WO2014182281A1 - Voltage-responsive coating for lithium-sulfur battery - Google Patents
Voltage-responsive coating for lithium-sulfur battery Download PDFInfo
- Publication number
- WO2014182281A1 WO2014182281A1 PCT/US2013/039834 US2013039834W WO2014182281A1 WO 2014182281 A1 WO2014182281 A1 WO 2014182281A1 US 2013039834 W US2013039834 W US 2013039834W WO 2014182281 A1 WO2014182281 A1 WO 2014182281A1
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- WIPO (PCT)
- Prior art keywords
- battery
- lithium
- sulfur
- transition metal
- metal compound
- Prior art date
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- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000014233 sulfur utilization Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present disclosure relates to batteries, particular to lithium- sulfur batteries, and especially to the cathodes of these.
- Electric-based vehicles or EVs e.g., hybrid electric vehicles
- HEV battery electric vehicles
- BEV battery electric vehicles
- EREV extended-range electric vehicles
- Lithium ion batteries can be used as a power source in many applications ranging from vehicles to portable electronics such as laptop computers, cellular phones, and so on.
- the EVs powered by the current lithium cobalt or lithium-iron phosphate batteries often have a driving range of less than 100 miles (160 km) per charge, while longer driving ranges would be desirable.
- Li-S battery technology offers an attractive technology that meets the two most pressing issues for electric-based transportation, the needs for low cost and high specific density.
- Li-S battery technology has been the subject of intensive research and development both in academia and in industry due to its high theoretical specific energy of 2600 Wh/kg as well as the low cost of sulfur.
- the discharge process starts from a crown S8 molecule and proceeds though reduction to higher-order polysulfide anions (Li 2 S 8, Li 2 S 6 ) at a high voltage plateau (2.3-2.4 V), followed by further reduction to lower-order polysulfides (Li 2 S 4 , Li 2 S 2 ) at a low voltage plateau (2.1 V), and terminates with the Li 2 S product.
- Li 2 S is oxidized back to S8 through the intermediate polysulfide anions S x .
- the S x polysulfides generated at the cathode are soluble in the electrolyte and can migrate to the anode where they react with the lithium electrode in a parasitic fashion to generate lower- order polysulfides, which diffuse back to the cathode and regenerate the higher forms of polysulfide.
- Y.V. Mikhaylik & J.R. Akridge "Polysulfide Shuttle Study in the Li/S Battery System," J. Electrochem. Soc, 151, A1969-A1976 (2004) and J.R.
- Li/S fundamental chemistry and application to high-performance rechargeable batteries Solid State Ionics, 175, 243-245 (2005) describe this shuttle effect, which leads to decreased sulfur utilization, self-discharge, poor ability to repeatedly cycle through oxidation and reduction, and reduced columbic efficiency of the battery.
- the insulating nature of S and Li 2 S results in poor electrode rechargeablity and limited rate capability.
- an 80 % volume expansion takes place during discharge. Overall, these factors preclude the commercialization of Li-S batteries for EVs.
- conductive scaffolds such as conductive polymers (e.g., polythiophene, polypyrrole, and polyaniline) and porous carbons (e.g., active carbons, mesoporous carbons, hollow carbon spheres, carbon fibers, and graphene).
- conductive polymers e.g., polythiophene, polypyrrole, and polyaniline
- porous carbons e.g., active carbons, mesoporous carbons, hollow carbon spheres, carbon fibers, and graphene.
- the sulfur and the polymer may be crosslinked, leading to electrodes with further improved cycling life.
- carbon scaffolds offer many advantages, such as better stability and conductivity, low cost, and controllable pore structure, which make them more attractive candidates for sulfur cathodes.
- Polymers e.g., poly(ethylene oxide) and poly(3,4-ethylenedioxythiophene)- poly(styrene sulfonate) may be coated on the carbon/sulfur composites to further improve the cycling life and coulomb efficiency.
- current sulfur cathodes still fail to meet the requirement of high- performance Li/S batteries.
- Current sulfur cathodes do not sufficiently retard polysulfide migration to be able to prolong cathode cycling life.
- the cyclic Sg molecules are converted to polysulfides (Li 2 S n , 2 ⁇ n ⁇ 8) that are smaller than the Sg molecules.
