WO2016153886A1 - Suspension d'électrode biphasique pour pile à flux semi-solide - Google Patents

Suspension d'électrode biphasique pour pile à flux semi-solide Download PDF

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WO2016153886A1
WO2016153886A1 PCT/US2016/022740 US2016022740W WO2016153886A1 WO 2016153886 A1 WO2016153886 A1 WO 2016153886A1 US 2016022740 W US2016022740 W US 2016022740W WO 2016153886 A1 WO2016153886 A1 WO 2016153886A1
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particles
biphasic
suspension
electrode suspension
carbonate
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Jennifer A. Lewis
Teng-Sing WEI
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President And Fellows Of Harvard College
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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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/20—Indirect fuel cells, e.g. fuel cells with redox couple being irreversible
    • 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
    • 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
    • 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
    • H01M4/583—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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • 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
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present disclosure is related generally to rechargeable battery technology and more particularly to electrode suspensions for semi-solid flow cells.
  • a typical flow battery includes an anolyte and a catholyte containing one or more electroactive materials that flows through an electrochemical cell, reversibly converting chemical energy directly to electricity. Additional electrolyte may be stored externally, generally in tanks, and is usually pumped through the cell (or cells) of the reactor. Flow batteries can be rapidly recharged by replacing the electrolyte while simultaneously recovering the spent material for re-energization.
  • a biphasic electrode suspension for a semi-solid flow cell comprises a polar solvent, a nonionic dispersant, a first plurality of particles having repulsive interactions and comprising an electrochemically active material, and a second plurality of particles having attractive interactions and
  • the nonionic dispersant is present in an amount sufficient to sterically stabilize the first plurality of particles, but insufficient to sterically stabilize the second plurality of particles.
  • the second plurality of particles forms a percolating conductive network through the first plurality of particles.
  • a method of making a biphasic electrode suspension for a semisolid flow cell comprises mixing together a polar solvent, a salt, a first plurality of particles comprising an electrochemically active material, and a non-ionic dispersant to form a first suspension.
  • a second plurality of particles comprising an electrochemically active material, and a non-ionic dispersant to form a first suspension.
  • FIG. 1 A is a 3D reconstruction (top) and 2D x-y slice (bottom) of a nano-CT scan acquired on a biphasic suspension containing 20 vol.% LFP, 1 .25 vol.% KB and 0.3 wt.% PVP.
  • FIG. 1 B is a 3D reconstruction (top) and 2D x-y slice (bottom) of a nano-CT scan acquired on a purely attractive suspension containing 20 vol.% LFP, 1 .25 vol.% KB and 0 wt.% PVP.
  • FIGs. 1 C-1 F show electron micrographs of exemplary biphasic suspensions including increasing amounts (0 vol.%, 10 vol.%, 20 vol.% and 30 vol.%, respectively) of repulsive particles for a constant volume fraction (2 vol.%) of attractive particles.
  • FIG. 1 G shows the influence of repulsive particle volume fraction on the electronic conductivity of an exemplary biphasic suspension.
  • FIG. 2A is a plot of shear elastic modulus and electronic conductivity as a function of varying KB content (at 20 vol.% LFP, 0.3 wt.% PVP).
  • FIG. 2B is a plot of shear elastic modulus and electronic conductivity as a function of varying LFP content (at 1 .5 vol.% KB, 0.3 wt.% PVP).
  • FIG. 2C is a plot of shear elastic modulus and electronic conductivity as a function of varying PVP content (at 20 vol.% LFP, 1 .5 vol.% KB).
  • FIG. 3A is a log-log plot of shear stress as a function of shear rate for biphasic (0.3 wt.% PVP) and purely attractive (0 wt.% PVP) electrode suspensions including 20 vol.% LFP and 1 .25 vol.% KB.
  • the lines represent fits of the Herschel-Bulkley model to the experimental data.
  • FIG. 3B is a log-log plot of shear elastic storage (G') and loss (G") moduli for biphasic (0.3 wt.% PVP) and purely attractive (0 wt.% PVP) electrode suspensions composed of 20 vol.% LFP and 1 .25 vol.% KB.
  • FIG. 4A shows flow curves for a biphasic LFP suspension
  • FIG. 4B shows flow curves for a biphasic LTO suspension
  • FIG. 5A shows apparent viscosity as a function of shear rate for biphasic (20LFP/1 .25KB/ 0.3PVP) and purely attractive (20LFP/1 .25KB/0PVP) LFP suspensions.
  • the flow curves for the biphasic suspensions are slip- corrected, while those reported for the purely attractive suspensions are acquired at a rheometer plate gap of 0.8 mm. The latter data provide a lower bound on the true flow curves for these suspensions.
  • FIG. 5B shows apparent viscosity as a function of shear rate for biphasic (20LTO/1 .5KB/0.3PVP) and purely attractive (20LTO/1 .5KB/0PVP) LTO suspensions.
