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WO2024167863A1 - Soudage électrochimique d'un collecteur de courant à un séparateur dans un dispositif électrochimique - Google Patents

Soudage électrochimique d'un collecteur de courant à un séparateur dans un dispositif électrochimique Download PDF

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Publication number
WO2024167863A1
WO2024167863A1 PCT/US2024/014498 US2024014498W WO2024167863A1 WO 2024167863 A1 WO2024167863 A1 WO 2024167863A1 US 2024014498 W US2024014498 W US 2024014498W WO 2024167863 A1 WO2024167863 A1 WO 2024167863A1
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Prior art keywords
separator
metal
layer
conductive substrate
kpa
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English (en)
Inventor
Lincoln Miara
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Pure Lithium Corp
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Pure Lithium Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • 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
    • 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
    • H01M2300/0071—Oxides

Definitions

  • the lithium electrode is bonded to a solid separator.
  • the separator is a key component of a battery as it allows for the flow of ions while preventing direct contact between the anode and the cathode, thereby preventing a short circuit.
  • Current collectors are made from metals like copper or aluminum, while solid separators are commonly polymer or ceramic materials. These materials may not naturally adhere to each other, requiring special binders or adhesives. Therefore, bonding a current collector to a solid separator is challenging. For example Li 7 La 3 Zr 2 O 12 (LLZO) and copper are not easily joined. Three main techniques have been employed to effect such bonding:
  • I mhium is soft and provides a strong adhesion to both a current collector such as copper and to a separator such as Li 7 La 3 Zr 2 O 12 (LLZO) when properly applied.
  • This disclosure provides a new method for joining current collectors and separators via electrochemical deposition of the lithium between the current collector and the separator, in such a manner that the thickness of the weld is easily controllable to enable a strong bond between current collector and separator. In contrast to so-called “anodeless” batteries, the resultant bond persists even when the battery is fully discharged.
  • the method is suitable for but not limited to a copper current collector and an LLZO separator.
  • the present disclosure relates to the assembly of metal batteries, particularly to the bonding of electrodes to solid separators during such battery assembly. In some embodiments, the present disclosure relates to the bonding of lithium meta! electrodes to solid separators during the assembly of lithium metal batteries.
  • a method is di sclosed of bondi ng a conductive substrate to a separator which includes the steps of:
  • an electrolytic cell with a first and a second chamber, a conductive substrate as a negative electrode, disposed in the first chamber, a positive electrode, disposed in the second chamber, a source of ions of a metal, disposed in the second chamber, and a separator separating the first chamber and the second chamber, the separator configured to allow traversal of the ions of the metal from the second chamber to the first chamber;
  • the layer of metal is electrodeposited to a thickness of between about 0.5 ⁇ m and about 40 ⁇ m.
  • the layer of metal may be electrodeposi ted at a temperature of less than about 90 °C.
  • One or both of the conductive substrate and the separator may be coated with a layer of coating material that enhances the ability of the layer of metal to penetrate into one or both of the conductive substrate and or the separator prior to electrodepositing the layer of metal.
  • the layer of coating material is selected from the group consisting of Si, SiO 2 , Zn, ZnO, AI 2 O 3 , Ga, Sr, Ag, and combinations thereof.
  • the layer of coating material may have a thickness of between about 50 nm and about 1 ⁇ m.
  • the layer of coating material may be deposited by a method selected from the group consisting of pulsed laser deposition (PLD), evaporation, and spin coating.
  • PLD pulsed laser deposition
  • evaporation evaporation
  • spin coating evaporation
  • the bonded conductive substrate and separator may be treated with one or both of heat and pressure.
  • the method further includes a step wherein the bonded conductive substrate and separator are cleaned to remove manufacturing residue.
  • the electrodeposited metal is selected from the group consisting of an alkali metal, alkaline earth metal, aluminum, and combinations thereof.
  • the metal may be electrodeposited as an alloy.
  • the electrodeposited metal may include lithium.
  • the conductive substrate is selected from the group consisting of copper, nickel, stainless steel, and metal alloys.
  • the separator includes a material selected from the group consi sti ng o f a polymer, a sul fide, an oxi de, an d combi nation s thereof.
  • the second chamber includes an aqueous solution in contact with the separator, and the separator inhibits the passage of water from the second chamber to the first chamber.
  • the method further includes the step of incorporating the bonded assembly of the conductive substrate and the separator into an electrochemical device.
  • the separator includes a materia! selected from the group consisting of a polymeric matrix, a sulfide, an oxide, and combinations thereof.
  • the separator includes an organogel and a lithium salt.
  • the organogel may include a polymeric matrix selected from the group consisting of polyethyleneoxide and a polyimide.
  • the organogel may include an ether solvent.
  • the ether solvent may include dimethoxyethane and the lithium salt may be selected from the group consisting of lithium bis(tluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, and combinations thereof.