- the polysulfides unavoidably diffuse away from the cathodes, causing fast capacity fading with poor cycling life. Nevertheless, a functioning cathode also requires effective lithium ion transport between the electrolyte and the electrodes. Because electrolyte molecules, lithium ions, and the polysulfides exhibit comparable diffusion coefficients, carbon materials that are able to retard the outward polysulfide diffusion will also retard the transport of electrolyte and lithium ions, resulting in poor rate performance or even dysfunction of the cathode. This fundamental dilemma has until now prevented the art from realizing the great potential of Li/S batteries.
- a sulfur-containing electrode with an outer surface including voltage responsive metal compound that expands in volume when the metal of the compound is reduced in oxidation state.
- a battery with a sulfur-containing cathode having in pores of its outer surface a voltage responsive material that expands in volume during battery discharge.
- the expanded volume of the voltage responsive material slows or at least partially prevents outward diffusion of polysulfide compounds from the cathode, resulting in improved cycling stability (capacity retention with repeated cycles of discharge and recharge of the battery).
- the battery may be a lithium-sulfur or silicon-sulfur battery.
- a battery that has a sulfur-containing cathode having in its outer surface pores a reducible transition metal oxide, the transition metal oxide being one that, in its reduced state, is permeable to lithium ions but slows or at least partially prevents outward diffusion of polysulfide compounds from the cathode.
- the battery may be a lithium-sulfur or silicon- sulfur battery.
- a sulfur-containing cathode has vanadium oxide (V 2 O 5 ) deposited or coated in pores of an outer surface layer.
- the vanadium oxide forms Li x V 2 05 during discharge of a Li/S battery.
- the Li x V 2 0 5 during discharge compound has a greater volume than V 2 0 5 , slowing or at least partially preventing outward diffusion of polysulfides from the cathode when it forms while allowing transport of Li + during discharge of the battery.
- a Li/S or Si/S battery having a sulfur-containing cathode with a voltage-responsive material such as vanadium oxide in its pores has improved cycling stability over a battery in which the cathode lacks the voltage-responsive material.
- the voltage-responsive material may be a transition metal compound.
- the voltage-responsive material is a transition metal oxide or a mixed oxide of two or more transition metals.
- a method of making a voltage-responsive sulfur- containing electrode in which a porous sulfur-containing electrode is infiltrated at its surface with a solution of a transition metal alkoxide in anhydrous solvent to deposit in pores or coat in pores the transition metal alkoxide; the solvent is evaporated, the transition metal alkoxide is hydrolyzed with water (for example in the form of water vapor) and then annealed (for example at 100° C to 150° C) to form the sulfur-containing electrode having an outer layer including a transition metal oxide in pores of the electrode.
- a method of making a lithium- sulfur or silicon- sulfur cell or battery in which a porous sulfur-containing electrode with a transition metal oxide in its pores, particularly in pores at its surface, is connected as the battery cathode.
- the transition metal oxide expands in volume to constrict passage of polysulfides when voltage is applied to the cell or battery.
- Figure 1 is schematic illustration of one configuration for a lithium sulfur cell
- Figure 2 is an idealized representation of a response of an anode surface layer of intercalated vanadium oxide during battery discharge
- Figure 1 illustrates one configuration for a lithium sulfur or silicon sulfur cell or battery 10 in which sheets of a anode 12 and cathode 14, separated by a sheet of a polymer separator 16, are wound together or stacked in alternation inside of a cell enclosure 18.
- the polymer separator 16 is electrically nonconductive and ion-pervious via the electrolyte solution that fills its open pores.
- the polymer separator 16 is a microporous polypropylene or polyethylene sheet.
- the enclosure 18 contains a nonaqeuous lithium salt electrolyte solution to conduct lithium ions between the electrodes.
- the anode connects to an anode current collector 20; the cathode connects to a cathode current collector 22.
- the terminals can be connected in a circuit to either discharge the battery by connecting a load (not shown) in the circuit or charge the battery by connecting an external power source (not shown).
- the anode 12 is a lithium anode in a lithium sulfur battery or is a silicon anode in a silicon sulfur battery.
- the lithium sulfur or silicon sulfur cell can be shaped and configured to specific uses as is known in the art.
- the loads may be electric motors for automotive vehicles and aerospace applications, consumer electronics such as laptop computers and cellular phones, and other consumer goods such as cordless power tools, to name but a few.