  • the flow curves for the biphasic suspensions are slip- corrected, while those reported for the purely attractive suspensions are acquired at a rheometer plate gap of 0.8 mm. The latter data provide a lower bound on the true flow curves for these suspensions.
  • FIG. 6A shows a log-log plot of shear stress as a function of shear rate for biphasic (0.3 wt.% PVP) and purely attractive (0 wt.% PVP) electrode suspensions composed of 20 vol.% LTO and 1 .5 vol.% KB.
  • the lines represent fits of the Herschel-Bulkley model to the experimental data.
  • FIG. 6B shows a log-log plot of shear elastic storage (G') and loss (G") moduli for biphasic (0.3 wt.% PVP) and purely attractive (0 wt.% PVP) electrode suspensions composed of 20 vol.% LTO and 1 .5 vol.% KB.
  • FIG. 7A shows analytical predictions of the electrode thickness, C- rate, and mean velocity as a function of electronic conductivity for biphasic and purely attractive LFP suspensions of varying composition, under the constraint of constant 90% voltage efficiency between charge and discharge.
  • FIG. 7B shows predicted pressure drop contours for suspensions with 20 vol.% (solid lines) and 5 vol.% LFP (dotted lines).
  • the effective ionic conductivity is calculated for 1 mol L "1 LiTFSI in a PC solvent, which has a viscosity of 8 mPa-s.
  • Contours of electronic transference number, defined as T a eff /(a eff + K eff , where a eff and K eff are effective electronic and ionic conductivity of the suspension, are also shown.
  • FIG. 7C shows surfaces of constant pressure-drop in the three- dimensional space of active-material loading, shear yield-stress, and electronic conductivity.
  • the six data points represent a biphasic LFP suspension (20LFP/1 .25KB/0.3PVP), a purely attractive LFP suspension (20LFP/ 1 .25KB/0PVP), a biphasic LTO suspension (20LTO/1 .5 KB/0.3 P VP), and a purely attractive LTO suspension (20LTO/1 .5KB/0PVP) along with two reference samples (22.4LCO/0.6KB) and (7.9LTO/2.2KB) reported by other groups.
  • FIGs. 8A-8C show 3D CAD images of the electrochemical measurement cells used for electronic conductivity testing, including a static galvanostatic cycling cell and a flow galvanostatic cycling cell.
  • FIG. 9A shows capacity and Coulombic efficiency as a function of cycle number for a biphasic LFP suspension (20LFP/1 .5KB/0.3PVP) galvanostatically cycled vs. Li metal anode in a non-flowing Swagelok cell.
  • FIG. 9B shows selected cycles obtained for the same LFP. Cycles 1 and 90 are performed at C/8; Cycle 6 is performed at C/4.
  • FIG. 9C shows intermittent-flow cycling of the biphasic LFP suspension (20LFP/1 .25KB/0.3PVP) in a lab-scale flow cell. Two consecutive aliquots are first charged, then the second one is discharged, and finally the first aliquot is discharged.
  • the flow channel is 20 mm long and has a 1 .5 mm x 1 .5 mm square cross-section.
  • FIG. 10A shows charge capacity and Coulombic efficiency for a biphasic LTO suspension (25LTO/2KB/0.8PVP) cycled galvanostatically between 2.5 V and 1 .0 V, with the first cycle at C/5 and subsequent cycles at C/8 rate.
  • FIG. 10B shows selected cycles for galvanostatic cycling of the same suspension as in FIG. 10A: cycle 1 is performed at C/5, while the other cycles are performed at C/8.
  • FIG. 1 1 and 12 show the results of cyclic voltammetry experiments to compare the cycling stability of two nonionic dispersants, Triton X-100 and PVP, respectively.
  • Described herein are biphasic electrode suspensions for semi-solid flow cells (SSFCs) that may exhibit high energy density, fast charge transport and low-dissipation flow.
  • a key element of optimizing semi-solid flow cells is maximizing the active material content of the electrode suspensions while retaining satisfactory flowability and electrical conductivity.
  • One challenge is that an increased solids loading of the electrode suspensions can lead to dramatic changes in rheological properties, which can inhibit flow, and the electrochemically active materials may be inherently resistive.
  • the inventors have recognized that it is possible to achieve a high active material content without sacrificing flowability or conductivity by tailoring the interactions among the particles present within the electrode suspensions.
  • a biphasic electrode suspension for a semi-solid flow cell includes a polar solvent, a nonionic dispersant, a first plurality of particles having repulsive interactions and comprising an electrochemically active material, and a second plurality of particles having attractive interactions and comprising an electronically conductive material.
  • the dispersant is present in an amount sufficient to sterically stabilize the first plurality of particles, but insufficient to sterically stabilize the second plurality of particles.
