WO2018109626A1 - Électrolyte résistant aux chocs activé par cisaillement - Google Patents

Électrolyte résistant aux chocs activé par cisaillement Download PDF

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Publication number
WO2018109626A1
WO2018109626A1 PCT/IB2017/057762 IB2017057762W WO2018109626A1 WO 2018109626 A1 WO2018109626 A1 WO 2018109626A1 IB 2017057762 W IB2017057762 W IB 2017057762W WO 2018109626 A1 WO2018109626 A1 WO 2018109626A1
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WIPO (PCT)
Prior art keywords
impact resistant
ceramic particles
passively impact
composite electrolyte
shear thickening
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PCT/IB2017/057762
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English (en)
Inventor
Brian H. SHEN
Gabriel M. Veith
Beth L. Armstrong
Wyatt E. Tenhaeff
Sergiy Kalnaus
Hsin Wang
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Ut-Battelle, Llc
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Priority claimed from US15/382,082 external-priority patent/US10347934B2/en
Application filed by Ut-Battelle, Llc filed Critical Ut-Battelle, Llc
Publication of WO2018109626A1 publication Critical patent/WO2018109626A1/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • 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 electrolytes for energy storage devices such as batteries, and more particularly to impact resistant electrolytes having shear thickening ceramic particles.
  • Advanced energy storage materials contain a significant amount of energy.
  • Engineers design protective shrouds to prevent penetration of the battery compartments and the resulting electrical shorting. This electrical shorting spontaneously discharges the battery releasing all the energy at once causing a significant amount of local heating. When the heating is above the ignition temperature of the aprotic flammable organic electrolyte the electrolyte will catch on fire causing personnel or property damage. These fire events limit market penetration of advanced high energy batteries and limit energy storage applications. The remote chance of such an event must be eliminated to ensure consumer confidence and development of new devices/applications.
  • a passively impact resistant composite electrolyte composition includes an electrolyte solvent, up to 6M of an electrolyte salt, and shear thickening ceramic particles having an outer surface.
  • the shear thickening ceramic particles have an absolute zeta potential of greater than ⁇ 40 mV.
  • the ceramic particles have bonded to the outer surface steric stabilizing polymers.
  • the steric stabilizing polymers have a chain length of from 0.5 nm to 100 nm.
  • the shear thickening ceramic particles have a polydispersity index of no greater than 0.1 , and an average particle size of in a range of 50 nm to 1 urn.
  • the steric stabilizing polymers can have a chain length of greater than double the thickness of an electrochemical double layer surrounding the particles.
  • the steric stabilizing polymers can have a chain length of no more than 60 nm.
  • the steric stabilizing polymers have a chain length of no more than 40 nm.
  • the steric stabilizing polymers can include from 1 to 145 monomer units.
  • the passively impact resistant composite electrolyte composition can be stable to an operating voltage of 4.6V (versus Li/Li + ) in a cell.
  • the steric stabilizing polymers can be at least one selected from the group containing of hydrolytically stable, electrically insulating and ionically conducting.
  • the steric stabilizing polymers can include monomer units selected from the group consisting of styrenes, acrylates, methacrylates, acrylonitrile, acrylamides, and methacrylamides, 4-vinylpyridine, 2,2'-dichloroethene, 2-methyl-1 ,3-butadiene acrylic acids and methacrylic acids, vinyl ester, N-vinyl carbazole, N-vinyl pyrrolidone and mixtures thereof.
  • the steric stabilizing polymers comprise poly(methyl methacrylate) (PMMA).
  • the steric stabilizing polymers can be bonded to at least one selected from the group consisting of Si polymer, oxygen groups, surface hydroxyls, an Si-Ox groups of the ceramic particles.
  • the passively impact resistant composite electrolyte composition can include at least one steric stabilizing polymer per square nanometer of the outer surface of the ceramic particles.
  • the shear thickening ceramic particles can include at least one material selected from the group consisting of T1O2, AI2O3, Zr02, Y2O3, Hf02, Ge02, SC2O3, Ce02, MgO, S1O2, BN, and B2O3.
  • the shear thickening ceramic particles can include silica.
  • the shear thickening ceramic particles can have a polydispersity index of no greater than 0.09.
  • the shear thickening ceramic particles can have a polydispersity index of no greater than 0.07.
  • the shear thickening ceramic particles can have a polydispersity index of no greater than 0.05.
  • the shear thickening ceramic particles can have an average particle size of in a range of 100 nm to 500 nm.
  • the shear thickening ceramic particles can have an average particle size of in a range of 150 nm to 300 nm.
  • the polymer chain can include a polyelectrolyte.
  • the polyelectrolyte can be at least one selected from the group consisting of pectin, carrageenan, alginates, polyacrylic acid, poly(sodium styrene sulfonate) (PSS),
  • polymethacrylic acid poly vinyl amine, poly 2-vinylpyridine, carboxym ethyl cellulose, poly(2-acrylamido-2-methyl-1 -propanesulfonic acid), poly(2- acrylamido-2-methyl-1 -propanesulfonic acid-co-acrylonitrile), poly(styrene sulfonic acid), poly(4-styrenesulfonic acid-co-maleic acid), and
  • the shear thickening ceramic particles can be essentially free of materials that volatilize at 80 °C.
