Indium oxide coated current collector

Abstract

Methods for forming current collectors and batteries, and vehicles incorporating such current collectors and batteries, are provided. One method for forming a current collector includes providing a current collector material and forming indium oxide on the current collector material.

Description

Introduction

[0001] The technical field generally relates to rechargeable electrochemical devices. In particular, aspects of this disclosure relate to current collectors and methods for manufacturing current collectors for forming lithium batteries.

[0002] High-energy-density electrochemical cells, such as lithium-ion batteries, can be used in a wide variety of consumer products and vehicles, including hybrid electric vehicles (HEVs) and electric vehicles (EVs). Typical lithium-ion and lithium-sulfur batteries include a primary electrode, a secondary electrode, an electrolyte, and a separator. One electrode serves as the positive electrode or cathode, and the other serves as the negative electrode or anode. A stack of battery cells can be electrically connected to increase overall power. Conventional rechargeable lithium-ion batteries operate by reversibly transferring lithium ions back and forth between the negative and positive electrodes. A separator and electrolyte may be placed between the negative and positive electrodes.The electrolyte is suitable for conducting lithium ions and can be in solid (e.g., solid-state diffusion) or liquid form. During charging, lithium ions move from a cathode (positive electrode) to an anode (negative electrode), and during discharging, they move in the opposite direction.

[0003] Many different materials can be used to create components for a lithium-ion battery. Common negative electrode materials include lithium insertion materials or alloy host materials, such as carbon-based materials like lithium-graphite intercalation compounds or lithium-silicon compounds, lithium-tin alloys, and lithium titanates. When the negative electrode is made of metallic lithium, the electrochemical cell is considered a lithium-metal battery or cell. Metallic lithium for use in the negative electrode of a rechargeable battery has several potential advantages, including the highest theoretical capacity and the lowest electrochemical potential.Thus, batteries containing lithium-metal anodes can have a higher energy density, potentially doubling the storage capacity, allowing the battery to be half the size while still providing the same runtime as other lithium-ion batteries. This makes lithium-metal batteries one of the most promising candidates for high-energy storage systems. However, lithium-metal batteries also have potential drawbacks, including potentially unreliable or reduced performance and the potential for premature failure of electrochemical cells.

[0004] For example, performance degradation of the negative lithium electrodes can be caused by the growth of branch-like or fibrous metal structures called dendrites on the negative electrode when the lithium metal is recharged. The metal dendrites can form sharp protrusions that potentially pierce the separator and cause an internal short circuit, which can lead to self-discharge of the cell or cell failure due to thermal runaway.

[0005] Accordingly, it would be desirable to develop reliable, high-performance lithium-containing negative electrode materials for use in high-energy electrochemical cells that reduce or suppress the formation of lithium metal dendrites. Furthermore, other desirable features and properties of the present disclosure will become apparent from the following detailed description and the attached claims in conjunction with the attached drawings and the preceding introduction. Summary

[0006] In one embodiment, a method for forming a current collector is provided. The method includes providing a current collector material and forming indium oxide on the current collector material.

[0007] In certain embodiments of the process, the formation of indium oxide on the current collector material involves forming indium on the current collector material; and converting the indium into the indium oxide.

[0008] In certain embodiments of the process, the formation of indium on the current collector material involves electrochemical deposition of the indium on the current collector material.

[0009] In certain embodiments of the process, the conversion of the indium to the indium oxide involves annealing the indium in the presence of oxygen.

[0010] In certain embodiments of the process, the conversion of the indium to the indium oxide involves annealing the indium in the presence of air.

[0011] In certain embodiments of the process, the tempering of the indium in the presence of air involves carrying out a tempering process at a temperature of at least 250°C.

[0012] In certain embodiments, the method further includes controlling the thickness of the indium on the current collector material while the indium is being formed on the current collector material.

[0013] In certain embodiments of the method, the thickness ranges from 25 nanometers (nm) to 1 micrometer (µm).

[0014] In certain embodiments, the process further includes controlling the thickness of the indium oxide while the indium is converted into the indium oxide.

