  • MOFs For instance, trifluoroacetic acid, trichloroactic acid, formic acid, acetic acid, pivalic acid, benzoic acid, and stearic acid, etc., are effective in creating massive missing ligands by replacement of terephthalic acid and decomposition upon activation, thus resulting MOFs possess defective structure and abundant sites for coordinating anions.
  • these defects throughout the frameworks are also classified as immobilization sites for anion and transport facilitator for cations.
  • the activated MOF material powder is combined with, and is soaked in, a non-aqueous liquid electrolyte including metal salt(s) dissolved in non-aqueous solvent(s).
  • the non-aqueous liquid electrolyte solvent(s) include, but are not limited to, 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, g-butyrolactone, 1,2-di-ethoxymethane, tetrahydr
  • the metal salt dissolved in the liquid electrolyte solvent includes, but are not limited to, a lithium salt, a sodium salt, a magnesium salt, a zinc salt and/or an aluminum salt.
  • lithium salts examples include, but are not limited to, lithium
  • 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 tetrafluorob orate, lithium perchlorate, lithium tetrachloroaluminate, lithium chloride, and combinations thereof.
  • LiTFSI lithium bis(trifluoromethlysulfonylimide)
  • LiTFSI lithium bis(trifluorosulfonylimide)
  • lithium trifluoromethanesulfonate lithium fluoroalkylsufonimides, lithium fluoroarylsufonimides, lithium
  • Suitable sodium salts include sodium trifluoromethanesulfonate, NaCIO 4 , NaPF 6 , NaBF 4 , NaTFSI (sodium(I) Bis(trifluoromethanesulfonyl)imide), NaFSI (sodium(I) Bis(fluorosulfonyl)imide), and the like.
  • magnesium salts include, but are not limited to, magnesium trifluoromethanesulfonate, Mg(ClO 4 ) 2 , Mg(PF 6 ) 2 , Mg(BF 4 ) 2 , Mg(TFSI) 2 (magnesium(II) Bis(trifluoromethanesulfonyl)imide), Mg(FSI) 2 (magnesium(II) Bis(fluorosulfonyl)imide), and the like.
  • Suitable Zn salts include, but are not limited to, zinc
  • the metal salt is selected to have a suitably sized anion, which depends, at least in part, upon the MOF material that is used.
  • the anion size may be selected to ensure that the salt can infiltrate into at least some of the MOF pores, and then become immobilized therein to form the ionic conducting channel.
  • the weight percentage of activated MOFs varies by different applications.
  • the electrode preparation is exemplified but not restricted by traditional slurry casted method, for example, aerosol sprayed electrodes, ink printed electrodes, calendared electrodes, electrospun electrodes and electroplated electrodes, etc., are also applicable.
  • the uniformity of combined electrode components including active materials, conductive additives, binders and MOFs can be achieved by mixing dry powders or wet mixing using dispersing solvent.
  • the approach of combining MOF with other electrode components is exemplified but not restricted by physical mixing. Due to versatile functional groups existing in MOFs, it is also applicable to form composite materials between the MOFs and other electrode components including active materials, electrodes, conductive additives and binder.
  • MOFs incorporated electrodes possess intrinsic porosity from MOFs and
  • injected electrolyte can readily be infiltrated into the porous structure.
  • Soaking activated MOFs in liquid electrolyte e.g., LiC1O 4 in propylene carbonate (PC)
  • the anions e.g., ClO 4 -
  • the metal salt allows the anions (e.g., ClO 4 -) of the metal salt to bind to the unsaturated metal sites of the MOFs and spontaneously form anion-bound MOF channels.
  • the anions are bound to metal atoms of the MOFs such that the anions are positioned within the pores of the MOFs.
  • the negatively charged MOF channels are ion transport channels that allow for effective transport of the solvated cations (e.g., PC-solvated Li + or Na + or Zn 2+ or Mg 2+ ).
  • the solvated cations may hop through and/or between the plurality of negatively charged MOF channels. More particularly, the solvated cations can transfer within and/or between the channels by hopping among each of the anions and/or solvents. In the pores, composed by the MOF units, the cations transfer with the help of the solvent.
  • the electron blocking separator membranes between two redox electrodes can either be ionic conductive (any gel forming polymer electrolyte or solid electrolyte) or non-conductive, which can be selected from poly-propylene (PP), poly-ethylene (PE), glass fiber (GF), polyethylene oxide (PEO), polyvinylidene fluoride (PVDF),
  • PP poly-propylene
  • PE poly-ethylene
  • GF glass fiber
  • PEO polyethylene oxide
  • PVDF polyvinylidene fluoride
  • PTFE pol ytetrafl uoroethyl en e
  • PAN polyacrylonitrile
  • PMMA polymethylmethacrylate
  • Ptetraethylene glycol diacrylate copolymers thereof
  • the foregoing MOF porous solids serve as an electrolyte modulator, transforming ionic chemistry of electrolyte by immobilizing anion and facilitating cation transport.
  • the polarization induced by anion movements is reduced and resulting modified electrolyte is projected to benefit from following advantages.
  • (2) Parasitic reactions involving anion are mitigated, thereby prolonging the cycle life.
  • the MOF electrolyte modulator can also be applied to lithium metal batteries.