  • the shear thickening ceramic particles can be essentially free of materials that volatilize at 110 °C.
  • the shear thickening ceramic particles can be essentially free of materials that volatilize at 120 °C.
  • the shear thickening ceramic particles can be present in the composition in an amount in the range of 10 to 50 weight percent.
  • the electrolyte solvent can include at least one material selected from the group consisting of ethylene carbonate, dimethyl carbonate, propylene carbonate, dimethoxyethane, dioxolane, sulfone, dinitriles, ethyl methyl carbonate, and an ionic liquid.
  • the electrolyte salt can include at least one material selected from the group consisting of lithium hexafluorophosphate, lithium triflate, lithium perchlorate, lithium tetrafluoride borate, lithium hexafluoro lithium arsenate, lithium bis(trifluoromethane sulphone)imide, lithium bis(oxalate) borate, sodium perchlorate, sodium tetrafluoro borate, sodium hexafluoro arsenate, sodium bis(trifluoromethane sulphone)imide, sodium bis(oxalate) borate.
  • the shear thickening ceramic can be functionalized with at least one material selected from the group consisting of a styrene, an acrylate, a methacrylate, a vinyl ester, an acrylamide, a methacrylamide, an acrylonitrile, N-vinyl carbazole, and N-vinyl pyrrolidone.
  • a passively impact resistant battery includes an anode; a cathode, and a passively impact resistant composite electrolyte disposed between the anode and the cathode.
  • the electrolyte includes a passively impact resistant composite electrolyte composition including an electrolyte solvent, up to 6M of an electrolyte salt, and shear thickening ceramic particles having an outer surface.
  • the shear thickening ceramic particles have an absolute zeta potential of greater than ⁇ 40 mV.
  • the shear thickening ceramic particles have a polydispersity index of no greater than 0.1 , and an average particle size of in a range of 50 nm to 1 urn.
  • the shear thickening ceramic particles have bonded to the outer surface steric stabilizing polymers.
  • the steric stabilizing polymers have a chain length of from 0.5 nm to 100 nm.
  • a method of making a passively impact resistant composite electrolyte composition can include the steps of: [0018] a. Preparing shear thickening ceramic particles so that the shear thickening ceramic particles have passively a polydispersity index of no greater than 0.1 , an average particle size of in a range of 50 nm to 1 ⁇ ⁇ , and an absolute zeta potential of greater than ⁇ 40 mV.
  • the shear thickening ceramic particles have an outer surface, and the shear thickening ceramic particles have bonded to the outer surface steric stabilizing polymers.
  • the steric stabilizing polymers have a chain length of from 0.5 nm to 100 nm.
  • the method can include the step of, prior to polymerization of the steric stabilizing polymers on the surface of the shear thickening ceramic particles, treating the outer surface of the particles with halogen-terminated silane polymerization initiator.
  • the polymerization initiator can be 3-trimethoxysilyl)propyl 2-bromo-2- methylpropionate.
  • the polymerization process can be electron transfer (ARGET) atom transfer radical polymerization (ATRP).
  • the method of can include the step of providing silica as the ceramic particles.
  • the silica particles can be derived from a Stober process.
  • the silica particles can be derived from diatomaceous earth.
  • Figure 1 is graph illustrating the TGA of PMMA treated silica, showing characteristic loss of water monolayer at 190 °C, and additional severe loss at 340 °C, indicating burn off of PMMA.
  • Figure 2 is a graph illustrating the DSC of PMMA treated silica, confirming strong exotherm at 340 °C.
  • Figure 3 is a graph illustrating the ATR-FTIR spectrum of poly(methyl methacrylate) standard.
  • Figure 4 is a graph illustrating the ATR-FTIR spectrum of silica particles vacuum dried at room temperature and subsequently functionalized with poly(methyl methacrylate) chains.
  • Figure 5 is a graph illustrating the charge capacity (triangles) and discharge capacity (squares) over cycle number with PMMA functionalized S1O2 Dreamweaver Gold 40 separator heat treated at 80 °C.
  • Figure 6 is a graph illustrating the discharge profile for battery with functionalized S1O2 on Dreamweaver Gold 40 separator heat treated at 80 °C.
  • Figure 7 is a graph illustrating the charge capacity (triangles) and discharge capacity (squares) over cycle number with PMMA functionalized S1O2 Dreamweaver Gold 40 separator heat treated at 80 °C.
  • Figure 8 is a graph illustrating the discharge profile for battery with PMMA functionalized S1O2 on Dreamweaver Gold 40 separator heat treated at 80 °C.
  • Figure 9 is a graph illustrating the charge capacity (triangles) and discharge capacity (squares) over cycle number with PMMA functionalized S1O2 Dreamweaver Gold 40 separator with heat treated at 110 °C.
  • Figure 10 is a graph illustrating the discharge profile for battery with PMMA functionalized S1O2 on Dreamweaver Gold 40 separator with heat treated at 110 °C.
  • Figure 11 is a graph illustrating the charge capacity (triangles) and discharge capacity (squares) over cycle number with PMMA functionalized S1O2 Dreamweaver Gold 40 separator heat treated at 1 10 °C.
