WO2014036513A1 - Dispositifs de stockage de courant faisant intervenir de l'oxyde de manganèse à plusieurs valences - Google Patents

Dispositifs de stockage de courant faisant intervenir de l'oxyde de manganèse à plusieurs valences Download PDF

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WO2014036513A1
WO2014036513A1 PCT/US2013/057705 US2013057705W WO2014036513A1 WO 2014036513 A1 WO2014036513 A1 WO 2014036513A1 US 2013057705 W US2013057705 W US 2013057705W WO 2014036513 A1 WO2014036513 A1 WO 2014036513A1
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manganese
molecular sieve
octahedral molecular
composition
oms
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Steven L. Suib
Hui Huang
Linping XU
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Suib Steven L
Hui Huang
Xu Linping
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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
    • H01M4/13—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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/50—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
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to metal-substituted manganese-based octahedral molecular sieves, compositions of metal-substituted manganese-based octahedral molecular sieves in combination with at least one additional component, electrodes for power storage devices, and power storage devices using metal-substituted manganese-based octahedral molecular sieves or compositions thereof.
  • Zeolites and zeolite-like materials constitute a well-known family of molecular sieves. These materials are tetrahedral coordinated species with T0 4 tetrahedra (in which T is silicon, aluminum, phosphorus, boron, beryllium, gallium, etc.) serving as the basic structural unit. Through secondary building units, a variety of frameworks with different pore structures can be constructed. Like tetrahedra, octahedra can also serve as the basic structural units of molecular sieves.
  • Manganese oxide octahedral molecular sieves possessing mono- directional tunnel structures constitute a family of molecular sieves wherein chains of Mn0 6 octahedra share edges to form tunnel structures of varying sizes.
  • Such materials have been detected in samples of terrestrial origin and porous manganese oxide natural materials are also found as manganese nodules. These materials when dredged from the ocean floors have been used as excellent adsorbents of metals such as from electroplating wastes and have been shown to be excellent catalysts.
  • the natural systems are often found as mixtures, are poorly crystalline, and have incredibly diverse compositions due to exposure to various aqueous environments in nature. Such exposure allows ion-exchange to occur.
  • Such materials have also been produced synthetically. Rationale for synthesis of novel OMS materials is related to the superb conductivity, mixed valency, microporosity, and catalytic activity of the natural materials. Variable pore size materials have been synthesized using structure directors and with a variety of synthetic methodologies. Transformations of tunnel materials with temperature and in specific atmospheres have recently been studied with in situ synchrotron methods. Conductivities of these materials appear to be related to the structural properties of these systems with more open structures being less conductive. Catalytic properties of these OMS materials have been shown to be related to the redox cycling of various oxidations states of manganese such as Mn 2+ , Mn 3+ , and Mn 4+ .
  • a manganese-based octahedral molecular sieve includes a framework substitution with at least one substituting metal.
  • the substituting metal can be, for example, lithium (Li), sodium (Na), silver (Ag), copper (Cu), or a combination of vanadium (V) and copper (Cu).
  • the substituting metal can be, for example, silver (Ag), gold (Au), iron (Fe), copper (Cu), cobalt (Co), nickel (Ni), scandium (Sc), titanium (Ti), zinc (Zn), or a combination of these, or a combination of any one of these with vanadium.
  • the manganese-based octahedral molecular sieve can have a 2x2,
  • the molar amount of each at least one substituting metal divided by the molar amount of manganese can be in a range of from about 0.0001% to about 40%, can be in a range of from about 1% to about 10%, or can be about 1%.
  • the molar amount of vanadium can be about 1% of the molar amount of manganese and the molar amount of copper can be about 1% of the molar amount of manganese.
  • a manganese-based octahedral molecular sieve can have a rod-like morphology, with rods having a length in the range of from about 100 nm to about 500 nm and a diameter in the range of from about 10 nm to about 20 nm.
  • a composition can include a manganese- based octahedral molecular sieve and at least one of a polymer binder, carbon material, carbon nanomaterial, and/or silicon nanomaterial.
  • the composition can include a polymer binder, graphite, and a carbon material.
  • the polymer binder can be a polyvinylidene fluoride polymer
  • the carbon material can be graphite and/or conductive carbon black
  • the carbon nanomaterial can be a nanotube, nanofiber, or fullerene.
  • the manganese-based octahedral molecular sieve can be l%V-Cu-OMS-2.
  • the manganese-based octahedral molecular sieve can be from about 10 wt% to about 99 wt% of the composition.
  • the manganese-based octahedral molecular sieve can be about 60 wt% of the composition.
  • the discharge capacity of the composition can be at least about 174 mAh/g, at least about 170 mAh/g, at least about 130 mAh/g, at least about 105 mAh/g, or at least about 60 mAh/g.
  • the discharge capacity of the composition can be at least about 0.15 mAh-cm "2 .
  • an electrode for a battery can include a manganese-based octahedral molecular sieve or a composition including a manganese-based octahedral molecular sieve.
  • the electrode can include a charge collector.
  • a charge storage device can include a first electrode, a second electrode, and an electrolyte between the first and second electrode.
  • the charge storage device can be a lithium-ion battery, a lithium-air battery, or a lithium-02 battery.
  • the charge storage device can include a cathode including or essentially only including l%V-Cu-OMS-2, polyvinylidene fluoride, graphite, and carbon, a metallic lithium anode, and an electrolyte including or essentially only including lithium hexafluorophosphate dissolved in a mixture of ethylene carbonate, dimethyl carbonate, and diethyl carbonate.
