US20210151737A1 - Laminated films of alkali metal or alloy thereof and apparatus for making same - Google Patents

Laminated films of alkali metal or alloy thereof and apparatus for making same Download PDF

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Publication number
US20210151737A1
US20210151737A1 US16/951,301 US202016951301A US2021151737A1 US 20210151737 A1 US20210151737 A1 US 20210151737A1 US 202016951301 A US202016951301 A US 202016951301A US 2021151737 A1 US2021151737 A1 US 2021151737A1
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lithium
alloy film
center portion
film
ppm
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US16/951,301
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English (en)
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Jonathan Dube
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Blue Solutions Canada Inc
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Blue Solutions Canada Inc
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Publication of US20210151737A1 publication Critical patent/US20210151737A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/40—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling foils which present special problems, e.g. because of thinness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B27/00—Rolls, roll alloys or roll fabrication; Lubricating, cooling or heating rolls while in use
    • B21B27/06—Lubricating, cooling or heating rolls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B27/00—Rolls, roll alloys or roll fabrication; Lubricating, cooling or heating rolls while in use
    • B21B27/02—Shape or construction of rolls
    • B21B27/021—Rolls for sheets or strips
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B27/00—Rolls, roll alloys or roll fabrication; Lubricating, cooling or heating rolls while in use
    • B21B27/06—Lubricating, cooling or heating rolls
    • B21B27/10—Lubricating, cooling or heating rolls externally
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B29/00—Counter-pressure devices acting on rolls to inhibit deflection of same under load, e.g. backing rolls ; Roll bending devices, e.g. hydraulic actuators acting on roll shaft ends
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B31/00—Rolling stand structures; Mounting, adjusting, or interchanging rolls, roll mountings, or stand frames
    • B21B31/08—Interchanging rolls, roll mountings, or stand frames, e.g. using C-hooks; Replacing roll chocks on roll shafts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B38/00—Methods or devices for measuring, detecting or monitoring specially adapted for metal-rolling mills, e.g. position detection, inspection of the product
    • B21B38/02—Methods or devices for measuring, detecting or monitoring specially adapted for metal-rolling mills, e.g. position detection, inspection of the product for measuring flatness or profile of strips
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/02—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for lubricating, cooling, or cleaning
    • B21B45/0239—Lubricating
    • B21B45/0245—Lubricating devices
    • B21B45/0248—Lubricating devices using liquid lubricants, e.g. for sections, for tubes
    • B21B45/0251—Lubricating devices using liquid lubricants, e.g. for sections, for tubes for strips, sheets, or plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B30—PRESSES
    • B30B—PRESSES IN GENERAL
    • B30B3/00—Presses characterised by the use of rotary pressing members, e.g. rollers, rings, discs
    • B30B3/005—Roll constructions
    • 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
    • H01M4/0435—Rolling or calendering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B21B2003/001—Aluminium or its alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B27/00—Rolls, roll alloys or roll fabrication; Lubricating, cooling or heating rolls while in use
    • B21B27/02—Shape or construction of rolls
    • B21B27/021—Rolls for sheets or strips
    • B21B2027/022—Rolls having tapered ends
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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 technology relates to working rollers for a rolling mill for laminating a sheet of alkali metal or alloy thereof into a film and to rolling mills having such working rollers.
  • the present technology also relates to laminated films of alkali metal or alloy thereof obtained from a rolling mill comprising such working rollers.
  • Rechargeable batteries manufactured from laminates of solid polymer electrolytes and thin films anodes and cathodes display many advantages over conventional liquid electrolytes batteries. These advantages include lower overall battery weight, high specific energy, longer service life, and environmental friendliness since the danger of spilling toxic liquid into the environment is eliminated.
  • Solid polymer battery components include positive electrodes, negative electrodes and an insulating material capable of permitting ionic conductivity, such as a solid polymer electrolyte sandwiched between the electrodes.
  • the anodes or negative electrodes are usually made of lightweight metals films, such as alkali metals and alloys thereof, such as lithium metal, lithium-aluminum alloys and the like.
  • the composite cathodes or positive electrodes are usually formed of a mixture of active material such as transitional metal oxide, an electrically conductive filler, usually carbon particles, an ionically conductive polymer electrolyte material and a current collector usually a thin sheet of aluminum.
  • Composite cathode thin films are usually obtained by coating onto a current collector.
  • Cold extrusion is used for the continuous production of sheets of 100 microns or more. These thicknesses are generally adapted to the production of lithium cells utilizing liquid electrolytes. For lower thicknesses, the films obtained by extrusion are thereafter laminated between working rollers made of hard materials.
  • the laminated lithium metal often reacts with, and/or deforms, and adheres to the working rollers with which it is in contact during the lamination process.
  • This problem can be solved by the use of a lubricating agent as described in U.S. Pat. Nos. 5,837,401, 5,528,920 and 6,019,801, all incorporated herein by reference.
  • the lubricating agent comprises additives which prevent the thin laminated lithium film from reacting or excessively adhering to the working rollers and does not effect the electrochemistry of the resulting electrochemical cell.
  • Working rollers are traditionally made of polyacetal, a hard plastic material which is compatible with lithium (i.e. it does not react with lithium).