  • Figure 12 is a graph illustrating the discharge profile for battery with PMMA functionalized S1O2 on Dreamweaver Gold 40 separator heat treated at 110 °C.
  • Figure 13 is a graph illustrating the shear thickening response of 30 wt% PMMA treated S1O2 nanoparticles in propylene carbonate.
  • Figure 14 is a graph illustrating the shear thickening response of 15 wt % PMMA treated S1O2 particles in propylene carbonate.
  • Figure 15 is a graph of the zeta potential versus pH for particles with 40 nm polymer chains with 1.5 OH groups reacted per square nanometer, based on TGA analysis.
  • Figure 16 is a plot of viscosity/Pa-s vs shear rate/ s "1 for 10 wt % PMMA (40 nm) coated S1O2 particles dispersed in propylene carbonate.
  • Figure 17 is a schematic diagram illustrating poly chains grown on a silica surface.
  • Figure 18 is a schematic diagram of silica particles having bonded thereto polymer chains according to the invention.
  • a passively impact resistant composite electrolyte composition according to the invention includes an electrolyte solvent, up to 6M of an electrolyte salt, and shear thickening ceramic particles.
  • the shear thickening ceramic particles without polymer bonded thereto, have an absolute zeta potential of greater than ⁇ 40 mV, a polydispersity index of no greater than 0.1 , and an average particle size of in a range of 50 nm to 1 urn.
  • These ceramic particles have bonded to an outer surface steric stabilizing polymers.
  • the steric stabilizing polymers have a chain length of from 0.5 nm to 100 nm.
  • the steric stabilizing polymers can have a chain length of greater than double the thickness of an electrochemical double layer surrounding the particles.
  • the chain length can be no more than 100 nm, or no more than 60 nm.
  • the chain length can be no more than 40 nm.
  • the chain length can be 0.5, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 44, 45, 46, 47, 48, 49, 50, 51 , 52, 53, 54, 55, 56, 57, 58, 59, 60, 61 , 62, 63, 64, 65, 66, 67, 68, 69, 70, 71 , 72, 73, 74, 75, 76, 77, 78, 79, 80, 81 , 82, 83, 84, 85, 86, 87, 88, 89, 90, 91 , 92, 93, 94, 95, 96, 97, 98, 99, and 100 nm, or within a range of any high and low value among these.
  • the steric stabilizing polymers can be comprised from monomers and can include from 1 to 145 monomer units.
  • the steric stabilizing polymers can be comprised of 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 44, 45, 46, 47, 48, 49, 50, 51 , 52, 53, 54, 55, 56, 57, 58, 59, 60, 61 , 62, 63, 64, 65, 66, 67, 68, 69, 70, 71 , 72, 73, 74, 75, 76, 77, 78, 79, 80, 81 , 82, 83, 84, 85, 86, 87, 88, 89, 90, 91 , 92, 93, 94, 95, 96, 97, 98,
  • the passively impact resistant composite electrolyte composition can be stable to an operating voltage of 4.6 V (versus Li/Li+) in a cell.
  • the steric stabilized polymers can be selected so as not be soluble in the aprotic solvents and to have an electrochemical stability window such that they are stable in contact with an anode such as graphite, silicon or lithium metal and they must be stable in contact with the cathode at a voltage > 4.6V vs Li/Li + .
  • the steric stabilizing polymers are selected to have one or more suitable properties, and can be selected from polymers that are hydrolytically stable, electrically insulating and/or ionically conducting.
  • Suitable steric stabilizing polymers can be comprised of monomer units selected from the group consisting of styrenes, acrylates, methacrylates, acrylonitrile, acrylamides, and methacrylamides, 4-vinylpyridine, 2,2'-dichloroethene, 2-methyl-1 ,3-butadiene acrylic acids and methacrylic acids, vinyl ester, N-vinyl carbazole, N-vinyl pyrrolidone and mixtures thereof. Other monomer units are possible.
  • An example of a steric stabilizing polymers is poly(methyl methacrylate) (PMMA).
  • the steric stabilizing polymers can also be a polyelectrolyte having an ionizable group.
  • An ionically conductive polymer contributes to the ionic conductivity of the battery, possibly to the dispersability of the ceramic particles, and will possibly also improve the shear thickening behavior.
  • polyelectrolyte polymer can be at least one selected from the group consisting of pectin, carrageenan, alginates, polyacrylic acid, poly(sodium styrene sulfonate) (PSS), polymethacrylic acid, poly vinyl amine, poly 2-vinylpyridine, carboxymethyl cellulose, poly(2-acrylamido-2-methyl-1 -propanesulfonic acid), poly(2-acrylamido-2-methyl-1 -propanesulfonic acid-co-acrylonitrile), poly(styrene sulfonic acid), poly(4-styrenesulfonic acid-co-maleic acid), and poly(vinylsulfonic acid).
  • the steric stabilizing polymers are bonded to the ceramic particles.
  • the bond is a covalent bond.
  • the bond can be terminal, at one end of the chain, with the other end untethered and free to move.
  • the polymers can be bound to different sites on the ceramic polymer constituents.
  • the polymers can be bonded to at least one selected from the group consisting of surface Si, oxygen groups, surface hydroxyls, and Si-Ox groups of the ceramic particles.