  • the reversibility of electrical capacity from the first discharge to the charge cycle of the charge storage device can be at least about 85.9%.
  • a method of the invention includes providing a manganese solution, heating the manganese solution at about 200 °C to form a precipitate of manganese-based octahedral molecular sieve, washing the precipitate of manganese-based octahedral molecular sieve, and drying the precipitate to yield a manganese-based octahedral molecular sieve.
  • the manganese solution can include, essentially only include, or be manganese sulfate, potassium sulfate, and potassium persulfate dissolved in water.
  • a dopant precursor can be added to the manganese solution.
  • Silver (Ag), gold (Au), iron (Fe), copper (Cu), chromium (Cr), cobalt (Co), zinc (Zn), vanadium (V), titanium (Ti), nickel (Ni), scandium (Sc), lithium (Li), sodium (Na), or combinations of these can be added to the manganese solution as pure element(s), as compound(s), or as combinations of pure element(s) and compound(s).
  • sodium orthovanadate and/or cupric sulfate can be added to the manganese solution.
  • a method of making an electrode of the invention includes preparing a slurry from a manganese-based octahedral molecular sieve and at least one of a binder, graphite, carbon, and a solvent, spreading the slurry as a coating onto a metal foil, evaporating the solvent from the coated foil, for example, by drying the coated foil at a temperature of, e.g., about
  • the manganese-based octahedral molecular sieve can include or be l%V-Cu-OMS-2
  • the binder can include, essentially only include, or be polyvinylidene fluoride, graphite, carbon, and N-methyl-2-pyrrolidone
  • the metal foil can include or be aluminum foil.
  • a method of making a charge storage device of the invention includes providing a cathode, providing a metallic anode, providing an electrolyte, and assembling the cathode, metallic anode, and electrolyte as the charge storage device.
  • the metallic anode can essentially only include or be metallic lithium.
  • the electrolyte can essentially only include or be lithium hexafluorophosphate dissolved in a mixture of ethylene carbonate, dimethyl carbonate, and diethyl carbonate.
  • Figure 1 is (a) a 2D (two-dimensional), and (b) 3D (three-dimensional) representation of the crystal structure of OMS-2 materials.
  • Figure 2 shows (a) the X-ray diffraction (XRD) pattern for the as-synthesized
  • Ag-OMS-2 product (b) the field emission scanning electron microscopy (FE-SEM) image of Ag-OMS-2, and (c), (d), and (e) transmission electron microscopy images.
  • FE-SEM field emission scanning electron microscopy
  • Figure 3 shows X-ray diffraction (XRD) patterns of (a) OMS-2, (b) l%V-Cu-
  • Figure 4 shows a FE-SEM image of the OMS materials with different incorporation amounts of V and Cu for (a) pure OMS-2, (b) OMS-2 at high magnification, (c) l%V-Cu-OMS-2, (d) 2%V-Cu-OMS-2, (e) 5%V-Cu-OMS-2, and (f) 10%V-Cu-OMS-2.
  • Figure 5 shows a representation of an OMS-2 sample disk and a schematic plot for 4-probe resistivity measurements.
  • Figure 6 shows resistivities of OMS-2 and doped OMS-2 materials.
  • Figure 7 shows a discharge profile for Ag-OMS-2 materials in Li-0 2 batteries with an initial open-circuit test of 2 h (hours).
  • Figure 8 shows the specific discharge capacity of different OMS-2 samples.
  • Figure 9 shows discharge curves for different OMS-2 materials.
  • Figure 10 shows curves for charge and discharge cycling of l%V-Cu-OMS-2 materials.
  • Figure 1 1 shows XRD patterns of LiMnO x materials having an OMS-2 structure.
  • Figures 12A and 12B show scanning electron microscopy (SEM) images of LiMnOx materials.
  • Figure 13 shows current density curves for Na-OMS-5 and Ag-OMS-2 materials.
  • Figure 14 is a representation of coin half-cells.
  • Figure 15 is a flowchart of a process for incorporating materials in an embodiment of the present invention into an electrode for a battery.
  • Figure 16A shows charge and discharge curves.
  • Figure 16B shows the discharge capacity of nanostructured LiMnO x over several cycles.
  • Figure 17 shows the discharge capacity of nanostructured LiMnO x over several cycles.
  • Figure 18 shows the discharge profile of Na-OMS-5.
  • Figure 19 shows the discharge profile of Ag-OMS-2.
  • Figure 20 illustrates various tunnel structures.
  • Embodiments of the invention include electrodes for a battery using manganese- based octahedral molecular sieves, or compositions thereof.
  • Other embodiments include charge storage devices where at least one electrode uses manganese-based octahedral molecular sieves.
  • the charge storage device may be, for example, a battery, such as a lithium-ion battery, lithium- air battery, or lithium-0 2 battery.
  • MMS Manganese-based octahedral molecular sieves
  • Some embodiments of the invention include manganese-based octahedral molecular sieves having a framework substitution with at least one substituting metal, wherein the substituting metal is silver (Ag), gold (Au), iron (Fe), copper (Cu), chromium (Cr), cobalt (Co), zinc (Zn), vanadium (V), titanium (Ti), nickel (Ni), scandium (Sc), or combinations thereof, or combinations of one of the above substituting metals with vanadium (V).
  • the substituting metal is a combination of vanadium and copper.
  • Some embodiments include manganese-based octahedral molecular sieves having a framework substitution with a substituting metal selected from lithium (Li), sodium (Na), or combinations thereof, or combinations of lithium (Li) and/or sodium (Na) with one or more of the above substituting metals.