  • the particles comprising the electrochemically active material are dispersed in the suspension, and the particles comprising the electrically conductive material form a percolating network through the first plurality of particles.
  • the biphasic nature of the electrode suspension is believed to enable advantageous rheological properties and excellent electrical conductivity in conjunction with a high active material content.
  • the polar solvent may comprise a nonaqueous polar solvent such as propylene carbonate (PC).
  • suitable nonaqueous polar solvents may include ethylene carbonate (EC), a linear ester or carbonate, a fluorinated ester, a fluorinated carbonate, a fluorinated ether, a cyclic carbonate, a sulfone, a sulfonamide, tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-Me- THF), polymethoxy ether, dimethoxy propane, diethyl ether, diethyoxyethane (DEE), dimethoxyethane (DME), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), propylmethyl carbonate (PMC)), chloroethylene carbonate (CIEC), fluoroethylene carbonate (FEC),
  • EC ethylene carbonate
  • the polar solvent may be a mixture of two or more nonaqueous polvent solvents.
  • the polar solvent may comprise an aqueous polar solvent, such as water.
  • the biphasic suspension may further comprise a salt, such as a lithium salt, at a suitable concentration to achieve a high ionic strength.
  • a salt such as a lithium salt
  • Lithium ions from the salt are a crucial part of the lithiation (discharge) and delithiation (charge) electrochemical reactions that occur during use of an electrochemical cell.
  • the salt may be incorporated at a concentration of up to about 5 M, although in some cases an ionic strength (or concentration) of up to about 1 M may be preferred. It is more typical for aqueous solvents to incorporate salts at higher ionic strengths (e.g., up to about 5 M) due to the high ionic conductivity of water, whereas nonaqueous solvents typically include one or more salts at an ionic strength of up to about 1 M.
  • a minimum concentration for the salt may be about 0.1 M.
  • the salt may comprise one or more of the following: lithium bis(trifluoromethane)sulfon- amide (LiTFSI), a derivative of LiTFSI , lithium nitrate (LiNO 3 ), lithium perchlor- ate (LiCIO 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium 4,5-dicyano-1 ,2,3-triazo- late, lithium bis(trifluoroborane)imidazolide (Lild), lithium tris(trifluoromethane- sulfonyl)methide (LiMe), lithium borate with aromatic ligands, and/or lithium fluoroalkyl phosphate (LiFAP).
  • LiTFSI lithium bis(trifluoromethane)sulfon- amide
  • LiTFSI lithium nit
  • nonionic dispersant or nonionic surfactant
  • Particles that are sterically stabilized have primarily or
  • a suitable amount of the nonionic dispersant to achieve selective stabilization may be at least about 0.1 wt.%, and is preferably at least about 0.3 wt.%.
  • the nonionic dispersant may be present in the biphasic suspension in an amount no greater than about 3 wt.%, e.g., from about 0.3 wt.% to about 3 wt.%.
  • the nonionic dispersant may be polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl pyridine or another nonionic polymer, such as those based on acrylics, esters, ethers, vinyl acetates, vinyl esters, carbonates, and ketones, or block copolymers, such as PPO-PEO-PPO (e.g., 25R4 Pluronic copolymer) with a combination of hydrophobic and hydrophilic groups.
  • PVP polyvinylpyrrolidone
  • PVA polyvinyl alcohol
  • polyvinyl pyridine another nonionic polymer, such as those based on acrylics, esters, ethers, vinyl acetates, vinyl esters, carbonates, and ketones
  • block copolymers such as PPO-PEO-PPO (e.g., 25R4 Pluronic copolymer) with a combination of hydrophobic and hydrophilic groups.
  • PVP is believed to be especially
  • dispersant is octylphenol ethoxylate, or TritonTM X-100, which is commercially available from Dow Chemical Company.
  • Octylphenol ethoxylate which may be referred to as Triton X-100 in the present disclosure, may have some advantages over other nonionic dispersants in terms of electrochemical cycling stability.
  • a nonionic dispersant having good electrochemical cycling stability does not break down within the operating voltage window during cycling.
  • the electrochemically active material may be selected from among: lithium titanate (Li 4 Ti 5 Oi2; LTO), lithium manganese nickel oxide
  • the electronically conductive material may comprise carbon.
  • suitable carbon particles may include carbon black, carbon nanotubes, carbon nano- or microfibers, graphene particles, graphite flakes, or carbon-coated particles and flakes.
  • the interactions among the particles comprising the electrochemically active material are primarily or exclusively repulsive, and interactions among the particles comprising the electronically conductive material are primarily or exclusively attractive.
  • electrochemically active material are dispersed in the suspension, and the particles comprising the electronically conductive material form a percolating conductive network through the first plurality of particles.
