WO2020058529A1 - Électrolyte solide amorphe li+, procédé de production de l'électrolyte solide amorphe et utilisation de l'électrolyte solide amorphe - Google Patents

Électrolyte solide amorphe li+, procédé de production de l'électrolyte solide amorphe et utilisation de l'électrolyte solide amorphe Download PDF

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WO2020058529A1
WO2020058529A1 PCT/EP2019/075534 EP2019075534W WO2020058529A1 WO 2020058529 A1 WO2020058529 A1 WO 2020058529A1 EP 2019075534 W EP2019075534 W EP 2019075534W WO 2020058529 A1 WO2020058529 A1 WO 2020058529A1
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ion conductive
inorganic solid
conductive inorganic
lithium
whereat
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PCT/EP2019/075534
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English (en)
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Bernhard Roling
Stefan SPANNENBERGER
Vanessa MISS
Nico Kaiser
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Philipps-Universität Marburg
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Publication of WO2020058529A1 publication Critical patent/WO2020058529A1/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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
    • C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
    • C03C3/323—Chalcogenide glasses, e.g. containing S, Se, Te containing halogen, e.g. chalcohalide glasses
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/14—Compositions for glass with special properties for electro-conductive glass
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/02—Amorphous compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/04—Compounds with a limited amount of crystallinty, e.g. as indicated by a crystallinity index
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/16—Halogen containing crystalline phase
    • 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
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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

  • Amorphous Solid Li + Electrolyte Process for production of the Amorphous Solid Electrolyte and usage of the Amorphous Solid Electrolyte
  • the invention relates to an amorphous solid electrolyte (“Amorphous Solid Elec- trolyte”) containing lithium ions enabling the conductivity, a process for the produc- tion of the amorphous solid electrolyte and the usage of the amorphous solid electrolyte.
  • Amorphous Solid Elec- trolyte amorphous Solid electrolyte
  • the field of the invention is the area of energy storage, namely the storage of electrochemical energy.
  • the available methods for short and long-time storage (times scales between seconds and several months) of renewable electrical energy by electrochemical means are still insufficient for thoroughly implementing a sustainable energy management system.
  • electrochemical energy storage systems providing high power density and allowing up to thousands of charging- discharging cycles - as are necessary in the automotive sector for e-mobility - are still considered to be insufficient.
  • a progressive use of renewable sources for electrical energy production calls the development of next generation energy storage systems. While for stationary ap- plications a solution without electrochemical devices is a possible option, especially in the field of electric mobility, where the use of lithium ion batteries is state of the art, new approaches are required to ensure adequate power and safety. All- solid-state-batteries (ASSBs) hold promise to fulfil these requirements, and are likely to become the next generation automotive energy source.
  • ASSBs All- solid-state-batteries
  • SE non-inflammable solid electrolytes
  • the mentioned compatibility means either a thermodynamic stability towards Li metal or, which is more likely, a formation of an insulating interlayer with negligible ionic resistance at the electrode/electrolyte inter face.
  • L12S-P2S5 abbreviated“LPS” based glass-ceramics, i.e. crystallized glasses
  • LPS liquid-crystalline glass-ceramics
  • a proper temperature treatment of LPS glasses prepared by mechanochemical milling is a famous example to increase the Li + -conductivity dramatically due to the formation of glass- ceramics containing superionic U7P3S11 crystals.
  • an addition of Lil to the LPS-System favours high ionic conductivities (cf. EP 2 779 298 B1) and has been shown to enable good compatibility in contact to metallic lithium.
  • U7P3S11 crystals formed within the LPS-System one would expect a crystalline Li4PS4l-phase to form upon annealing of the LPSI-system.
  • An objective of the present invention is to provide amorphous materials (amorphous solid electrolytes, respectively ion conductive inorganic solids) being composed of the elements lithium, iodine, sulphur and phosphorus that exhibit an extraordinary high Li + -conductivity of about 6.5 mS cnr 1 or more, i. e. at least 3 mS cm -1 .
  • the objective of the present invention is also to provide amorphous materials (amorphous solid electrolytes, respectively ion conductive inorganic solids) being composed of the elements lithium, sulphur and phosphorus that exhibit a Li + - conductivity of at least 0.6 mS cm -1 , respectively an increased conductivity which is at least 300 per cent of the Li + -conductivity of the corresponding crystalline material.
  • amorphous materials amorphous solid electrolytes, respectively ion conductive inorganic solids
  • the present invention provides new types of amorphous materials composed of these elements which are summarized under the acronym“LPSI”; one of the most preferable compositions within this LPSI- system is: 0.33 Lil + 0.67 (0.75 LhS + 0.25 P2S5), which achieves the above mentioned conductivity of (for example) 6.5 mS cnr 1 via a simple one step heat treatment under conservation of its amorphous structure.