  • the steric stabilizing polymer is bound to all sides of the ceramic particles.
  • the coverage of polymer binding sites per unit area of ceramic particle surface can vary.
  • a typical ceramic oxide like S1O2 there are approximately 4.6- 4.9 surface hydroxyl groups per square nanometer of surface.
  • the number of bound polymers to surface sites has to be less than 5 per square nanometer, or 1 , 1.5, 2, 2.5, 3, 3.5, 4, or 4.5 per square nanometer, or within a range of any high or low value among these.
  • the invention can react only half of these groups, from 1.5 to 3.5 per square nanometer, to form covalent bonds and the resulting bound polymers. Additional coverage can result in the loss of surface charge.
  • the shear thickening ceramic particles can be comprised of any suitable ceramic material.
  • the ceramic particles comprise at least one material selected from the group consisting of T1O2, AI2O3, r02, Y2O3, Hf02, Ge02, SC2O3, Ce02, MgO, S1O2, BN, and B2O3.
  • the shear thickening ceramic particles can comprise silica.
  • the shear thickening ceramic particles can have a polydispersity index of no greater than 0.09.
  • the shear thickening ceramic particles can have a polydispersity index of no greater than 0.05, 0.06, 0.07, 0.08, or 0.09, or within a range of any high and low value among these.
  • the shear thickening ceramic particles can have an average particle size, without the polymer bound thereto, of in a range of 50 nm to 1 ⁇ , 100 nm to 500 nm, or 150 nm to 300 nm.
  • the shear thickening ceramic particles can have an average size of 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 20, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, and 1000 nm, or within a range of any high and low value among these.
  • the shear thickening ceramic particles can be essentially free of materials that volatilize at 80 °C.
  • the shear thickening ceramic particles can be essentially free of materials that volatilize at 110 °C.
  • the shear thickening ceramic particles can be essentially free of materials that volatilize at 120 °C.
  • the shear thickening ceramic particles with the steric stabilizing polymer can be present in the composition in an amount in the range of 10 to 50 weight percent, or 20 to 40 weight percent, based upon the total weight of the total weight of the ceramic/polymer particles and the electrolyte.
  • the electrolyte solvent can be any suitable electrolyte solvent.
  • the electrolyte solvent can include at least one material selected from the group consisting of ethylene carbonate, dimethyl carbonate, propylene carbonate, dimethoxyethane, dioxolane, sulfone, dinitriles, ethyl methyl carbonate, and an ionic liquid.
  • ionic liquids include, but are not limited to, for example, N-alkyl- N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-imide, N-alkyl-N- methylpyrrolidinium bis(fluorosulfonyl)imide, and 1 -ethyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide.
  • a mixture of ethylene carbonate and dimethyl carbonate is often used as a solvent in preparing electrolytes, a commonly used mixture being 3:7 weight % ratio mixture of ethylene carbonate and dimethyl carbonate (for example, a mixture containing 30 grams ethylene carbonate and 70 grams dimethyl carbonate), referred to elsewhere herein as 3:7 EC/DMC.
  • electrolyte solvents are possible.
  • Conventional electrolyte additives may also be used; examples include, but are not limited to fluorinated ethylene carbonate, vinyl carbonate to promote solid electrolyte interface (SEI) formation on the anode or cathode with no substantial effect on shear thickening.
  • the electrolyte salt can be any suitable electrolyte salt.
  • the electrolyte salt can include lithium hexafluorophosphate, lithium triflate, lithium perchlorate, lithium tetrafluoride borate, lithium hexafluoro lithium arsenate, lithium
  • bis(trifluoromethane sulphone)imide lithium bis(oxalate) borate, sodium perchlorate, sodium tetrafluoro borate, sodium hexafluoro arsenate, sodium bis(trifluoromethane sulphone)imide, sodium bis(oxalate) borate, and mixtures thereof.
  • Other electrolyte salts are possible.
  • a passively impact resistant battery can include an anode; a cathode, and a passively impact resistant composite electrolyte between the anode and the cathode.
  • the electrolyte includes a passively impact resistant composite electrolyte composition comprising an electrolyte solvent, up to 6M of an electrolyte salt, and shear thickening ceramic particles having an outer surface.
  • the shear thickening ceramic particles have an absolute zeta potential of greater than ⁇ 40 mV.
  • the ceramic particles have bonded to the outer surface steric stabilizing polymers.
  • the steric stabilizing polymers have a chain length of from 0.5 nm to 100 nm.
  • the shear thickening ceramic particles having a polydispersity index of no greater than 0.1 , an average particle size of in a range of 50 nm to 1 urn.
  • a method of making a passively impact resistant composite electrolyte composition includes the step of preparing shear thickening ceramic particles so that the shear thickening ceramic particles have a polydispersity index of no greater than 0.1 , an average particle size of in a range of 50 nm to 1 ⁇ ⁇ , and an absolute zeta potential of greater than ⁇ 40 mV, without polymer bonded thereto.
  • the shear thickening ceramic particles have bonded to an outer surface steric stabilizing polymers.
  • the steric stabilizing polymers having a chain length of from 0.5 nm to 100 nm.