[0015] In certain embodiments of the process, some of the indium remains on the current collector material after the indium has been converted into indium oxide.

[0016] In certain embodiments, the process also includes the formation of lithium on the indium oxide.

[0017] In certain embodiments, the process further includes forming lithium on the indium oxide, which involves electroplating the lithium onto the indium oxide.

[0018] In certain embodiments of the process, the formation of lithium on the indium oxide involves rolling the lithium onto the indium oxide.

[0019] In certain embodiments of the method, the current collector material consists of copper.

[0020] In another embodiment, a method for manufacturing a battery is provided. The method includes forming an anode current collector by forming indium oxide on copper and forming a layer of lithium on the indium oxide; separating the anode current collector from a cathode current collector with a separator; and contacting the anode current collector and the cathode current collector with an electrolyte.

[0021] In certain embodiments of the process, the formation of the indium oxide on the copper involves electrochemical deposition of indium on the copper.

[0022] In certain embodiments of the process, the formation of the indium oxide on the copper involves annealing the indium in the presence of oxygen to convert the indium into the indium oxide.

[0023] In certain embodiments, the process further includes controlling the thickness of the indium on the copper while the indium is electrochemically deposited on the copper; and controlling the thickness of the indium oxide while the indium is converted into the indium oxide.

[0024] In another embodiment, a vehicle is provided with a rechargeable energy storage system (RESS) comprising an electric drive motor; and a battery pack operationally connected to the electric drive motor. The battery pack includes a lithium-ion battery. The lithium-ion battery comprises an anode current collector comprising a copper current collector material, a layer of indium oxide over the copper current collector material, and a layer of lithium on the indium oxide layer, the indium oxide layer being configured to inhibit the growth of lithium dendrites during the charge and discharge cycles of the lithium-ion battery; a cathode current collector; a porous separator between the anode current collector and the cathode current collector; and an electrolyte in contact with the cathode current collector.

[0025] In certain embodiments of the vehicle, the anode current collector also includes indium between the layer of indium oxide and the copper current collector material. Brief description of the drawings

[0026] The present disclosure is described below in conjunction with the following drawing figures, where the same reference numerals denote the same elements and where: Fig. 1 a schematic representation of a representative vehicle with an electrified powertrain according to aspects of the disclosed concepts; Fig. 2 a schematic representation of a representative electrochemical device in the vehicle of Fig. 1 is, which operates according to aspects of the present revelation; Fig. 3 is a flowchart that presents a process for manufacturing a current collector and for manufacturing a battery according to aspects of the present disclosure; Fig. 4 is a schematic representation depicting the electrolytic deposition of indium on a current collector according to aspects of the present disclosure; and Fig. 5-8 schematic cross-sectional views of a current collector during processing after electrolytic deposition of indium according to aspects of the present disclosure. Detailed description

[0027] The following detailed description is merely exemplary and is not intended to limit the application and uses of embodiments herein. Furthermore, there is no intention to be bound by any expressed or implied theory presented in the preceding introduction, summary, or the following detailed description. As used herein, the term "module" refers to any hardware, software, firmware, electronic control unit or component, processing logic, and / or processor device, individually or in any combination, including, without limitation: application-specific integrated circuits (ASICs), electronic circuits, processors (shared, dedicated, or grouped), and memory executing one or more software or firmware programs, combinational logic circuits, and / or other suitable components providing the described functionality.

[0028] Embodiments of the present disclosure can be described herein with respect to functional and / or logical block components and various processing steps. It is understood that such block components can be implemented by any number of hardware, software, and / or firmware components configured to perform the specified functions. For example, an embodiment of the present disclosure may employ various integrated circuit components, such as memory elements, digital signal processing elements, logic elements, lookup tables, or the like, which can perform a variety of functions under the control of one or more microprocessors or other control devices.Furthermore, the person skilled in the art will recognize that embodiments of the present disclosure can be implemented in conjunction with any number of automated drive systems, including cruise control systems, automated driver assistance systems and autonomous drive systems, and that the vehicle system described herein is merely an exemplary embodiment of the present disclosure.

