Classifications

• • 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
  • H01M4/40—Alloys based on alkali metals
  • H01M4/405—Alloys based on lithium
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C1/00—Making non-ferrous alloys
  • C22C1/02—Making non-ferrous alloys by melting
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C19/00—Alloys based on nickel or cobalt
  • C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C24/00—Alloys based on an alkali or an alkaline earth metal
• • 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
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/043—Processes of manufacture in general involving compressing or compaction
• • 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
  • H01M4/134—Electrodes based on metals, Si or alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/027—Negative electrodes
• • 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
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
• • 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
  • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• • 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

• Lithium metal is described as the ideal anode material for rechargeable batteries because of its very high theoretical specific capacity (3860 mAh g -1 ), its low density (0.53 g cm -3 ) and because he has the most low electrochemical potential (-3.04 vs. ENH) (Xu, W. et al Energy Environ Sci 7.2 (2014): 513-537).
• "All-solid" lithium batteries have many advantages over conventional liquid electrolyte batteries. These advantages generally include: a lower weight as well as a much higher power density and specific energy. In addition, these batteries are considered to be more environmentally friendly since with them the risk of toxic liquid electrolyte flowing into the environment would be eliminated.
• lithium is a metal which, in addition to having a very high reactivity with moist air, has very weak mechanical characteristics and a strong tendency to adhere to most materials (US 5,528,920 and US20170179491 A1). These are all factors that make it difficult to obtain thin sheets of lithium by rolling, particularly when it is necessary to obtain thicknesses of less than 200 m.
• several critical issues are related to the use of the traditional metal lithium anode; for example, security problems and particularly problems related to the formation of a dendritic structure during repetitive cycles resulting in a loss of coulombic efficiency affecting the rechargeability and performance of the system.
• Another problem intrinsic to the use of a negative metal lithium electrode is its low melting point (180.6 ° C.) which limits the use of the electrochemical cell at temperatures lower than this (US Pat. No. 5,705,293).
• the anode is generally made of a light metal strip based on alkali metals such as lithium metal, lithium aluminum alloys or the like. Pure solid lithium, or having a low percentage of alloyed metals, is so ductile that it can easily be cut and worked at room temperature.
• the production of the thin metal lithium film is generally carried out by extrusion (see FIG. 1, US 7,194,884).
• the metallic lithium flows through the matrix, gradually reducing the metal flux to its desired final shape.
• a thin strip with a thickness of 150-300 m can be obtained directly by extrusion.
• the thin strip is then laminated to obtain an ultrathin lithium film (15-50 ⁇ ) (see Figure 1, US 5,528,920).
• Aluminum or magnesium containing alloys (US 5,102,475) also adhere less to the surface of the rollers. These lithium alloys improve the rheology of lithium during the shaping of ultra-thin strips.
• the Li-Mg alloy can also result in an increase in the melting point allowing the anode to withstand higher temperatures, and thus its use of the battery over a larger temperature range (US 5,705,293). However, these do not significantly improve the life cycle. This property is mainly controlled by the stability of the lithium interface with the solid electrolyte.
• the present technology relates to an electrode material comprising, in alloy form:
• a metal component X 2 selected from alkali metals, alkaline earth metals, rare earths, zirconium, copper, silver, manganese, zinc, aluminum, silicon, tin, molybdenum and iron; wherein the metal component X 2 is different from the metal component X 1 and different from the metallic lithium; and wherein the lithium metal is present at a concentration of at least 65% by weight, the metal component X 1 is present at a concentration between 0.1 and 30% by weight, the X 2 component is present at a concentration between 0.1 and 5% by weight, and wherein the concentration in the material of the components [X 1 + X 2 ] is between 0.2% and 35% by weight. %, where [Li]> [X 1 ]> [X 2 ].