  • the separator includes a sulfide having the formula LU- where x ⁇ 0.5.
  • the separator includes a garnet type oxide selected from the group consisting of LLZO, tantalum-doped and sodium (Na) Super Ionic Conductors (Nasicons).
  • the conductive substrate comprises copper
  • the separator comprises LLZO or LLZTO.
  • Embodiments of the method may be used to manufacture a bonded assembly of a conductive substrate and a separator manufactured according to the method of claim 1.
  • the bonded assembly may include copper and the separator may include LLZO or LLZTO.
  • the bonded assembly thus manufactured may be incorporated as a negative electrode into a battery.
  • Fi g. 1 provides a method of electrochemically welding a current collector to a separator, The resulting welded assembly can be used directly in an electrochemical cell.
  • Fig. 2 embodies an electrolytic cell with an electro lytical ly welded assembly according to the present application, wherein an electrochemical weld 60 secures a conductive substrate 40 to a separator 30.
  • Fig. 3 embodies an electrolytic cell with an electro lytieally welded assembly according to the present application, wherein an electrochemical weld 60 secures a conductive substrate 40 to a separator 30, wherein the metal ions M z " that are reduced to form the weld are present in a brine, and wherein an aqueous protective separator 70 prevents water from the brine from penetrating through to the electrochemical weld 60.
  • Fig. 4 embodies an electrolytic cell with an electro lytieally welded assembly according to the present application, wherein an electrochemical weld 60 secures a conductive substrate 40 to a separator 30, wherein a positive electrode 50 is in direct contact with the separator 30, and wherein the positive electrode functions as an anode to provide the source of the metal ions M' : " that are reduced to form the weld.
  • F ig. 5 embodies an electrolytic cell according to Fig. 2 for which the surface of the conductive substrate 40 and/or the surface of the separator 30 are coated with a layer of coating material 80a, 80b.
  • Fig. 6 embodies an electrolytic ceil according to Fig. 3 for which the surface of the conducti ve substrate 40 and/or the surface of the separator 30 are coated wi th a layer of coating material 80a, 80b.
  • Fig. 7 embodies an electrolytic cell according to Fig. 4 for which the surface of the conductive substrate 40 and/or the surface of the separator 30 are coated with a layer of coating material 80a, 80b.
  • a range should be considered to have specifically disclosed ail the possible subranges as well as individual numerical values within that range.
  • description of a range such as from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example. 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
  • the term “about” a number refers to that number plus or minus 10% of that number.
  • the term “about” a range refers to that range minus 10% of its lowest value and plus 10% of its greatest value.
  • a “cathode” is an electrode where reduction occurs.
  • An “anode” is an electrode where oxidation occurs.
  • a “working anode” is the anode in a galvanic cell.
  • a “positive electrode” is the anode in an electrolytic cell, and the cathode in a galvanic cell.
  • a “negative electrode” is the cathode in an electrolytic cell and the anode in a galvanic cell. Consequently, a lithium metal electrode is always a “negative electrode” even though it is a cathode in an electrolytic cell and an anode in a galvanic cell.
  • a “conductive substrate” is a metallic or other material that is able to conduct electrons when placed in an electrochemical cell.
  • a “current collector” is synonymous with a “conductive substrate,”
  • a “separator” is a material that separates a conductive substrate from a source of metal ions and is configured to allow traversal of the metal ions from the source of metal ions to a surface of the conductive substrate.
  • An “electrochemical weld” is a bonding connection between a conductive substrate and a separator that is formed as metal ions traverse the separator, contact a surface of the conductive substrate, and are electrochemically reduced to form a layer of metal between the surface of the conductive substrate and the separator.
  • close proximity includes a range from about 0 to about 40 ⁇ m.
  • a “brine” is synonymous with an “aqueous salt solution.”
  • LiPON Lithium phosphorous oxynitride
  • NNICON refers to a family of solids with high ionic conductivity having a chemical formula of where M’ is selected from Al, Ga, and other irivalent metals and M” is selected from Ti, Ge, Zr, other tetravalent cations, and mixtures thereof.
  • LLZO lithium conductive crystalline solid having the formula
  • LLZTO tantalum -doped LLZO having the formula Li?.
  • the method is for bonding a conductive substrate to a separator.