  • the shear thickening ceramic particles are heat treated under negative pressure at a temperature of at least 80 °C to drive off volatile materials.
  • the heat treated shear thickening ceramic particles are combined with an electrolyte solvent and up to 6 M of an electrolyte salt to make a composite electrolyte that comprises shear thickening ceramic particles in an amount in the range of 10 to 50 weight percent.
  • the method can include the step of, prior to polymerization of the steric stabilizing polymers on the surface of the shear thickening ceramic particles, treating the outer surface of the particles with halogen-terminated silane polymerization initiator.
  • the polymerization initiator can be any suitable initiator, for example 3- trimethoxysilyl)propyl 2-bromo-2-methylpropionate.
  • the polymerization process comprises electron transfer (ARGET) atom transfer radical polymerization (ATRP), or any suitable polymerization process.
  • the silica particles are derived from a Stober process.
  • the silica particles can be derived from diatomaceous earth.
  • the particles can be spherical in shape, but do not have to be spherical so long as the polydispersity is acceptable.
  • a passively impact resistant composite electrolyte composition includes an electrolyte solvent, up to 6M of an electrolyte salt, and shear thickening ceramic particles having a polydispersity index of no greater than 0.1 , an average particle size of in a range of 50 nm to 1 ⁇ , and a method to stabilize the particles against flocculation.
  • the stabilization process includes sterically stabilizing the particles with a chemically bound polymer coating, or a chemically bound charged polyelectrolyte.
  • the passively impact resistant composite electrolyte composition of the invention undergoes a passive shear thickening phenomenon upon application of an external force, introducing a significant passive resistance against mechanical damage. Integration of a passive shear thickening effect and enhanced transport of a specific silica material into a liquid electrolyte provides greatly improved stability and safety.
  • a laminated battery cell can include the passively impact resistant composite electrolyte sandwiched between an anode and a cathode.
  • the passive shear thickening effect is not needed until the occurrence of an impact or intrusion upon a battery cell, which is generally caused by an external force. Passive shear thickening enables the material to form a solid barrier which prevents the cathode from touching the anode electrode, thus circumventing a potentially catastrophic electrical short. Since the effect is passive, there is generally no need for expensive electronic monitoring and no need to over-engineer a battery cell. Moreover, the liquid-like nature of the electrolyte enhances its compatibility with conventional battery cell manufacturing technology. The invention is applicable to sundry battery cell types, including, for example, those that employ lithium ion, sodium ion, and/or metal-air electrolyte systems.
  • the key component of the passively impact resistant composite electrolyte composition is a particulate shear thickening ceramic material.
  • ceramic materials that will undergo shear thickening include, but are not limited to Ti0 2 , Al 2 0 3 , Zr0 2 , Y 2 0 3 , Hf0 2 , Ge0 2 , Sc 2 0 3 , Ce0 2 , MgO, Si0 2 , and combinations of any of the foregoing.
  • Other ceramics include insulating nitrides and sulfides like BN,
  • the polymers that are suitable for steric stabilization of ceramic particles must have an electrochemical stability window such that they are stable in contact with an anode such as graphite, silicon or lithium metal and they should also be stable in contact with the cathode at a voltage > 4.6V vs Li/Li + .
  • the polymers should be mostly linear with any branching confined to the end of the polymer, more than half of the chain length, away from the ceramic surface.
  • Branching near the ceramic surface will prevent a high enough concentration of polymers to bind to the surface sites to be useful. This is estimated at about 1 polymer per square nanometer of ceramic surface. Any crosslinking between bound polymers should be confined to no more than 3 polymer backbones to ensure the polymer is dangling off the ceramic surface and free to interact with other polymers bound to adjacent ceramic particles. The polymer should be bound to the ceramic surface, not simply coating the surface. This is a significant distinction since many polymers in battery applications coat particles with a surface layer over the particle, as opposed to forming a covalent bond with the ceramic surface, and particularly a terminal bond.
  • Candidate polymers include but are not limited to oligoethers like poly (ethylene oxide) (PEO), poly (methyl methacrylate) (PMMA), poly(acrylonitrile) (PAN), poly(vinylidene fluoride) (PVDF), poly (vinyl chlorides)(PVC), polypropylene (PP), polyethylene(PE), poly(vinylidene fluoride-co- hexafluoropropylene) (PVDF-HFP) and polystyrenes (PS).
  • these polymers contain C-C backbones with pendent groups resulting in a large separation between the highest and lowest occupied orbitals (HOMO/LUMO).
  • HOMO/LUMO highest and lowest occupied orbitals
  • Candidate materials have pendant groups with high electronegativities like O, N, F, CI.
  • Unstable polymers include polysiloxanes which decompose at chemical potentials seen in batteries.
  • the steric stabilizing polymers prevent the ceramic particles from touching each other so they don't flocculate.
  • Chains grown on the silica particles described above can be grown to lengths greater than 0.5 nm should be no longer than 100 nm in length, preferably no greater than 60 nm, most preferably no greater than 40 nm. Beyond 100 nm in length reduces the concentration of ceramic particles in solution below 40 wt% and causes a decrease in the shear thickening response and the material becomes oily.