- the load may also be a power- generating apparatus that charges the lithium sulfur battery 10 for purposes of storing energy. For instance, the tendency of windmills and solar panel displays to variably or intermittently generate electricity often results in a need to store surplus energy for later use.
- a lithium sulfur battery 10 can generate a useful electric current during battery discharge by way of reversible electrochemical reactions that occur when an external circuit is closed to connect the anode 12 and the cathode 14 at a time when the cathode contains electrochemically active lithium.
- the average chemical potential difference between the cathode 14 and the anode 12 drives the electrons produced by the oxidation of intercalated lithium at the anode 12 through an external circuit towards the cathode 14.
- lithium ions produced at the anode are carried by the electrolyte solution through the microporous polymer separator 16 and towards the cathode 14.
- Li + ions from the solution recombine with electrons at interface between the electrolyte and the cathode, and the lithium concentration in the active material of the cathode increases.
- the electrons flowing through an external circuit reduce the lithium ions migrating across the microporous polymer separator 16 in the electrolyte solution to form intercalated lithium cathode 14.
- the electric current passing through the external circuit can be harnessed and directed through the load until the intercalated lithium in the anode 12 is depleted and the capacity of the battery 10 is diminished below the useful level for the particular practical application at hand.
- the lithium sulfur battery 10 can be charged at any time by applying an external power source to the lithium sulfur battery 10 to reverse the electrochemical reactions that occur during battery discharge and restore electrical energy.
- the connection of an external power source to the lithium sulfur battery 10 compels the otherwise non-spontaneous oxidation of the lithium polysulfides at the cathode 14 to produce electrons and lithium ions.
- a lithium sulfur anode 12 has a base electrode material such as lithium metal, which can serve as the anode active material.
- the lithium metal may be in the form of, for example, a lithium metal foil or a thin lithium film that has been deposited on a substrate.
- the lithium metal may also be in the form of a lithium alloy such as, for example, a lithium-tin alloy, a lithium aluminum alloy, a lithium magnesium alloy, a lithium zinc alloy, a lithium silicon alloy, or some combination of these.
- a silicon sulfur battery includes a porous silicon anode, for example prepared with silicon nanoparticles made from high purity silicon.
- the sulfides are oxidized back to crown Sg.
- the materials of the positive electrode including the active lithium-transition metal compound and conductive carbon or other conductive host material, are held together by means of a binder, such as any of those already mentioned above.
- the cathode 14 has a porous host material 32 containing sulfur 34.
- the cathode 14 has an outer layer 30 in which pores or openings 36 of the host material 32 at the cathode's surface are infiltrated with voltage-responsive material.
- the voltage responsive material is a material that expands in volume during battery discharge while sulfur 34 is reduced to smaller- volume compounds, as represented by the configuration on the right-hand side of Figure 2 .
- the expanded volume of the voltage responsive material in outer layer 30 at least partially plugs pore openings 36, as shown by the lack of pore openings 36 in outer layer 30 on the right-hand side of the arrows, to slow or prevent egress of the lower volume polysulfides being formed, while still permitting ingress of lithium ions. For example, this may happen as a transition metal compound forms a lithium- transition metal compound.
- a sulfur-containing cathode may be prepared using a high-pore-volume carbon scaffold, then infiltrating the scaffold with molten crown Sg.
- Porous carbon particles may be synthesized using an aerosol or spraying process.
- surfactants e.g., surfactants that are block copolymers of ethylene oxide and propolyene oxide, such as those sold by BASF under the trademark PLUR.ONJC®
- silicate clusters e.g., silicate clusters, and silica colloidal particles of different sizes
- Pore volume may be controlled by adjusting the amount of the porogens added.
- Carbonization conditions e.g., temperature and time
- Carbon nanotube networks may also be added into the carbon particle precursor solutions to further improve the conductivity and the rate capability.
- High pore volume permits high sulfur loading; however, this must be balanced against a need to maintain adequate electrical conductivity.
- a black powder was then collected and immersed in a 5 M NaOH solution and stirred for 48 h. The solution was then filtered, rinsed several times with deionized water, and dried in an oven at 100 °C.
- the porous conductive carbon or other host material e.g., conductive polymers or metal oxides
- the porous conductive carbon or other host material is infiltrated with molten sulfur and then mixed with a binder and optionally additives and formed into an electrode.
- an outer surface layer is coated or infiltrated with a transition metal compound that reduces when voltage is applied to expand in volume and constrict the outer cathode pores to slow or prevent elution into the electrolyte of the lower volume, reduced sulfide compounds being formed when a battery is discharging.