  • Embodiments also include manganese-based octahedral molecular sieves with lithium or sodium counterions or a combination of these.
  • Embodiments also include manganese-based octahedral molecular sieves with lithium or sodium counterions having a framework substitution with at least one substituting metal, wherein the substituting metal is silver (Ag), gold (Au), iron (Fe) copper (Cu), chromium (Cr), cobalt (Co), zinc (Zn), nickel (Ni) or combinations thereof, or combinations of one of the above substituting metals with vanadium (V).
  • the substituting metal is silver (Ag), gold (Au), iron (Fe) copper (Cu), chromium (Cr), cobalt (Co), zinc (Zn), nickel (Ni) or combinations thereof, or combinations of one of the above substituting metals with vanadium (V).
  • the manganese-based octahedral molecular sieves are synthetic. In other words, they are not naturally occurring.
  • Manganese-based octahedral molecular sieve(s) constitute an example class of molecular sieves. These materials have one-dimensional tunnel structures and unlike zeolites, which have tetrahedrally coordinated species serving as the basic structural unit, these materials are based on six-coordinate manganese surrounded by an octahedral array of anions (e.g., oxide).
  • the OMS framework architecture is dictated by the type of aggregation (e.g., corner-sharing, edge-sharing, or face- sharing) of the ⁇ ⁇ octahedra.
  • the ability of manganese to adopt multiple oxidation states and of the ⁇ ⁇ octahedra to aggregate in different arrangements affords the formation of a large variety of OMS structures.
  • the OMS further comprises an additional transition metal within the molecular framework, where the metal is silver (Ag), gold (Au), iron (Fe), copper
  • Suitable additional metals include, e.g., a transition metal, for example from Groups IB, IIB and VIII of the Periodic Table of the elements, lanthanum, iridium, rhodium, palladium and platinum.
  • a transition metal for example from Groups IB, IIB and VIII of the Periodic Table of the elements, lanthanum, iridium, rhodium, palladium and platinum.
  • useful framework-substituting metals include Mg, Fe, Co, Ni, Cu, Ti, V, Cd, Mo, W, Cr, Zn, Sc, Mo, Zr, Ta, Hf, and lanthanide series metals.
  • the hydrated larger counter cations such as potassium and barium can themselves serve as templates for crystallization and remain in the tunnel structures of some manganese oxide hydrates, particularly those of the [M]-OMS-2 structure where they may also be referred to as tunnel cations.
  • the counter cation can be selected to facilitate the selection, formation and stabilization of a desired product, such as the aforementioned [MJ-OMS-2 structure, or to have a lesser effect (as with the smaller cations such as sodium and magnesium) so as to allow other preferred structures to form and/or to permit template materials other than the counter ion to act on the reaction solution.
  • Framework substituted OMS may be prepared according to the methods described in US Patent Number 5,702,674, incorporated herein by reference in its entirety. Accordingly a general synthesis of an [M]-OMS-l material comprises the following steps: a) reacting a source of manganese cation, a source of framework-substituting metal cation and a source of permanganate anion under basic conditions to provide an [M]-OL in which [M] designates the framework-substituting metal and OL designates the manganese oxide octahedral layered material; b) exchanging the [M]-OL with a source of counter cation; and, c) heating the exchanged [M]-OL to provide the [M]-OMS-l material.
  • the framework-substituting metal cation should be present in the reaction mixture in a concentration effective to introduce the desired proportions of the metal(s) into the framework of the product's structure during the course of the reaction. Therefore, any suitable salt (inorganic or organic) of the selected metal(s) can be used which is sufficiently soluble provided that the anion does not interfere with the other reactants over the course of the reaction.
  • any suitable salt (inorganic or organic) of the selected metal(s) can be used which is sufficiently soluble provided that the anion does not interfere with the other reactants over the course of the reaction.
  • the oxides, nitrates, sulfates, perchlorates, alkoxides, acetates, and the like can be used with generally good results.
  • nitrates of cobalt, nickel, copper, zinc, lanthanum or palladium include nitrates of cobalt, nickel, copper, zinc, lanthanum or palladium, sulfates of chromium, iron, cobalt, nickel or copper, and chlorides of magnesium, cobalt, nickel, copper, zinc or cadmium. Oxides of iron and titanium may also be used. Salts of noble metals, such as titanium, gold, palladium, or platinum, or other metals, such as copper, nickel, or silver, or combinations thereof may also be used.
  • the amount of metal substitution may vary up to any amount of substitution as long as the incorporation of the additional transition metal does not collapse the one-dimensional tunnel structure.
  • the amount of substitution is highly dependent on the specific cation, the coordination number of that cation, its charge, and polarizability and may vary based on the substituting metal.
  • the amount of substitution may be varied by changing the weight ratio between manganese (Mn) and substituting metal.
  • the amount of substitution may range, for example between about 1 ppm (0.0001%) and about 40% of the manganese in the OMS material.
  • the amount of substitution may be, for example, greater than about 1 ppm, greater than about 5 ppm, greater than about 10 ppm, greater than about 15 ppm, greater than about 20 ppm, greater than about 50 ppm, greater than about 75 ppm, greater than about 0.01%, greater than about 0.05%, greater than 0.1%, greater than 0.5%, greater than about 1%, or greater than about 2%.
  • the amount of substitution may be, for example, less than about 40%, less than about 35%, less than about 30%, less than about 25%, less than about 20%, less than about 15%, less than about 12%, less than about 10%, or less than about 5%.