  • the polyacetal rollers wear out rapidly and necessitate frequent replacement and discarding of the worn-out rollers, thereby drastically increasing cost. This renders the lamination manufacturing process economically difficult.
  • a laminated lithium or lithium alloy film obtained by a rolling mill comprising: a frame; a first working roller rotationally mounted to the frame; a second working roller rotationally mounted to the frame, the first and second working roller being positioned to receive the sheet therebetween; at least two first actuators operatively connected to opposite ends of the first working roller for bending the first working roller; and at least two second actuators operatively connected to opposite ends of the second working roller for bending the second working roller, each of the first and second working rollers comprising: a cylindrical center portion defining a central axis, the center portion having an outer surface defining a lamination surface; a first frustoconical portion extending from a first end of the center portion; and a second frustoconical portion extending from a second end of the center portion, when the central axis is straight, an angle between the outer surface of the center portion and an outer surface of each of the first and second frustoconical portions being less than 0.05 degrees
  • the present technology relates to a laminated lithium or lithium alloy film obtained by a rolling mill comprising a working roller, the working roller comprising: a cylindrical center portion defining a central axis, the center portion having an outer surface defining a lamination surface; a first frustoconical portion extending from a first end of the center portion; and a second frustoconical portion extending from a second end of the center portion, when the central axis is straight, an angle between the outer surface of the center portion and an outer surface of each of the first and second frustoconical portions being less than 0.05 degrees, a width of the center portion being greater than a width of each of the first and second frustoconical portions, and the width of the center portion being less than a sum of the widths of the first and second portion.
  • the present technology relates to a lithium or lithium alloy film comprising a metallic element, the metallic element being present in the lithium or lithium alloy film in an amount of at least 3000 ppm; the lithium or lithium alloy film having a thickness to width ratio of between about 1 ⁇ 10 ⁇ 4 and about 7 ⁇ 10 ⁇ 4 .
  • the present technology relates to a laminated lithium or lithium alloy film comprising at least about 3000 ppm aluminum, the laminated lithium or lithium alloy film having a thickness, a width and a length, wherein the thickness to width ratio is between about 1 ⁇ 10 ⁇ 4 and about 7 ⁇ 10 ⁇ 4 and is even over the entire length of the lithium or lithium alloy film.
  • Roughness Average Ra
  • hardness represents the resistance to localized deformation of a material (e.g., sheets and films) which deformation is induced by either mechanical indentation or abrasion.
  • tensile strength TS refers to the capacity of a material (e.g., sheets and films) loads tending to elongate such material. The tensile strength is measured by the maximum stress that the material can withstand while being stretched or pulled before breaking.
  • the term “about” is used herein, explicitly or not; every quantity given herein is meant to refer to the actual given value, and it is also meant to refer to the approximation to such given value that would reasonably be inferred based on the ordinary skill in the art, including equivalents and approximations due to the experimental and/or measurement conditions for such given value.
  • the term “about” in the context of a given value or range refers to a value or range that is within 20%, preferably within 15%, more preferably within 10%, more preferably within 9%, more preferably within 8%, more preferably within 7%, more preferably within 6%, and more preferably within 5% of the given value or range.
  • Embodiments of the present technology each have at least one of the above-mentioned object and/or aspects, but do not necessarily have all of them. It should be understood that some aspects of the present technology that have resulted from attempting to attain the above-mentioned object may not satisfy this object and/or may satisfy other objects not specifically recited herein.
  • FIG. 1 is a schematic side cross-sectional view of a rolling mill and associated components for laminating a lithium or lithium alloy sheet into a thin film;
  • FIG. 2 is a schematic side elevational view illustrating the main components of the rolling mill of FIG. 1 that enable control of the thickness and shape of the lithium or lithium alloy film being laminated;
  • FIG. 3 is a schematic front elevational view of the main components of the rolling mill of FIG. 2 ;
  • FIGS. 4A to 4C are schematic front elevational views of backup rollers and working rollers of the rolling mill of FIG. 2 shown in different adjustments, with angles of frustoconical portions of the working rollers and the degree of bending of the working rollers having been exaggerated for illustration purposes;
  • FIG. 5 is a front elevation view of one working roller of the rolling mill of FIG. 2 ;
  • FIG. 6A is a close-up of section 6 of FIG. 5 according to one embodiment of the roller of FIG. 5 ;
  • FIG. 6B is a close-up of section 6 of FIG. 5 according to another embodiment of the roller of FIG. 5 ;
  • FIG. 7 is a schematic cross-sectional profile of the lithium or lithium alloy sheet supplied to the rolling mill of FIG. 2 ;
  • FIG. 8 is a perspective view of a lamination lubricant dispensing unit for lubricating an upper working roller of the rolling mill of FIG. 1 ;
  • FIG. 9 is a perspective view of a lamination lubricant dispensing unit for lubricating a lower working roller of the rolling mill of FIG. 1 ;
  • FIG. 10 is a top plan view of the lamination lubricant dispensing unit of FIG. 9 ;
  • FIG. 11 is a front elevation view of the lamination lubricant dispensing unit of FIG. 9 ;
  • FIG. 12 is a cross-sectional view of the lamination lubricant dispensing unit of FIG. 9 taken through line 12 - 12 of FIG. 10 ;
  • FIG. 13 is a close-up of portion 13 of FIG. 12 .
