WO2015009912A1 - Solution solide de linixfe1- xpo4, composites de solution solide de linixfe1- xpo4, et procédés de fabrication associés - Google Patents

Solution solide de linixfe1- xpo4, composites de solution solide de linixfe1- xpo4, et procédés de fabrication associés Download PDF

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WO2015009912A1
WO2015009912A1 PCT/US2014/046998 US2014046998W WO2015009912A1 WO 2015009912 A1 WO2015009912 A1 WO 2015009912A1 US 2014046998 W US2014046998 W US 2014046998W WO 2015009912 A1 WO2015009912 A1 WO 2015009912A1
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solid solution
lini
fei
carbon
high electron
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PCT/US2014/046998
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English (en)
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Rui QING
Wolfgang M. Sigmund
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The University Of Florida Research Foundation, Inc.
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Publication of WO2015009912A1 publication Critical patent/WO2015009912A1/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
    • H01M4/36—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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • 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
    • 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

  • Embodiments of the present disclosure provide for electrodes, devices including electrodes, lithium ion batteries, methods of making electrodes, and the like.
  • An embodiment of the present disclosure includes a composition, among others, that includes: a LiNi x Fei_ x P0 4 solid solution material, wherein 0 ⁇ x ⁇ 1.
  • the composition can also include a high electron conducting material such as amorphous carbon, a carbon nanotube, graphene, carbon black, and a combination thereof.
  • An embodiment of the present disclosure includes a cathode material, among others, that includes: a composition including a LiNi x Fei_ x P0 4 solid solution material, wherein 0 ⁇ x ⁇ 1.
  • the composition can also include a high electron conducting material.
  • An embodiment of the present disclosure includes a lithium ion battery, among others, that includes: an anode; a cathode made of a composition a composition including a LiNi x Fei_ x P0 4 solid solution material, wherein 0 ⁇ x ⁇ 1; and an electrolyte disposed between the anode and the cathode.
  • Figure 1 illustrates a field-emission scanning electron microscopy picture
  • LiNio. 6 Feo.4PO4 selected nanocomposites without carbon coating in low and high magnifications.
  • Figure 2 illustrates X-ray diffraction patterns for LiNi x Fei_ x P0 4 solid solution nanocomposites without carbon coating.
  • Figure 3 illustrates X-ray diffraction patterns for LiNi x Fei_ x P0 4 solid solution nanocomposites with carbon coating.
  • Figure 4 illustrates the lattice parameter for LiNi x Fei_ x P0 4 and LiNi x Fei_ x P0 4 /C nanocomposites.
  • Figure 5 illustrates charging/discharging profile for the comparison test of chemical delithiation of LiNio. 6 Feo.4PO4 nanocomposites (inner graph showed the whole charging/discharging process).
  • Figures 6A-6D illustrate X-ray diffraction pattern for (A): pure phase
  • LiNio. 6 Feo.4PO4 nanocomposites (B): electrochemically charged LiNio. 6 Feo.4PO4; (C): chemically delithiated LiNio. 6 Feo.4PO4 by NO2BF4 in ratio 1 : 1; and (D): chemically delithiated LiNio.6Feo.4PO4 by N0 2 BF 4 in ratio 1 :2 DETAILED DESCRIPTION
  • Embodiments of the present disclosure will employ, unless otherwise indicated, techniques of material science, chemistry, and the like, which are within the skill of the art. Such techniques are explained fully in the literature.
  • the present disclosure is not limited to particular materials, reagents, reaction materials, manufacturing processes, dimensions, frequency ranges, applications, or the like, as such can vary. It is also to be understood that the terminology used herein is for purposes of describing particular embodiments only, and is not intended to be limiting. It is also possible in the present disclosure that steps can be executed in different sequence, where this is logically possible. It is also possible that the embodiments of the present disclosure can be applied to additional embodiments involving measurements beyond the examples described herein, which are not intended to be limiting. It is furthermore possible that the embodiments of the present disclosure can be combined or integrated with other measurement techniques beyond the examples described herein, which are not intended to be limiting.