  • the method comprises (i) providing an electrolytic cell comprising a first and a second chamber, a conductive substrate as a negative electrode disposed in the first chamber, a positi ve electrode disposed in the second chamber, a source of metal ions disposed in the second chamber, and a separator, (ii) applying a voltage across the positive electrode and the conducti ve substrate, thereby causing the ions of the metal to traverse the separator from the second chamber to the first chamber, and to be reduced at a surface of the conductive substrate, thereby electrodepositing a layer of the metal onto the surface of the conductive substrate, and (iii) continuing to apply the voltage and to electrodeposit the metal in such a manner that the layer of metal grows in thickness, contacts the separator, and forms a bond between the conductive substrate and the separator, thereby forming a bonded assembly of the conductive substrate and the separator
  • the separator separates the first chamber and the second chamber. In some embodiments, the separator is configured to allow traversal of the ions of the metal from the second chamber to the first chamber. In some embodiments, one or both of the conductive substrate and the separator are coated with a layer of coating materia! that enhances the ability of the layer of metal to penetrate into one or both of the conductive substrate and the separator prior to electrodepositing the layer of meta!. In some embodiments, the method further comprises incorporating the bonded assembly of the conductive substrate and the separator into an electrochemical device.
  • a current collector and a separator are coated with a coating layer 1.
  • the purpose of applying the coating layer is to improve the adhesive strength of the electrochemical weld between the collector and the separator.
  • the coating layer may maintain the necessary electrical conductivity for the current collector and permit the transport of ions from the electrode to the separator.
  • the coating layer is chemically stable.
  • the coating layer may not introduce un desired side reactions during the battery's operation.
  • the coating layer may be impermeable to the electrolyte but permeable to lithium ions, maintaining the overall ion flow within the battery while preventing any detrimental leaks.
  • the material of the coating layer is selected depending on several factors including but not limited to compatibility with the separator and collector materials, electrical and ionic conductivity, stability over time, and resistance to various environmental and operational stresses.
  • the coating layer comprises material including but not limited to polymers, ceramics, or a certain types of conductive materials.
  • the coating layer comprises material selected from the group consisting of Si, SiCh, Zu, ZnO, AhOs, Ga, Sr, Ag, and combinations thereof. In some embodiments, the coating layer comprises material selected from the group consisting of Si, Al, ZnO, and combinations thereof. In some embodiments, the coating layer comprises Si. In some embodiments, the coating layer comprises Al, In some embodiments, die coating layer comprises ZnO. In some embodiments, the coating material is an alloy.
  • the coating layer has a thickness of between about 2 nm and about 1 urn. Such a coating layer has a thickness that is preferably between about 50 and about 200 nm. In some embodiments, the coating layer has a thickness of at least about 2 nm, 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 run, 170 run, 180 run, 190 nm, 200 nm, 210 nm, 220 nm, 230 nm, 240 nm, 250 nm, 260 nm, 270 nm, 280 nm, 290 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm,
  • the coating layer has a thickness of at most about 2 nm, 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 1 10 nm, 120 nm, 130 nm, 140 nm,150 nm, 160 nm, 170 nm, 180 nm, 190 nm, 200 nm, 210 nm, 220 nm, 230 nm, 240 nm, 250 nm, 260 nm, 270 nm, 280 nm, 290 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950
  • the coaling layer is deposited with electrodeposition, pulsed laser deposition (PLD), physical vapor deposition (PVD), chemical vapor deposition (CVD), by evaporation, or by means of spin coating, spray coating, or dip coating.
  • the coating layer is deposited with pulsed laser deposition (PLD), by evaporation, or by means of spin coating.
  • the coating layer is deposited with pulsed laser deposition (PLD).
  • the coating layer is deposited by evaporation, hi some embodiments, the coating layer is deposit ed by means of spin coating.
  • the coaled current collector and separator are placed in close proximity 3, where close proximity as used herein means at a separation of less than about 40 ⁇ m.
  • a gap between the coated current collector and the separator is about 0 ⁇ m, 0.1 ⁇ m, 0.5 ⁇ m, 1 ⁇ m, 5 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m, 30 ⁇ m, 35 ⁇ m, 40 ⁇ m, 45 ⁇ m, or 50 ⁇ m.
  • a gap between the coated current collector and the separator is al least about 0.1 ⁇ m. 0.5 ⁇ m, 1.
  • a gap between the coated current collector and the separator is at most about 0.1 ⁇ m, 0.5 ⁇ m, 1 ⁇ m, 5 ⁇ m, 1.0 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m, 30 ⁇ m, 35 ⁇ m, 40 ⁇ m, 45 ⁇ m, or 50 ⁇ m.
  • a gap between the coated current collector and the separator is between about 0 ⁇ m and 50 ⁇ m, between about 0.1 ⁇ m and 45 ⁇ m, between about 0.5 ⁇ m and 40 ⁇ m, between about 1 ⁇ m and 35 ⁇ m, between about 5 ⁇ m and 30 ⁇ m, between about 10 ⁇ m and 25 ⁇ m, or between about 15 ⁇ m and 20 ⁇ m,
  • pressure is applied to improve the physical contact between the current collector and the separator and ensure a better connection for electron transport. In that case, the pressure may secure enough contact between the current collector and the separator, not leading to poor electrical connectivity. The pressure does not disrupt the coating layer. In some embodiments, the pressure applied is uniform across the entire interlace between the current collector and the separator. In some embodiments, the properties of the current collector and separator materials, including their hardness and elasticity, may determine how much pressure they can withstand.