  • the composition as de- scribed afore means that 0.33 mol of Lil are mixed with 0.67 mol of a mixture of 0.75 mol LhS with 0.25 mol P2S5 and is treated according to the method described below.
  • Li + -conductivity is not based on crystalline structures of the LPSI-system, but still resting upon the amorphous structure of the LPSI-system. This is proven by electrochemical impedance spectroscopy (EIS) and powder X-ray diffractometry (XRD) data presented herein below.
  • EIS electrochemical impedance spectroscopy
  • XRD powder X-ray diffractometry
  • Fig. 1A shows XRD pattern for the as-prepared glass as well as for the same sample after several temperature cycles between 20 °C and 180 °C.
  • the LlPSI glass crystallizes at about 170 °C.
  • the XRD data shows that it is possible to precipitate L14PS4I crystals from the glass through annealing at 180 °C.
  • the glass is not very sensitive to crystallization. Long-term temperature treatment, including several repeated heat up and cool down cycles and various hold times at 180°C, is required to obtain a state of crystallinity comparable to Fig. 1A.
  • Fig. 1 B shows the time dependent evolution of the Li + -conductivity tr L .+ at 25 °C for the sample shown in Fig.
  • the first heat up cycle yields a remarkable increase in ff Li+ up to 2.1 x 10 3 S-cnrr 1 , which is about 2.6 times higher than the initial value obtained for the pristine, i. e. not tempered (treated by applying heat), sample (8 x 10 4 S-errr 1 ), and about 17 times higher than the conductivity of pure U4PS4I (1.2 x 10 4 S cnr 1 ). That a u ⁇ of the crystalline phase is much lower than that of the glass is highly unexpected.
  • Fig. 2A shows exemplary Arrhenius plots of the ionic conductivity for the as- prepared LPSI-system (continuous curve) and for the same sample after an simple one-step annealing process at 180 °C (amorphous solid electrolyte, dashed curve), respectively.
  • the optimized temperature treatment yields a Li + -conductivity of about 6.5 x 10 ⁇ 3 S cnr 1 , which is about 7.2 times the initial value before heat treatment.
  • the activation energy is lowered from 0.31 eV for the pristine glass to 0.28 eV for the annealed sample.
  • the XRD measurements in Fig. 2B reveal that the material remains basically in an amorphous state during heat treatment.
  • the so far optimized temperature treatment comprise heating from room temperature (about 20 - 25 °C) in about 25 minutes up to about 180 °C, holding this temperature of about 180 °C for about 5 - 10 minutes and then cooling down to room temperature (about 20 - 25 °C) with a cooling rate of about 2 k/min.
  • the entire annealing process is performed under inert gas atmosphere, e. g. argon, and atmospheric pressure of about 1013 mbar.
  • Fig. 3 shows representative exemplary results of the EIS measurements for the pristine glass (filled squares), and the corresponding same sample after optimized heat treatment (the amorphous solid electrolyte, crosses). Since the material is a very good Li + -conductor, the semi-circle formed by the measured curve, which is related to the bulk conduction process, is completely observed only at very low temperatures. Thus the shown data is recorded at a sample temperature of -120 °C. Both spectra are characterized by a semi-circle followed by a steep in- crease in the low frequency part due to electrode polarization.
  • the semi-circles represent the bulk conduction process with capacitances of 28 pF crrr 2 for the pristine glass and 39 pF crrr 2 for the annealed glass, respectively. These capacitance values indicate the Li + ion transport takes place in the bulk of the amor phous phase. It is well known to the person skilled in the art, how to perform a fit- ting analysis of the impedance spectra and how to interpret the resulting values so that it is not necessary to describe it in more detail herein.
  • amorphous materials amorphous solid electrolytes, respectively ion conductive inorganic solids
  • amorphous materials amorphous solid electrolytes, respectively ion conductive inorganic solids
  • the objective of the present invention is also achieved by providing amorphous materials (amorphous solid electrolytes, respectively ion conductive inorganic solids) being composed of the elements lithium, sulphur and phosphorus that exhibit a Li + - conductivity of at least 0.6 mS cm -1 , respectively an increased conductivity which is at least 300 per cent of the Li + -conductivity of the corresponding crystalline material (cf.
