WO2012100301A1 - Matériau soufre-carbone et utilisation en tant que cathodes pour batteries à haute énergie - Google Patents

Matériau soufre-carbone et utilisation en tant que cathodes pour batteries à haute énergie Download PDF

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WO2012100301A1
WO2012100301A1 PCT/AU2012/000067 AU2012000067W WO2012100301A1 WO 2012100301 A1 WO2012100301 A1 WO 2012100301A1 AU 2012000067 W AU2012000067 W AU 2012000067W WO 2012100301 A1 WO2012100301 A1 WO 2012100301A1
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sulfur
carbon material
micropores
gof
porous carbon
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Da-Wei Wang
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The University Of Queensland
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • 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
    • 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 generally relates to a new sulfur-carbon material, for example for use as a cathode material in high energy batteries, such as lithium-sulfur batteries, and more particularly to selectively confined sulfur carbon-based cathodes for use in high energy batteries.
  • Lithium-sulfur batteries can deliver a significant energy density of theoretically 2500 W h kg -1 or 2800 W h ⁇ 1 .
  • This class of high energy batteries comprehensively outperforms lithium ion batteries with varying configurations.
  • the outstanding performance of LSBs arises from the distinct non- topotactic cathode reaction of S 8 + 16 Li « ⁇ 8 Li 2 S, which offers an extreme capacity of 1675 mA h g _1 , more than five times of the theoretical upper limit of 300 mA h g _1 for conventional cathode materials.
  • LSBs are intrinsically protected from overcharging and lithium dendrite short-circuiting, and promise high levels of safety.
  • the soluble polysulfide irreversibly deposits as insulating lithium sulfides (Li 2 S 2 /Li 2 S) coverage on the cathode surface, preventing the penetration of lithium ions and also reducing the electrode conductivity.
  • sulfur is inherently dual -insulating to both electrons and lithium ions.
  • the electrical conductivity of sulfur at room temperature is 5 * 10 ⁇ 30 S cm -1 , more than 20 orders of magnitude lower than that of normal lithium transition-metal oxides (>10 ⁇ 4 S cm -1 ).
  • Solid state sulfur normally exists as cyclic crown-shaped Sg molecules with a S-S chain length of ca. 2.06 A.
  • a lack of intrinsic voids in the crystallographic structure of sulfur limits the conductivity of solvated lithium ions.
  • Carbon materials combine good electrical conductivity and high porosity; porous carbons have been demonstrated to immobilize sulfur (see US Patent Publication No. 2009/0311604). Immobilization of sulfur in pores with varying sizes has shown quite different cathode behavior, while the challenge of stable high rate capacity remains unmet due to either the weak adsorption potential of mesopores or the blocked porous networks post sulfur-filling.
  • a sulfur-carbon material and a method of producing a sulfur-carbon material.
  • the sulfur-carbon material forms at least part of an electrode, such as a cathode.
  • the cathode is part of a battery, such as a lithium-sulfur battery.
  • a method of producing a sulfur-carbon material including the steps of adsorbing sulfur into a porous carbon material, and selectively or preferentially extracting or removing sulfur from pores larger than micropores of the porous carbon material, while leaving sulfur remaining in micropores of the porous carbon material.
  • a sulfur-carbon material comprising a porous carbon material having a distribution of different pore sizes including micropores and mesopores, wherein sulfur is present in the micropores and the rriesopores are substantially free of sulfur.
  • the porous carbon material includes micropores less than a few nanometers in size, micropores less than a couple of nanometers in size, micropores less than about 1.6 nm in size, and/or sub-nanometer micropores less than about 1.0 nm in size.
  • the porous carbon material includes pores larger than micropores such as mesopores greater than several nanometers in size, and/or mesopores greater than about 6 nm in size.
  • the sulfur is adsorbed as molten sulfur, and/or the sulfur is selectively extracted by exposure to a sulfur solvent.
  • selectively extracting sulfur is by preferential dissolution of sulfur adsorbed into pores larger than micropores, such as the mesopores, over dissolution of sulfur adsorbed into micropores by the sulfur solvent.