  • repulsive particles particles having repulsive interactions
  • particles having attractive forces may be referred to as repulsive particles, and particles having attractive
  • biphasic is used in reference to a suspension comprising two populations of particles, where one population makes up a repulsive phase and the other population makes up an attractive phase. Cross-interactions between the two populations of particles tend to be repulsive. Also, the terms “biphasic suspension” and “biphasic electrode suspension” are used interchangeably.
  • the method used to prepare the biphasic suspension may influence the selective stabilization of the two populations of particles.
  • the selective stabilization may be aided by a substantial difference in the particle size, and consequently the specific surface area, of the particles in the first and second pluralities.
  • the particles in the second plurality (which comprise the electronically conductive material) may have a smaller mean particle size and a higher specific surface area compared to the particles in the first plurality (which comprise the electrochemically active material).
  • the second plurality of the particles Given the higher specific surface area of the second plurality of the particles and the order in which they are added to the mixture during synthesis, as discussed further below, it is possible to preferentially coat the first plurality of particles with the dispersant while the particles in the second plurality remain substantially uncoated, or are insufficiently coated to effect stabilization.
  • the specific surface area of the second plurality of particles may be an order of magnitude or more greater than the specific surface area of the first plurality of particles.
  • the particles of the first plurality may have a microscale mean particle size, while the particles of the second plurality may have a nanoscale mean particle size.
  • the first plurality of particles may comprise a mean particle size of from about 0.1 micron to about 20 microns, or from about 1 microns to about 10 microns, and they may have a specific surface area of from about 1 m 2 /g to about 100 m 2 /g, or from about 10 m 2 /g to about 100 m 2 /g.
  • the second plurality of particles may have a mean particle size of from about 1 nm to about 1000 nm, from about 1 nm to about 500 nm, or from about 10 nm to about 200 nm, and they may have a specific surface area of from about 100 m 2 /g to about 2000 m 2 /g, or from about 500 m 2 /g to about 2000 m 2 /g.
  • the first plurality or population of particles may comprise LiFePO 4 (LFP) having a mean particle size in the range of 0.1 -5 microns
  • the second plurality or population of particles may comprise carbon black (e.g., Ketjenblack EC-600JD; "KB") having a mean particle size in the range of 30-100 nm (0.03-0.1 micron).
  • LFP LiFePO 4
  • carbon black e.g., Ketjenblack EC-600JD; "KB” having a mean particle size in the range of 30-100 nm (0.03-0.1 micron.
  • PC propylene carbonate
  • Polyvinylpyrrolidone (PVP) is employed in a suitable amount to selectively stabilize the first plurality of particles, but not the second plurality.
  • Triton X-100 may be employed.
  • the carbon black may be added to the mixture after the PVP or Triton X-100 is mixed with the LFP particles.
  • the first plurality or population of particles may comprise Li 4 Ti 5 Oi2 (LTO) having a mean particle size in the range of 0.1 -5 microns
  • the second plurality or population of particles may comprise carbon black (e.g., KB) having a mean particle size in the range of 30-100 nm (0.03-0.1 micron).
  • LTO Li 4 Ti 5 Oi2
  • carbon black e.g., KB
  • PC propylene carbonate
  • PC propylene carbonate
  • Polyvinylpyrrolidone (PVP) is employed in a suitable amount to selectively stabilize the first plurality of particles, but not the second plurality.
  • Triton X-100 may be employed.
  • the carbon black may be added to the mixture after the PVP or Triton X-100 is mixed with the LTO particles.
  • the first plurality or population of particles may comprise LiTi 2 (PO 4 )3 having a mean particle size in the range of 0.1 -5 microns
  • the second plurality or population of particles may comprise carbon black (e.g., KB) having a mean particle size in the range of 30-100 nm (0.03-0.1 micron).
  • aqueous polar solvent such as water with up to 5 M of LiNO 3
  • PVP is employed in a suitable amount to selectively stabilize the first plurality of particles, but not the second plurality.
  • Triton X- 100 may be employed.
  • the carbon black may be added to the mixture after the PVP or Triton X-100 is mixed with the LiTi 2 (PO 4 )3 particles.
  • the first plurality or population of particles may comprise LFP having a mean particle size in the range of 0.1-5 microns
  • the second plurality or population of particles may comprise carbon black (e.g., KB) having a mean particle size in the range of 30-100 nm (0.03-0.1 micron).
  • aqueous polar solvent such as water with up to 5 M of UNO3.
  • PVP is employed in a suitable amount to selectively stabilize the first plurality of particles, but not the second plurality.
  • Triton X-100 may be employed.
  • the carbon black may be added to the mixture after the PVP or Triton X-100 is mixed with the LFP particles.
  • the electrochemically active material may be present at
  • the conductive material may be present at a concentration of at least about 0.1 vol.%, at least about 0.5 vol.%, at least about 1 vol.%, or at least about 1.5 vol.%, and is typically no higher than 5 vol.%.