  • the corresponding crystalline material (the reference material to the mainly amorphous material according to the invention) is prepared in the same way as the material according to the invention, except that the annealing temperature is equivalent to the Temperature where crystallization is taking place, Tcryst.. Tcryst. is above the annealing temeperature accord ing to the invention, e.g. above 180 °C, and sometimes below the annealing temperature according to the invention. The latter is the case for compositions comprising more than about 40 per cent Lil by weight. In these cases (content of Lil roughly above 40%) it is observed that the Li + -conductivity is decreasing in accordance with the increasing degree of crystallinity.
  • - Fig. 4B shows that in any composition an enhancement of the conductivity is taking place after the annealing at, e.g., 180°C.
  • the conductivity is basically enhanced with an increase of the Lil content.
  • the maximum increasement of the conductivity is shown by the composi- tion 0.33 Lil + 0.67 (0.75 U 2 S + 0.25 P2S5).
  • the increasement of the conductivity according to the invention decreases at a Lil content of 40% and higher after the annealing at, e.g., 180°C.
  • the crystallization temperature of these compositions is, e.g., 180°C or lower which is shown in Fig. 5.
  • Fig. 6 shows an increase of the crystallinity on the XRD pattern after the annealing at, e.g., 180°C, so the decrease of the conductivity at higher contents of Lil is caused by the crystallization of these materials.
  • thermal expansion, melting point etc. is dependent from the chemical composition (as is known to the person skilled in the art), the material of the invention with a certain desired Li + -conductivity can be produced with different physical properties, e.g. thermal expansion, melting point etc. This is a major technical improvement beyond the state of the art.
  • the invention comprises an ion conductive inorganic solid comprising the chemi- cal elements lithium (Li), sulfur (S) and phosphor (P), whereat
  • the content of lithium is between 5 % and 15 % by mass and
  • the content of sulfur is between 25 % and 75 % by mass and
  • the content of phosphor is between 5 % and 20 % by mass
  • the ion conductive inorganic solid is mainly of amorphous structure
  • the ion conductive inorganic solid exhibits a Li + -conductivity of at least
  • the invention further comprises an ion conductive inorganic solid according to claim 1 comprising the chemical elements lithium (Li), sulfur (S), phosphor (P) and iodine (I), whereat
  • the content of lithium is between 5 % and 15 % by mass and
  • the content of sulfur is between 25 % and 75 % by mass and
  • the content of phosphor is between 5 % and 20 % by mass and
  • the content of iodine is between 0.001 % and 60 % by mass
  • the ion conductive inorganic solid is mainly of amorphous structure
  • the ion conductive inorganic solid exhibits a Li + -conductivity of at least
  • the invention comprises an ion conductive inorganic solid comprising the chemical elements lithium (Li), sulfur (S), phosphor (P) and iodine (I), whereat
  • the content of lithium is between 5 % and 15 % by mass and
  • the content of sulfur is between 25 % and 65 % by mass and
  • the content of phosphor is between 5 % and 20 % by mass and
  • the content of iodine is between 10 % and 60 % by mass
  • the ion conductive inorganic solid is mainly of amorphous structure
  • amorphous conductive inorganic solid as described in the previous paragraph may additionally or alternatively be described by use of the capacitance which is about 30 pF-cnr 2 or more, measured by impedance spectroscopy.
  • This technical feature (capacitance) may alternatively be described as having a value of about 1.4 (between 1.1 - 2.0) times higher than the value of the pristine glass.
  • the ion conductive inorganic solid may also additionally or alternatively be described by showing an increase of capacitance upon annealing - but still having mainly amorphous structure - of about 10% - 100%, preferred of about 20% - 80%, more preferred of about 30% - 70% and most preferred of about 40% - 60%.
  • the invention further comprises an ion conductive inorganic solid as previously described, having a molar composition of x Lil + (1-x) (0.75 LteS + 0.25 P2S5) whereat x has a value between 0.5 and 0.1 , preferred between 0.4 and 0.1 , most preferred between 0.35 and 0.14.
  • the invention further comprises an ion conductive inorganic solid as previously described, having a molar composition of 0.33 Lil + 0.67 (0.75 LteS + 0.25 P2S5) or a molar composition of 0.25 Lil + 0.75 (0.75 U2S + 0.25 P2S5) or a molar composition of 0.20 Lil + 0.80 (0.75 LteS + 0.25 P2S5) or a molar composition of 0.15 Lil + 0.85 (0.75 LteS + 0.25 P2S5).
  • the invention further comprises the usage of the ion conductive inorganic solid as previously described for the production of lithium ion batteries.
  • the invention further comprises the usage of the ion conductive inorganic solid as previously described for the production of all-solid-state-batteries.