  • Embodiments of the present disclosure provide for electrodes, devices including electrodes, lithium ion batteries, methods of making electrodes, and the like. Embodiments of the present disclosure can be advantageous since they can be used in devices that require high energy density, high energy power, and/or long cycling life. Embodiments of the present disclosure can have superior electrical conductivity than LiNiP0 4 . Embodiments of the present disclosure can be used in lithium ion batteries, energy storage devices, portable devices, power tools, electric vehicles, and the like.
  • An embodiment of the present disclosure includes a LiNi x Fei_ x P0 4 solid solution, where 0 ⁇ x ⁇ 1, and specifically, x can be about 0.01 to 0.99 in any increment of about 0.01 and this includes all possible ranges of about 0.01 to 0.99, in increments of about 0.01 (e.g., any of about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6 about, 0.7, about 0.8, about 0.9 to any of about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9).
  • An embodiment of the LiNi x Fei_ x P0 4 solid solution can have an olivine-type structure with Pnma space group.
  • the LiNi x Fei_ x P0 4 particles e.g., spherical, semi-spherical, polygonal, non-spherical, and the like
  • the LiNi x Fei_ x P0 4 particles can have a diameter (or longest dimension) of about 10 to 500 nm, about 10 to 100 nm, or about 40 nm, while other dimensions (e.g., length, width, height) can have the same or smaller ranges.
  • Embodiments of the LiNi x Fei_ x P0 4 solid solution can have an electrical conductivity of about 0.1 x 10 "09 S/cm to 9.9 x 10 "7 S/cm.
  • Embodiments of the LiNi x Fei_ x P0 4 solid solution can have a lithium diffusion coefficient of about 1 x 10 "14 cm 2 /s to 2 x 10 "13 cm 2 /s.
  • Another embodiment includes a composite of a LiNi x Fei_ x P0 4 solid solution material and a high electron conducting material (e.g., LiNi x Fei_ x P0 4 /C
  • the high electron conducting material can be disposed on the surface of the particles of the LiNi x Fei- x P04.
  • the LiNi x Fei_ x P0 4 solid solution can be about 90 to 99.999 weight % of the composite.
  • the LiNi x Fei_ x P0 4 solid solution material can have the same characteristics and dimensions as described herein.
  • the high electron conducting material can include a material having a high electron conducting characteristic, while not detrimentally reacting with LiNi x Fei_ x P0 4 particles.
  • the high electron conducting material can include amorphous carbon, carbon nanotubes, graphene sheets, and combinations thereof. In an embodiment, the high electron conducting material is about 0.001 to 10 weight % of the composite.
  • the LiNi x Fei_ x P0 4 /C nanocomposite particles can have a diameter (or longest dimension) of about 10 to 500 nm, about 10 to 100 nm, or about 40 nm.
  • Embodiments of the LiNi x Fei_ x P0 4 /C nanocomposite can have an electrical conductivity of about 0.1 x 10 ⁇ 3 S/cm to 9.9 x 10 ⁇ 3 S/cm.
  • Amorphous carbon is less ordered at the microscopic scale than crystalline graphite that includes a hexagonal or rhombohedral crystal structure.
  • amorphous carbon can include activated carbon, carbon black, charcoal, a combination thereof, and the like.
  • the carbon nanotubes are generally described as fullerenes of closed-cage carbon molecules typically arranged in hexagons and pentagons.
  • the carbon nanotubes can be single wall nanotubes (SW T) or multi-walled nanotubes (MWNT).
  • the MWNT can include 2 or more walls, 5 or more walls, 10 or more walls, 20 or more walls, or 40 or more walls.
  • the carbon nanotubes including SWNTs and MWNTs may have diameters from about 0.6 nanometers (nm) up to about 3 nm, about 5 nm, about 10 nm, about 30 nm, about 60 nm or about 100 nm.
  • the single-wall carbon nanotubes may have a length from about 50 nm up to about 1 millimeter (mm), or greater. In an embodiment, the diameter of the single-wall carbon nanotube is about 2 to 5 nm and has a length of about 50 to 500 nm.
  • Embodiments of the LiNi x Fei_ x P0 4 solid solution and the composite of a LiNi x Fei_ x P0 4 solid solution material and a high electron conducting material can be made using solid state reaction methods. Exemplary methods of making LiNi x Fei_ x P0 4 solid solution and the composite of a LiNi x Fei- x P0 4 solid solution material and the high electron conducting material are described in Example 1.