  • An example steric stabilizing polymer would be poly(methyl
  • PMMA methacrylate methacrylate
  • ARGET electron transfer
  • ATRP atom transfer radical polymerization
  • This process allows polymer chains to be grown on the surface of the particles continuously to any desired length until stopped, usually done by exposing the polymerization media to air.
  • the silica nanoparticle surface Prior to polymerization, the silica nanoparticle surface is treated with a halogen-terminated silane polymerization initiator like (3- trimethoxysilyl)propyl 2-bromo-2-methylpropionate upon which the chains are grown.
  • the density of the polymer chains covering the silica nanoparticle surface is limited by the number of active sites available to the silane polymerization initiator to tether, which specifically targets and bonds to Si-Ox groups. Assuming a silane molecule will occupy one square nanometer, each 200 nm diameter silica nanoparticle should ultimately be covered by 1 .26x10 5 PMMA chains.
  • the specific ARGET ATRP procedure we used to functionalize the silica particles has a polymer growth rate for PMMA of approximately 10 nm/hour at room temperature.
  • the diameter of the methyl methacrylate monomer group, and PMMA brush thickness, is estimated to be 0.696 nm based on the equation below.
  • Polymer grown on the silica particles described above can be grown to lengths greater than 0.5 nm (one polymer monomer unit) should be no longer than 100 nm in length (about 145 monomer units), preferably no greater than 60 nm (about 85 monomer units), most preferably no greater than 40 nm (about 58 monomer units).
  • PMMA polymers are hydrolytically stable, electrically insulating, and when plasticized with a salt ionically conducting, all of which are important in maintaining high capacity and stability in lithium ion batteries. This is due in large part to the carbonyl structure present in the methyl methacrylate monomer.
  • similar monomers such as acrylic acid, methacrylic acid, or methoxy polyethylene glycol methacrylate (MP EG MA) can be used for surface treatments and will exhibit these desired behaviors.
  • Other monomers include styrenes, acrylates,
  • methacrylates acrylonitrile, acrylamides, and methacrylamides
  • 4-vinylpyridine 2,2'- dichloroethene, 2-methyl-1 ,3-butadiene acrylic acids and methacrylic acids. And mixtures thereof.
  • the length of the polymer chains or polymer groups need to be greater than double the thickness of the electrochemical double layer on the ceramic particles. Specifically, the separation distance between the ceramic particles needs to be greater than twice the polymer chain layer thickness.
  • the dielectric properties of the particles and solvent will affect the electrochemical double layer thickness on the surface of the ceramic particles and thus will affect the length of the polymer brush or monomers on the surface.
  • the electrolyte composition prepared by generally conventional methods, is an essentially homogeneous mixture comprising the stabilized particles and up to 6M of a selected salt in a selected solvent.
  • the stabilized particles loading must be in an amount in the range of 10-50 wt. %, preferably 20-40 wt. %.
  • the salt content must be in the range of 0.5 to 6M, more preferably in the range of 0.8 to 2 M.
  • Electrodes described herein can be used with various conventional electrode systems.
  • Anode materials can include, for example, graphite, Li, Si, Sn, Cu2Sb, Mo3Sb7, Sb, CueSns, Al, Pt, Au, In, and the like.
  • Cathode materials can include, for example, Li, Si, Sn, Cu 2 Sb, Mo 3 Sb 7 , Sb, Cu 6 Sn 5 , Al, Pt, Au, In, and the like.
  • Cathode materials can include, for example, LiNi 1/3 Mn 1/3 Co 1/3 0 2 (NMC), LiCo0 2 ,
  • the invention can be utilized in many convention energy storage devices or devices employing energy storage subsystems.
  • Example include electrochemical devices, sensors displays, windows, and photochromic optical armor.
  • silica sample batches were prepared using the procedure described hereinabove. The silica particles were grown at 0 °C. After preparation the Silica was washed with ethanol and dried under vacuum at temperatures between ambient (about 21 °C) and 130 °C. The resulting silica powders were dispersed in 3:7 EC/DMC containing between 0 and 1.2M LiPF6 to have 10-50 wt% silica.
  • Electrochemical test cells were constructed using a standard
  • LiNi 1/3 Mn 1/3 Co 1/3 0 2 (NMC) cathode and either a graphite (Gr) or lithium metal (Li) anode.
  • Separators made of various materials, including glass fiber, polyacrylonitrile; polypropylene, or a mixture of polypropylene and polyethylene were disposed between the anodes and cathodes.
  • To prepare a cell the electrolyte was added drop- wise to the separator which was placed between the cathode and anode electrodes. Cells tested were standard.
  • Example 1 This example focuses on the steric stabilization of spherical particles.
  • the Stober derived silica prepared as described was dried at 120°C for 3 hours.
  • Poly(methyl methacrylate) (PMMA) polymer chains were grown via activators regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP) on the silica surface.
  • ARGET electron transfer
  • ATRP atom transfer radical polymerization
  • the silica nanoparticle surface Prior to polymerization, the silica nanoparticle surface was treated with a halogen-terminated silane polymerization initiator like (3-trimethoxysilyl)propyl 2-bromo-2-methylpropionate upon which the chains are grown.