  • the sulfur is substantially removed from the mesopores and the mesopores are mostly free or devoid of sulfur.
  • the sulfur and the porous carbon material are solids and ground together and then heated so as to adsorb the sulfur into the porous carbon material.
  • the porous carbon material with adsorbed sulfur is immersed into the sulfur solvent, which is then infiltrated through a membrane, and then remaining porous carbon material is dried.
  • the sulfur solvent is carbon disulfide.
  • the sulfur solvent is carbon disulfide
  • the porous carbon material is graphitic open framework (GOF).
  • Figure 1 illustrates an example method of preparing a sulfur-carbon material
  • Figure 2 illustrates a schematic demonstration of adsorption and extraction toward substantially sub-nanometer sulfur immobilization
  • Figure 3A illustrates a low-magnification TEM image of example GOF showing an interconnected open porous network
  • Figure 3B illustrates a high-resolution TEM image of example GOF showing the homogeneous distribution of graphite nanoribbons with thickness ca. 5 nm and abundant micropores within the open porous network;
  • Figure 4A illustrates an example distribution of pore volume and corresponding sulfur occupation ratio against varying pore size regimes
  • Figure 4B illustrates wide angle XRD patterns of pure sulfur and sulfur confined in pores of different sizes, showing the phase evolution of sulfur (rhombic-monoclinic- amorphous) corresponding with an example implementation of the present adsorption- extraction method
  • Figure 5 illustrates a zero-loss low-magnification image of example S m j C ro/GOF showing an open meso-macroporous texture
  • Figure 6 illustrates an example EELS spectrum of sulfur (165 eV) and carbon (284 eV) edges with an energy window of 20 eV;
  • Figures 7A and 7B illustrate element mapping distributions of (A) carbon and (B) sulfur elements in a porous texture of an example composite material, the contrast among porous regions and elemental regions suggests the element localization dependent on pore size;
  • Figure 8A illustrates a zero-loss low-magnification image showing the porous texture of example S m icro/GOF maintained after a first discharge to 1.5 V vs. Li + /Li°;
  • Figures 8B and 8C illustrate mapping distributions of (B) carbon and (C) sulfur elements in a porous texture of an example composite material after discharge, the contrast between porous regions and sulfur element regions suggests the distribution of lithium sulfides depending on pore size;
  • Figure 9A illustrates the discharge capacity of an example S m j Cro /GOF cathode against cycles under varying current densities;
  • Figure 9B illustrates the cycle stability of the example S m j cro /GOF cathode evaluated for 50 cycles at room temperature at 750 raA g ⁇ ', 1.5 A g -1 , and 3 A g -1 within 1.5 V - 2.8 V vs. Li + /Li°;
  • Figure 10 schematically illustrates the electrode process of a micropore confined sulfur-GOF cathode, regions labeled with S m j Cro represent amorphous sulfur confined in micropores, balls indicate lithium ions in mesopores, balls with arrows illustrate facilitated electron transfer through graphitic nanoribbons;
  • Figure 11 illustrates pore size distribution of example GOF, S me so GOF and Smicro/GOF composites
  • Figure 12 illustrates XPS spectra
  • Figure 13 illustrates (A, C) SEM images and (B, D) EDS mapping pictures of (A, B) S meso /GOF and (C, D) S miero /GOF;
  • Figure 14 illustrates thermogravimetric analyses of example GOF and sulfur/GOF composites
  • Figure 15 illustrates electrochemical characteristics of example sulfur/GOF composites
  • Figure 16 illustrates XPS S2p3/2 spectrum of S micro /GOF before and after a first discharge
  • Figure 17 illustrates SEM images of (top) S micro /GOF and (bottom) S meS o GOF example cathodes after a first discharge;
  • Figure 18 illustrates an electrochemical impedance spectroscopy
  • Figure 19 illustrates (A) reversible discharge-recharge profiles of a second cycle, (B) cycle stability of S m j cro /GOF cathode at 150 raA g '1 , and (C) coulombic efficiency and capacity retention ratio versus cycle number tested at 3 A g -1 for 550 cycles (started from the second cycle);
  • Figure 20 illustrates discharge-recharge profiles of an example S me so/GOF material for a second cycle.