  • FIG. 1 schematically illustrates a rolling mill 10 and associated components adapted to produce a lithium or lithium alloy thin film 12 of less than 100 microns thick from a previously extruded lithium or lithium alloy sheet 14 of about 100 to 500 microns thick.
  • the rolling mill 10 has a main frame 16 , a pair of working rollers 18 a and 18 b , a backup roller 20 a adjacent to and in contact with the working roller 18 a , a backup roller 20 b adjacent to and in contact with the working roller 18 b , a lamination lubricant dispensing unit 22 for dispensing lubricant onto the working roller 18 a and a lamination lubricant dispensing unit 200 for dispensing lubricant onto the working roller 18 a .
  • the working roller 18 a is disposed below the working roller 18 b .
  • the working rollers 18 a , 18 b and the lamination lubricant dispensing units 22 , 200 will be described in more detail below.
  • the working rollers 18 a , 18 b and the backup rollers 20 a , 20 b are rotationally mounted on support frames 50 and 52 ( FIG. 2 ) as will be described in more detail below.
  • a roll 24 of wound extruded lithium or lithium alloy sheet 14 is placed on a feeding roller 26 comprising a drive motor control unit (not shown) adapted to control the tension of the lithium sheet 14 prior to reaching the working rollers 18 a and 18 b .
  • the sheet 14 snakes its way through a series of free rollers 28 leading to an encoder roller 41 measuring the exact speed of the traveling sheet 14 , and to a tension roller 43 equipped with a load cell adapted to precisely measure the tension on the sheet 14 entering the lamination apparatus 10 .
  • the load cell of tension roller 43 may be electronically coupled to the control unit of the drive motor of roll 24 to automatically adjust the tension exerted onto the sheet 14 .
  • the sheet 14 is then fed into a straightener 30 which rapidly winds the sheet 14 through a series of tightly packed rollers 32 which has the effect of eliminating lateral displacement of the sheet 14 and preventing zigzagging motion of the sheet 14 thereby ensuring that the sheet 14 is fed straight into the center portion of the working rollers 18 a and 18 b without any lateral weaving motion that would be detrimental to the lamination process.
  • the sheet 14 is therefore fed into the working rollers 18 a and 18 b at a fixed position between the rollers 18 a , 18 b.
  • the lubricant dispensing units 22 and 200 discharge an adequate amount of lamination lubricant compatible with lithium onto the working surfaces of each working roller 18 a and 18 b upstream from the lamination area such that the sheet 14 is laminated with properly lubricated working rollers 18 a and 18 b thereby preventing undesirable adhesion of the laminated film 12 onto either on of the working rollers 18 a , 18 b .
  • One suitable lubricant is described in U.S. Pat. Nos. 5,837,401 and 6,019,801, the entirety of which are incorporated herein by reference.
  • the lubricant is based on toluene, hexane and a polyoxyethylene distereate and is used in sufficient quantity onto each working roller 18 a and 18 b to prevent excessive adhesion of the laminated film 12 onto either of them.
  • the sheet 14 passes between the two working rollers 18 a and 18 b where its thickness is reduced from about 100 to 500 microns to about 20 to 100 microns depending on the desired final thickness of the film 12 .
  • Pressure is applied by the backup rollers 20 a and 20 b onto the working rollers 18 a and 18 b which in turn exert pressure on the sheet 14 sufficient to reduce its thickness and transform it into a film 12 .
  • the lamination pressure is applied through the backup rollers 20 a and 20 b instead of directly onto the working rollers 18 a and 18 b to help avoid any unwanted bending of the working rollers 18 a and 18 b which would be reflected on the shape and thickness of the film 12 .
  • the surface roughness of the working rollers 18 a and 18 b should be minimal to produce a thin film 12 of quality.
  • the pressure applied by the backup rollers 20 a and 20 b onto the working rollers 18 a and 18 b is evenly distributed on the surfaces of each roller 18 a and 18 b , thereby leaving the shape of the working rollers 18 a and 18 b undisturbed. If however the working rollers 18 a and 18 b are sufficiently rigid, the necessary pressure required to reduce the thickness of the sheet 14 and transform it into the film 12 may be applied directly by the working rollers 18 a and 18 b without the use of any backup rollers.
  • a plurality of backup rollers could be used to apply even pressure on each of the working rollers 18 a and 18 b .
  • two pairs of backup rollers may be positioned on either side of the working rollers 18 a and 18 b.
  • the laminated film 12 is pulled through an optical refractory system 36 which measures the evenness of the surface of the film 12 and also detects any porosity on the film 12 and cracks along the edges of the film 12 .
  • An optical system can also be used to measure the thickness of the film 12 .
  • Controlled tension is applied onto the film 12 by a driven winding roller 38 to ensure that the film 12 is properly wound.
  • the laminated film 12 snakes its way under controlled tension through a series of rollers.