• the present technology relates to an electrode material comprising, in the form of an alloy:
• a metal component X 1 chosen from magnesium and aluminum
• a metal component X 2 selected from alkali metals, alkaline earth metals, rare earths, Zr, Cu, Ag, Bi, Co, Zn, Al, Si, Sn,
• the metal component X 1 is magnesium. According to another embodiment, the metal component X 1 is aluminum.
• the metal component X 2 is selected from Na, K, Zr and rare earths. In another embodiment, the metal component X 2 is an alkali metal selected from Na, K, Rb and Cs. In one embodiment, the metal component X 2 is an alkaline earth metal selected from Mg, Ca, Sr and Ba. In another embodiment, the metal component X 2 is a metal of the rare earth family selected from Se, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm. , Yb, Lu and their mixtures (as a mischmetal). In another embodiment, the metal component X 2 is chosen from Zr, Cu, Ag, Bi, Co, Zn, Al, Si, Sn, Sb, Cd, Hg, Pb, Mn, B, In, Ti, Ni , or Ge.
• the electrode material is an ultrathin strip with a thickness of 15 to 300 m.
• the thickness is 15 to 200 m, or 15 to 100 m, or the thickness is 15 to 50 Mm.
• the present technology relates to a method of preparing an electrode material as defined herein, the method comprising the following steps: a. melting alloy of the metallic lithium with the metal component X 1 in a bath of molten alloy; b. adding the metal component X 2 to the bath of molten alloy; and c. solidification of the alloy obtained in (b) in a permanent mold in a form suitable for extrusion such as in the form of a billet.
• the method further comprises the steps of: d. transformation of the solid billet into a thin strip (100-300 mm) suitable for rolling; summer. transformation of the thin strip into an ultra-thin strip (15-50 mm) by rolling.
• the present technology relates to an anode comprising an electrode material as defined herein applied to a current collector.
• the present technology relates to an anode comprising the ultra-thin strip obtained in step (e) of the method as defined above applied to a current collector.
• the present technology relates to an electrochemical cell comprising a cathode, an electrolyte and an anode, wherein the anode comprises an electrode material as defined herein.
• the electrochemical cell comprises a cathode, an electrolyte and an anode as defined in the preceding paragraph.
• the electrochemical cell comprises a cathode, an electrolyte and an anode comprising the electrode material obtained by the method as defined herein.
• the present technology relates to a lithium battery comprising an electrochemical cell as defined herein.
• Figure 1 is an exploded view illustrating the different layers of a pouch-type stack according to one embodiment.
• Figure 2 is an exploded view illustrating the different layers of a symmetrical bag-type cell according to one embodiment.
• Figure 3 shows an electrochemical impedance measurement on Cell 1 of Example 5.
• Figure 4 shows the measurement of the short circuit time on Cell 2 of Example 5 at a current density of 0.8 mA / cm 2 .
• Figure 5 shows the results of short-circuit time at current densities of 0.6 mA / cm 2 , 0.7 mA / cm 2 and 0.8 mA / cm 2 on Cell 1 (line including the circles filled), Cell 2 (line comprising the unfilled circles), Cell 3 (line comprising the filled squares) and Cell 4 (line comprising the unfilled squares) of Example 5.
• lithium compatible means the absence of a chemical reaction with lithium or a limited chemical reaction leading to the formation of a passivation film that is not detrimental to electrochemical exchanges. at the lithium / electrolyte interface of an electrochemical cell.
• lithium compatible when used in reference to a cathode material, it refers to an electrochemically compatible cathode material of opposite polarity to that of the anode.
• the component X 1 is magnesium and the component X 2 is selected from Na, K, Zr, Al, and rare earths.
• the component X 1 is aluminum and component X 2 is selected from Na, K, Mg, Zr, and rare earths.
• the X 2 component is selected from Zr, Cu, Ag, Bi, Co, Zn, Al, Si, Sn, Sb, Cd, Hg, Pb, Mn, B, In, Tl, Ni and Ge.
• the material is composed of a ternary alloy, that is to say that it does not comprise any additional element in significant concentration.