- the porous sulfur-containing electrode is infiltrated at least at its surface with a voltage responsive material.
- this may be done by introducing into the pores a solution of a transition metal alkoxide, for example a transition metal isopropoxide, in anhydrous solvent such as tetrahydrofuran or ethanol to deposit in pores or coat in pores the transition metal alkoxide.
- a transition metal alkoxide for example a transition metal isopropoxide
- anhydrous solvent such as tetrahydrofuran or ethanol
- suitable transition metal alkoxides include the ethoxides, isopropoxides, and tert-butoxides of vanadium, titanium, molybdenum, and zirconium; these may be used in combination to prepare mixed metal oxides.
- the solvent After being introduced into the pores of the cathode, the solvent is evaporated and the transition metal alkoxide is hydrolyzed with water (for example in the form of water vapor) and then annealed (for example at 100° C to 150° C) for 24 hours to form the sulfur-containing electrode having an outer layer including 2 wt.% a transition metal oxide in pores of the electrode.
- water for example in the form of water vapor
- annealed for example at 100° C to 150° C
- the cathode current collector 22 may be formed from aluminum or another appropriate electrically-conductive material.
- An electrically insulating separator 16 is generally included between the electrodes, such as in batteries configured as shown in Figure 1.
- the separator must be permeable for the ions, particularly lithium ions, to ensure the ion transport for lithium ions between the positive and the negative electrodes.
- Nonlimiting examples of suitable separator materials include polyolefms, which may be homopolymers or a random or block copolymers, either linear or branched, including polyethylene, polypropylene, and blends and copolymers of these; polyethylene terephthalate, polyvinylidene fluoride, polyamides (nylons), polyurethanes, polycarbonates, polyesters, polyetheretherketones (PEEK), polyethersulfones (PES), polyimides (PI), polyamide-imides, polyethers,
- polyolefms which may be homopolymers or a random or block copolymers, either linear or branched, including polyethylene, polypropylene, and blends and copolymers of these; polyethylene terephthalate, polyvinylidene fluoride, polyamides (nylons), polyurethanes, polycarbonates, polyesters, polyetheretherketones (PEEK), polyethersulfones (PES), polyimi
- polyoxymethylene acetal
- polybutylene terephthalate polyethylene naphthenate
- polybutene acrylonitrile-butadiene styrene copolymers
- ABS acrylonitrile-butadiene styrene copolymers
- styrene copolymers polymethyl methacrylate, polyvinyl chloride, polysiloxane polymers (such as polydimethylsiloxane (PDMS)), polybenzimidazole, polybenzoxazole,
- polyphenylenes polyarylene ether ketones, polyperfluorocyclobutanes,
- PTFE polytetrafluoroethylene
- polyvinylidene fluoride copolymers and terpolymers polyvinylidene chloride, polyvinylfluoride, liquid crystalline polymers, polyaramides, polyphenylene oxide, and combinations of these.
- the microporous polymer separator 16 may be a woven or nonwoven single layer or a multi-layer laminate fabricated in either a dry or wet process.
- the polymer separator may be a single layer of the polyolefin.
- a single layer of one or a combination of any of the polymers from which the microporous polymer separator 16 may be formed e.g., the polyolefin or one or more of the other polymers listed above for the separator 16.
- multiple discrete layers of similar or dissimilar polyolefms or other polymers for the separator 16 may be assembled in making the microporous polymer separator 16.
- a discrete layer of one or more of the polymers may be coated on a discrete layer of the polyolefin for the separator 16.
- the polyolefin (and/or other polymer) layer, and any other optional polymer layers may further be included in the microporous polymer separator 16 as a fibrous layer to help provide the microporous polymer separator 16 with appropriate structural and porosity characteristics.
- Suitable electrolytes for the lithium sulfur or silicon sulfur batteries include nonaqueous solutions of lithium salts.