  • the electrochemically active material comprises LFP
  • the electrochemically active material comprises LFP
  • conductive material comprises KB
  • the dispersant comprises PVP.
  • LFP may be advantageous as it has a low volume expansion (Cnnear ⁇ 2.2%) when charged or discharged. For comparison, purely attractive electrode
  • suspensions that do not include a dispersant are also prepared and
  • the microstructures of exemplary biphasic and purely attractive electrode suspensions are characterized using nanoscale-computed tomography (nano-CT).
  • nano-CT nanoscale-computed tomography
  • the 3D reconstructed images and 2D slices obtained from each system are provided FIGs 1A and 1 B.
  • the exemplary compositions are 20LFP/1.25KB/0.3PVP (FIG. 1A) and 20LFP/1.25KB/0PVP (FIG. 1 B), where the numbers denote the volume percent of LFP and KB particles and weight percent of PVP (in solution) in each suspension.
  • the biphasic mixtures, which contain PVP-stabilized LFP particles can be observed to be more homogeneous than their purely attractive counterparts, which do not contain PVP.
  • FIGs. 1 C-1 F show the
  • repulsive S1O2 particles S1O2 particles stabilized by PVP
  • repulsive S1O2 particles are used to mimic the effect of PVP-stabilized electrochemically active particles in a biphasic suspension containing attractive carbon black particles (Ketjenblack EC-600JD or "KB") at a concentration of 2 vol.%.
  • Repulsive SiO 2 particles are used due to their optical transparency in the index-matched liquid medium, and thus it is possible to observe the de-agglomeration of the attractive KB particles.
  • FIG. 1 C-1 F show the biphasic microstructure at 0 vol.% S1O2, 10 vol.% SiO 2 , 20 vol.% SiO 2 and 30 vol.% SiO 2 , respectively.
  • FIG. 1 G shows that the conductivity of the biphasic suspension rises exponentially as a function of SiO 2 volume fraction for a constant volume (2 vol.%) of the KB particles.
  • Biphasic suspensions comprising a varying amount of conductive material (KB) and a fixed amount of electrochemically active material and dispersant (20 vol.% LFP and 0.3 wt.% PVP, respectively) are investigated first. A positive correlation between the electronic
  • the amounts of KB (1.5 vol.%) and PVP (0.3 wt.%) are fixed and the LFP content is varied (from 0 vol.% to 25 vol.%) to explore the effect on the electronic conductivity and shear elastic modulus of the biphasic suspensions (FIG. 2B).
  • the presence of LFP particles having repulsive interactions alters both the long-range and local structure of the percolating network, which includes KB particles having attractive interactions.
  • the percolating KB network comprises large, dense clusters that surround open regions filled with solvent and salt species.
  • the percolating network of attractive KB particles becomes more homogenous, favoring the formation of more tenuous, linear chains with fewer bonds between the KB particles.
  • the repulsive particles may have a significantly slower mobility than do solvent molecules or ionic species. When randomly distributed amongst a population of attractive particles, these species can frustrate the formation of attractive particle bonds, thereby yielding aggregated systems that are kinetically trapped in a more structurally uniform state.
  • the concomitant rise in electronic conductivity and shear elastic modulus with increasing LFP content at a fixed number density of attractive KP particles reflects the microstructural evolution within these biphasic suspensions.
  • the shear elastic modulus is indeed quite small (1.2 Pa), indicative of a structureless liquid state expected for a well-dispersed LFP suspension (20 vol.% LFP, 0.3 wt.% PVP).
  • both the LFP and KB contents are fixed at 20 vol.% and 1.5 vol.%, respectively, and the amount of PVP is varied from 0 to 0.5 wt.% to determine its effects on performance.
  • Results show that once a critical amount of PVP (0.3 wt.%) is introduced to the suspension to stabilize the particles, both electronic conductivity and shear elastic modulus vary minimally with further addition of PVP, as can be seen in FIG. 2C.
  • the above data reveal that optimizing biphasic electrode
  • the biphasic suspension may be designed with advantageous flow properties in conjunction with an electronic conductivity of at least about 1 mS/cm, at least about 5 mS/cm, or at least about 10 mS/cm. In general, it is desirable to have the electronic conductivity match the magnitude of the ionic conductivity of the suspension, which may be determined by the electrolyte.
  • the biphasic suspension may exhibit flow properties that far surpass conventional electrode suspensions.
  • the apparent viscosity may be no greater than about 10 4 Pa s at a shear rate of 10 ⁇ 1 s ⁇ 1
  • the shear yield stress may be no greater than about 700 Pa.