[0029] Finally, for the sake of brevity, conventional techniques and components relating to mechanical vehicle parts and other functional aspects of the system (and the individual operating components of the system) may not be described in detail herein. Furthermore, the connecting lines shown in the various figures contained herein are intended to represent exemplary functional relationships and / or physical couplings between the various elements. It should be noted that many alternative or additional functional relationships or physical connections may exist in an embodiment. It is also understood that the figures are for illustrative purposes only and may not be drawn to scale.

[0030] Additionally, the following description refers to elements or features that are "connected" or "coupled" to one another. As used herein, "connected" may refer to an element / feature that is directly connected to (or communicates directly with) another element / feature, and not necessarily mechanically. Likewise, "coupled" may refer to an element / feature that is directly or indirectly connected to (or communicates directly or indirectly with) another element / feature, and not necessarily mechanically. It is understood, however, that although two elements may be described below as "connected" in one embodiment, in alternative embodiments similar elements may be "coupled" and vice versa.Thus, although the schematic diagrams shown herein represent exemplary arrangements of elements, additional intermediate elements, devices, features or components may be present in an actual embodiment.

[0031] An exemplary battery, a method for making a current collector or electrode, and a method for making a battery are provided.

[0032] Dendrites formed by three-dimensional lithium growth on current collectors are undesirable. It has been found that a high lithium nucleation overpotential primarily contributes to the formation of dendrites or, in general, large-surface-area lithium deposits. The embodiments described herein reduce the lithium nucleation overpotential.

[0033] In certain embodiments, a lithiophilic coating is formed on a copper current collector to inhibit the growth of lithium dendrites on the copper current collector. For example, certain embodiments form a layer of indium oxide on the copper current collector. These embodiments form indium oxide without the use of expensive high-vacuum techniques.

[0034] Certain embodiments first form a layer of indium on the current collector, for example, through an electroplating or electrodeposition process. Then, at least some of the indium is converted to indium oxide. For example, a annealing process can be carried out in an oxygen-containing environment. Certain embodiments involve forming a layer of lithium on the indium oxide before arranging the battery components and during the charging and discharging cycles of the lithium-ion battery.

[0035] In certain embodiments, an indium oxide (In₂O₃) current collector coating leads to a reduced lithium nucleation overpotential, which in turn results in uniform lithium deposition, less dendritic lithium growth, and improved capacity retention. Thus, a cost-effective and scalable process for coating the current collector surface with an indium oxide lithiumophilic coating is provided.

[0036] With reference to Fig. Figure 1 represents certain characteristics of a vehicle 10 in the form of a functional block diagram. In certain examples, the vehicle 10 comprises an automobile. In other examples, the vehicle 10 can be any one of a number of different types of automobiles, such as a sedan, a station wagon, a truck, or an SUV, and in certain examples, it can be two-wheel drive (2WD) (that is, rear-wheel drive or front-wheel drive), four-wheel drive (4WD), or all-wheel drive (AWD), and / or various other types of vehicles or mobile platforms.

[0037] The depicted vehicle 10 is merely an exemplary application with which novel aspects of this disclosure can be implemented. Likewise, the incorporation of the present concepts into a purely electric vehicle powertrain should also be considered a non-restrictive implementation of disclosed features. Thus, it is understood that aspects and features of this disclosure can be applied to other powertrain architectures, implemented for any logically relevant type of vehicle, and used with both DC- and AC-based EV charging stations. Furthermore, only selected components of the motor vehicles and battery systems are shown and described in additional detail herein.Nevertheless, the vehicles and vehicle systems discussed below may include numerous additional and alternative features and other available peripheral components for performing the various procedures and functions of this disclosure.

[0038] As in Fig. As shown in Figure 1, the exemplary vehicle 10 generally comprises a body 14 and wheels 16. The body 14 essentially encloses components of the vehicle 10. The wheels 16 are rotatably coupled to the vehicle 10 near each corner of the body 14.