  • the first of these rollers is a tension roller 45 equipped with a load cell adapted to precisely measure the tension on the laminated film 12 exiting the rolling mill 10 .
  • the load cell of the tension roller 45 may be electronically coupled to the control unit of the drive motor of the winding roller 38 to automatically adjust the tension exerted onto the sheet 12 .
  • the film 12 then passes over an encoder roller 47 measuring the exact speed of the traveling film 12 .
  • the film 12 then passes through a series of free rollers 34 leading to the winding roller 38 .
  • a thin insulating film 90 such as a polypropylene film, is also wound around the winding roller 38 to separate the layers of film 12 such that they will not adhere to each other.
  • the insulating film 90 is pulled by the winding roller 38 from a roll 92 . From the roll 92 , the insulating film 90 passes over a tension roller 94 before reaching the roller 38 .
  • the tension roller 94 is equipped with a load cell adapted to precisely measure the tension on the insulating film 90 . This tension measurement is used to control the tension exerted by the winding roller 38 onto the film 12 since the tension exerted by the winding roller 38 is divided between the film 12 and the insulating film 90 .
  • the encoder rollers 41 and 47 respectively measure the speed of the sheet 14 entering the rolling mill 10 and the speed of the laminated film 12 exiting the rolling mill 10 .
  • the relation between the entry speed of the sheet 14 and the exit speed of the laminated film 12 is directly proportional to the thickness reduction from the initial sheet 14 to the film 12 .
  • the thickness of the laminated film 12 may be determined mathematically when the thickness of the initial sheet 14 is known.
  • the thickness of the laminated film 12 is thus controlled and verified through the speed differential between the speeds measured by the encoder rollers 41 and 47 . It is contemplated that the thickness of the laminated film 12 could be controlled and verified differently.
  • the lamination process is carried out in an anhydride atmosphere containing less than 1% relative humidity to prevent any unwanted chemical reactions of the lithium film 12 with water particles that would render the lithium film 12 unsuitable for use in electrochemical cells.
  • FIGS. 2 and 3 the main components of the rolling mill 10 that enable control of the thickness and shape of the film 12 being laminated will be described.
  • the illustrated rolling mill 10 is one exemplary embodiment of a rolling mill adapted to control the shape and thickness of the laminated film 12 and that other embodiments are contemplated.
  • support members and frames may have different configurations, and various hydraulic system configurations may be used.
  • the backup rollers 20 a and 20 b are each rotationally mounted on bearings of support frames 50 and 52 respectively.
  • the support frame 52 is slidably mounted onto vertical members of the main frame 16 through any suitable means, such as sliding channels or bearings.
  • the support frame 50 is fixedly mounted onto the vertical members of the main frame 16 .
  • the support frame 52 may therefore move vertically.
  • the working rollers 18 a and 18 b are each driven by electric or hydraulic motors (not shown).
  • the working rollers 18 a , 18 b drive the backup rollers 20 a and 20 b by friction.
  • a pair of hydraulic linear actuators 66 is mounted to upper horizontal members of the main frame 16 .
  • the hydraulic actuators are connected to the support frame 52 .
  • the hydraulic linear actuators 66 control the up and down movements of the support frame 52 , as well as the pressure applied onto the working rollers 18 a and 18 b .
  • the working rollers 18 a and 18 b are rotationally mounted onto supporting members 54 and 56 respectively.
  • the supporting members 54 and 56 are operationally linked to the support frames 50 and 52 respectively.
  • the end portions 58 and 59 of the supporting members 54 are operatively connected to the support frame 50 via a pair of hydraulic linear actuators 60 and 61 and the end portions 62 and 63 of supporting members 56 are operatively connected to the support frame 52 via a pair of hydraulic linear actuators 64 and 65 .
  • the speed of lamination is set by the speed of working rollers 18 a and 18 b .
  • the pressure P necessary to reduce the thickness of the film 12 to the desired thickness is adjusted through hydraulic valves controlling the hydraulic linear actuators 66 .
  • the backup roller 20 b transfers the pressure P to the working roller 18 b .
  • the final shape of laminated film 12 is fine-tuned by regulating the fluid pressure to each of the hydraulic linear actuators 60 , 61 , 64 and 65 thereby adjusting the forces exerted by each of the hydraulic linear actuators 60 , 61 , 64 and 65 onto the supporting members 54 and 56 as will be explained in more detail below.
  • the hydraulic linear actuators 60 , 61 , 64 , 65 and 66 may be replaced by other types of actuators capable of generating sufficient forces, such as electric actuators.
  • additional hydraulic linear actuators are connected between the supporting members 54 , 56 .
  • the hydraulic linear actuators 60 , 61 , 64 , 65 and 66 are used to push the supporting members 54 , 56 toward each other and the additional hydraulic linear actuators are used to push the supporting members 54 , 56 toward each other.
  • FIGS. 4A to 4C Note that the shapes of the working rollers 18 a and 18 b illustrated in FIGS. 4A to 4C are greatly exaggerated for the sake of clarity, but it should be understood that the tapering of the end portions of the working rollers 18 a , 18 b and the bent profiles are in fact not visible to the naked eye as they represent mere microns of deviations from a perfectly linear profile.