  • the amount of pressure applied in bringing the current collector and the separator into close proximity is less than about 1 megapascal (MPa), preferably less than about 200 kilopascal (kPa), less than about 100 kPa, less than about 50 kPa.
  • MPa megapascal
  • kPa kilopascal
  • the pressure applied in bringing the current collector and the separator into close proximity is al least about 0.5 kPa, 1 kPa, 5 kPa, 10 kPa, 15 kPa, 20 kPa, 25 kPa, 30 kPa, 35 kPa, 40 kPa, 45 kPa, 50 kPa, 55 kPa, 60 kPa, 65 kPa, 70 kPa, 75 kPa, 80 kPa, 85 kPa, 90 kPa, 95 kPa, 100 kPa, 110 kPa, 120 kPa, 130 kPa, 140 kPa, 150 kPa, 160 kPa, 170 kPa, 180 kPa, 190 kPa, 200 kPa, 500 kPa, or 1000 kPa.
  • the pressure applied in bringing the current collector and the separator into close proximity is at most about 0.5 kPa, 1 kPa, 5 kPa, 10 kPa, 15 kPa, 20 kPa, 25 kPa, 30 kPa, 35 kPa, 40 kPa, 45 kPa, 50 kPa, 55 kPa, 60 kPa, 65 kPa, 70 kPa, 75 kPa, 80 kPa, 85 kPa, 90 kPa, 95 kPa, 100 kPa, 1 10 kPa, 120 kPa, 130 kPa, 140 kPa, 150 kPa, 160 kPa, 170 kPa, 180 kPa, 190 kPa, 200 kPa, 500 kPa, or 1000 kPa.
  • the current collector and separator are situated as a combined part, in close proximity to each other, in an electrolytic cell 5.
  • the separator is configured to allow passage of metal ions from a source of metal ions, and acts to separate the current collector from the source of metal ions, so that the metal ions pass through the separator in order to reach a surface of the current collector.
  • metal ions traverse the separator and are reduced at the surface of the current collector, electrodepositing a weld layer of meta! between the current collector and the separator 7.
  • the weld layer attaches to surfaces of the current collector and the separator, thereby forming an adhesive bond between the surfaces.
  • the applied current is between about 1 mA cm' and 100 mA/cnr. In some embodiments, the applied current is at least about 1 mA/cm 2 , 5 mA/cm 2 , 10 mA/cm 2 , 15 niA/cnr, 20 mA/cm 2 , 25 mA cm 2 , 30 mA/cnr, 35 mA/cnr, 40 mA/cm 2 .
  • the applied current is at most about 1 mA/cnr, 5 mA/cm 2 .
  • the applied current is about 10 mA cm 2 In some embodiemnts, the applied current is about 30 mA cm 2 . In some embodiemnts, the applied current is about 50 mA/cm 2 , In some embodiemnts, the applied current is about 70 mA/cm 2 . In some embodiemnts, the applied current is about 90 mA/cnr.
  • the weld layer continues to grow until it reaches a desired thickness 9.
  • the desired thickness of the weld layer is between about 0,5 ⁇ m and about 40 ⁇ m, between about 5 ⁇ m and about 25 ⁇ m, between about 2 ⁇ m and about 20 ⁇ m, between about 5 ⁇ m and about 10 ⁇ m, or between about 20 ⁇ m and about 30 ⁇ m.
  • the thickness of the weld layer is at least about 0.1 ⁇ m, 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 12 ⁇ m, 14 ⁇ m, 16 ⁇ m, 18 ⁇ m, 20 ⁇ m, 22 ⁇ m, 24 ⁇ m, 26 ⁇ m, 28 ⁇ m, 30 ⁇ m, 32 ⁇ m, 34 ⁇ m, 36 ⁇ m, 38 ⁇ m, 40 ⁇ m, 42 ⁇ m, 44 ⁇ m, 46 ⁇ m, 48 ⁇ m, or 50 ⁇ m.
  • the thickness of the weld layer is at most about 0.1 ⁇ m, 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 12 ⁇ m, 14 ⁇ m, 16 ⁇ m, 18 ⁇ m, 20 ⁇ m, 22 ⁇ m, 24 ⁇ m, 26 ⁇ m, 28 ⁇ m, 30 ⁇ m, 32 ⁇ m, 34 ⁇ m, 36 ⁇ m, 38 ⁇ m, 40 ⁇ m, 42 ⁇ m, 44 ⁇ m, 46 ⁇ m, 48 ⁇ m, or 50 ⁇ m.