  • the LiNi x Fei_ x P0 4 solid solution and the composite of a LiNi x Fei_ x P0 4 solid solution material and a high electron conducting material can be used as a cathode material to form a cathode in a device, such as, a lithium battery, for example.
  • the device can include an anode (e.g., graphite, multi-walled nanotube (MWNT), Ti0 2 , Li 4 Ti 5 0i 2 ,and the like), an electrolyte (e.g., LiPF 6 :EC-DMC (ethylene carbonate-dimethyl carbonate and other stable electrolytes), and the like), and a cathode made of the LiNi x Fei_ x P0 4 solid solution and/or the composite of a
  • anode e.g., graphite, multi-walled nanotube (MWNT), Ti0 2 , Li 4 Ti 5 0i 2 ,and the like
  • an electrolyte e.g., LiPF 6 :EC-DMC (ethylene carbonate-dimethyl carbonate and other stable electrolytes), and the like
  • a cathode made of the LiNi x Fei_ x P0 4 solid solution and/or the composite of a
  • LiNi x Fei_ x P0 4 solid solution material e.g., LiNi x Fei_ x P0 4 solid solution material, a polymer binder (e.g., polyethlyene glycol, polypropylene, polyvinylidene fluoride (PVDF), and the like), and a high electron conducting material, where the electrolyte is disposed between the anode and cathode.
  • the electrolyte can be a solid electrolyte or a liquid electrolyte.
  • Nanosize LiNi x Fei_ x P0 4 solid solution and Li i x Fei_ x P0 4 /C nanocomposites were prepared via a solid state reaction method under argon atmosphere.
  • a single phase olivine-type structure with Pnma space group was determined by X-Ray diffraction. Crystallite sizes were found to be around 40 nm. Linear relationship was observed between lattice parameters and chemical composition. Synthesized materials displayed electronic conductivity similar to previous reported value of LiFePC ⁇ . Carbon coating also helps to increase the overall conductivity of nanocomposites to the order of 10 "3 S/cm.
  • olivine structure materials have been under investigation by numerous researchers as cathodes for lithium ion batteries, especially considered as potential solution for electric vehicles (EV) and plug-in hybrid vehicles (PHV) [2-4].
  • space group Pnma One dimensional lithium transport channel is observed along [010] direction [5, 6].
  • Olivine type structure materials attracted common interests as cathode in lithium ion batteries due to their abundance in nature, low cost, non-toxicity and good electrochemical performance [7, 8].
  • LiMnP0 4 and LiFeP0 4 [9, 10] .
  • LiNiP0 4 has the highest operation voltage of 5.1V against lithium metal, according to computational results [11-14] .
  • the value is significantly superior to the currently commercialized LiFeP0 4 which has an operation voltage around 3.4 V.
  • LiNi x Fei- x P0 4 solid solution nanocomposites were prepared via solid state reaction method.
  • L12CO 3 lithium carbonate, 99.5+%, A.C.S certified, Fisher
  • FeC 2 0 4 iron (ii) oxalate dehydrate, 99+%, Alfa Aesar
  • Ni(CH 3 COO) 2 nickel(ii) acetate tetrahydrate, 99+%, for analysis, Acros organics
  • NH 4 H 2 P0 4 ammonium dihydrogen phosphate, 99+%, for analysis, Acros organics
  • LiNi x Fei_ x P0 4 series solid solution materials synthesized with surface carbon coating Alternative phases evolved during the synthesis process, marked with a star label in the graph.
  • the phases were labeled to be nickel phosphides such as 3 P, N1 7 P 3 , etc. These phases were believed to emerge from the reducing atmosphere created by the excessive carbon content from decomposition of the cellulose.
  • Nickel ion was subjected to transition from [Ni 3+ ] state to [Ni 2+ ] state in reducing atmosphere, through which these off-stoichiometric impurity phases were formed. These impurity phases would decrease the overall electrochemical capacity, but were beneficial in overall electronic conductivity as proposed by Nazar et al[32].
  • Superior charge-discharge capacity and cycleability were observed for our carbon-coated sample tested towards a low voltage limit at 4.5 V as compared to the non-carbon coated ones.