  • FIG. 4A illustrates the working rollers 18 a and 18 b in a neutral position.
  • the backup rollers 20 a and 20 b apply a pressure P onto the working rollers 18 a and 18 b sufficient to reduce the thickness of the sheet 14 to the desired thickness of film 12 while no lateral force is applied to the supporting members 54 and 56 of the working rollers 18 a , 18 b.
  • the backup rollers 20 a and 20 b still apply a pressure P onto the working rollers 18 a and 18 b sufficient to reduce the thickness of the sheet 14 to the desired thickness of film 12 .
  • the center portion of the working rollers 18 a and 18 b have expanded through heat build-up generated by friction of the center portions 100 against the sheet 14 .
  • inwardly oriented lateral forces Fx are applied to the supporting members 54 and 56 .
  • the lateral forces Fx slightly bend the working rollers 18 a and 18 b outwardly, thereby flattening the center portions 100 as depicted in FIG. 4B .
  • the outside edges of the working rollers 18 a and 18 b are bent inwardly to straighten the center portions 100 .
  • the resulting laminated film 12 will therefore be flat and have an even thickness.
  • Thermal dilation of the working rollers 18 a , 18 b is also partly counteracted by the application of the lamination lubricant onto the working rollers 18 a , 18 b . It is also contemplated that additional means of cooling the working rollers 18 a , 18 b could be used to help counteract the thermal dilation of the working rollers 18 a , 18 b.
  • the center portions of the working rollers 18 a and 18 b dilate marginally.
  • the lateral forces Fx are proportionally reduced to maintain the center portions 100 straight such that the resulting laminated film 12 will have an even thickness throughout its entire width.
  • the central portion of the sheet 14 being laminated can be thicker than its edges.
  • more pressure must be applied by the working rollers 18 a and 18 b onto the central portion of the sheet 14 and therefore to the central portions of center portions 100 .
  • outwardly oriented lateral forces Fy are applied to the supporting members 54 and 56 .
  • the lateral forces Fy slightly bend the central portion of the working rollers 18 a and 18 b inwardly forcing the central portions of the center portions 100 inwardly thereby applying more pressure onto the central portion of the sheet 14 and laminating a film 12 having an even thickness throughout its entire width.
  • the adjustments of the profile and thickness of laminated film 12 may either be performed by an operator on site that fine tunes the pressures applied by backup rollers 20 a and 20 b and the pressures applied to the supporting members 54 and 56 or this task may be performed electronically by linking the measurement readings and the actuators controlling the various pressures and forces of the backup rollers 20 a , 20 b and the working rollers 18 a , 18 b to a computer providing real-time adjustments of theses parameters.
  • the working roller 18 a will be described in more detail.
  • the working roller 18 b is identical to the working roller 18 a , as such the working roller 18 b will not be separately described herein. It is contemplated that the working roller 18 b could differ in part from the working roller 18 a.
  • the working roller 18 a has a center portion 100 .
  • the center portion 100 is a cylindrical center portion 100 .
  • An outer surface 102 of the center portion 100 defines a lamination surface which rolls over the sheet 14 during the lamination process.
  • the center portion 100 has a width W 1 that is slightly wider than a width W 2 ( FIG. 7 ) of the sheet 14 to be laminated.
  • the center portion 100 defines a central axis 104 of the working roller 18 a.
  • Frustoconical portions 106 extend from the ends of the center portion 100 .
  • the frustoconical portions 106 are mirror images of each other. In FIG. 5 the outer surfaces 110 of the frustoconical portions 106 do not appear to taper. This is because the tapering angle is very small and is not visible to the naked eye. This angle has been exaggerated in FIGS. 6A and 6B which illustrate two different embodiments of the working roller 18 a and will be described below.
  • Each frustoconical portion 106 has a width W 3 . The width W 1 of the center portion 100 is greater than the width W 3 of each frustoconical portion 106 .
  • the width W 1 of the center portion 100 is less than a sum of the widths W 3 of both frustoconical portions 106 (i.e. W 1 ⁇ W 3 +W 3 ).
  • the width W 1 is between 125 mm and 210 mm and the width W 3 is between 65 mm and 110 mm.
  • the frustoconical portions 106 taper as they extend away from the center portion 100 .
  • This embodiment is the one shown in FIGS. 4A to 4C where the tapering has been exaggerated.
  • shoulders 108 are defined between the center portion 100 and each frustoconical portion 106 (shown for one frustoconical portion in FIG. 6A ).
  • the shoulders 108 have a height H 1 that is less than 0.05 mm. In some embodiments, the height H 1 is less than 0.02 mm. It is contemplated that the shoulders 108 could be omitted.
  • an angle A between the outer surface 102 of the center portion 100 and an outer surface 110 of the frustoconical portion 106 is less than 0.05 degrees. In some embodiment, the angle A is less than 0.03 degrees. In some embodiments, the angle A is less than 0.02 degrees. In some embodiments, the angle A is less than 0.02 degrees but more than 0.01 degrees. In some embodiments, the center portion 100 has a diameter D 1 between 70 mm and 90 mm. In some embodiments, a difference between the smallest diameter D 2 and the greatest diameter D 3 of each frustoconical portion 106 is between 0.03 mm and 0.17 mm.