- suitable lithium salts include lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium bis(trifluoromethlysulfonylimide), lithium bis(trifluorosulfonylimide), lithium trifluoromethanesulfonate, lithium fluoroalkylsufonimides, lithium
- fluoroarylsufonimides lithium bis(oxalate borate), lithium
- the lithium salt is dissolved in a non-aqueous solvent, which may be selected from: ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, methylpropyl carbonate, butylmethyl carbonate, ethylpropyl carbonate, dipropyl carbonate, cyclopentanone, sulfolane, dimethyl sulfoxide, 3-methyl-l,3-oxazolidine-2-one, ⁇ - butyrolactone, 1 ,2-di-ethoxymethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3- dioxolane, methyl acetate, ethyl acetate, nitromethane, 1,3-propane sultone, ⁇ - valerolactone, methyl isobutyryl acetate, 2-methoxyethyl acetate, 2-ethoxye
- the electrolyte may further include one or more appropriate additives, such as any of those disclosed in S.S. Zhang, “J. Power Sources,” 162 (2006) 1379-1394 (available at www.sciencedirect.com), for example additives to increase the mobility of lithium ions.
- the voltage responsive material e.g., a reducible transition metal oxide
- the voltage responsive material expands in volume, for example by forming a lithium transition metal compound.
- the voltage responsive material is V 2 O 5 , which forms Li x V 2 05 (x ⁇ 2.5) during discharge.
- the expanded volume of the voltage responsive material slows or at least partially prevents outward diffusion of polysulfide compounds from the cathode, resulting in improved cycling stability (capacity retention with repeated cycles of discharge and recharge of the battery).
- cycling stability capacity retention with repeated cycles of discharge and recharge of the battery.
- a mesoporous carbon-sulfur cathode is treated in this was with V 2 0 5
- the Li x V 2 0 5 formed during discharge prevents (at least to a large extent) polysulfides from leaching from the cathode but allows lithium ions into the cathode for continued satisfactory battery operation.
- suitable transition metal oxides and mixed transition metal oxides are titanium dioxide, molybdenum dioxide, molybdenum trioxide, and mixed oxides of two or more of vanadium, titanium, and molybdenum.
- the voltage responsive material may have a volume increase of at least about 10%, for example 10%-40% in response to voltage during battery discharge.
- the particular voltage responsive material is selected, and the average pore size of the cathode (at least at its surface) is controlled to obtain a desired amount of blocking of the pore by the volume increase.
- the sulfur/carbon cathode was soaked in ethanol solution containing triisopropoxide vanadium oxide at room temperature and stirred for a specific duration. The concentration and duration time could be adjusted to modify the amount of V 2 O 5 coated on sulfur/carbon cathode. The coated cathode was collected by centrifugation and dried at 70 0 C in air allowing complete hydrolysis of vanadium precursor.
- a conventional slurry-coating process was used to fabricate electrode.
- the vanadium oxide coated sulfur/carbon cathode, carbon black and polyvinylidenedifluoride (PVDF) binder were mixed in a mass ratio of 80: 5:15, and homogenized in N-methylpyrrolidinone (NMP) to form slurries.
- NMP N-methylpyrrolidinone
- the homogeneous slurries were coated onto aluminum foil substrates and dried at 70° C in air for 5 hrs.
- the mass loading of active materials was controlled to be 1.25 to 3.75 mg cm-2 on each current collector.
- 2032-type coin cells were assembled in an argon-filled glovebox, using Celgard 2500 membrane as the separator, lithium foil as the counter electrode.
- Figure 3 is a graph in which the capacity versus cycle number of the cathode of the Example is compared to that of a control cathode that was not treated with the vanadium oxide but that was otherwise the same.
- the y-axis 102 is capacity (mAh/g-s) and the x-axis 100 is cycle number.
- Line 1110 is the Example being charged; line 112 is the Example being discharged.
- Line 114 is the uncoated control cathode being charged; line 116 is the uncoated control cathode being discharged. This comparison shows that the vanadium oxide treatment was highly effective in increasing capacity retention with repeated cycles of discharge and recharge of the battery.
- Figure 4 is a graph in which the capacity retention (%, on y-axis 122) versus cycle number (on x-axis 120) out to 500 cycles is plotted for the cathode of the Example.
Abstract
Description
Claims
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PCT/US2013/039834 WO2014182281A1 (en) | 2013-05-07 | 2013-05-07 | Voltage-responsive coating for lithium-sulfur battery |
CN201380078043.5A CN105359305A (en) | 2013-05-07 | 2013-05-07 | Voltage-responsive coating for lithium-sulfur battery |
US14/889,758 US20160111721A1 (en) | 2013-05-07 | 2013-05-07 | Voltage-responsive coating for lithium-sulfur battery |
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