  • the layer of metal is electrodeposited at a temperature of less than about 90 °C. In some embodiments, the weld layer is electrodeposited at a temperature between about 0 °C and about 200 °C, between about 15 °C and about 90 °C, or between about 15 °C and about 50 °C. In some embodiments, the weld layer is electrodeposited at a temperature of at least about 0 °C, 5 °C, 10 °C, 15 °C, 20 °C, 25 °C, 30 °C, 35 °C, 40 °C, 45 °C, 50 A/ 55 °C, 60 °C, 65 C.
  • the weld layer is electrodeposited at a temperature of at most about 0 °C, 5 °C, 10 °C, 15 °C, 20 °C, 25 °C, 30 °C,
  • the welded assembly is removed for use in an electrochemical device 11.
  • the electrochemical device incorporates the welded assembly as an electrode.
  • the electrochemical device is a rechargeable battery.
  • the electrochemical device is a lithi ⁇ m meta! battery.
  • the welded assembly may be further treated with temperature and. or pressure in order to strengthen the bond betw een the current collector and the separator, prior to use in an electrochemical device.
  • the treatment with temperature and/or pressure is performed for temperatures between about 100 C C and about 300 °C and pressures between about 100 kPa and about 5 MPa,
  • the temperature is at least about 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, 160 °C, 170 °C, 180 °C, 190 °C, 200 °C, 210 °C, 220 °C, 230 °C, 240 °C, 250 °C, 260 °C, 270 °C, 280 °C, 290 °C, 300 °C, 310 °C, or 320 °C.
  • the temperature is at most about 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, 160 °C, 170 °C, 180 °C, 190 °C, 200 °C, 210 "C, 220 °C, 230 °C, 240 °C, 250 °C, 260 °C, 270 °C, 280 °C, 290 °C, 300 °C, 310 °C, or 320 °C.
  • the pressure is at least about 80 kPa, 85 kPa, 90 kPa, 95 kPa, 100 kPa, 110 kPa, 120 kPa, 130 kPa, 140 kPa, 150 kPa, 160 kPa, 170 kPa, 180 kPa, 190 kPa, 200 kPa, 500 kPa, 1000 kPa, 2000 kPa, 3000 kPa, 4000 kPa, 5000 kPa, 6000 kPa, or 7000 kPa.
  • the pressure is at most about 80 kPa, 85 kPa, 90 kPa, 95 kPa, 100 kPa, 1 10 kPa, 120 kPa, 130 kPa, 140 kPa, 150 kPa, 160 kPa, 170 kPa, 180 kPa, 190 kPa, 200 kPa, 500 kPa, 1000 kPa, 2000 kPa, 3000 kPa, 4000 kPa, 5000 kPa, 6000 kPa, or 7000 kPa.
  • the welded assembly is cleaned with a cleaning agent to remove manufacturing residue prior to use in an electrochemical device.
  • the cleaning agent includes, but is not limited to, ethanol, hexane, and xylene.
  • the welded assembly is rinsed with wthylene carbonate or other battery solvents.
  • Figs. 2 through 7 provide embodiments of electrolytic cells for performing the above-described methods.
  • the electrolytic cell includes two chambers, a first chamber 10 separated from a second chamber 20 by a separator 30.
  • the first chamber includes a conductive substrate 40 functioning as a cathode.
  • the second chamber 20 includes a positive electrode 50 and a source of metal ions 25.
  • the electrolytic cell is configured so that upon application of a voltage V the metal ions flow from the second chamber 20 and pass through the separator 30 into the first chamber 10.
  • the metal ion is selected from the group consisting of one or more alkali metal ions, Al ", and combinations thereof.
  • the metal ion is Li"'.
  • the metal ion is Na".
  • the metal ion is A1 J *.
  • the metal ions M z " are derived from the positive electrode 50.
  • the source of metal ions is an aqueous source.
  • the aqueous source is brine.
  • the aqueous source comprises a geological resource.
  • the metal is selected from the group consisting of an alkali metal, alkaline earth metal, al ⁇ min ⁇ m, and combinations thereof. In some embodiments, the metal is lithi ⁇ m,
  • the metal is electrodeposited. In some embodiments, the metal is electrodeposited as an alloy.
  • the current collector comprises a metal current collector or a carbon current collector.
  • the current collector is a metal current collector.
  • the metal current collector comprises titani ⁇ m (Ti), al ⁇ min ⁇ m (Al), magnesi ⁇ m (Mg), zinc (Zn), tin (Sn), or any metal that is capable of forming an ahoy with lithi ⁇ m
  • the current collector comprises vanadi ⁇ m oxide ( V 2 O 5 ).
  • the current collector comprises metal oxide.
  • the current collector is a carbon current collector.
  • the carbon current collector comprises graphite.
  • the metal current collector comprises copper, al ⁇ min ⁇ m, graphite-coated copper, nickel, silicon, silver, carbon (e.g., rough-surface carbon, graphene), a lithophilic material, al ⁇ min ⁇ m, gold, a copper alloy (Cu-Zn, Cu-AI, Cu-Sn), or any combination thereof.