  • a method 100 of producing a sulfur-carbon material there is illustrated a method 100 of producing a sulfur-carbon material. Initially and optionally, sulfur is melted at step 110 for improved adsorption into a porous carbon material. At step 120, sulfur is adsorbed into a porous carbon material. At step 130, sulfur is selectively or preferentially extracted from some but not all pores of the porous carbon material depending on pore size. This consequently provides step 140 of preferentially leaving sulfur remaining in micropores of the porous carbon material, whilst preferentially removing sulfur from pores larger than micropores, for example from mesopores of the porous carbon material. Selective or preferential removal of sulfur from larger pore sizes or volumes can be achieved using a sulfur-extraction method using a sulfur solvent.
  • the sulfur solvent can be used to selectively dissolve sulfur from the pores larger than micropores, such as the mesopores;
  • the sulfur solvent containing dissolved sulfur can be infiltrated through a membrane.
  • the remaining sulfur-carbon material can be then slowly dried.
  • the porous carbon material includes a range of pore sizes, including sub-nanometer pores less than 1 nm in size and pores greater than 1 nm in size.
  • a "micropore” is a pore less than a few nanometers in characteristic size.
  • a "mesopore” is a pore greater than several nanometers in characteristic size.
  • a micropore is less than a couple of nanometers in characteristic size.
  • a micropore is less than about 1.6 nm in size.
  • a micropore in one form, can also be considered as a sub-nanometer pore less than about 1.0 nm in size.
  • a mesopore is greater than about 6 nm in size.
  • selective extraction of sulfur means that sulfur is preferentially, substantially or dominantly removed from mesopores and any larger sized pores, that is for example from pores greater than about 6 nm in size.
  • the method thus provides a sulfur-carbon material, which includes a porous carbon material that has a distribution of different pore sizes including micropores and mesopores, and where sulfur is dominantly, or at least substantially, present in the micropores, whereas the mesopores are mostly, or at least substantially, free or devoid of sulfur.
  • sulfur is selectively or preferentially confined in micropores, which may be sub-nanometer pores/spaces, in a porous carbon material to provide at least part of a cathode.
  • This cathode material can be produced using the adsorption-extraction method developed by the Applicant.
  • the present method uses site-targeted immobilization of sulfur substantially, preferentially or dominantly in micropores, preferably sub-nanometer pores, which restricts the soluble polysulfides inside sub-nanometer spaces or micropores (in one example the spaces/micropores are smaller than a picoliter), retains the open network of the porous carbon material (in one example a Graphitic Open Framework (GOF)) for fast ion transport and displays enhanced cathode reaction efficiency, durability and kinetics.
  • GAF Graphitic Open Framework
  • the resulting novel sulfur-carbon material can be used in an example application as a cathode, or part thereof, in batteries such as lithium-sulfur batteries (LSBs) with higher energy density and safety level, for example to replace Li-ion batteries.
  • batteries such as lithium-sulfur batteries (LSBs) with higher energy density and safety level, for example to replace Li-ion batteries.
  • sulfur is selectively confined in micropores conjugated with a carbon framework, for example a GOF, which efficiently improves cathode durability and reaction kinetics.
  • This enhanced sulfur-carbon cathode improves efficiency by restricting soluble polysulfides inside micropores, particularly inside sub-nanometer spaces, and produces reversible high activity of the sulfur-carbon cathode.
  • the sulfur confined in micropores of the GOF provides a cathode having an ultrafast recharge of LSBs in about 4 minutes with durable capacity around about 200 mA h g -1 upon cycling for over 500 times.
  • Step I represents the melt of sulfur with a GOF mixture allowing the adsorption of melted sulfur into the GOF.
  • Step II represents the removal of solid sulfur from a meso-macroporous system, and the adhesion of sulfur in small micropores.
  • a "macropore" is a pore much greater than a mesopore in characteristic size.