• the ternary alloy does not include an additional element at a concentration of 0.1% or more, preferably the ternary alloy does not include additional element at a concentration of 0.05% or more.
• alkali metals Na, K, Rb or Cs
• X 2 M
• the alloy comprising lithium metal, magnesium or aluminum and comprising the metal component X 2 is prepared by melting at a temperature above 180 ° C and cast using conventional metallurgical methods and respecting the usual precautions concerning the manufacture of lithium.
• the composition is made from commercially pure materials. This merger can be done in one or more steps. For example, lithium can be melted before adding the other metal components, which can be added together or separately. For example, the lithium is first melted, then the X 1 component is added to form a first binary alloy, the X 2 component is then added to form a molten ternary alloy.
• the alloy comprises metallic lithium in a concentration higher than that of the metal component X 1 ([Li]> [X 1 ] and X 2 ([Li]> [X 2 ]).
• the alloy comprises the metal lithium in a concentration higher than that of the metal component X 1 which is, itself, greater than the concentration of the metal component X 2 ([Li]> [X 1 ]> [X 2 ]).
• X 2 Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Se, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, a mischmetal, Zr, Cu
• the concentration of additives in the material of [X 1 + X 2 ] is less than the lithium concentration, for example, between 0.15% and 35% by weight, for example between 0.2% and 35% by weight. weight, or between 2% and 35% by weight, or between 2 and 30% by weight, between 10 and 35% by weight, between 20 and 35% by weight, between 2 and 25% by weight, between 5 and 25% by weight, or between 2 and 20% by weight.
• the metal component X 2 may be chosen from alkali metals including sodium, potassium, rubidium or cesium and excluding lithium metal.
• the metal component X 2 may also be chosen from alkaline earth metals including magnesium, calcium, strontium, or barium, the metal component X 2 being different from the metal component X 1 .
• the metal component X 2 can be chosen from rare earths including scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, or lutecium and mischmetal.
• the billet made of the electrode material is conventionally extruded, for example, using a hydraulic press to obtain a thin strip of a thickness of about 100 to 300 microns.
• the pressure applied to the ingot obviously depends on the plasticity of the alloy, but generally varies between 100 and 500 tonnes for a billet 6 inches in diameter (US 7,194,884).
• the strong deformation of the billet during extrusion improves the chemical homogeneity of the alloy.
• the thickness of the strip is reduced by rolling to obtain the ultra-thin strip at room temperature and in dry air. Rolling is accomplished by the use of a conventional method, for example, between two work rolls with sufficient pressure, speed and angle to reduce the thickness of the film to obtain an ultra-thin strip, for example , of a thickness between about 15 m and 50 m.
• the rolling can be accomplished in a single continuous step, and at a rolling speed of up to 50 m / min, preferably up to 20 m / min (US 5,528,920).
• the strong reduction in thickness of the strip heats the alloy and allows homogenization by hardening and recrystallization of its structure.
• the rolling step also significantly influences the finish of the strip surface as well as the grain size of its crystalline structure.
• the electrochemical cells comprise at least one cathode, an anode comprising an electrode material of the present technology (for example, in the form of an ultrathin strip) and an electrolyte located between the cathode and the anode. at. cathodes
• the present application describes the use of symmetrical cells to evaluate the performance of different lithium alloys in dendritic growth; therefore, an anode (and a cathode) of lithium alloy.
• the present application describes the use of ultra-thin lithium alloy (anode) alloy strips in combination with lithium iron phosphate (LFP) as an electrochemically active cathode material.
• the described anode could be used in combination in an electrochemical cell having all active materials compatible with lithium.
• electrochemically active cathode materials include lithiated metal phosphates and metal phosphates (eg LiM'PO 4 and M'PO 4 where M 'is Fe, Ni, Mn, Co or a combination thereof), vanadium oxides (e.g.