[0039] The representative vehicle 10 of Fig. 1 can be equipped with an electrified powertrain capable of generating traction torque and delivering it to one or more of the vehicle's road wheels 16. The powertrain is in Fig. 1 is generally represented by a rechargeable energy storage system (RESS), which may be in the form of a chassis-mounted traction battery pack 70 operationally connected to an electric drive motor 40. The traction battery pack 70 generally consists of one or more battery modules 72, each comprising a stack of battery cells 110, such as lithium-ion, lithium-polymer, or nickel-metal hydride battery cells of the pouch, can, or prismatic type. One or more electric machines, such as drive motor / generator units 40, draw electrical power from the battery pack 70 of the RESS and optionally supply electrical power to it. A dedicated power inverter module (PIM) can electrically connect the battery pack 70 to the motor / generator unit(s) 40 and modulate this transfer of electrical current between them.

[0040] The battery pack 70 can be configured so that module management, including cell sensing, thermal management, and module-to-host communication functionality, is integrated directly into each battery module 72 and performed wirelessly via a wirelessly enabled cell monitoring unit (CMU). The CMU can be a microcontroller-based sensor array mounted on a printed circuit board (PCB). Each CMU can include a GPS transceiver and RF capabilities and can be located on or within a battery module housing. The battery module cells 110, the CMU, the housing, coolant lines, busbars, etc., together define the module assembly.

[0041] In Fig. Figure 2 shows an exemplary electrochemical device in the form of a rechargeable battery 110, which supplies a desired electrical load, such as the automobile 10. Fig. 1, is powered and offers fast-charging capabilities, such as DCFC. The battery 110 includes a pair of electrically conductive electrodes, namely a first (negative or anode) working electrode 122 and a second (positive or cathode) working electrode 124, which are housed within a protective outer casing 120. In at least some configurations, the battery casing 120 can be a pouch-like bag formed from aluminum foil or another suitable sheet material. Both sides of a metallic bag can be coated with a polymer coating to insulate the metal from the internal cell elements and from adjacent cells, if any.Alternatively, the battery casing (or “cell casing”) 120 can assume a cylindrical metal can configuration, that is, for cylindrical battery cell configurations, or a polyhedral metal box configuration, that is, for prismatic battery cell configurations. Referring to either the working electrode 122, 124 as the “anode” or “cathode,” or in this context as “positive” or “negative,” does not restrict the electrodes 122, 124 to a specific polarity, since the system polarity may change depending on whether the battery 110 is operating in a charging mode or a discharging mode. Although… Fig. 2 represents a single battery cell unit that is inserted into the battery housing 120, it is understood that the housing 120 can accommodate a stack of several cell units (for example, five to five thousand cells or more).

[0042] With further reference to Fig. 2. The anode electrode 122 can be manufactured with an active anode electrode material capable of containing ions during a battery charging process and releasing ions during a battery discharging process. In at least some implementations, the anode electrode 122 is manufactured wholly or partially from a lithium metal, such as lithium-aluminum (LiAl) alloy materials with a Li / Al atomic ratio in the range of 0 at.% ≤ Li / Al < 70 at.% and / or aluminum alloys with an Al atomic ratio > 50 at.% (for example, lithium metal is melted). Additional examples of suitable active anode electrode materials include carbon-containing materials (for example, graphite, hard carbon, soft carbon, etc.), silicon, silicon-carbon composites (silicon-graphite composites), and Li₄Ti₅O₄. 12, transition metals (alloy types, for example Sn), metal oxides / sulfides (for example SnO2, FeS and the like) and so on.

[0043] Within the battery housing 120, between the two electrodes 122 and 124, a porous separator 126 is arranged, which may be in the form of a microporous or nanoporous polymer separator. The porous separator 126 may contain a non-aqueous liquid electrolyte composition and / or a solid electrolyte composition, collectively designated 130, which may also be present in the negative electrode 122 and the positive electrode 124.

[0044] The negative electrode 122 may include or be provided with a negative electrode current collector 132, which is positioned on or near the active anode electrode material. The positive electrode 124 may include or be provided with a positive electrode current collector 134, which is positioned on or near the active cathode electrode material.