  • An example method of producing the sulfur-carbon material involves sulfur being selectively immobilized into micropores or sub-nanometer pores of GOF via a two-step adsorption-extraction method.
  • Sulfur powder was firstly melted, for example at about 155 °C, to allow for better incorporation of sulfur into interwoven channels in GOF particles (the resulting material referred to as "S me so GOF").
  • a sulfur solvent such as carbon disulfide in which sulfur has a high solubility of 24 wt% at 22 °C, was used to dissolve and extract sulfur loosely adsorbed in the large pores, e.g. mesopores and any macropores, of the GOF (the resulting material referred to as "S m j Cr o GOF").
  • porous carbon materials can be used, for example microporous carbon, mesoporous carbon, hierarchical porous carbon, activated carbon, activated carbon nanofibers, carbon aerogels, carbon nanotubes, expanded graphite, graphene nanosheets, graphene oxide nanosheets, carbide-derived carbon and zeolite- templated carbon.
  • sulfur solvents for example dialkyl disulfides, which can be used with a range of catalysts or co-solvents added, water, ethanol, acetone, carbon disulfide, carbon tetrachloride, toluene, dimethylformamide, methylpyrrolidone, natural rubber, synthetic elastomer and liquid sulfur dioxide.
  • dialkyl disulfides which can be used with a range of catalysts or co-solvents added, water, ethanol, acetone, carbon disulfide, carbon tetrachloride, toluene, dimethylformamide, methylpyrrolidone, natural rubber, synthetic elastomer and liquid sulfur dioxide.
  • the mixed system of resin, alkaline, salt and hydroxide precipitates was evaporated slowly for 24 h in a glass utensil at 60 °C under ambient pressure to obtain an inorganic filler containing resin composite.
  • the composite was carbonized at 600 °C in a tubular furnace under inert argon atmosphere. After carbonization, the inorganic species were removed with 3 M HC1 solution at 100 °C.
  • the S meS o GOF composite material was prepared following a melt-adsorption strategy. GOF powder (1 g) and sulfur (1 g) were ground together, and heated at 155 °C for 12 h in an inert gas, preferably Argon gas.
  • S m j cro /GOF composite material a sulfur-extraction method using carbon disulfide was used. Firstly, the S m .so GOF was immersed into 30 ml carbon disulfide and stirred for 10 minutes at room temperature, other stirring times and temperatures could be used. The carbon disulfide containing dissolved sulfur was quickly infiltrated through a membrane driven by atmospheric force. A trace amount of clean carbon disulfide was dropped to soak the exterior surface of S m j cr o/GOF and remove the physically adsorbed sulfur. The remaining S m j Cro /GOF was dried slowly in a vacuum oven at 50 °C for 8 h, although other temperatures and times could be used.
  • FIG. 3 A an open porous texture of a GOF material is visible from transmission electron microscopy (TEM) images.
  • the homogeneous graphitic ribbons have average thickness around 5-20 nm, and micropores can be observed surrounding the large pores and the graphitic ribbons (refer to Fig. 3B).
  • the large pores, i.e. mesopores and macropores, with weak adsorption potential can hardly hold sulfur against its strong affinity with sulfur solvents, such as carbon disulfide (CS 2 ).
  • CS 2 carbon disulfide
  • XPS x-ray photoelectron spectroscopy
  • EDS low-magnification energy dispersive spectroscopy
  • XRD x-ray diffraction
  • FIGs. 5, 6, 7A and 7B there is illustrated element mapping images of sulfur and carbon in an example S m j Cr o/GOF cathode using electron energy loss spectroscopy (EELS).
  • EELS electron energy loss spectroscopy
  • electrochemical impedance spectroscopy recorded after discharge confirms the superior cathode kinetics of S m icro/GOF to that of S meso /GOV, which is reasonably attributed to the unfilled porous framework due to the nanoconfined lithium sulfide formation.
  • the nano-confinement effect of micropores or sub-nanometer pores is thus believed to be twofold.