  • the specific ARGET ATRP procedure that was used to functionalize the silica particles has a polymer growth rate for PMMA of
  • Figure 1 shows TGA data collected for the PMMA coated silica. The data show the loss of water at 190°C followed by PMMA decomposition at 340°C.
  • Figure 2 shows DSC data for the PMMA coated silica. The endotherm at 340°C confirms the decomposition of PMMA chains in the TGA data ( Figure 1). From the weight loss and BET surface area one can estimate the PMMA brush loading and the thickness described above.
  • Figure 3 shows a reference spectra for PMMA.
  • Figure 4 shows ATR-FTIR spectra of the silica particles functionalized with PMMA as evident by the characteristic vibrational bands centered around 3000, 1800 and 1400 cm 1 for PMMA along with the vibrational bands for S1O2 centered around 1100, 900, 800, and 450 cm 1 .
  • the PMMA loaded separator was dried at 80 °C under vacuum for an estimated weight loading of 5.0 mg/cm 2 .
  • the dried PMMA-S1O2 loaded separator was placed in an electrochemical test cell constructed using a standard LiNii/ 3 Mni/ 3 Coi/302 (NMC) cathode and a graphite (Gr) anode. 110 microliters of 3:7 EC/DMC solvent containing 1.2M LiPF6 purchased from BASF were added to the cell resulting in a 20 wt% solution of shear thickening material.
  • Figure 5 shows capacity as a function of cycle for these electrochemical cells indicating good cycle retention.
  • Figure 6 shows the voltage profile for these electrochemical cells indicating a stable voltage profile which is essential for battery applications.
  • Example 3 The resulting particles were evaluated for performance as an electrolyte.
  • the PMMA coated S1O2 was drop cast onto a separator
  • Example 4 The resulting particles were evaluated for performance as an electrolyte.
  • the PMMA coated S1O2 was drop cast onto a separator
  • the PMMA loaded separator was dried at 110 °C under vacuum for an estimated weight loading of 4.9 mg/cm 2 .
  • the dried PMMA-S1O2 loaded separator was placed in an electrochemical test cell constructed using a standard LiNii/ 3 Mni/ 3 Coi/302 (NMC) cathode and a graphite (Gr) anode.
  • 110 microliters of 3:7 EC/DMC solvent containing 1.2M LiPF6 purchased from BASF were added to the cell resulting in a 20 wt% solution of shear thickening material.
  • Figure 9 shows capacity as a function of cycle for these electrochemical cells indicating good cycle retention.
  • Figure 10 shows the voltage profile for these electrochemical cells indicating an unstable voltage profile indicating the heating protocol damages the PMMA resulting in electrical shorts or passivation of the electrode from polymer components.
  • drying should be limited in temperature and duration.
  • Example 5 The resulting particles were evaluated for performance as an electrolyte.
  • the PMMA coated S1O2 was drop cast onto a separator
  • the PMMA loaded separator was dried at 110 °C under vacuum for an estimated weight loading of 5.0 mg/cm 2 .
  • the dried PMMA-S1O2 loaded separator was placed in an electrochemical test cell constructed using a standard LiNii/3Mni/3Coi/302 (NMC) cathode and a graphite (Gr) anode.
  • 110 microliters of 3:7 EC/DMC solvent containing 1.2M LiPF6 purchased from BASF were added to the cell resulting in a 20 wt% solution of shear thickening material.
  • Figure 11 shows capacity as a function of cycle for these electrochemical cells indicating good cycle retention.
  • Figure 12 shows the voltage profile for these electrochemical cells indicating an unstable voltage profile indicating the heating protocol damages the PMMA resulting in electrical shorts or passivation of the electrode from polymer components.
  • drying should be limited in temperature and duration.
  • Example 6 The Stober derived silica prepared as described was dried at 120°C for 3 hours. Poly( methyl methacrylate) (PMMA) polymer chains were grown via activators regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP) on the silica surface. Prior to polymerization, the silica nanoparticle surface was treated with a halogen-terminated silane polymerization initiator like (3-trimethoxysilyl)propyl 2-bromo-2-methylpropionate upon which the polymer chains are grown. The specific ARGET ATRP procedure that was used to functionalize the silica particles has a polymer growth rate for PMMA of
  • Example 7 The Stober derived silica prepared as described was dried at 120°C for 3 hours. Poly( methyl methacrylate) (PMMA) polymer chains were grown via activators regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP) on the silica surface. Prior to polymerization, the silica nanoparticle surface was treated with a halogen-terminated silane polymerization initiator like (3-trimethoxysilyl)propyl 2-bromo-2-methylpropionate upon which the chains are grown. The specific ARGET ATRP procedure that was used to functionalize the silica particles has a polymer growth rate for PMMA of
  • Example 8 The Stober derived silica prepared as described was dried at 120°C for 3 hours. Poly( methyl methacrylate) (PMMA) polymer chains were grown via activators regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP) on the silica surface. Prior to polymerization, the silica nanoparticle surface was treated with a halogen-terminated silane polymerization initiator like (3-trimethoxysilyl)propyl 2-bromo-2-methylpropionate upon which the chains are grown. The specific ARGET ATRP procedure that was used to functionalize the silica particles has a polymer growth rate for PMMA of
  • the silica nanoparticle surface Prior to polymerization, the silica nanoparticle surface was treated with a halogen-terminated silane polymerization initiator like (3-trimethoxysilyl)propyl 2-bromo-2-methylpropionate upon which the chains are grown.