  • the invention further comprises a method for manufacturing an ion conductive inorganic solid as previously described, characterized in that the method comprises the following steps:
  • halogen X is independently chosen from the list comprising chlorine (Cl), bromine (Br) and iodine (I);
  • step b) mixing the educts provided according to step a) by means of
  • step b) applying temperature to the intermediate product from step b) - i. e annealing the intermediate product from step b) - at least
  • the invention further comprises a method for manufacturing an ion conductive inorganic solid as previously described, characterized in that the method compris- es the following steps
  • step b) mixing the educts provided according to step a) by means of
  • step c) applying temperature to the intermediate product from step b) at least
  • the invention further comprises a method as previously described, characterized in that step b) is performed under inert gas.
  • the invention further comprises a method as previously described, characterized in that step b) is performed under exclusion of dispersion media.
  • the invention further comprises a method as previously described, characterized in that step c) is performed under inert gas.
  • the inert gas may be nitrogen (N2), argon (Ar) or any other inert gas suitable for the desired purpose as is well known to the person skilled in the art without leaving the scope of the invention or its equivalents.
  • the invention further comprises a method as previously described, characterized in that the application of temperature to the intermediate product according to step c) comprises:
  • heating for example from room temperature, i.e. 20 - 25 °C) within 10 to 40 minutes
  • the U2S-P2S5-UI glasses are prepared by the means of mechanical milling using a high energy planetary ball mill (e.g. Pulverisette 7, Fritsch, Idar-Oberstein, Germany).
  • a stoichiometric mixture of reagent grade LhS (98%, abcr GmbH, Karls- ruhe, Germany), P2S5 (99%, Sigma Aldrich, Taufkirchen, Germany) and Lil (99%, Alfa Aesar, Düsseldorf, Germany) powders is placed into an air-tight Zirkonia pot (20 ml volume) with 10 Zr02 balls (10 mm diameter) and is then milled at a rotational speed of 500 rpm for about 8 hours (5min milling; 15min rest; 99 cycles).
  • the received product is once again ground in an agate mortar to obtain the final glass-powders.
  • agate mortar to obtain the final glass-powders.
  • the as-prepared powders are pressed into pellets with a diameter of 6 mm by applying a pressure of 276 MPa for 30 min at room temperature (e.g. at 20 - 25 °C) by means of a hydraulic press (e.g. P/O/Weber, Remshalden, Germany) using polished stainless steel extrusion dies.
  • the thickness of the pellets is determined using a micrometer caliper (e.g. Mi- tutoyo, Neuss, Germany).
  • the pellets are coated with a gold layer on both faces using a sputter coater (e.g. 108auto, Cressington, Watford, England) inside a glovebox.
  • the pellets are then placed inside a home-build, air-tight sample cell in a two- electrode arrangement.
  • Impedance measurements are carried out using an Alpha- AK impedance analyzer (e.g. Novocontrol, Montabaur, Germany) in a frequency range from 1 MHz to 0.1 Hz with an applied AC voltage of 10 mV/root mean square).
  • the temperature is varied in the range from -120 X to 180 X using - for example - the Novocontrol Quatro Cryosystem.
  • the maximum temperature offset during the measurements is fixed to a limit of ⁇ 1 X.
  • the impedance analysis software RelaxIS RHD Instruments, Darmstadt, Germany
  • X-ray diffraction measurements are performed using a powder diffractometer, e.g. STOE STADI MR (STOE, Darmstadt, Germany) using Cu-Ka radiation in a Debye-Scherrer geometry.
  • the powder samples are sealed inside a XRD glass sample tube (e.g. Hilgenberg, Malsfeld, Germany) under Argon atmosphere.
  • DTA Differential thermal analyses
  • a thermal analyser system e.g. Mettler Toledo DSC 1 (Mettler-Toledo, Columbus, USA).
  • the powder samples are sealed inside Al pans under Argon atmosphere and heated up to 350 X with a heating rate of 10 X/min.
  • inert gas atmosphere is provided by a N2 gas flow.
  • Fig. 1A Exemplary XRD pattern of an as-prepared glass as well as of the same sample after 8h of alternate annealing at 180°C.
  • Fig. 1B Exemplary corresponding time-dependent evolution of the room temperature conductivity of the sample shown in Fig. 1A.
  • the abscissa declares the sum of the 180 °C hold times.
  • Fig. 1C Exemplary DTA curve of a sample with composition 0.33 Lil + 0.67
  • Fig. 2A Exemplary Arrhenius plots of the ionic conductivity, for the as-prepared glass (continuous curve) as well as for the same sample after annealing at 180 °C according to the inventive process (amorphous solid electrolyte, dashed curve).