  • the strong adsorption potential can constrain the highly soluble polysulfide inside small micropores, which curtails the redox shuttle mechanism to a large degree and produces a high coulombic efficiency.
  • insoluble Li 2 S2/Li2S from polysulfides is thus restricted in nanoconfined spaces, which releases the stress from volume change, prevents the coverage of cathode with dual- insulating sulfide layer, and retains the good electric/ionic connections with the current collector and electrolyte.
  • the S m j cr o/GOF cathode can deliver a reversible capacity around 200 mA h g "1 under an ultrahigh current density of 3 A g -1 for 550 cycles or probably even longer with a coulombic efficiency close to 100% (refer to Figs. 9A and 9B, and Fig. 19).
  • XPS analysis was performed on ESCALAB 250 instrument with Al Ka radiation (15 kV, 150 W) under a pressure of 4x 10 -8 Pa.
  • TEM and EELS were performed on a Tecnai F30.
  • SEM and EDS were carried out on a FEI Nova NanoSEM 430, 15 kV. Porous parameters were determined using a Micromeritics ASAP 2010 M instrument at 77 K. Before measurement of GOF, the powder was degassed at 200 °C until a manifold pressure of 2 mm Hg was reached.
  • Sulfur/GOF composite cathodes were comprised 80 wt% active composite, 10 wt carbon black and 10 wt% poly(vinylidene fluorid) binder.
  • the cathode materials were slurry-cast from N-methyl-2-pyrrolidone onto an aluminum foil current collector.
  • the electrolyte was composed of a 1 M LiPF 6 solution in ethylene carbonate, diethyl carbonate and ethylmethyl carbonate (EC/DMC/EMC, 1 :1 :1 vol) electrolyte.
  • the electrodes after discharge were washed extensively with DMC to remove soluble sulfur-containing species for the characterizations of morphology and elemental composition.
  • pore size distribution of the GOF, Smeso/GOF and S m j Cr0 /GOF composites there is illustrated pore size distribution of the GOF, Smeso/GOF and S m j Cr0 /GOF composites. Selective immobilization of sulfur in pores with varying sizes can be realized via this adsorption-extraction method and was evident according to the pore size distributions.
  • the sulfur melt was imbedded into the voids of the GOF by capillary forces, whereupon it solidified causing the significant loss of pore volume. This infiltration process clearly resulted in the disappearance of 6-16 nm mesopores in the GOF.
  • the melt-filled GOF is thus denoted as S mes o/GOF.
  • the pore volume in the range beyond 16 nm also decreased sharply due to the presence of sulfur.
  • sulfur was removed completely from 6-16 nm mesopores and mostly from larger pores as was clear from the similar pore volume distribution to that of the original GOF, and only micropores were still occupied by sulfur in the extracted sample, which is labeled as S m i C ro GOF.
  • S m i C ro GOF For both S meS o/GOF and S m icro/GOF, the 0.65 nm micropores were filled with sulfur. It is noted that no mesopores in the range between 1.6-6 nm were measured for the GOF based on liquid nitrogen cryosorption analysis.
  • FIG. 12 there is illustrated XPS spectra showing clear evidence of sulfur incorporation within GOF. All the XPS profiles were standardized based on a C ls binding energy of 284.6 eV.
  • FIG. 13 there is illustrated (A, C) SEM images and (B, D) EDS mapping pictures of (A, B)S meso /GOF and (C, D) S micro /GOF.
  • Fig. 14 there is illustrated thermogravimetric analyses of GOF and sulfur/GOF composites.
  • the sulfur sublimed gradually when heating the composites in Argon from room temperature to 500 °C.
  • the proportional weight loss determined at 500 °C is used here to represent the sulfur mass ratio.
  • 43 wt% of sulfur was confined, while only 16 wt% was left thereafter.
  • the weight loss of pure GOF within the same temperature range has been taken into account in the calculations.
  • the weight loss rate of sulfur from the composites can be divided into three regions. Region I lies below 150 °C and exhibits weight decreasing at a rate comparable with that of GOF, which is due to the removal of adsorbed water.