  • the profiles of the working rollers 18 a and 18 b according to this embodiment facilitate their bending by providing free zones 84 ( FIG.
  • this embodiment of the working roller 18 a is particularly well suited for laminating a sheet 14 which has been extruded with a central portion 112 having a height H 2 ( FIG. 7 ) that is smaller than a height H 3 of its side portions 114 ( FIG. 7 ).
  • a height H 2 FIG. 7
  • H 3 the height of its side portions 114 ( FIG. 7 ).
  • the heights H 2 and H 3 do not appear to be different because the difference is not visible to the naked eye.
  • the height H 2 is less than 15 microns smaller that the height H 3 .
  • each frustoconical portions 106 tapers as is extends from its outer end toward the center portion 100 (i.e. D 2 is greater than D 3 ).
  • D 2 is greater than D 3 .
  • an angle B between the outer surface 102 of the center portion 100 and an outer surface 110 of the frustoconical portion 106 is less than 0.05 degrees.
  • the angle B is less than 0.03 degrees.
  • the angle B is less than 0.02 degrees.
  • the angle B is less than 0.02 degrees but more than 0.01 degrees.
  • the center portion 100 has a diameter D 1 between 70 mm and 90 mm.
  • a difference between the greatest diameter D 2 and the smallest diameter D 3 of each frustoconical portion 106 is between 0.03 mm and 0.17 mm.
  • this embodiment of the working roller 18 a is particularly well suited for laminating a sheet 14 which has been extruded with a central portion 112 having a height H 2 ( FIG. 7 ) that is greater than a height H 3 of its side portions 114 ( FIG. 7 ).
  • the height H 2 is less than 15 microns bigger that the height H 3 .
  • the working roller 18 a has support shafts 116 , 118 extending from the ends of the frustoconical portions 106 .
  • the supports shafts 116 , 118 are received in bearings (not shown) for rotationally mounting the working roller 18 a to the supporting members 54 (or to the supporting members 56 for the working roller 18 b ).
  • the support shaft 118 has an extension 120 adapted for connection to the motor driving the working roller 18 b .
  • the portions 100 , 106 , and the support shafts 116 , 118 are integrally formed.
  • the lamination lubricant dispensed onto the working rollers 18 a and 18 b helps prevent adhesion of the lithium film 12 onto the working rollers 18 a , 18 b such that the film 12 exits the working rollers 18 a and 18 b in a straight line.
  • the use of lubricant enables to laminate lithium and lithium alloys with the working rollers 18 a , 18 b made of material that would normally not be adequate because of their adhesion to lithium.
  • the lubricant negates this restriction. Therefore, for large-scale production, the working rollers 18 a , 18 b are preferably made of durable hard material such as steel or stainless steel or even ceramic.
  • the steel or stainless steel rollers 18 a , 18 b have a thin chrome coating for added hardness.
  • the chrome coating is applied at least on the center and frustoconical portions 100 , 106 of the working rollers 18 a , 18 b .
  • the chrome coating is a hard chrome coating.
  • the outer surfaces 102 , 110 of the center and frustoconical portions 100 , 106 have a surface roughness in a range between 0.025 microns Ra and 0.5 microns Ra. In other embodiments, the surface roughness is in a range between 0.05 microns Ra and 0.30 microns Ra
  • the lamination lubricant dispensing unit 22 includes four nozzles 150 mounted to a rail 152 . It is contemplated that the lamination lubricant dispensing unit 22 could have more or less than four nozzles 150 .
  • Lamination lubricant is supplied to a passage (not shown) inside the rail 152 via an intake connector 154 .
  • the intake connector 154 is fluidly connected to a pump (not shown) that supplies lubricant to the intake connector 154 from a lubricant reservoir (not shown) holding the lamination lubricant therein.
  • the four nozzles 150 fluidly communicate with the passage inside the rail 152 .
  • the lamination lubricant dispensing unit 22 is disposed upstream of the lamination area and is spaced from the working roller 18 b .
  • the lamination lubricant dispensing unit 22 is disposed above the central axis 104 of the working roller 18 b and is angled such that the nozzles 150 continuously spray lamination lubricant on the lamination surface of the working roller 18 b .
  • the sprays from the nozzles 150 cover an area slightly wider than the lamination surface.
  • Each nozzle 150 has a nozzle body 156 , a filter, a nozzle head 158 and a nut 160 .
  • the nozzle body 156 is threaded into the rail 152 .
  • the filter is disposed inside the nozzle body 156 .
  • the nozzle head 158 defines a spray aperture 162 and is disposed on the end of the nozzle body 156 .
  • the nut 160 is disposed over the nozzle body 156 and is threaded onto the nozzle body 156 to maintain the nozzle head 158 and the filter in position.
  • the lamination lubricant dispensing unit 200 is made from a single piece of static-dissipative acetal copolymer. It is contemplated that other types of materials could be used such as polyamide, polypropylene, polyethylene, acrylonitrile butadiene styrene, polyethylene terephthalate, polystyrene, thermoplastic polyurethane, poly(methyl methacrylate), polyvinyl chloride, brass and aluminum for example. Other materials are also contemplated. It is also contemplated that the lamination lubricant dispensing unit 200 could be made from multiple parts bonded or otherwise connected to each other.