  • the biphasic suspension may also exhibit desirable values of shear elastic modulus, such as a shear elastic storage modulus (G') of no greater than about 6 x 10 4 Pa, and a shear elastic storage modulus (G') of no greater than about 1 x 10 4 Pa.
  • a method of making a biphasic electrode suspension for a semi-solid flow cell may entail mixing together a polar solvent, a salt, a first plurality of particles comprising an electrochemically active material, and a nonionic dispersant to form a first suspension.
  • a second plurality of particles comprising an electronically conductive material may be mixed into the first suspension, thereby forming the biphasic suspension.
  • Nonionic polymers can physically or chemically absorb onto particle surfaces to effect stabilization.
  • PVP, PVA, and Triton X-100 are examples of phys-absorbing nonionic dispersants, which may be effective when added to the first suspension either before or after the salt is added.
  • chem- absorbing nonionic dispersants e.g., comb polymers with anionic or cationic backbones with non-ionic teeth
  • the polar solvent, the first plurality of particles and the non-ionic dispersant may be mixed together before adding the salt.
  • the polar solvent, the non-ionic dispersant and the salt may be mixed together before adding the first plurality of particles.
  • the mixing is carried out in a controlled environment comprising a moisture and oxygen content of less than 0.5 ppm.
  • the polar solvent may be propylene carbonate (PC) or another suitable nonaqueous or aqueous polar solvent, as described above.
  • the biphasic suspension may comprise an ionic strength or salt concentration of typically up to about 1 M, and the salt may be a lithium salt.
  • the nonionic dispersant may be polyvinylpyrrolidone (PVP), Triton X-100 or another nonionic polymer such as one of those named above. To achieve the desired characteristics of the biphasic suspension, the dispersant may be present at a concentration of at least about 0.3 wt.%.
  • the biphasic suspension may have any of the characteristics set forth in this disclosure.
  • the first plurality of particles may have a mean particle size of from about 0.1 to about 20 microns and/or a specific surface area of from about 1 m 2 /g to about 100 m 2 /g.
  • the second plurality of particles may have a mean particle size of from about 1 nm to about 1000 nm and/or a specific surface area of from about 100 m 2 /g to about 2000 m 2 /g.
  • the electrochemically active material employed in the above-described method may be present at concentration of at least about 20 vol.%, and may be selected from among: Li 4 Ti 5 Oi2 (LTO), LiNio.5Mn1.5O4 (LNMO), LiCoO 2 , LiFePO 4 (LFP), V 2 O 5 , LiV 3 O 8 , MnO 2 , Sn-based oxides and composite alloys.
  • the conductive material may be present at a concentration of at least about 0.5 vol.% and may comprise carbon.
  • the model couples charge-transfer and rheology properties by accounting for the high flow velocities required to cycle thin electrodes at a given current density.
  • q is the volumetric charge-capacity of the suspension that depends on the type and loading of electroactive material used. Because electrode thickness decreases with decreasing electronic conductivity, the mean velocity increases as electronic conductivity decreases. A Bingham- plastic rheology (where shear stress increases linearly with shear rate 1341 ) is assumed to estimate the corresponding pressure drop ⁇ , which increases with the flow's dimensionless Bin ham number:
  • the Bingham number (a characteristic ratio of elastic-to-viscous stresses in the flow) is defined in terms of the fluid's yield stress r 0 and plastic viscosity ⁇ ⁇
  • the model provides a contour plot as shown in FIG. 7B, where the pressure drops can be estimated for
  • biphasic LFP and LTO electrode suspensions exhibit electronic conductivities that are nearly two orders of magnitude higher than prior art electrode suspensions, which allows for roughly 25 times thicker electrodes (see FIG. 7A), greatly reducing the time-average pumping rate.
  • the biphasic suspensions also lead to higher areal capacities compared to suspensions with lower electronic conductivity or active material content, enabling longer discharge time at the same current density. Furthermore, the biphasic suspensions possess nearly optimal electronic transference numbers, where electronic and ionic conductivities are of similar magnitude, as indicated in FIG. 7B. These properties are ideal for maximizing cell cycling rates, while minimizing the shunt currents between multiple cells in a stack. By contrast, the low electronic conductivities measured for prior art cells would give rise to dramatic ionic shunt currents owing to their low transference numbers as shown in FIG. 7B, if electrodes of moderate thickness are employed (e.g., from 100 ⁇ to about 1 mm). FIG.
  • the vertical axis is a surrogate scale for energy-density. Based on the plot, it appears that only biphasic suspensions can produce
  • high energy-density i.e., high active-material loading
  • fast charge transfer i.e., high electronic conductivity
  • low-dissipation flow i.e., low pressure drop
  • an electrode for a semi-solid flow cell that comprises a biphasic suspension as set forth herein, where the biphasic suspension may have any of the characteristics and/or compositions described above.
  • the electrode may comprise a thickness of at least about 100 ⁇ .