• LiVsOe, V2O5F, L1V2O5 and the like) and other lithium and metal oxides such as LiMn204, LiM-O2 (M “being Mn, Co, Ni, or a combination thereof) Li (NiM "') 02 (where M” is Mn, Co, Al, Fe, Cr, Ti, Zr and the like, or a combination thereof), or a combination of two or more of the above materials when they are compatible with each other and with the lithium anode.
• the active cathode material is lithium iron phosphate (LFP).
• the cathode active material may also be in the form of particles optionally coated with carbon, for example produced by pyrolysis of an organic precursor.
• the electrochemically active cathode material may also include an electron-conducting material, for example, a carbon source such as carbon black, Ketjen TM black, acetylene black, graphite, graphene, carbon fibers, carbon, carbon nanofibers (eg VGCF) or carbon nanotubes.
• a carbon source such as carbon black, Ketjen TM black, acetylene black, graphite, graphene, carbon fibers, carbon, carbon nanofibers (eg VGCF) or carbon nanotubes.
• the active material includes acetylene black and VGCF.
• the electrochemically active material may also comprise a binder.
• the binder is a polymer used in polymeric electrolytes.
• the present application describes a lithium film that can be used with a solid polymer electrolyte in an electrochemical cell or lithium cell, for example, an "all solid” lithium battery.
• a solid polymer electrolyte may comprise one or more polar solid polymers, crosslinked or not, and at least one salt, for example a lithium salt such as LiTFSI, LiPFe, LiDCTA, LiBETI, LiFSI, LiBF 4 , LiBOB, etc.
• Polyether-type polymers such as poly (ethylene oxide) based (PEO) based polymers can be used, but several other lithium compatible polymers are also known for the production of solid polymeric electrolytes.
• Compatible liquid electrolytes include, without limitation, organic liquid electrolytes comprising an aprotic polar solvent such as ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), dimethyl carbonate (DMC) methyl and ethyl carbonate (EMC), ⁇ -butyrolactone ( ⁇ -BL), vinyl carbonate (VC), and mixtures thereof, and lithium salts.
• organic liquid electrolytes comprising an aprotic polar solvent such as ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), dimethyl carbonate (DMC) methyl and ethyl carbonate (EMC), ⁇ -butyrolactone ( ⁇ -BL), vinyl carbonate (VC), and mixtures thereof, and lithium salts.
• EC ethylene carbonate
• DEC diethyl carbonate
• PC propylene carbonate
• DMC dimethyl carbonate
• EMC methyl and ethyl carbonate
• ⁇ -BL ⁇
• Compatible gel-type polymeric electrolytes may include, for example, polymer precursors and lithium salts, an aprotic polar solvent, and a polymerization / crosslinking initiator when required.
• examples of such gel electrolytes include, without limitation, the gel electrolytes described in WO200911860A1 and WO2004068610A2.
• the gel electrolyte just like the liquid electrolyte, can impregnate a separator as a polymer separator.
• the electrolyte is a plugged polymer electrolyte comprising an ethylene oxide copolymer in which a LiTFSI lithium salt is dissolved.
• the anode comprises the material as defined herein, preferably in the form of thin or ultra-thin strip, applied to a current collector.
• a current collector includes copper or nickel, but other current collector types compatible with the metal lithium or the alloy of the present application could also be used.
• the electrochemical cells of the present application are of the bag stack type and comprise the following components: a laminated and aluminized bag, two connectors for connection, two current collectors, a cathode, a mask of defined size, an electrolyte and a lithium alloy anode.
• a diagram of the assembly of a bag stack is shown in Figure 1.
• the cells of the present application are symmetrical cells of the bag stack type according to FIG. 2 and comprise the following components: a laminated and aluminized bag, two connectors for connection, two current collectors, a mask of defined size, an electrolyte and two lithium alloy electrodes.
• C.ssot's doctoral thesis C.
• the electrode material described here could also be used in lithium batteries such as lithium, lithium-air or lithium-sulfur batteries.