  • the conductive substrate is selected from the group consisting of copper, nickel, stainless steel, and meta! alloys. In some embodiments, the conductive substrate comprises copper. In some embodiments, the conductive substrate comprises nickel. In some embodiments, the conductive substrate comprises stainless steel.
  • a width of the electrode comprises at least about 50 mm, 60 mm, 70 mm, 80 mm, 90 mm, 100 mm, 1 10 mm, 120 mm, 130 mm, 140 mm, 150 mm, 160 mm, 170 mm, 180 mm, 190 mm, 200 mm, 210 mm.
  • a width of the electrode comprises at most about 50 mm, 60 mm, 70 mm, 80 mm, 90 mm, 100 mm, 1 10 mm, 120 mm, 130 mm, 140 mm, 150 mm, 160 mm, 170 mm, 180 mm, 190 mm, 200 mm, 210 mm, 220 mm, 230 mm, 240 mm, 250 mm, 260 mm, 270 mm, 280 mm, 290 mm, 300 mm, 310 mm, 320 mm, 330 mm, 340 mm, 350 mm, 360 mm, 370 mm, 380 mm, 390 mm, 400 mm, 410 mm, 420 mm, 430 mm, 440 mm, 450 mm, 460 mm, 470 mm, 480 mm, 490 mm, 500 mm, 510 mm, 520 mm, 530 mm, 540 mm, 550 mm, 560 mm
  • a length of the electrode compri ses at least about 50 mm, 100 mm, 200 mm, 300 mm, 400 mm, 500 mm, 600 mm, 700 mm, 800 mm, 900 mm, 1000 mm, 2000 mm, 3000 mm, 4000 mm, or 5000 mm.
  • a length of the electrode comprises at most about 50 mm, 100 mm, 200 mm, 300 mm, 400 mm, 500 mm, 600 mm, 700 mm, 800 mm, 900 mm, 1000 mm, 2000 mm, 3000 mm, 4000 mm, or 5000 mm,
  • the applied voltage is between about 0.1 V and about 10 V. In some embodiments, the applied voltage is at least about 0, 1 V, 0,5 V, 1 V, 1.5 V, 2 V, 2,5 V, 3 V, 3.5 V, 4 V, 4.5 V, 5 V, 5.5 V, 6 V, 6.5 V, 7 V, 7.5 V, 8 V, 8.5 V, 9 V, 9.5 V, or 10 V.
  • the applied voltage is at most about 0,1 V, 0.5 V, 1 V, 1.5 V, 2 V, 2.5 V, 3 V, 3,5 V, 4 V, 4.5 V, 5 V, 5.5 V, 6 V, 6,5 V, 7 V, 7.5 V, 8 V, 8.5 V, 9 V, 9.5 V, or 10 V.
  • the applied voltage is about 1 V.
  • the applied voltage is about 3 V.
  • the applied voltage is about 4.5 V.
  • the applied voltage is about 6.5 V.
  • the applied voltage is about 8 V.
  • the applied voltage is about 9.5 V,
  • the source of metal ions M z * is a brine (i.e. an aqueous salt solution).
  • a brine provides the source of metal ions
  • an aqueous protective layer 70 can be provided to prevent water flow through the separator 30.
  • the aqueous protective layer 70 is configured to allow the flow of metal ions from the first chamber through the protective layer 70, and through the separator into the first chamber, where they are reduced to metallic form, thereby growing a weld layer 60 within the first chamber 10 between the conductive substrate 40 and the separator 30.
  • the source of metal ions is the positive electrode 50, the positive electrode 50 being in direct physical contact with a surface of die separator.
  • the surface of the separator may be polished.
  • the second chamber includes an aqueous solution in contact with the separator.
  • the separator inhibits the passage of water from the second chamber to the first chamber.
  • the conductive substrate 40 comprises a material selected from the group consisting of copper, nickel, and stainless steel, In some embodiments, the conductive substrate 40 comprises an alloy, hi some embodiments, the conductive substrate 40 comprises copper. In some embodiments, the conductive substrate 40 comprises nickel, In some embodiments, the conductive substrate 40 comprises stainless steel.
  • the separator 30 comprises a material selected from the group consisting of a polymer, a sulfide, an oxide, and combinations thereof.
  • the separator comprises a polymer having monomers chosen from the group consisting of oxyalkenes, methacrylates, poly(oxyalkene) methacrylates, dimethyl sulfoxides, and combinations thereof.
  • methacrylate monomers are chosen from the group consisting of alkyl methacrylates, poly(oxy alkene) methacrylates, and combinations thereof.
  • the alkyl methacrylates are laurel methacrylates.
  • the poly(oxyalkene) methacrylates are poly(oxyethylene) methacrylates.