  • lattice parameters for as-prepared nanocomposites were calculated using least square method and summarized in Table 1. The results were plotted against composition in Figure 4, where a, b, c denoted the three dimensions of the orthorhombic cell. A linear correlation between lattice parameters and the content ratio of nickel in the composition was found. Lattice parameter a and b decreased linearly with the increasing ratio of nickel due to the smaller Shannon radii of [Ni 2+ ] (0.69 A) compared to [Fe 2+ ] (0.78 A). Lattice parameter c remained relatively unchanged.
  • lattice parameter a and b were slightly larger than that of carbon-free sample with the same composition. This could correspond to the fact that off-stoichiometric impurity phases of nickel phosphide ( 3 P, N1 7 P 3 ) were formed due to the reducing atmosphere. Nickel content was partially consumed so the main phase switched towards the iron rich end. Selected samples had also been chosen to do multiple XRD tests in order to establish an error bar for the calculation. By repeat experiments the standard deviation for our test was determined to be ⁇ 0.5%.
  • K is the shape factor, typically 0.9
  • ⁇ is the X-ray wavelength
  • ⁇ is half maximum intensity broadening (FWHM) in radians
  • ⁇ is the Bragg angle
  • ⁇ is the calculated mean size of the crystalline domains, equal to the particle size of single crystallites. Crystal lengths along the three strongest peaks were calculated. No dendritic growth was observed. Typical crystallite size of 42+9 nm for as-prepared samples was obtained. No correlation between crystallite size and composition has been found for our synthesis route. Also no significant change in the crystallite size had been observed when introducing carbon coating into our solid solution system.
  • Electrochemical delithiation process and its first cycle charge-discharge capacity were shown in Figure 5.
  • Peak shift towards high 2 theta angle was shown in the diagram.
  • the shift of the peaks corresponding to each lattice plane indicated the contraction of the whole crystal lattice, induced by the removal of lithium content within oxygen octahedrons.
  • LiNi x Fei_ x P0 4 solid solution materials further electrochemical tests with high voltage electrolyte would be needed to further reveal the full potential of these series of materials to be used as cathodes for lithium ion batteries.
  • Various electrolytes in combination with our LiNi x Fei_ x P0 4 nanocomposites are ongoing and the results would be reported in our next paper.
  • LiFePC-4 10.328 6.003 4.692
  • LiNiPO 4 10.060 5.776 4.683
  • ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
  • a concentration range of "about 0.1% to about 5%” should be interpreted to include not only the explicitly recited concentration of about 0.1 wt% to about 5 wt%, but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%) within the indicated range.
  • the term "about” can include traditional rounding according to the measuring technique and the numerical value.
  • the phrase “about 'x' to 'y'” includes “about 'x' to about 'y" ⁇

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne, dans plusieurs modes de réalisation, des électrodes, des dispositifs comprenant des électrodes, des batteries au lithium-ion, des procédés de fabrication d'électrodes, et analogue. Dans un mode de réalisation, cette invention concerne une composition, entre autres, comprenant une matière de solution solide de LiNixFe1-xP04, formule dans laquelle 0 < x < 1. Dans un mode de réalisation, la composition peut également comprendre un matériau conducteur à haute mobilité d'électrons tel que du carbone amorphe, un nanotube de carbone, du graphène, du noir de carbone et une combinaison correspondante.
PCT/US2014/046998 2013-07-18 2014-07-17 Solution solide de linixfe1- xpo4, composites de solution solide de linixfe1- xpo4, et procédés de fabrication associés WO2015009912A1 (fr)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130112915A1 (en) * 2011-11-08 2013-05-09 Gue-Sung Kim Composite cathode active material, cathode and lithium battery that include the composite cathode active material, and method of preparing the composite cathode active material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130112915A1 (en) * 2011-11-08 2013-05-09 Gue-Sung Kim Composite cathode active material, cathode and lithium battery that include the composite cathode active material, and method of preparing the composite cathode active material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
QING ET AL.: "Synthesis of LiNixFe1-xP04 solid state solution as cathode materials for lithium ion batteries.", ELECTROCHIMICA ACTA., vol. 108, pages 827 - 832 *

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