  • the synthesis of UiO-66 MOF includes the following steps. About 1.23 g of BDC ligand and about 1.25 g of ZrCl 4 were dissolved in 100 mL of N,N- dimethylformamide (DMF) and about 50/10 mL of DMF/hydrochloric acid (37 wt% HC1, concentrated) mixture, respectively. These two fully dissolved solutions were combined and magnetically stirred for an additional about 30 min. The resulting transparent precursor solution was loaded in a tightly sealed glass vial and heated at about 150 °C for about 20 hours.
  • DMF N,N- dimethylformamide
  • the precipitate was separated from solvents by centrifugation and first washed by DMF three times (3x40 mL). Methanol exchange was performed on the DMF-washed sample over a period of about 3 days. The sample was replenished with fresh methanol twice a day (each for about 40 mL). Eventually the sample was dried at about 80 °C for about 1 day prior to further characterization.
  • the crystal structure was determined by X-ray diffraction pattern, all peaks were indexable to simulated patterns for UiO-66 and no impurities were detected.
  • the texture property of porous MOF solids was evaluated by N2 adsorption/desorption isotherms. Before surface area measurements, the porous powders undergo a heat treatment at about 180 °C for about 12 hours under a pressure of about 20 um Hg. As shown in FIG. 2D, the Brunauer- Emmett-Teller (BET) surface area is calculated to be about 1375 cm 2 g -1 and the majority pores are micropores as indicated by dominate adsorption at a low relative pressure.
  • BET Brunauer- Emmett-Teller
  • the morphology and particle size were examined by scanning electron spectroscopy (SEM), as shown in FIG. 2E, the products include microsized aggregates of intergrown crystals. It is worthy to note that, the crystallinity, particle size, surface area and defects of the MOF can further be readily tuned by a variety of synthetic strategies, like using more water or other acid modulator, hydrochloric acid, acetic acid, trifluoroacetic acid, stearic acid, etc.
  • the MOF additive used herein is exemplified while not restricted to UiO-66.
  • the synthesized UiO-66 underwent a heat treatment (about 350 °C) under vacuum for thermal activation purposes.
  • the activated UiO-66 were homogeneously mixed with
  • NCM LiNio . 33Coo . 33Mno . 33O2
  • CB acetylene black
  • PVDF polyvinylidene fluoride
  • NMP N-Methyl-2-pyrrolidone
  • the NCM content is about 93.3% instead while maintaining contents of CB and PVDF the same.
  • the prepared electrodes were tailored into electrode disks with a diameter of about 14 cm for use.
  • metallic lithium disks (15.6 cm diameter, MTI ® ) were used as both counter and reference electrodes
  • the 25 um trilayer polypropylene- polyethylene-polypropylene membrane is purchased from Celgard ® .
  • 3A-3B show respectively the cyclic voltammetry of an NCM cathode (LiNio . 33Coo . 33Mno . 33O2, REF) and an NCM cathode with the MOF additive (HPE) at a variety of sweep rate, where metallic Li was used as both the reference and counter electrodes.
  • NCM cathode LiNio . 33Coo . 33Mno . 33O2, REF
  • HPE MOF additive
  • the diffusion coefficient of Li + within the electrodes were characterized by cyclic voltammetry technique. As known from
  • Coulmobic efficiency of the HPE is improved from about 99.88% for REF to about 99.94%.
  • the superior cycling performance demonstrates that MOF additive is able to alleviate the parasitic reactions between positive electrodes and electrolyte.
  • the long-term cycling performance comparison between REF and HPE using NCM-NCM symmetric cell configurations is shown in FIG. 4.
  • NCM-C full cell weight ratio between NCM and graphite is 15 : 7.5 mg cm -2
  • MOF additives were added to the cathode side.
  • the combination of NCM and graphite is for demonstrative purposes and any combination of aforementioned electrodes is applicable.
  • the cells were tested under 0.1C, 1C and 2C between 2.5 to 4.2V for prolonged cycling.
  • FIGS. 7A- 7C show the cycling performance comparisons between the REF and HPE using NCM-C full cell configurations at different rates.
  • the HPE (NCM-C) exhibit superior rate performance than the REF, especially at 2C rate, the HPE can deliver almost one-fold higher specific capacity than the REF.
  • the cycling results from full cells suggest that the improvement in terms of rate capability is more evident in full cell configuration, where the electric field might influence the concentration polarization of anion.
  • NCM-C full cells were further extended to punch cells configuration for practical application purposes.
  • the designed capacity for punch cell is 300 mAh and corresponding mass loading of active material is identical to those electrodes used in coin cell.
  • FIG. 8 shows the cycling performance comparisons between the REF and HPE using NCM-C pouch cell, where reproducible results were obtained in punch cells configuration in terms of rate and cycling performances.

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Abstract

L'invention concerne un type général de solides de coordination poreux, de structures organométalliques (MOF), en tant qu'additif d'électrode pour améliorer la stabilité thermique, le taux et les performances de cycle de batteries, et une électrode ayant l'additif d'électrode. L'incorporation de l'additif MOF dans l'électrode est complètement compatible avec le processus de fabrication de batterie actuel. L'additif MOF activé sert de modulateur d'électrolyte pour améliorer le transport cationique et atténuer la résistance interfaciale par interaction d'électrolyte liquide avec des sites métalliques ouverts insaturés. De plus, le liquide sans écoulement en configuration solide est réalisé par encapsulation d'électrolyte liquide dans un support poreux de MOF, ce qui offre une stabilité thermique supérieure.
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