  • the separator comprises an organogel, a lithi ⁇ m salt, or a combination thereof.
  • the organogel comprises a polymeric matrix selected from the group consisting of polyethyleneoxide and a polyimide.
  • the organogel comprises an ether solvent.
  • the ether solvent is dimethoxyethane.
  • the lithi ⁇ m salt is selected from the group consisting of lithium bis(fluorosulfonyl)imide, lithi ⁇ m bis(trilluoromethariesulfonyl)imide, and combinations thereof
  • the separator 30 includes a sulfide. In some embodiments the separator 30 comprises a sulfide chosen from the group consisting of combinations of 0.75. In some embodiments, the sulfide in the separator 30 has the formula l..h ; -x wher . In a preferred embodiment, the sulfide included in the separator
  • the oxide included in the separator 30 is chosen from the group consisting o ), nasicons. and lithi ⁇ m phosphorous oxynitride (LiPON).
  • the conductive substrate comprises copper
  • the separator comprises LLZO or LLZTO.
  • T he electrolytic cells of Figs. 5-7 provide embodiments for which a coating layer is present on the conductive substrate 80a and/or on the separator 80b, in order to improve the permeability of the electrodeposi ted metal forming the weld layer 60. thereby leading to improved adhesive strength.
  • the coating layer on the conductive substrate 80a is disposed between the conductive substrate 40 and the weld layer 60.
  • the coating layer on the separator 80b is disposed between the separator 30 and the weld layer 60.
  • the permeability of the electrodeposi ted metal can be monitored by Scanning Electron Microscopy (SEM) combined with one or more of Energy-Dispersive X-ray spectroscopy (EDS), X-ray photon spectroscopy (XPS), and Electron Energy Loss Spectroscopy (EELS).
  • SEM Scanning Electron Microscopy
  • EDS Energy-Dispersive X-ray spectroscopy
  • XPS X-ray photon spectroscopy
  • EELS Electron Energy Loss Spectroscopy
  • the adhesive strength can be monitored by mechanical tests including scratch tests and peel tests.
  • the coating layer 80a, 80b inc ludes material selected from the group consisting of , and combinations thereof.
  • the coating layer 80a, 80b is an alloy.
  • the coating layer 80a, 80b is deposited by a method selected from the group consisting of pulsed laser deposition (PLD), evaporation, and spin coating. In some embodiments the thickness of the coating layer 80a, 80b is between 50 nm and 1 gm.
  • Embodiment I A method of bonding a conductive substrate to a separator comprising the steps of: providing an electrolytic cell with: a first and a second chamber, the conductive substrate as a negative electrode, disposed in the first chamber, a positive electrode, disposed in the second chamber.
  • a source of ions of a metal disposed in the second chamber, and the separator separating the first chamber and the second chamber, the separator configured to allow traversal of the ions of the metal from the second chamber to the first chamber; applying a voltage across the positive electrode and the conductive substrate, thereby causing the ions of the metal to traverse the separator from the second chamber to the first chamber, and to be reduced at a surface of the conductive substrate, thereby electrodepositing a layer of the metal onto the surface of the conductive substrate; continuing to apply the voltage and to electrodeposit the metal in such a manner that the layer of metal grow s in thickness, contacts the separator, and forms a bond between the conductive substrate and the separator, thereby forming a bonded assembly of the conductive substrate and the separator, wherein one or both of the conductive substrate and the separator are coated with a layer of coating material that enhances the ability 7 of the layer of metal to penetrate into one or both of the conductive substrate and the separator prior to electrodepositing the layer of metal.
  • Embodiment 3 The method of embodiment 1 , wherein the layer of coating material is selected from the group consisting of Si, SiCh, Zn, ZnO, AhOs, Ga, Sr, Ag, and combinations thereof
  • Embodiment 4 The method of embodiment 1, wherein the layer of coating material has a thickness of between about 50 nm and about 1 ⁇ m.
  • Embodiment 5 The method of any of embodiments 1 to 4, wherein the layer of metal is electrodeposited at a temperature of less than about 90 °C.
  • Embodiment 6 The method of any of embodiments 1 to 5, wherein the layer of meta! is electrodeposited to a thickness of between about 0.5 ⁇ m and about 40 ⁇ m.
  • Embodimen t 7 The method of any of embodiments 1 to 6, further comprising a step wherein the bonded conductive substrate and separator are treated with one or both of heat and pressure.
  • Embodiment 8 Th e method of any of embodi ments 1 to 7, further comprisin g a step wherein the bonded conductive substrate and separator are cleaned to remove manufacturing residue.
  • Embodiment 9 The method of any of embodiments 1 to 8, wherein the electrodeposited meta! is selected from the group consisting of an alkali metal, alkaline earth metal, al ⁇ min ⁇ m, and combinations thereof.