• Example 1 Preparation of electrode materials in the form of a binary alloy
• Li-Al0.2 1 .8 kg of base alloy Li-Al0.2 is first prepared to perform all ternary alloy melting batches as well as a binary alloy reference.
• This lithium-based alloy was prepared by combining lithium metal (99.8% by weight) with the X 1 component in cases where there is aluminum (0.2% by weight).
• the alloy is prepared in a melting system consisting of a tilting resistance furnace with a power of 5.5 kW and equipped with a lid having a central orifice, a 316L stainless steel crucible and a removable mechanical stirrer made of 316L stainless steel.
• the fusion system is installed in a glove box under an argon atmosphere to avoid any reaction that may contaminate the lithium alloy.
• the solidification of the liquid binary mixture is carried out in a permanent mold of cylindrical shape having an inner diameter of 6 inches, also in 316L stainless steel.
• the 1.8 kg billet is removed from the mold and both ends are cut with a band saw.
• the billet is then extruded using a 500 ton hydraulic press, in an anhydrous room at room temperature, in the form of a thin strip of approximately 300 m thick (US 7, 194,884) in order to to obtain a homogeneous binary alloy that can serve as a basis for the production of ternary alloys.
• Chemical analysis by ICP-OES spectrometry was carried out on the Li-AIO.2 binary alloy thin strip and an aluminum content of 0.206% by weight was obtained.
• Li-Mg10 binary alloy A quantity of 1.8 kg Li-Mg10 base alloy is prepared with the same melting system as in Example 1 (a). This lithium-based alloy was prepared by combining lithium metal (90% by weight) with the X 1 component, if appropriate magnesium (10% by weight).
• the agitator is then removed to allow tilting of the resistance furnace.
• the resistance furnace is gradually switched to flow the liquid metal into the mold at a constant rate for a period of 5 minutes.
• a thermal insulator is then arranged to cover the top opening of the mold and allow the alloy to fully solidify to room temperature.
• the 1.8 kg billet is removed from the mold and both ends are cut with a band saw.
• the billet is then extruded using a 500 ton hydraulic press, in an anhydrous room at room temperature, in the form of a thin strip about 300 m thick (US 7, 194, 844) to obtain a homogeneous binary alloy that can serve as a basis for the production of ternary alloys.
• the ternary alloy is made by melting 44.8 g of binary alloy prepared according to Example 1 (a) with 0.095 g of the X 2 component, where appropriate sodium (0.2 % in weight).
• the cylinder is loaded in a glove box with an inert helium atmosphere to avoid any reaction that may contaminate the lithium alloy.
• the copper seals are tightly tightened to ensure no leakage of liquid lithium.
• the assembly is deposited so as to allow the closed crucible to be rolled in the resistance furnace and thus allow the sporadic stirring of the liquid metal.
• the closed crucible remains in the oven at 300 ° C. for 3 hours.
• the crucible is then removed from the oven and placed on the side of the flat lid (the side of the strip of stainless steel downwards) in order to solidify a cylindrical lithium ternary alloy ingot.
• Example 2 (a) In a similar manner to Example 2 (a), several other examples of Li-X 1 -X 2 ternary alloys were made. Table 1 summarizes the alloys manufactured and tested.
• the jacket of the crucible containing the ingot is reassembled in an extrusion device in an anhydrous room (dew point: ⁇ -40 ° C.).
• the ingot is then extruded using a 100 ton hydraulic press, at room temperature and in dry air, in the form of a thin tape (about 600 m thick and 40 mm wide).
• the extruded ribbons of Example 3 are then rolled with a jeweler's mill in an anhydrous room (dew point: ⁇ -40 ° C.) at room temperature. to obtain a thin tape with a thickness of 200 ⁇ in a single step.
• rolling significantly improves the surface finish of the lithium ribbon (US 5,528,920).
• Example 5 Preparation of cells
• the binary (Li-X 1 ) and ternary (Li-X 1 -X 2 ) alloy strips of Example 4 are used to manufacture symmetrical cells of packet type.