  • a 1% incorporation means that 1% of the total manganese atoms have been substituted by the substituting metal.
  • the ratio between manganese and the substituting metal can be adjusting by adjusting the concentration of the metal cation sources used to prepare the OMS material.
  • the framework-substituted OMS. material may be prepared by refluxing a metal permanganate solution in water, followed by addition of acid and a manganese (II) salt.
  • the metal counterion in the metal permanganate is the substituting metal.
  • Ag-OMS-2 may be prepared by dissolving AgMn0 4 in water, followed by addition of nitric acid (HN0 3 ), and addition of manganese (II) acetate and refluxing.
  • the prepared OMS may be filtered and dried.
  • a synthesis of an example material Ag-OMS-2 is described in EXAMPLE 1, below.
  • the framework-substituted OMS may be prepared by dissolving a manganese salt, metal salt, and source of counter cation in water and heated in a sealed vessel to a temperature greater than the boiling point of water.
  • the resulting OMS material may be isolated by filtering, washing, and drying. Synthesis of an example material V- Cu-OMS-2 is described in EXAMPLE 2, below.
  • the manganese cation can be supplied by manganous salts such as MnCl 2 ,
  • the permanganate anion can be supplied by permanganate salts such as Na(Mn0 4 ), KMn0 4 , Mg(Mn0 4 )2, Ca(Mn0 ) 2 , Ba(Mn0 4 ) 2 , NH 4 (Mn0 4 ), etc.
  • Bases which can be used to provide an alkaline reaction medium include NaOH, KOH, tetraalkyl ammonium hydroxides, and the like.
  • the basic reaction mixture is preferably aged, e.g., for at least 1 day and more preferably for at least about 7 days prior to the exchanging step.
  • the source of counter cation used to ion exchange the [M]-OL can be a magnesium salt, e.g., MgCl 2 or Mg(CH 3 COO) 2 , or MgS0 4 .
  • the conditions of heating, e.g., autoclaving, of the exchanged [M]-OL can include a temperature of from about 100,°C to about 200°C for at least about 10 hours, for example, from about 130 °C to about 170 °C from about 2 to about 5 days.
  • a counter cation for maintaining overall charge neutrality can be, for example, H,
  • Any suitable salt (inorganic or organic) of the selected metal(s) can be used which is sufficiently soluble provided, of course, that the anion does not interfere with the other reactants or the course of the reaction.
  • oxides, halides, nitrates, sulfates, disulfates, perchlorates, alkoxides, acetates, and the like can be used with generally good results.
  • the OMS comprises materials wherein the Mn0 6 octahedra share edges to form double chains and the double chains share corners with adjacent double chains to form a 2x2 tunnel structure.
  • the size of an average dimension of these tunnels is about 4.6 A.
  • a counter cation for maintaining overall charge neutrality such as H, Ba, K, Na, Pb, Rb, Cs, Li, Mg, Ca, Sr, Sn, Ge, Si, and the like, is present in the tunnels and is coordinated to the oxides of the double chains.
  • the identity of the counter cation determines the mineral species or structure type.
  • Hollandites are generally represented by the formula (M)Mn 8 0i 6 , wherein M represents the counter cation and manganese is present in at least one oxidation state. Further, the formula may also include waters of hydration and is generally represented by (M) y Mn 8 0] 6 .xH 2 0, where y is from about 0.8 to about 1.5 and x is from about 3 to about 10.
  • Suitable materials include hollandite (BaMn 8 Oi 6 ), cryptomelane (KMn80 ]6 ), manjiroite (NaMn 8 0i 6 ), coronadite (PbMn 8 Oi 6 ), and the like, and variants of at least one of the foregoing hollandites.
  • the OMS comprises cryptomelane-type materials.
  • some or all of the counter cation is K + .
  • the 2x2 tunnel structure, shown in 2D and 3D representations, of OMS-2 is diagrammatically depicted in Fig. 1. Unless otherwise stated, it is to be understood that an example or embodiment described as using OMS-2 or another form of octahedral molecular sieves, such as OMS-1, also comprises other forms of octahedral molecular sieves that can have a range of counter cations.
  • K-OMS-2 may be prepared, for example, by combining an aqueous solution of KMn0 4 (0.2 to 0.6 molar), an aqueous solution of MnS0 4 .H 2 0 (1.0 to 2.5 molar) and a concentrated acid such as HNO3. The aqueous solution is refluxed at 100 °C for 18- 36 hours. The product is filtered, washed and dried, typically at a temperature of 100 to 140 °C. Similar procedures are known in the literature, for example, DeGuzman et al., Chem. Mater. 1994, 6, 815-821 , which is hereby incorporated by reference in its entirety. The counter cation may be changed by using other salts of permanganate in the process or may be prepared by ion exchange.
  • K-OMS-2 may be prepared by dissolving KMn0 4 in water and stirring to form a homogeneous solution.
  • concentration of KMn0 4 may be, for example, between about 0.195 and about 0.292 mol/L.
  • the solution may then be subjected to hydrothermal treatment at a temperature between, for example, about 230 °C and about 250 °C.
  • the solution is subjected to hydrothermal treatment of a temperature of about 240 °C.
  • the hydrothermal treatment may proceed for from about 3 to about 5 days.
  • the hydrothermal treatment proceeds for about 4 days.
  • the resulting slurry may be washed with water to remove impurities and dried.
  • the material can be washed with DDW to remove impurities.
  • the OMS comprises materials wherein the Mn0 6 octahedra share edges to form triple chains and the triple chains share corners with adjacent triple chains to form a 3x3 tunnel structure.