  • the lines (both, continuous one and dashed one) represent the best linear fit. Since the ionic conductivity of the annealed glass is very high, room temperature conductivity was extrapolated from measurements between -120 °C and 0 °C. Both fits exhibit regression coefficients > 0.9999.
  • the extrapolated values are: 6.5 mS/cm for the sample annealed according to the inventive process, and 0.9 mS/cm for the same sample before annealing.
  • Fig. 2B Exemplary XRD pattern of the same sample as shown in Fig. 2A, before annealing (upper graph) and after annealing (amorphous solid electrolyte, lower graph) showing that nearly no crystallisation has oc- curred.
  • Fig. 3 Exemplary Nyquist plot of the complex impedance behaviour for the as- prepared glass (filled squares) and the same sample after annealing at 180 °C (amorphous solid electrolyte, crosses), respectively.
  • the spectra are recorded at a temperature of -120 °C.
  • the semi-circle described by the measuring points indicates the bulk conduction process, while the low frequency part is characterised by electrode polarization. Lowest shown frequencies are 0.1 Hz for both samples.
  • Fig. 4 Exemplary composition dependence of the Li + -conductivity at 25 °C for the xLil + (1-x) (0.75LfeS + 0.25 P2S5) glass as prepared by high energy ball milling.
  • Fig. 4B Exemplary composition dependence of the Li + -conductivity at 25 °C for the xLil +(1-x) (OJSL S + 0.25 P2S5) glass as prepared by high energy ball milling and after a single annealing step at 180 °C.
  • Fig. 5 Exemplary DSC curve of the x Li I + (1-x) (0.75 U2S + 0.25 P2S5) glass in a temperature range from room temperature up to 350 °C. The heating rate at each measurement was 15 °C/min.
  • Fig. 6 XRD pattern of the same sample as shown in Fig. 4B, each composition is measured as the as prepared material and after the annealing at 180°C. Only the materials 60% U3PS4 + 40% Lil, 55% U3PS4 + 45% Lil and 50% LbPS 4 + 50% Lil after annealing at 180°C show partly crystal- lisation, the other compositions show nearly no crystallisation.

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Abstract

L'invention comprend un solide inorganique conducteur d'ions amorphe présentant une conductivité comprise entre 3 mS/cm et 10 mS/cm ou plus. Le solide inorganique amorphe comprend les éléments chimiques lithium (Li), soufre (S), phosphore (P) et, éventuellement, iode (I), ayant la formule générale xLil + (1-x) (0,75Li2S + 0,2 P2S5), l'indice x pouvant accepter toute valeur entre 0,0 et 0,5. L'invention comprend en outre un procédé de fabrication du solide inorganique conducteur d'ions amorphe et l'utilisation du solide inorganique conducteur d'ions amorphe pour la fabrication de batteries lithium-ion.
PCT/EP2019/075534 2018-09-21 2019-09-23 Électrolyte solide amorphe li+, procédé de production de l'électrolyte solide amorphe et utilisation de l'électrolyte solide amorphe WO2020058529A1 (fr)

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EP18195958.6 2018-09-21
EP18195958 2018-09-21

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008120666A (ja) * 2006-10-17 2008-05-29 Idemitsu Kosan Co Ltd ガラスセラミック及びその製造方法
EP2779298A1 (fr) 2011-11-07 2014-09-17 Idemitsu Kosan Co., Ltd Electrolyte solide
US20160149259A1 (en) * 2013-06-28 2016-05-26 Toyota Jidosha Kabushiki Kaisha Sulfide solid electrolyte material, sulfide glass, solid state lithium battery, and method for producing sulfide solid electrolyte material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008120666A (ja) * 2006-10-17 2008-05-29 Idemitsu Kosan Co Ltd ガラスセラミック及びその製造方法
EP2779298A1 (fr) 2011-11-07 2014-09-17 Idemitsu Kosan Co., Ltd Electrolyte solide
US20140302382A1 (en) * 2011-11-07 2014-10-09 Idemitsu Kosan Co., Ltd. Solid electrolyte
US20160149259A1 (en) * 2013-06-28 2016-05-26 Toyota Jidosha Kabushiki Kaisha Sulfide solid electrolyte material, sulfide glass, solid state lithium battery, and method for producing sulfide solid electrolyte material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FUDONG HAN ET AL: "Suppressing Li Dendrite Formation in Li2S-P2S5 Solid Electrolyte by LiI Incorporation", ADVANCED ENERGY MATERIALS, vol. 8, no. 18, 12 March 2018 (2018-03-12), DE, pages 1703644, XP055644241, ISSN: 1614-6832, DOI: 10.1002/aenm.201703644 *

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