  • Embodiment 10 The method of any of embodiments 1 to 9. wherein, the metal is electrodeposited as an alloy.
  • Embodiment 1 1 The method of any of embodiments 1 to 10, wherein the electrodeposi ted metal is lithi ⁇ m.
  • Embodiment 12 The method of any of embodiments 1 to 1 1 , wherein the conductive substrate is selected from the group consisting of copper, nickel, stainless steel, and meta! alloys.
  • Embodiment 13 The method of any of embodiments 1 to 12, wherein the separator comprises a material selected from the group consisting of a polymer, a sul fide, an oxide, and combinations thereof.
  • Embodiment 14 The method of any of embodiments 1 to 13, wherein the second chamber includes an aqueous solution in contact with the separator, and wherein the separator inhibits the passage of water from the second chamber to the first chamber.
  • Embodiment 15 The method of any of embodiments 1 to 14. further including the step of incorporating the bonded assembly of the conductive substrate and the separator into an electrochemical device.
  • Embodiment 16 The method of any of embodiments 1 to 15, wherein the separator comprises a material selected from the group consisting of a polymeric matrix, a sulfide, an oxide, and combinations thereof.
  • Embodiment 17 The method of any one of embodiments 1 to 15, wherein the separator includes an organogel and a lithi ⁇ m salt.
  • Embodimen t 18 The method of embodiment 1.7, wherei n the organogel comprises a polymeric matrix selected from the group consisting of polyethyleneoxide and a poly imide.
  • Embodiment 19 The method of embodimen t 17 or embodiment 18, wherein the organogel includes an ether solvent.
  • Embodiment 20 The method of embodiment 19, wherein the ether solvent is dimethoxyethane and the lithi ⁇ m salt is selected from the group consisting of lithi ⁇ m bis(fluorosulfony])imide, lithi ⁇ m bis(trif1uoromethanesulfonyl)imide, and combinations thereof.
  • Embodiment 21 The method of any one of embodiments 1 to 15, wherein the separator includes a sulfide having the formula
  • Embodiment 22 The method of any one of embodiments 1 to 15. wherein the separator includes a garnet type oxide selected from the group consisting of LLZO, LLZTO, and NASICONs.
  • the separator includes a garnet type oxide selected from the group consisting of LLZO, LLZTO, and NASICONs.
  • Embodiment 23 The method of any one of embodiments! to 15, wherein the conductive substrate comprises copper, and the separator comprises LLZO or LLZTO.
  • Embodimen t 24 The bonded assembly of a conductive substrate and a separator manufactured according to the method of any of embodiments 1 to 23.
  • Embodiment 25 The bonded assembly according to embodiment 24, wherein the conductive substrate comprises copper and the separator comprises LLZO or LLZTO.
  • Embodiment 26 An electrochemical device that incorporates the bonded assembly of embodiment 24 as an electrode.
  • Embodiment 27 An electrochemical device according to embodiment 26, the electrochemical device comprising a rechargeable battery.

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Abstract

Procédé électrolytique de fabrication d'un ensemble lié d'un substrat conducteur et d'un séparateur destiné à être utilisé en tant qu'électrode négative. Le substrat et le séparateur sont placés à proximité étroite et liés ensemble au moyen d'un métal électrodéposé tel que le lithium, d'autres métaux alcalins ou l'aluminium. L'électrodéposition se produit par un processus électrolytique dans lequel une tension appliquée à travers le substrat conducteur et une électrode positive amène des ions du métal à traverser le substrat conducteur et un dépôt électrolytique entre des surfaces du substrat conducteur et du séparateur, formant ainsi une "soudure" électrochimique maintenant ensemble le substrat conducteur et le séparateur en tant qu'ensemble lié.
PCT/US2024/014498 2023-02-06 2024-02-05 Soudage électrochimique d'un collecteur de courant à un séparateur dans un dispositif électrochimique Ceased WO2024167863A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210218055A1 (en) * 2020-01-15 2021-07-15 Polyplus Battery Company Methods and materials for protection of sulfide glass solid electrolytes
US20220069282A1 (en) * 2020-08-28 2022-03-03 Pure Lithium Corporation Lithium Metal Anode and Battery
US20220416325A1 (en) * 2021-06-25 2022-12-29 Ascend Elements, Inc. RECYCLING ALL SOLID-STATE BATTERIES (ASSBs) AND ANODE RECOVERY

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210218055A1 (en) * 2020-01-15 2021-07-15 Polyplus Battery Company Methods and materials for protection of sulfide glass solid electrolytes
US20220069282A1 (en) * 2020-08-28 2022-03-03 Pure Lithium Corporation Lithium Metal Anode and Battery
US20220416325A1 (en) * 2021-06-25 2022-12-29 Ascend Elements, Inc. RECYCLING ALL SOLID-STATE BATTERIES (ASSBs) AND ANODE RECOVERY

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