  • the size of an average dimension of these tunnels is about 6.9 A.
  • a counter cation, for maintaining overall charge neutrality, such as K, Na, Ca, Mg, and the like, is present in the tunnels and is coordinated to the oxides of the triple chains.
  • Todorokites are generally represented by the formula (M)Mn 3 0 7 , wherein M represents the counter cation and manganese is present in at least two oxidation states.
  • the formula may also include waters of hydration and is generally represented by (M) y Mn 0 7 .xH 2 0, where y is from about 0.3 to about 0.5 and x is from about 3 to about 4.5.
  • (M) y Mn 0 7 .xH 2 0 where y is from about 0.3 to about 0.5 and x is from about 3 to about 4.5.
  • the 3x3 tunnel structure of OMS-1 is depicted in Fig. 20, and may be prepared according to the methods described by O'Young et al. in U.S. Patent Number 5,340,562, which is hereby incorporated by reference in its entirety.
  • the OMS-1 structure may be prepared, for example by (a) preparing a basic mixture of a manganous (Mn +2 ) salt, a permanganate salt and a soluble base material and having a pH of at least about 13; (b) aging said mixture at room temperature for at least 8 hours; (c) filtering and washing said aged material to render said material essentially chlorine-free; (d) ion exchanging said filtered material with a magnesium salt at room temperature for about 10 hours; and (e) filtering, washing and autoclaving said exchanged material to form the product.
  • the manganous salt may be, for example, MnCl 2 , Mn(N0 3 ) 2 , MnS0 4 , or Mn(CH 3 COO) 2 .
  • the permanganate salt may be, for example, Na(Mn0 ), KMn0 4 , CsMn0 4 , Mg(Mn0 4 ) 2 , Ca(Mn0 4 ) 2 , or Ba(Mn0 4 ) 2 .
  • the base material may be selected from the group consisting of KOH, NaOH, and tetraalkyl ammonium hydroxides.
  • the magnesium salt used to ion exchange the filtered material this salt may be, for example, MgCl 2 , Mg(CH 3 COO) 2 , and MgS0 4 .
  • the ion-exchanged material is autoclaved at a temperature ranging from about 100 °C to about 200 °C for at least about 10 hours or preferably at from about 130 °C to about 170 °C for about 2 to 5 days.
  • the OMS may have other tunnel structures, for example, 3x2, 3x4, 3x5, 2x4, or 4x4 tunnel structures.
  • Other tunnel structures are described, for example, in U.S. Patent Number 5,578,282, which is hereby incorporated by reference in its entirety.
  • the OMS has an average Mn oxidation state of about 3 to about 4. Within this range the average oxidation state may be greater than or equal to about 3.2, for example, greater than or equal to about 3.3. The average oxidation state may be determined by potentiometric titration.
  • the OMS may be used in any form that is convenient, such as particulate, aggregate, film, or a combination thereof.
  • the OMS may be affixed to a substrate.
  • a general synthesis of an [M]-OMS-2 material comprises heating a reaction mixture which includes a source of manganese cation, a source of framework-substituting metal cation, a source of counter cation and a source of permanganate anion under acidic conditions to provide the [M]-OMS-2.
  • Suitable acids for adjusting the pH of the reaction mixture include the mineral acids, e.g., HC1, H 2 S0 4 , and HN0 3 , and strong organic acids, such as toluene sulfonic acid and trifluoroacetic acid.
  • Embodiments of the invention include compositions having a manganese-based octahedral molecular sieve, described herein, and at least one of a polymer binder, carbon material, carbon nanomaterial, and/or silicon nanomaterial. Any polymer suitable for use in power storage devices, or in electrodes for power storage devices may be used in combination with the manganese-based octahedral molecular sieves described herein.
  • the polymer binder may be, for example, any thermoplastic resin or thermosetting resin.
  • the polymer binder is a thermoplastic resin.
  • the polymer binder may be, for example, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene-butadiene rubber, a copolymer of tetrafluoroethylene-hexafluoropropylene (FEP), a copolymer of tetrafluoroethylene- perfluoroalkyl vinyl ether (PFA), a copolymer of vinylidene fluoride-hexafluoropropylene, a copolymer of vinylidene fluoride-chlorotrifluoroethylene, a copolymer of ethylene- tetrafluoroethylene (ETFE), polychlorotrifluoroethylene (PCTFE), a copolymer of vinylidene fluor fluor flu
  • the polymer binder may be polyvinylidene fluoride, such as KYNARFLEX® 2801. Other polymers suitable for use in power storage devices or batteries may also be used.
  • Carbon materials are forms of elemental carbon suitable for use in battery electrodes, and may be used singly or in combination. Examples include conductive carbon (for example Super P carbon from Comilog, SA.) or graphite (such as KS-15 graphite from Timcal) or graphene. Some embodiments include both conductive carbon and graphite.
  • Carbon nanostructures include forms of elemental carbon with three-dimensional frameworks, such as fullerenes, nanotubes, and nanofibers.
  • Silicon nanomaterials include silicon-based materials, such as silicon nanoparticles, nanospheres, nanorods, silicon nanosheets, silicon nanotubes, and other nanostructures.
  • the relative amounts of manganese-based octahedral molecular sieve, polymer binder, carbon material, carbon nanomaterial, and/or silicon nanomaterial may vary, so long as the resulting composition may be formed into an electrode for a charge storage device.
  • the manganese-based octahedral molecular sieve may range, for example, between about 10% and about 99% of the composition.