  • region II S meS o GOF shows more significant weight loss than, that of S m j Cr o/GOF.
  • region II corresponds to the evaporation of sulfur loosely confined in the large pores (> 6 nm).
  • the slow weight loss trend in region III is observed for both samples, and can be attributed to the removal of sulfur firmly confined in the small pores ( ⁇ 1.6 nm).
  • Fig. 15A shows first cycle CV
  • Fig. 15B shows second cycle CV curves for S m j cro /GOF and S me so/GOF cathodes recorded at 0.5 mV s "1 at room temperature.
  • the complete loss of current responses of S meS o GOF cathode indicates the thorough deactivation of active sulfur materials due to the unsuccessful sulfur confinement in large pores.
  • Fig. 15C shows CV profiles of S m j cr o/GOF from the first to fifth cycles.
  • 15D shows EIS Nyquist profiles of S m j Cr o GOF and S meS o/GOF cathodes recorded from 10 kHz to 10 mHz at room temperature at cathode polarization potentials of open circuit potential (2.8 V vs. Li + /Li°).
  • the much smaller real impedance of S m j C ro/GOF cathode demonstrates its feasibility for high rate operations.
  • the small peak is most likely caused by the reduction of a trace, of external sulfur into polysulfide ions, which are weakly adsorbed and easily dissolved into the electrolyte.
  • the tiny magnitude of this reaction with respect to the strong reduction peak at 1.62 V suggests the considerable confinement of sulfur in small pores.
  • the cathodic peak at 1.62 V is in accordance with the deep reduction of polysulfide ions to insoluble Li 2 S2 Li2S.
  • mesopore-confined sulfur composites the conversion of polysulfides to lithium sulfide occurs at around 2.0 V. This potential hysteresis is also observed in micropore-rich carbon-sulfur cathodes.
  • the low potential reduction can be attributed to the extra electrode polarization required to overcome the nanoconfinement barrier of strong adsorption energy.
  • the cathodic reaction of S meso GOF initiates at 2.4 V and reaches the peak current at 1.74 V.
  • Two slow plateaux are noticed with a transition point about 2.2 V.
  • the upper branch (2.4-2.2 V) indicates the formation of polysulfide ions from sulfur located in large pores.
  • the lower oblique branch (2.2-1.74 V) originates from the slow kinetics of lithium sulfide formation on the outer surface.
  • the probable surface coverage by exterior lithium sulfide limits the full reduction of polysulfide ions and hinders the approach of electrons and ions to sulfur confined in subnanometer pores.
  • the incomplete conversion of nanoconfined sulfur could be responsible for its higher peak potential (1.74 V, compared to 1.62 V of S m j cro /GOF), where the reaction is actually terminated.
  • the second cycle of S meso /GOF shows no current response, and clearly confirms the terminated cathode activity by exterior lithium sulfides.
  • the major 1.62 V peak of S m j Cr o/GOF was shifted to a higher potential within 1.66-1.78 V.
  • This potential shifting is mainly attributed to the formation of complexes with lower adsorption energy after the first anodic oxidation of lithium sulfides.
  • the anodic oxidation from the first to the fifth cycles keeps almost constant (see Fig. 15C), and indicates the excellent redox stability of lithium sulfides confined in small pores.
  • both the open circuit (2.8 V vs. Li + /Li°) EIS spectra comprise a semicircle at high frequency and an inclined tail in the low frequency region.
  • the interfacial charge-transfer resistance recognizable from the semicircle is due to the redox formation of high-order polysulfides and low-order lithium sulfides.
  • the monolayer adsorption of sulfur in sub-nanometer pores realizes a molecular level intimate electronic contact with GOF scaffold, while the bulky loading of sulfur in large pores fails to build up efficient circuits with conductive GOF.
  • the S me so GOF cathode gives nearly four times greater resistance than the S m j cr o/GOF cathode.
  • the mass transfer kinetics, mainly of lithium ions, inside the porous cathode can be compared qualitatively with reference to the slope of the low-frequency tail.