  • the electrode may exhibit a charge capacity of at least about 120 mAh/g at a rate of C/8 and/or a
  • FI Gs . 8A and 8B show 3D CAD images of electrochemical measurement cells used for electronic conductivity testing, including an electronic conductivity cell 800 and a static cycling cell 802, respectively.
  • the static cell 800 includes current collectors 810, a compression spring 808, a contact plate 806, a containment ring 804 and Swagelock fittings 812, and the flow cell 802 includes current collectors 810, a compression spring 808, a sample well 812, a separator (e.g., Celgard) 814 and a metal foil (e.g., lithium) 816.
  • a separator e.g., Celgard
  • a biphasic LFP suspension (20LFP/1 .5KB/0.3PVP) is first cycled in non-flowing configuration in a modified Swagelok cell.
  • the initial specific capacity of 129 mAh g "1 is obtained at a rate of C/8.
  • the capacity is stable for over 90 cycles, with a capacity of 123 mAh g "1 on the 90 th cycle, or a loss of 0.05% per cycle, as shown in FIG. 9A.
  • Capacity is roughly the same at a rate of C/4, but drops significantly at C/2.
  • the biphasic suspensions have a two-fold higher LFP content compared to prior reported systems.
  • a C-rate of C/4 for a 20 vol.% suspension represents a current equivalent to C/2 with a 10 vol.% suspension, or 1 C with a 5 vol.% suspension.
  • FIG. 9B reveals that polarization increases with cycle number, as given by the voltage differences between the galvanostatic charge and discharge curves, indicating that the capacity loss is due to impedance growth, rather than true capacity fading.
  • Coulombic efficiency is consistently over 99% for the biphasic LFP suspension (20LFP/1 .5KB/0.3PVP).
  • FIGs. 10A and 10B similar measurements were carried out for a biphasic LTO electrode suspension (25LTO/2KB/0.8PVP) and a capacity up to 170 mAh g "1 at a rate of C/8 was obtained, with Coulombic efficiencies exceeding 99%.
  • the optimized biphasic LFP suspensions are tested in a lab-scale half-flow cycling cell (FIG. 8C) against a Li metal negative electrode, using the intermittent flow mode.
  • the half-flow cell 820 includes cathode and anode contacts 822,824, a separator 826, two inlets 828, two outlets 830, and flow channels 830.
  • the material inside the electroactive region is fully charged or discharged under non-flowing condition, and then the aliquot is quickly replaced with a fresh one using computer-controlled syringe pumps.
  • This protocol is known to reduce inefficiency due to pumping and electrochemical losses.
  • an amount of suspension equal to twice the channel volume is charged and discharged, as shown in FIG.
  • FIG. 10A shows charge capacity and Coulombic efficiency for a biphasic LTO suspension (25LTO/2KB/0.8PVP) cycled galvanostatically between 2.5 V and 1 .0 V, with the first cycle at C/5 and subsequent cycles at C/8 rate, and FIG. 10B shows selected cycles for galvanostatic cycling of the same suspension as in FIG. 10A. Cycle 1 is performed at C/5, while the other cycles are performed at C/8.
  • the cycling stability of two nonionic dispersants, PVP and Triton X- 100 are compared by dissolving each dispersant into an electrolyte (1 M LiTFSI in PC) and performing cyclic voltammetry experiments.
  • the three- electrode experimental set-up includes lithium reference and counter electrodes and a glassy carbon working electrode, with the experiments conducted at a scan rate of 20 mV/s.
  • the results are shown in FIG. 1 1 for Triton X-100 (in comparison with data from the electrolyte alone, upper curve) and in FIG. 12 for PVP.
  • the cycling data for the pure electrolyte and the electrolyte containing the dissolved Triton X-100 are also shown in FIG.
  • the electrode suspensions may comprise a high active material content while exhibiting improved flow behavior and enhanced electronic conductivity.
  • the ability to independently tune the stability of two (or more) particle populations enables one to engineer concentrated suspensions that exhibit flow behavior akin to that observed for purely attractive electrode systems, while achieving far higher electronic conductivities. Given their enhanced performance, thicker electrodes can be used, allowing for more desirable transference numbers and higher theoretical areal energy densities. This approach has been demonstrated for both LFP and LTO suspensions including carbon-based percolating networks but is more broadly applicable to other electrochemically active and electronically conductive materials.
  • the active materials consist of a carbon- coated LiFePO 4 (LFP) powder (M121 , Advanced Lithium Electrochemistry Co., Ltd., Taoyuan, Taiwan) with a mean particle size of 4 m, a specific surface area of 13 m 2 g "1 , and a density of 3.551 g cm “3 and carbon-coated Li 4 Ti 5 Oi2 (LTO) powder (LTO-1 , BTR NanoTech Co., Shenzhen, China) with a mean particle size of 1.1 ⁇ , a specific surface area of 10.68 m 2 g "1 , and a density of 3.539 g cm “3 .