  • the manganese-based octahedral molecular sieve may be, for example, more than about 10%, more than about 15%, more than about 20%, more than about 25%, more than about 30%, more than about 35%, more than about 40%, or more than about 45% of the composition.
  • the manganese-based octahedral molecular sieve may be, for example, less than about 99%, less than about 95%, less than about 90%, less than about 85%, less than about 80%, less than about 75%, or less than about 70% of the composition.
  • the polymer binder may range between about 10% and about 90%) of the composition.
  • the polymer binder may be more than about 10%, more than about 15%, more than about 20%, or more than about 25% of the composition.
  • the binder may be less than about 90%, less than about 80%, less than about 70%, less than about 60%, less than about 50%), or less than about 40% of the composition.
  • the carbon material may range between about 1% and about 40% of the composition.
  • the carbon material may be more than about 1%>, more than about 2%, more than about 4%, more than about 5%, or more than about 10% of the composition.
  • the carbon material may be less than about 40%, less than about 35%, less than about 30%), less than about 25%, less than about 20%, less than about 15%, or less than about 10% of the composition.
  • the carbon or silicon nanomaterial may range between about 1% and about 40% of the composition.
  • the carbon or silicon nanomaterial may be more than about 1%, more than about 2%, more than about 4%, more than about 5%, or more than about 10% of the composition.
  • the carbon or silicon nanomaterial may be less than about
  • Embodiments of the invention include electrodes for charge storage devices having a manganese-based octahedral molecular sieve or a composition described herein.
  • the electrode may include a current collector.
  • Any current collector may be used as long as it is an electron conductive substance, which is chemically stable in a battery.
  • a foil, mesh, or sheet composed of aluminum, aluminum alloy, stainless steel, nickel, titanium, carbon, a conductive resin, or the like may be used.
  • aluminum foil or nickel mesh is used as the current collector.
  • a layer of carbon or titanium may be furnished or an oxide layer may be formed.
  • concavity and convexity may be furnished, or a net, a punching sheet, a lath board, a porous substance, a foam substance, a fiber group formed substance, or the like may also be used.
  • the electrode may be an oxygen electrode with a multilayer structure.
  • Such multilayer thin film structures could be, for example, alternating layers of various porous metal oxides and doped porous metal oxides.
  • These multilayers could be prepared with a variety of methods including sol gel, precipitation, chemical vapor deposition, physical vapor deposition, atomic layer deposition, photochemical deposition, plasma methods, microwave methods, ultrasonic cavitation, resistive heating, sputtering, spin coating, electroless plating, electrospinning, other related techniques, and combined methods.
  • the electrode may include a polymer layer on the side of the electrode exposed to the gaseous environment. Any suitable polymer may be used that is porous to air or oxygen. In some embodiments, a microporous PTFE layer is used on the side exposed to the gaseous environment.
  • the electrode is a positive electrode. In some embodiments, the electrode is a negative electrode. In some embodiments, the electrode is an oxygen electrode. Charge Storage Devices
  • Embodiments include charge storage devices having a first electrode, second electrode, and electrolyte between the first and second electrodes, wherein one of the electrodes includes a manganese-based octahedral molecular sieve, composition, or electrode described herein.
  • the charge storage device includes an electrode having a manganese-based octahedral molecular sieve or composition described herein.
  • Examples of the shape of a non-aqueous air battery of the present invention include, but are not particularly limited to, a coin shape, a button shape, a sheet shape, a laminate shape, a cylindrical shape, a laminar shape, and a rectangular shape.
  • a non-aqueous air battery of the present invention may be applied as a large battery used for electric cars or the like.
  • the electrolyte may be, for example, a non-aqueous electrolyte solution or a nonaqueous solvent dissolved with a lithium salt.
  • non-aqueous solvents include, for example, cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate (VC); chained carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and dipropyl carbonate (DPC); aliphatic carboxylate esters such as methyl formate, methyl acetate, methyl propionate, and ethyl propionate; lactones such as gamma-butyrolactone, and gamma-valerolactone; chained ethers such as 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), and ethoxymethoxyethane (EME); cyclic ethers such as tetrahydrofuran and 2-methyltetrahydrofuran; dimethylsulfoxide,
  • a mixed solvent of cyclic carbonates and chained carbonates or a mixed solvent of cyclic carbonates, chained carbonates and aliphatic carboxylate esters can be used.
  • the lithium salt may be, for example, LiC10 4 , LiBF 4 , LiPF 6 , LiAlCU, LiSbF 6 ,
  • the lithium salt may be used alone or one or more kinds may be used in combination. In some embodiments, LiPF 6 is used. Concentration of the lithium salt in the non-aqueous solvent is not especially limited, however, but the concentration may be between about 0.2 and about 2 mol/L, or between about 0.5 mol/L and about 1.5 mol/L.
  • additives may be added to the electrolyte to improve charge and discharge characteristics of a battery.
  • additives for example, triethyl phosphite, triethanol amine, cyclic ether, ethylene diamine, n-glyme, pyridine, hexaphosphoric triamide, nitrobenzene derivatives, crown ethers, quaternary ammonium salts, ethylene glycol dialkyl ethers and the like may be included.
  • a separator may be inserted between the first and second electrodes.
  • any thin microporous membrane with high ion permeability, mechanical strength, and insulation performance may be used.
  • the thin microporous membrane one having the function of blocking the pores at elevated temperature, thus increasing resistance, may be used.
  • the material of the thin microporous membrane may be, for example, a polyolefin such as polypropylene, polyethylene, or the like, or any polymer with suitable organic solvent resistance and hydrophobicity.