  • the CS 2 extraction frees the occupied large pores, and surely results in the facilitated ion transfer in S m j cro /GOF cathode with a bigger tail slope.
  • the combination of intimate electric connection and open ionic transport as a result of selective nanoconfinement of sulfur in pores less than 1 nm, could be utilised in a cathode providing high rate capability.
  • FIG. 16 there is illustrated XPS S2p3/2 spectrum of S micro GOF before and after the first discharge.
  • FIG. 17 there is illustrated SEM images of sulfur/GOF composites recorded after the first discharge to 1.5 V vs. Li + /Li°.
  • the porous texture of Smicro GOF cathode in stark contrast to the dense surface coverage of Sm eso /GOF cathode, highlights the effectiveness of sub-nanometer pore confinement on entrapping soluble polysulfide ions, and hence restricting the formation of solid lithium sulfides coverage.
  • Fig. 18 there is illustrated an electrochemical impedance spectroscopy.
  • Nyquist profiles of Smj cro /GOF and Smeso/GOF cathodes were recorded from 10 kHz to 10 mHz at room temperature at cathode polarization of full discharge potential (1.5 V vs. Li + /Li°) after discharge but before recharge in the first cycle.
  • the much smaller real impedance of S m jcro/GOF cathode demonstrates the less occupied porosity by solid lithium sulfides coverage as shown in Fig. 17.
  • Fig. 18 Referring to Fig.
  • FIG. 20 there is illustrated discharge-recharge profiles of S meS o/GOF of the second cycle.
  • Optional embodiments of the present invention may also be said to broadly consist in the parts, elements and features referred to or indicated herein, individually or collectively, in any or all combinations of two or more of the parts, elements or features, and wherein specific integers are mentioned herein which have known equivalents in the art to which the invention relates, such known equivalents are deemed to be incorporated herein as if individually set forth.

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Abstract

L'invention concerne un matériau soufre-carbone. Dans un exemple, le matériau soufre-carbone forme au moins une partie d'une cathode dans une batterie, telle qu'une batterie lithium-soufre. L'invention concerne également un procédé de production du matériau soufre-carbone, qui comprend un procédé à deux étapes d'adsorption de soufre dans un matériau carboné poreux, puis d'extraction sélective ou préférentielle du soufre du matériau carboné poreux, en fonction de la taille des pores, laissant ainsi du soufre restant dans les micropores du matériau carboné poreux.
PCT/AU2012/000067 2011-01-27 2012-01-27 Matériau soufre-carbone et utilisation en tant que cathodes pour batteries à haute énergie WO2012100301A1 (fr)

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DE102013005082A1 (de) 2012-08-09 2014-03-06 Volkswagen Aktiengesellschaft Verfahren zur Herstellung eines Kohlenstoff-Schwefel-Komposits, mit dem Verfahren herstellbares Komposit sowie Elektrode für eine elektrochemische Zelle umfassend ein solches
WO2014137879A1 (fr) * 2013-03-04 2014-09-12 Lockheed Martin Corporation Dispositifs de stockage d'énergie contenant un aérogel de nanotubes de carbone et leurs procédés de fabrication
US20140265557A1 (en) * 2013-03-15 2014-09-18 GM Global Technology Operations LLC Single-lithium ion conductor as binder in lithium-sulfur or silicon-sulfur battery
CN104371153A (zh) * 2014-12-08 2015-02-25 济宁利特纳米技术有限责任公司 一种由碳纳米管和石墨烯共同改性的橡胶复合材料
CN104900880A (zh) * 2015-06-03 2015-09-09 中国地质大学（武汉） 一种锂硫电池复合正极材料及其制备方法