[0045] The negative electrode current collector 132 and the positive electrode current collector 134 collect and move free electrons to and from an external circuit 140, respectively. An interruptible external circuit 140 with a load 142 is connected to the negative electrode 122 via its respective current collector 132 and electrode strip 136, and to the positive electrode 124 via its respective current collector 134 and electrode strip 138. The current collectors 132 and 134 can be made of aluminum, copper, or another suitable material. The separator 126 can be a plate-like structure consisting of a porous polyolefin membrane, for example, with a porosity of about 35% to 65% and a thickness of about 25–30 micrometers. Electrically non-conductive ceramic particles (for example, silicon dioxide) can be coated onto the porous membrane surfaces of the separators 126.

[0046] The porous separator 126 can function as both an electrical insulator and a mechanical support structure by being positioned between the two electrodes 122, 124 to prevent the electrodes from physically touching each other and thus preventing a short circuit. In addition to providing a physical barrier between the electrodes 122, 124, the porous separator 126 can provide a minimal resistance path for the internal passage of ions (and related anions) during ion cycling to facilitate the operation of the battery 110. For some optional configurations, the porous separator 126 can be a microporous polymer separator incorporating a polyolefin. The polyolefin can be a homopolymer derived from a single monomer component or a heteropolymer derived from more than one monomer component and can be either linear or branched.In a solid-state battery, the role of the separator can be partially / completely provided by a solid electrolyte layer.

[0047] The battery 110, operating as a rechargeable energy storage system (RESS), generates electrical current that is transferred to one or more loads 142 connected to the external circuit 140. While the load 142 can be any number of electrically powered devices, some non-restrictive examples of power-consuming load devices include an electric motor for a hybrid or fully electric vehicle, a laptop or tablet computer, a cellular smartphone, cordless power tools and devices, portable power stations, and so on. The battery 110 can incorporate a variety of other components which, although not shown here for the sake of simplicity and brevity, are readily available.For example, the battery 110 may include one or more seals, terminal caps, strips, battery connectors, and other commercially available components or materials that may be located on or inside the battery 110. Furthermore, the size, shape, and operating characteristics of the battery 110 may vary depending on the specific application for which it is designed.

[0048] The cathode electrode 124 can be manufactured with an active cathode electrode material capable of supplying ions during a battery charging process and containing ions during a battery discharging process. The cathode material 124 can, for example, include lithium transition metal oxide, phosphate, or silicate, such as LiMO₂ (M = Co, Ni, Mn, or combinations thereof); LiM₂O₄ (M = Mn, Ti, or combinations thereof); LiMPO₄ (M = Fe, Mn, Co, or combinations thereof); and LiM x M' 2-xO4 (M, M' = Mn or Ni). Additional examples of suitable active cathode electrode materials include lithium nickel cobalt manganese oxide (NCM), lithium nickel cobalt aluminum oxide (NCA), lithium nickel cobalt manganese aluminum oxide (NCMA), and other lithium transition metal oxides. In embodiments herein, the second (positive or cathode) working electrode 124 may also include an ultraconductive additive, carbon black, and a binder material.

[0049] Embodiments described herein provide a coating for the copper anode current collector 132 to inhibit the growth of lithium dendrites during the charging and discharging cycles of the lithium-ion battery 110. In certain embodiments, an indium oxide coating is formed on the copper current collector 132. Fig. 3- Fig. 8 describe a process for forming a current collector, such as the anode current collector 132.

[0050] Fig. Figure 3 is a flowchart illustrating a process 300 for forming a coating on the anode current collector 132 and for making a battery.

[0051] As in Fig. As shown in Figure 3, method 300 involves providing a current collector material at action block 305. In certain embodiments, the current collector material is copper. The current collector material may comprise a non-porous metal foil, a perforated metal sheet, a porous metal mesh, or a porous open-cell metal foam.