  • a sheet, non-woven fabric, woven textile, or the like prepared by glass fibers or the like may be used.
  • the separator may be paper made of OMS materials described herein, including papers made of OMS-2 materials.
  • Papers of OMS materials may be produced by, for example, Yuan, J.; Gomez, S.; Villegas, J.; Laubernds, K.; Suib, S. L.
  • the other electrode may be, for example, a negative electrode.
  • the negative electrode may be any suitable negative electrode material used in batteries. For example, zinc, lithium foil, lithium alloy, or graphite may be used. For a rechargeable zinc alkaline manganese oxide battery the negative electrode would be zinc. In some embodiments, the negative electrode is lithium foil.
  • FIG. 2b shows the field emission scanning electron microscopy (FE-SEM) image of Ag-OMS-2.
  • FE-SEM field emission scanning electron microscopy
  • Such as-synthesized materials have fibrous morphology with a uniform diameter of 20-40 nm and a length of about several hundred nanometers. This was confirmed in Figures 2c-d providing images of transmission electron microscopy (TEM).
  • TEM transmission electron microscopy
  • Figure 3 shows the XRD patterns of OMS-2 materials. All of the diffraction peaks from the samples corresponded to those of OMS-2 materials.
  • FIG. 4 shows the FE-SEM images of the as-obtained OMS-2 materials, composed of fiber-like morphologies with different aspect ratios.
  • OMS-2 has long fibers with a length of about several microns and a diameter of 20 nm.
  • the length of the fibers decreased dramatically to 300 — 500 nm. Meanwhile, the diameters of the fibers were 10— 20 nm.
  • the listed resistivities here are the average of three measurements.
  • OMS-2 showed the lowest value of resistivity of all the samples, 49 ⁇ * ⁇ , which is consistent with the resistivity of OMS-2 material prepared by a reflux method.
  • the resistivities of the incorporated OMS-2 materials increased with an increase of the loading amounts of V and Cu.
  • 10%V-Cu-OMS-2 showed the highest resistivity, which is 287 Q*cm. The trend indicated that the incorporation of V and Cu weakened the electrical conductivity of the OMS-2 materials.
  • Li-0 2 cell was made from a pure lithium metal foil as the anode and an oxygen cathode with multilayer structures laminated with a microporous PTFE layer to the side exposed to the gaseous environment. Ni mesh was used as a current collector.
  • the electrolyte consisted of a solution of 1 M LiPF 6 (lithium hexafluorophosphate) in 1 : 1 : 1 volume EC/DEC/DMC (where EC is ethylene carbonate, DEC is diethyl carbonate, and DMC is dimethyl carbonate).
  • the cells were tested under dry 0 2 (g) at 1 atm and at 25 °C.
  • the test profile consisted of an initial 2 h monitored rest, followed by a discharge at a current density of 0.15 mA/cm 2 to a voltage cutoff of 1.5 V as shown in Fig. 7.
  • the battery cell reached an average capacity of 2741 mAh/g of carbon, as is indicated in Table 1, which shows the specific capacity for these Li-0 2 batteries of Ag-OMS-2.
  • Na-OMS-5 was also tested, with discharge profile shown in Fig. 18 and Table 2.
  • Na-OMS-5 The preparation of Na-OMS-5 can be found in Shen, X.; Ding, Y. S.; Liu, J.; Cai, J.; Laubernds,
  • Discharge profile for Ag-OMS-2 is shown in Fig. 19 and Table 3. Discharge profiles show the potential versus time and are a measure of the rate of loss of capacity in one cycle of the material.
  • cathode solids including 30 wt. % of KYNARFLEX® 2801 binder
  • the cathode coin half-cells containing metallic lithium as the anode, were assembled under an argon atmosphere inside a glove box.
  • the cells contained an electrolyte solution of 1.0 M LiPF 6 dissolved in a 1/1/1 (vol.) EC/DMC/DEC mixture.
  • the cells were discharged at room temperature with a 0.38 mA/cm 2 current density in order to determine the cell voltage, capacity, and the discharge cycling efficiency of the cathode.
  • the specific discharge capacities for all of the samples are listed in Fig. 8.
  • Discharge curves for OMS-2 materials with different incorporation amounts are shown in Fig. 9. All of the samples showed similar S-shape discharge curves.
  • OMS Zeolite-analogue manganese oxide octahedral molecular sieves
  • These OMS materials are environmentally benign, low cost, and semiconducting.
  • OMS materials can be used as electrode materials in lithium ion batteries and lithium air batteries for energy storage.
  • OMS-2 cryptomelane-type manganese oxide octahedral molecular sieve (OMS-2) materials with 2x2 tunnel form (Fig. 1) displayed high capacity (174 mAh/g) and lithium ion reversible properties.
  • OMS-2 materials also showed high capacity (2741 mAh/g of carbon) in lithium air batteries. These unique materials exhibit high performances in lithium batteries.
  • OMS-2 materials have abundant defects on the surface.
  • the relatively loose Mn-0 bonds on the metal oxides surface may favor the association and dissociation of molecular oxygen on the electrocatalyst surfaces, which makes this family of materials attractive for both primary and secondary Li-O? batteries.
  • the tunnel structure of manganese oxide allows lithium ions to be inserted and extracted.
  • the currently most used electrode material in lithium ion batteries is LiCo0 2 , which is costly and toxic.
  • Manganese oxides materials are only 3% of the cost of cobalt based oxides.