  • LFP carbon- coated LiFePO 4
  • M121 Advanced Lithium Electrochemistry Co., Ltd., Taoyuan, Taiwan
  • LTO carbon-coated Li 4 Ti 5 Oi2
  • the conductive material consists of a Ketjenblack (KB) powder (EC-600JD, Azko Nobel Polymer Chemicals LLC (Chicago, USA) with a mean particle size ranging from 30-100 nm, a specific surface area of 1400 m 2 g "1 , and a density of 2.479 g cm “3 .
  • KB Ketjenblack
  • LiTFSI bis(trifluoromethane)sulfonamide
  • PC propylene carbonate
  • Electrode suspensions are prepared in an argon-filled glovebox with moisture and oxygen content maintained under 0.5 ppm. All dry materials are heated at 120°C overnight under vacuum to remove moisture.
  • 250 ml HDPE bottles are filled with 200 g of 5 mm and 100 g of 0.5 mm yttrium stabilized zirconia (YSZ) milling beads.
  • 50 g of PC, 0.3 g of PVP, and 10 g of LFP or LTO powder are added. The bottles are sealed and the
  • suspensions are ball- milled under ambient conditions for 24 h.
  • suspensions are then filtered through 20 ⁇ stainless steel sieve in the argon- filled glovebox.
  • the filtered suspensions are then sealed and centrifuged at 12,500 g in the glove box for approximately 1 hour to collect the dispersed particles.
  • the dense sediment typically 70 wt.% solids
  • the dense sediment typically 70 wt.% solids
  • LiTFSI is then added to achieve a 1 M electrolyte concentration.
  • KB powder is added and homogenized.
  • Suspensions containing either 0 or 0.1 PVP% may be too flocculated to pass through a 20 ⁇ sieve.
  • those samples are prepared by planetary mixing of PC with PVP, followed by adding LiTFSI, then active material, and, finally KB.
  • Rheological characterization Rheological measurements are carried out on electrode suspensions of varying composition using a torsional rheometer (Malvern Kinexus Pro) enclosed in an argon-filled glove box. Both steady shear viscometry and oscillatory shear tests are performed using the smooth parallel plate geometry (diameter of 20 mm; mean roughness Rq of
  • Electronic conductivity characterization Electronic conductivity is measured by the DC method, where the voltage is swept from 0 V to 0.15 V (Biologic VMP-3).
  • the test cell used is a modified Swagelok cell with a cylindrical test geometry (6.35 mm wide, 200 ⁇ thick) sandwiched by two stainless steel electrodes. Contact resistance between suspension and current collector is neglected in these measurements.
  • Galvanostatic cycling characterization Static measurements are performed in two-electrode Swagelok-type cells, using lithium metal foil (Alfa Aesar) as a counter electrode. Electrode suspensions are placed in a stainless steel rod with a 0.5 mm deep well, which is sputter-coated with gold. A porous polymer separator (Celgard) soaked with electrolyte is sandwiched between the electrodes. All electrochemical tests are performed using a Biologic VMP-3 potentiostat.
  • Flow cell characterization The electrode suspensions are tested in a lab-scale half flow cell, with both the positive and negative sides consisting of a 1 .5 mm x 1 .5 mm x 20 mm electroactive region machined into a PVDF body. This region is metallized by sputter-coating with gold on the positive side. A lithium metal negative electrode is inserted into the region on the negative side, and the two halves are bolted together with a Celgard separator wetted with electrolyte in between. Pumping is performed using syringe pumps (Cetoni) with glass syringes (Hamilton Co.), at a flow rate of 30 ⁇ _ s "1 .
  • a syringe is connected to each end of the flow channel; during flow, the suspension is pushed from one syringe, while simultaneously pulled into the other.
  • Flow cell tests are performed in "intermittent flow" mode in which the material in the electroactive region is fully charged or discharged, before another suspension aliquot in pumped in.

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Abstract

L'invention concerne une suspension d'électrode biphasique pour pile à flux semi-solide qui comprend un solvant polaire, un dispersant non ionique, une première pluralité de particules ayant des interactions de répulsion et comprenant une matière électrochimiquement active, et une seconde pluralité de particules ayant des interactions d'attraction et comprenant une matière électroniquement conductrice. Le dispersant non ionique est présent en une quantité suffisante pour stabiliser stériquement la première pluralité de particules, mais insuffisante pour stabiliser stériquement la seconde pluralité de particules. La seconde pluralité de particules forme un réseau conducteur de percolation à travers la première pluralité de particules.
PCT/US2016/022740 2015-03-25 2016-03-17 Suspension d'électrode biphasique pour pile à flux semi-solide WO2016153886A1 (fr)

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