CN104904044A (zh) * 2012-12-05 2015-09-09 中国科学院化学研究所 硫-碳复合材料、其在锂-硫电池中的应用以及制备所述复合材料的方法
WO2015188915A3 (fr) * 2014-06-12 2016-02-04 Daimler Ag Matériau d'électrode pour accumulateur électrochimique, procédé de production d'un matériau d'électrode, et accumulateur d'énergie électrochimique
EP3208871A1 (fr) * 2016-02-16 2017-08-23 Basf Se Procédé de production de matériaux composites à base de soufre-carbon
WO2019197410A1 (fr) * 2018-04-11 2019-10-17 Saft Élément électrochimique de type lithium/soufre
US11611066B2 (en) * 2017-10-30 2023-03-21 Lg Energy Solution, Ltd. Sulfur-carbon composite and method for preparing same

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Cited By (18)

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DE102013005082A1 (de) 2012-08-09 2014-03-06 Volkswagen Aktiengesellschaft Verfahren zur Herstellung eines Kohlenstoff-Schwefel-Komposits, mit dem Verfahren herstellbares Komposit sowie Elektrode für eine elektrochemische Zelle umfassend ein solches
CN104904044A (zh) * 2012-12-05 2015-09-09 中国科学院化学研究所 硫-碳复合材料、其在锂-硫电池中的应用以及制备所述复合材料的方法
US10109847B2 (en) 2012-12-05 2018-10-23 Robert Bosch Gmbh Sulfur-carbon composite material, its application in lithium-sulfur battery and method for preparing said composite material
EP2929583A4 (fr) * 2012-12-05 2015-12-23 Chinese Acad Inst Chemistry Matériau composite soufre/carbone, son application dans une batterie lithium/soufre et procédé de préparation dudit matériau composite
WO2014137879A1 (fr) * 2013-03-04 2014-09-12 Lockheed Martin Corporation Dispositifs de stockage d'énergie contenant un aérogel de nanotubes de carbone et leurs procédés de fabrication
US9537144B2 (en) * 2013-03-15 2017-01-03 GM Global Technology Operations LLC Single lithium ion conductor as binder in lithium-sulfur or silicon-sulfur battery
US20140265557A1 (en) * 2013-03-15 2014-09-18 GM Global Technology Operations LLC Single-lithium ion conductor as binder in lithium-sulfur or silicon-sulfur battery
DE102013113376B4 (de) 2013-03-15 2021-12-16 GM Global Technology Operations LLC (n. d. Gesetzen des Staates Delaware) Einzellithiumionenleiter als bindemittel für elektrode in lithium-schwefel- oder silicium-schwefel-batterie, batterie mit einer schwefel enthaltende kathode und verfahren zur erhöhung der ladungshaltung in der batterie
WO2015188915A3 (fr) * 2014-06-12 2016-02-04 Daimler Ag Matériau d'électrode pour accumulateur électrochimique, procédé de production d'un matériau d'électrode, et accumulateur d'énergie électrochimique
CN106463693A (zh) * 2014-06-12 2017-02-22 戴姆勒股份公司 用于电化学存储器的电极材料、制造电极材料的方法以及电化学储能器
EP3155676A2 (fr) * 2014-06-12 2017-04-19 Daimler AG Matériau d'électrode pour accumulateur électrochimique, procédé de production d'un matériau d'électrode, et accumulateur d'énergie électrochimique
EP3155676B1 (fr) * 2014-06-12 2021-07-07 Daimler AG Matériau d'électrode pour accumulateur électrochimique, procédé de production d'un matériau d'électrode, et accumulateur d'énergie électrochimique
CN104371153A (zh) * 2014-12-08 2015-02-25 济宁利特纳米技术有限责任公司 一种由碳纳米管和石墨烯共同改性的橡胶复合材料
CN104900880A (zh) * 2015-06-03 2015-09-09 中国地质大学（武汉） 一种锂硫电池复合正极材料及其制备方法
EP3208871A1 (fr) * 2016-02-16 2017-08-23 Basf Se Procédé de production de matériaux composites à base de soufre-carbon
US11611066B2 (en) * 2017-10-30 2023-03-21 Lg Energy Solution, Ltd. Sulfur-carbon composite and method for preparing same
WO2019197410A1 (fr) * 2018-04-11 2019-10-17 Saft Élément électrochimique de type lithium/soufre
FR3080222A1 (fr) * 2018-04-11 2019-10-18 Saft Element electrochimique lithium/soufre

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