[0052] At action block 310, process 300 involves the formation of indium oxide (In₂O₃) on the current collector material. As shown, action block 310 can include a process of indium formation on the current collector material at action block 311. For example, action block 311 can involve the electrochemical deposition of indium on the current collector material, such as in an electroplating bath.

[0053] Furthermore, action block 310 can include a process at action block 312 for controlling the thickness of the indium deposited on the current collector material during the indium deposition process. The thickness of the indium deposited on the current collector material can be controlled by controlling the voltage, current, and deposition time / rate of the electroplating process.

[0054] In certain embodiments, the thickness of the indium formed on the current collector material is 25 nanometers (nm) to 1000 nm (i.e., 1 micrometer (µm)). For example, the thickness of the indium can be at least 25 mm, such as at least 50 mm, at least 75 mm, at least 100 nm, at least 150 nm, at least 200 nm, at least 250 nm, at least 300 nm, at least 350 nm, at least 400 nm, at least 450 nm, at least 500 nm, at least 550 nm, at least 600 nm, at least 650 nm, at least 700 nm, at least 750 nm, at least 800 nm, at least 850 nm, at least 900 nm, or at least 950 nm.Furthermore, the thickness of the indium can be at most 50 nm, such as at most 75 nm, at most 100 nm, at most 125 nm, at most 150 nm, at most 200 nm, at most 250 nm, at most 300 nm, at most 350 nm, at most 400 nm, at most 450 nm, at most 500 nm, at most 550 nm, at most 600 nm, at most 650 nm, at most 700 nm, at most 750 nm, at most 800 nm, at most 850 nm, at most 900 nm, at most 950 nm or at most 1000 nm.

[0055] As shown, action block 310 can involve a process of converting indium to indium oxide at action block 313. For example, action block 313 can involve annealing the indium in the presence of oxygen, such as air.

[0056] Furthermore, action block 310 at action block 314 can include a process for controlling the thickness of the indium oxide during the conversion of indium to indium oxide. The thickness of the indium oxide formed can be controlled by controlling the annealing temperature and time.

[0057] In certain embodiments, the tempering process is carried out at a temperature of at least 250°C. For example, the tempering process can be carried out at a temperature of at least 250°C, such as at least 300°C, at least 350°C, at least 400°C, at least 425°C, at least 450°C, at least 475°C, or at least 500°C. Furthermore, the tempering process can be carried out at a temperature of at most 275°C, such as at most 300°C, at most 325°C, at most 350°C, at most 375°C, at most 400°C, at most 425°C, at most 450°C, at most 475°C, at most 500°C, or at most 525°C.

[0058] In certain embodiments, the tempering process is carried out by increasing the temperature at a ramp rate of at least 1°C per minute, such as at least 2°C per minute, at least 3°C ​​per minute, at least 4°C per minute, at least 5°C per minute, at least 8°C per minute, or at least 10°C per minute. In certain embodiments, the ramp rate is at most 1°C per minute, such as at most 2°C per minute, at most 3°C ​​per minute, at most 4°C per minute, at most 5°C per minute, at most 8°C per minute, or at most 10°C per minute.

[0059] In certain embodiments, the tempering process is carried out for at least 20 minutes, such as at least 30 minutes, at least 40 minutes, at least 50 minutes, at least 60 minutes, at least 70 minutes, at least 80 minutes, at least 90 minutes, at least 100 minutes, at least 110 minutes, at least 120 minutes, at least 130 minutes, at least 140 minutes, or at least 150 minutes. In certain embodiments, the tempering process is carried out for at most 30 minutes, such as at most 40 minutes, at most 50 minutes, at most 60 minutes, at most 70 minutes, at most 80 minutes, at most 90 minutes, at most 100 minutes, at most 110 minutes, at most 120 minutes, at most 130 minutes, at most 140 minutes, at most 150 minutes, or at most 160 minutes.

[0060] In certain embodiments, all of the indium is converted to indium oxide. In other embodiments, some of the indium is converted to indium oxide, and a remaining portion of the indium stays on the current collector, such as between the indium oxide and the current collector.