• the symmetrical cells of the present Example comprise the following components: an aluminized plasticized bag, two tongues for nickel connection, two nickel current collectors, two lithium alloy electrodes, a mask of defined size and the solid polymer electrolyte.
• a diagram of the assembly of a symmetrical stack cell is shown in Figure 2 (Rosso, M. et al., Electrochim Acta 51.25 (2006): 5334-5340).
• the electrodes (positive and negative) are composed of the same lithium alloy according to Table 1 supported on a nickel current collector.
• the solid polymer electrolyte which also serves as a separator, consists of an ethylene oxide copolymer in which a lithium salt (CF3SO2) 2NLi (or LiTFSI) is dissolved in an O: Li ratio of 30: 1 (O being the number of oxygen atoms in the polymer).
• CF3SO2 lithium salt
• LiTFSI LiTFSI
• Patents US 4,578,326 and US 4,758,483 describe non-limiting examples of copolymers that can be used. These copolymers can be crosslinked if necessary by means known in the art.
• the electrolyte is also obtained by coating on a detachable support followed by transfer to the electrode.
• Cell 1 (reference: binary alloy), consists of the following elements:
• Cell 2 The second symmetrical cell, named Cell 2 (ternary alloy), consists of the following elements:
• Cell 3 (reference: binary alloy), comprises the following elements:
• the fourth symmetrical cell comprises the following elements: Ni / Li-Mg10-Na0.2 (200 Mm) / Electrolyte (46 Mm) / Li-Mg10-Na0.2 (200 Mm) / Or Example 6 Lithium Electrochemical Properties of Symmetrical Cells
• PEIS Potential electrochemical impedance spectroscopy
• ⁇ 5 mV
• a simple way to "measure the quality" of the contacts is to perform impedance measurements on the symmetric cells.
• a low amplitude alternating voltage ⁇ + ⁇ is applied to the circuit over a frequency range (1 MHz to 1 mHz).
• the measurement of the current i which passes through the cell makes it possible to determine the impedance Z of the cell and in particular to distinguish the contributions of the different elements of the cell.
• the resistance of the electrolyte (R e ) and the interface (Ri) are measured from the Nyquist representation (graph of -lm (Z) vs. Re (Z)) ( Figure 3).
• n 1 - t c ) L
• F the Faraday constant
• C the initial concentration of LiTFSI in the electrolyte
• D the ambipolar diffusion constant of LiTFSI
• t c the number of cationic transports of Li +
• L the inter-electrode distance
• n 1
• F the Faraday constant
• C the initial LiTFSI concentration in the electrolyte
• D the LiTFSI diffusion constant
• t c the number of cationic transports of Li + and the current density applied to the symmetric cell
• Figure 4 shows the results of a constant current density polarization of 0.8 mA / cm 2 leading to symmetrical cell short circuit failure (Cell 2) for 6, 13 hours.
• Figure 5 shows the results of short-circuit time at current densities of 0.6 mA / cm 2 , 0.7 mA / cm 2 and 0.8 mA / cm 2 for the cells of Example 5. It is possible to observe that the addition of 0.2% sodium to form ternary alloys results in an increase in short-circuit time compared to the corresponding binary alloys, which indicates a lower rate of formation of the dendrites on the surface of the anode and therefore a better stability.
• References, patents or scientific literature referred to herein are hereby incorporated by reference in their entirety and for all purposes.

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  • 2018-08-15 US US16/638,506 patent/US11417878B2/en active Active
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  • 2018-08-15 CN CN201880052548.7A patent/CN110998920B/zh active Active
  • 2018-08-15 CA CA3223455A patent/CA3223455C/fr active Active
  • 2018-08-15 WO PCT/CA2018/050988 patent/WO2019033211A1/fr unknown
  • 2018-08-15 EP EP18846110.7A patent/EP3669410A4/de active Pending
• 2023
  • 2023-01-23 JP JP2023008030A patent/JP2023041761A/ja active Pending

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