  • the manganese oxides in an anode part of a lithium ion battery can be lithiated first and then delithiated, thus functioning as an intercalative material in a lithium ion battery. In this case, a lithium foil is used as a cathode.
  • Oxygen reduction reactions (ORR) in lithium air batteries can be slow. The energy efficiency of lithium air batteries can be an issue, because the charge potentials that are used are higher than the cells' discharge potentials. Hence, good oxygen evolution reaction (OER) catalysts can be used.
  • ORR oxygen reduction reactions
  • OER catalysts include Pt, Au, or Pd nanometer-scale particles. These noble metals are expensive and hard to make. Manganese oxides materials have the potential to be used as bi-functional electrocatalysts for ORR reactions in discharge processes and OER reactions in charge processes in rechargeable lithium batteries.
  • These nanostructured OMS materials are inexpensive and feasible to manufacture on an industrial scale, so that they can be used in lithium batteries for energy storage.
  • Adding other carbon or silicon based materials, such as carbon black, graphite, graphene, carbon nanotubes, fullerene, and/or silicon nanomaterials into the OMS may result in the formation of advanced materials, such as OMS/C or OMS/Si composites.
  • Such composites can be used as electrode materials for lithium batteries.

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Abstract

La présente invention concerne des tamis moléculaires octaédriques à base de manganèse substitués par un métal, qui peuvent être dopés, des compositions comprenant ceux-ci, des électrodes formées de ceux-ci, et des dispositifs de stockage de courant comprenant celles-ci.
PCT/US2013/057705 2012-08-31 2013-08-30 Dispositifs de stockage de courant faisant intervenir de l'oxyde de manganèse à plusieurs valences WO2014036513A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103887515A (zh) * 2014-04-20 2014-06-25 天津市捷威动力工业有限公司 一种锂离子电池负极及使用该种负极的锂离子电池
WO2015191981A1 (fr) * 2014-06-12 2015-12-17 The University Of New Hampshire Compositions d'oxyde de manganèse et leur utilisation en tant qu'électrodes pour dispositifs de stockage d'énergie à phase aqueuse
CN105174314A (zh) * 2015-09-02 2015-12-23 首都师范大学 水溶性MnS纳米颗粒的制备方法及该纳米颗粒作为磁共振成像造影剂的用途
CN111370715A (zh) * 2020-03-23 2020-07-03 河北工业大学 过渡金属离子填充oms-2纳米棒的制备方法和应用
CN112551540A (zh) * 2020-12-09 2021-03-26 北京理工大学重庆创新中心 一种富锂锰基正极用硅铝分子筛添加剂及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060019130A1 (en) * 2004-07-20 2006-01-26 Katikaneni Sai P OMS-2 catalysts in PEM fuel cell applications
US20060049101A1 (en) * 2004-09-03 2006-03-09 Suib Steven L Manganese oxide nanowires, films, and membranes and methods of making
US20070111095A1 (en) * 2005-11-14 2007-05-17 Rovcal, Inc. Novel metal air cathode: manganese oxide contained in octahedral molecular sieve

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060019130A1 (en) * 2004-07-20 2006-01-26 Katikaneni Sai P OMS-2 catalysts in PEM fuel cell applications
US20060049101A1 (en) * 2004-09-03 2006-03-09 Suib Steven L Manganese oxide nanowires, films, and membranes and methods of making
US20070111095A1 (en) * 2005-11-14 2007-05-17 Rovcal, Inc. Novel metal air cathode: manganese oxide contained in octahedral molecular sieve

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JIN, LEI ET AL.: "Titanium Containing-Mn02 (TM) Hollow Spheres: One-Step Synthesis and Catalytic Activities in Li/Air Batteries and Oxidative Chemical Reactions", ADVANCED FUNCTIONAL MATERIALS, vol. 20, no. 19, 2010, pages 3373 - 3382 *
XU, LINPING: "Fabrication of functional transition metal oxide and hydroxide used as catalysts and battery materials", DOCTORAL DISSERTATIONS, 2010, Retrieved from the Internet <URL:http://digitalcommons.uconn.edu/dissertations/AAI3411463> *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103887515A (zh) * 2014-04-20 2014-06-25 天津市捷威动力工业有限公司 一种锂离子电池负极及使用该种负极的锂离子电池
WO2015191981A1 (fr) * 2014-06-12 2015-12-17 The University Of New Hampshire Compositions d'oxyde de manganèse et leur utilisation en tant qu'électrodes pour dispositifs de stockage d'énergie à phase aqueuse
US10468684B2 (en) 2014-06-12 2019-11-05 The University Of New Hampshire Manganese oxide compositions and their use as electrodes for aqueous phase energy storage devices
CN105174314A (zh) * 2015-09-02 2015-12-23 首都师范大学 水溶性MnS纳米颗粒的制备方法及该纳米颗粒作为磁共振成像造影剂的用途
CN111370715A (zh) * 2020-03-23 2020-07-03 河北工业大学 过渡金属离子填充oms-2纳米棒的制备方法和应用
CN111370715B (zh) * 2020-03-23 2022-05-06 河北工业大学 过渡金属离子填充oms-2纳米棒的制备方法和应用
CN112551540A (zh) * 2020-12-09 2021-03-26 北京理工大学重庆创新中心 一种富锂锰基正极用硅铝分子筛添加剂及其制备方法和应用
CN112551540B (zh) * 2020-12-09 2022-04-15 北京理工大学重庆创新中心 一种富锂锰基正极用硅铝分子筛添加剂及其制备方法和应用

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