[0061] As in Fig. As shown in Figure 3, the process 300 further includes forming lithium on the indium oxide at the action block 320. For example, the action block may include electroplating the lithium onto the indium oxide, rolling the lithium onto the indium oxide, molten wetting of the lithium onto the indium oxide, physical or chemical vapor deposition of lithium onto the indium oxide, or forming the lithium onto the indium oxide in another suitable way.

[0062] At action block 330, process 300 can produce an anode current collector from the current collector material.

[0063] To manufacture a battery, the method 300 can further include, at action block 340, the separation of the anode current collector, which is formed with a layer of lithium over an indium oxide layer, from a cathode current collector by means of a separator. For example, the current collectors and the active anode and cathode materials can be arranged with a separator between them, as in Fig. 2 shown.

[0064] The process 300 can proceed with contacting the anode current collector and the cathode current collector with an electrolyte on the action block 350. As a result, a battery is formed, as shown in Fig. 2 shown.

[0065] The procedure 300 can then involve performing a cycle of charging and discharging processes at action block 360. Afterward, the procedure 300 can involve operating a device, such as vehicle 10, with power from the battery.

[0066] Fig. Figure 4 is a schematic representation depicting the electroplating process of method 300. As shown, an electroplating bath 400 is formed in a tank 410. The bath 400 can be any electrolyte solution capable of transporting indium ions, for example, a solution of soluble indium salts, such as an indium sulfamate plating bath 400. The tank 410 can be located in an external heating / cooling bath 420.

[0067] In Fig. 4 An indium source 430, such as an indium plate or an indium ingot, is located in the electroplating bath 400. The embodiment of Fig. The three-electrode system comprises a working electrode 440, a reference electrode 450, and a counter electrode 460, all located in the electroplating bath 400. In this three-electrode electroplating system, the current is measured as a function of the applied voltage between the working electrode 440, where the deposition takes place, and the reference electrode 450, which maintains a constant potential and allows for precise monitoring of the working electrode potential. The counter electrode 460 completes the circuit by conducting the necessary current to balance the reactions at the working electrode 440. Essentially, the system enables precise control of the potential at the working electrode 440, while the resulting current flow is measured during the deposition process.

[0068] The deposition process can be carried out in a three-electrode cell, as shown, or in a two-electrode cell. Solid indium 430 can be used as the anode. 3+ -ions are supplied, and the current collector material 500 acts as a cathode, supplying electrons so that the following reaction can proceed: In 3+ +3e - → In, E 0 = -0.34V / NHE (normal hydrogen electrode)

[0069] As shown, the conductive collector material 500 is located in the electroplating bath 400 and is electrically connected to the working electrode 440. The conductive collector material 500 can be a non-porous metal foil, a perforated metal sheet, a porous metal mesh, or a porous open-cell metal foam. In certain embodiments, the conductive collector material 500 is copper.

[0070] An electric current is applied through the electrodes to the electroplating bath 400, as described above, to deposit a layer of indium 510 onto the conductive collector material 500. In particular, In 3+ -Cations 520 from bath 400 reduced and coated onto the conductive collector material 500.

[0071] Once the desired thickness of indium 510 has been formed on the conductive collector material 500, the conductive collector material 500 is removed from the electroplating bath 400. A cleaning process can be carried out, such as rinsing the conductive collector material 500 in deionized water for one to two minutes.

[0072] Fig. 5- Fig. Figure 7 shows cross-sectional views of a portion of the current collector material positioned in a 600°C heat chamber after the electroplating process during successive stages of the tempering process. Fig. 5- Fig. 7. To represent the part with a circular cross-section, the drawing format serves only for clarity and simplicity and is not restrictive.

[0073] In Fig. In step 5, the current collector material 500, coated with a layer of indium 510, is located in a heating chamber 600, such as an oven. A tempering process is carried out in an oxygen-containing atmosphere, such as air, as described above in relation to step 300.

[0074] Fig. Figure 6 represents a successive stage of the tempering process, which can be an intermediate or a final stage. As shown, the tempering process causes oxidation of the indium 510 and forms a layer of indium oxide 530.