  • the lamination lubricant dispensing unit 200 has a dispensing unit body 202 .
  • Each rear corner portion of the dispensing unit body 202 defines two apertures 206 .
  • Fasteners (not shown) are received in the apertures 206 to fasten the dispensing unit body 202 to the frame 16 of the rolling mill 10 at a position between the working roller 18 a and the straightener 30 .
  • the dispensing unit body 202 defines a laterally extending wall 208 .
  • a single lubricant passage 210 is defined in the dispensing unit body 202 as best seen in FIG. 12 .
  • the lubricant passage 210 has an inlet (not shown) defined in a rear wall 214 of the dispensing unit body 202 and an outlet 216 defined in the laterally extending wall 208 . As can be seen, the outlet 216 is laterally centered in the laterally extending wall 208 and is disposed at a bottom thereof. It is contemplated that multiple lubricant passages 210 could be defined in the dispensing unit body 202 , with the outlets of these passages being at different positions along the laterally extending wall 208 . It is also contemplated that at least some of these multiple lubricant passages 210 could have a common inlet.
  • Two side walls 218 extend forwardly from the laterally extending wall 208 . As can be seen in FIG. 10 , the side walls 218 are parallel to each other. As can be seen in FIG. 12 , the front ends 220 of the side walls 218 are angled from vertical so as to not interfere with the working roller 18 a.
  • the lamination lubricant dispensing unit 200 also has a ledge 222 .
  • the ledge 222 is connected to the lower end of the laterally extending wall 208 and extends forwardly therefrom.
  • the ledge 222 is also connected to the lower ends of the side walls 218 and extends therebetween.
  • the ledge 222 , the side walls 218 and the laterally extending wall 208 together define a recess 224 having an opened side at a front of the lamination lubricant dispensing unit 200 .
  • the ledge 222 has a front edge 226 that abuts the lamination surface of the working roller 18 a at a position vertically below the central axis 104 of the working roller 18 a , as can be seen in FIG. 12 .
  • the front edge 226 has a width W 4 ( FIG. 10 ) that is greater than the width W 1 of the lamination surface of the working roller 18 a to help ensure that lamination lubricant will be applied across and entire width of the
  • the ledge 222 has an angled portion 228 that extends upward and rearward from the front edge 226 toward the laterally extending wall 208 .
  • the corner 230 between the angled portion 228 and the front edge 226 is arcuate.
  • the angled portion 228 extends at an angle C between 5 and 25 degrees from horizontal. In some embodiments, the angle C is between 10 and 20 degrees from horizontal.
  • the ledge 222 also has a generally horizontal portion 232 extending between the angled portion 228 and the laterally extending wall 208 .
  • the portion 232 is horizontal when viewed from the side (i.e. as viewed in FIGS. 12 and 13 ). However, from a front view of the portion 232 (i.e.
  • the portion 232 slopes slightly downward on both sides of its lateral center, which therefore corresponds to the apex of the portion 232 .
  • the angle D ( FIG. 11 ) between the surfaces on both sides of the lateral center of the portion 232 is greater than 180 degrees but less than 185 degrees, and in some embodiments less than 182 degrees.
  • the portion 232 could also be flat (i.e. angle D being 180 degrees) as viewed from the front view of the portion 232 (i.e. as viewed in FIG. 11 ). As can be seen in FIGS.
  • the outlet 216 of the lubricant passage 210 is laterally aligned with the apex of the portion 232 and the bottom of the outlet 216 is vertically aligned with the top of the portion 232 of the ledge 222 adjacent to it. It is contemplated that the portion 232 could be omitted and that the angled portion 228 could extend from the front edge 226 to the laterally extending wall 208 .
  • a laterally extending gutter 234 is defined in the angled portion 228 of the ledge 222 . As best seen in FIG. 10 , the ends of the gutter 234 are spaced from the side walls 218 . The gutter 234 is spaced from the front edge 226 of the ledge 222 . As can be seen in FIG. 13 , the gutter 234 is closer to the front edge 226 than to the portion 232 of the ledge 222 .
  • the inlet of the lubricant passage 210 is fluidly connected to a pump 236 , which is itself fluidly connected to a lubricant reservoir 238 .
  • the lubricant reservoir 238 holds the lamination lubricant therein. It is contemplated that the lubricant reservoir 238 could also be used for supplying the lamination lubricant to the lamination lubricant dispensing unit 22 described above.
  • the pump 236 pumps lamination fluid from the lubricant reservoir 238 into the lubricant passage 210 . From the outlet 216 of the lubricant passage 210 , the lubricant flows forward and laterally (due to angle D) along the portion 232 of the ledge.
  • the lubricant then flows down along the angled portion 228 . Some of the lubricant will flow into the gutter 234 which helps ensure an even distribution of lubricant across a width of the ledge 222 .
  • the lubricant then flows to the front edge 226 where it makes contact with the lamination surface of the working roller 18 a .
  • the upwardly moving lamination surface of the working roller 18 a picks up lubricant which effectively coats the lamination surface that will make contact with the sheet 14 .