  • a halogen-terminated silane polymerization initiator like (3-trimethoxysilyl)propyl 2-bromo-2-methylpropionate upon which the chains are grown.
  • the specific ARGET ATRP procedure that was used to functionalize the silica particles has a polymer growth rate for PMMA of
  • Figure 17 is a schematic diagram illustrating poly chains grown on a silica surface.
  • Figure 18 is a schematic diagram of silica particles having bonded thereto polymer chains according to the invention.

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Abstract

La présente invention concerne une composition d'électrolyte composite résistant passivement aux chocs comprenant un solvant d'électrolyte, jusqu'à 6 M d'un sel d'électrolyte, et des particules de céramique à épaississement par cisaillement présentant une surface externe. Les particules de céramique à épaississement par cisaillement ont un potentiel zêta absolu supérieur à ± 40 mV. Les particules de céramique à épaississement par cisaillement ont un indice de polydispersité inférieur ou égal à 0,1, et une taille moyenne de particule se situant dans une plage de 50 nm à 1 µm. Les particules de céramique ont été liées aux polymères de stabilisation stérique de surface externe. Les polymères de stabilisation stérique ont une longueur de chaîne de 0,5 nm à 100 nm. L'invention concerne également une batterie stratifiée résistant passivement aux chocs et un procédé de fabrication de la composition d'électrolyte.
PCT/IB2017/057762 2016-12-16 2017-12-08 Électrolyte résistant aux chocs activé par cisaillement WO2018109626A1 (fr)

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US15/382,082 US10347934B2 (en) 2014-09-26 2016-12-16 Shear activated impact resistant electrolyte
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019113365A1 (fr) * 2017-12-08 2019-06-13 Ut-Battelle, Llc Électrolyte à rhéoépaississement stabilisé
US11233271B2 (en) 2018-04-20 2022-01-25 Ut-Battelle, Llc Fabrication of films and coatings used to activate shear thickening, impact resistant electrolytes
CN116936935A (zh) * 2023-09-14 2023-10-24 宁德时代新能源科技股份有限公司 电解质与固态电解质及各制备方法、电解液、电池及装置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6476317B1 (en) * 1997-07-15 2002-11-05 The United States Of America As Represented By The Secretary Of The Air Force Radiation shield using electrical insulating materials and the spacecharge fields therein
US20090059474A1 (en) * 2007-08-27 2009-03-05 Aruna Zhamu Graphite-Carbon composite electrode for supercapacitors
US7655361B2 (en) * 2006-10-17 2010-02-02 Samsung Sdi Co., Ltd. Electrolyte for high voltage lithium rechargeable battery and high voltage lithium rechargeable battery employing the same
US8357433B2 (en) * 2005-06-14 2013-01-22 Siemens Energy, Inc. Polymer brushes
US20160093917A1 (en) * 2014-09-26 2016-03-31 Ut-Battelle, Llc Impact Resistant Electrolytes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6476317B1 (en) * 1997-07-15 2002-11-05 The United States Of America As Represented By The Secretary Of The Air Force Radiation shield using electrical insulating materials and the spacecharge fields therein
US8357433B2 (en) * 2005-06-14 2013-01-22 Siemens Energy, Inc. Polymer brushes
US7655361B2 (en) * 2006-10-17 2010-02-02 Samsung Sdi Co., Ltd. Electrolyte for high voltage lithium rechargeable battery and high voltage lithium rechargeable battery employing the same
US20090059474A1 (en) * 2007-08-27 2009-03-05 Aruna Zhamu Graphite-Carbon composite electrode for supercapacitors
US20160093917A1 (en) * 2014-09-26 2016-03-31 Ut-Battelle, Llc Impact Resistant Electrolytes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BABU, K ET AL.: "Synthesis of polymer grafted magnetite nanoparticle with the highest grafting density via controlled radical polymerization", NANOSCALE RESEARCH LETTERS, vol. 4, 2009, pages 1090 - 1102, XP002758071 *
SHIVAPOOJA, P ET AL.: "ARGET-ATRP synthesis and characterization of pnipaam brushes for quantitative cell detachment studies", BIOINTERPHASES, vol. 7, no. 32, 2012, pages 1 - 9, XP055496634 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019113365A1 (fr) * 2017-12-08 2019-06-13 Ut-Battelle, Llc Électrolyte à rhéoépaississement stabilisé
US11233271B2 (en) 2018-04-20 2022-01-25 Ut-Battelle, Llc Fabrication of films and coatings used to activate shear thickening, impact resistant electrolytes
US11824163B2 (en) 2018-04-20 2023-11-21 Ut-Battelle, Llc Method of making a passively impact resistant battery
US11824162B2 (en) 2018-04-20 2023-11-21 Ut-Battelle, Llc Battery with shear thickening, impact resistant electrolytes
CN116936935A (zh) * 2023-09-14 2023-10-24 宁德时代新能源科技股份有限公司 电解质与固态电解质及各制备方法、电解液、电池及装置

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