[0075] In certain embodiments, when indium is reacted to form indium oxide, there may be no or only minimal physical growth. Any change in volume may be small or negligible because the oxygen atoms are relatively small compared to the indium atoms and integrate into the existing crystal lattice structure.

[0076] In certain embodiments, a remaining portion of the indium 510 is located between the indium oxide 530 and the copper current collector material 500 after the tempering process is complete, as shown in Fig. 6 shown. In other embodiments and as in Fig. As shown in Figure 7, the tempering process can continue until all the indium 510 has been converted into indium oxide 530. In both embodiments, a processed current collector material 550 with an outer layer of indium oxide 530 is formed.

[0077] As in Fig. As shown in Figure 8, after the tempering process is complete, the processed current collector material 550 is removed from the heating chamber 600 and allowed to cool. Then, lithium 580 is formed on the indium oxide 530. For example, lithium 580 can be electroplated onto the indium oxide 530, rolled onto the indium oxide 530, or formed on the indium oxide in another suitable manner. Thus, a finished current collector material 590 with an outer layer of lithium 580 is formed. In certain embodiments, the finished current collector material 590 is then assembled into the anode current collector 132. Fig. 2 manufactured. In other embodiments, the finished current collector material 590 may already be in the form of the current collector 132. In both cases, the current collector 132 may be positioned on a battery 110, as described in relation to Fig. 2 described.

[0078] Thus, as described herein, a cost-effective scalable electrochemical deposition (ECD) process and an open-air annealing process are provided for modifying the surface of current collectors with indium oxide lithiophilic coatings to prevent lithium delamination from current collectors, reduce lithium nucleation overpotential, minimize lithium dendrite growth, and improve capacity retention in lithium / copper cells and anode-free cells.

[0079] While at least one exemplary embodiment has been presented in the preceding summary and detailed description, it is understood that a large number of variations exist. It is also understood that the exemplary embodiment or embodiments are merely examples and are not intended to limit the scope, applicability, or configuration of this disclosure in any way. Rather, the preceding summary and detailed description provides the person skilled in the art with a suitable plan for implementing the exemplary embodiment or embodiments. It is understood that various modifications to the function and arrangement of elements can be made without deviating from the scope of the disclosure as set out in the appended claims and their legal equivalents.

Claims

[1] Method for forming a current collector, comprising: Providing a power collector material; and Formation of indium oxide on the current collector material. [2] The method of claim 1, wherein the formation of indium oxide on the current collector material comprises: Formation of indium on the current collector material; and Conversion of indium to indium oxide. [3] Method according to claim 2, wherein the formation of indium on the current collector material comprises electrochemical deposition of the indium on the current collector material. [4] Method according to claim 3, wherein the conversion of the indium to the indium oxide comprises tempering the indium in the presence of oxygen. [5] Method according to claim 4, wherein the conversion of the indium to the indium oxide comprises tempering the indium in the presence of air. [6] Method according to claim 5, wherein the tempering of the indium in the presence of air comprises carrying out a tempering process at a temperature of at least 250°C. [7] Method according to claim 2, further comprising: Controlling the thickness of the indium on the current collector material while the indium is being formed on the current collector material; and Controlling the thickness of the indium oxide while the indium is converted into the indium oxide. [8] The method of claim 1, further comprising forming lithium on the indium oxide. [9] Vehicle equipped with a rechargeable energy storage system (RESS), comprising: an electric drive motor; and a battery pack that is operationally connected to the electric drive motor, wherein the battery pack comprises a lithium-ion battery, comprising: an anode current collector comprising a copper current collector material, a layer of indium oxide over the copper current collector material and a layer of lithium on the layer of indium oxide, wherein the layer of indium oxide is configured to attenuate the growth of lithium dendrites during charge and discharge cycles of the lithium-ion battery; a cathode current collector; a porous separator between the anode current collector and the cathode current collector; and an electrolyte in contact with the cathode current collector and the cathode current collector. [10] Vehicle according to claim 9, wherein the anode current collector further comprises indium between the layer of indium oxide and the copper current collector material.

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