  • the alkali metal or alkali metal alloy film of the present technology is a laminated lithium film or a laminated lithium alloy film obtained using the rolling mill and working rollers as defined herein.
  • the lithium alloys that may be used to prepare the films of the present technology include, but are not limited to: Lithium-Silicon, Lithium-Aluminum, Lithium-Magnesium, Lithium-Strontium, Lithium-Barium and the like.
  • the lithium or lithium alloy films of the present technology comprise an amount of metallic element.
  • a metallic element to the lithium or lithium alloy films allows to decrease the overall thickness of the film and to improve its overall mechanical strength.
  • the metallic element is present in the lithium or lithium alloy film in an amount that improves the mechanical strength throughout the width, thickness and length of the film.
  • the metallic element that may be used in the preparation of the lithium or lithium alloy films of the present technology is preferably electrically conductive. It is to be understood that the presence of the metallic element should not impede the electrical conductivity of the lithium or lithium alloy film.
  • aluminum is a metallic element that can be used in the lithium or lithium alloy film. In some instances, aluminum is present in the film in an amount ranging between about 3000 ppm and about 10 000 ppm, or between about 3000 ppm and about 9000 ppm, or between about 3000 ppm and about 8000 ppm, or between about 3000 ppm and about 7000 ppm, or between about 3000 ppm and about 6000 ppm, or between about 3000 ppm and about 5000 ppm. In some instances, aluminum is present in the film in an amount that is equal to or greater than 3000 ppm.
  • the lithium or lithium alloy film of the present technology has a hardness as measured by a Shore durometer (Shore A scale) that ranges between about 50 and about 85, or between about 60 and about 80, or between about 60 and about 75, or between about 50 and about 70, or between about 60 and about 75, or between about 65 and about 75, or between about 66 and 70, or between about 66 and 69.
  • the hardness is of at least 65. In some other instances, the hardness is of at least about 66. In some instances, the hardness is even throughout the entire lithium or lithium alloy film.
  • the lithium film obtained by the technology defined herein has a width (which corresponds to the distance from one edge of the film to the other) that ranges between about 140 mm and about 200 mm, or between about 150 mm and about 200 mm, or between about 160 mm and about 180 mm, or between about 160 mm and about 175 mm, or between about 160 mm and about 170 mm, or between about 160 mm and 165 mm and has a thickness that ranges between about 20 microns and about 100 microns, or between 20 microns and about 90 microns, or between about 20 microns and about 75 microns, or between about 20 microns and about 50 microns, or between about 20 microns and 30 microns.
  • the thickness of the lithium or lithium alloy film is even throughout the entire width of the film. The thickness being even throughout the entire width of the film encompasses a variation in thickness of about +/ ⁇ 2 microns.
  • the lithium or lithium alloy films obtained by the technology defined herein have a thickness to width (t/w) ratio that is between about 1 ⁇ 10 ⁇ 4 and about 7 ⁇ 10 ⁇ 4 . In some instances, this t/w ratio is maintained throughout the entire length of the film.
  • the present technology allows to maintain the width, thickness and hardness of the lithium or lithium alloy films even over extended film lengths.
  • the lithium or lithium alloy film of the present technology maintains its width, thickness and hardness over at least about 15000 meters, over at least about 10000 meters, over at least about 9000 meters, over at least 8000 meters, over at least 7000 meters, over at least 6000 meters, over at least 5000 meters, over at least 4000 meters, over at least 3000 meters, over at least 2000 meters, or over at least over 1000 meters.
  • a laminated lithium film was prepared using a rolling mill comprising the working rollers as defined herein.
  • the lithium film obtained had a width of 170 mm, a thickness of 60 microns and an aluminum content of 3000 ppm. Hardness of the film was assessed using a Shore durometer (PTC model 320—A Scale). The results are presented in Table 1.
  • a laminated lithium film was prepared using a rolling mill comprising the working rollers as defined herein.
  • the lithium film obtained had a width of 170 mm, a thickness of 60 microns and an aluminum content of 5000 ppm. Hardness of the film was assessed using a Shore durometer (PTC model 320—A Scale). The results are presented in Table 2.
  • a laminated lithium-aluminum film was prepared using a rolling mill comprising the working rollers as defined herein.
  • the lithium film had a width of 170 mm, a thickness of 60 microns and an aluminum content of 3000 ppm.
  • Tensile strength of the lithium film was assessed using a testometric M500 25 kN. The results are presented in Table 3.
  • a laminated lithium-aluminum film was prepared using a rolling mill comprising the working rollers as defined herein.
  • the lithium film had a width of 170 mm, a thickness of 60 microns and an aluminum content of 5000 ppm.
  • Tensile strength of the lithium film was assessed using a testometric M500 25 kN. The results are presented in Table 4.

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  • Chemical & Material Sciences (AREA)
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WO2021097566A1 (en) 2021-05-27
EP4061551A4 (en) 2024-01-24
KR20220099568A (ko) 2022-07-13
CA3156599A1 (en) 2021-05-27
EP4061553A4 (en) 2024-01-17
JP2023501751A (ja) 2023-01-18

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