Patent Application
20240186591
The subject matter described herein relates generally to battery technology and more specifically to protective mechanisms for a battery cell subjected to low-voltage exposure or zero-voltage exposure.
The high energy density and high current output of metal ion battery cells, such as lithium (Li) ion battery cells, mean that metal ion battery cells may be suitable for a variety of high energy and high power applications. However, a metal ion battery cell may be susceptible to internal morphological deformations caused by parasitic reactions that occur during the charging and discharging of the metal ion battery cell. The development of internal morphological deformations may diminish the capacity and cycle life of the metal ion battery cell. Moreover, some internal morphological deformations, such as the formation of dendrites on the electrodes of the metal ion battery cell, may give rise to significant safety hazards.
Systems, methods, and articles of manufacture, including batteries and battery components, are provided. In some implementations of the current subject matter, there is provided a battery having a low voltage sacrificial electrode. The battery may include: a positive electrode coupled with a positive current collector; a negative electrode coupled with a negative current collector; and a sacrificial electrode coupled with the negative electrode but not the positive electrode, the sacrificial electrode formed from a first material having a lower decomposition voltage than a second material forming the negative current collector such that the sacrificial electrode decomposes instead of the negative current collector while the battery cell is discharged below a minimum voltage of the battery cell.
In some variations, one or more features disclosed herein including the following features can optionally be included in any feasible combination. The negative current collector may include copper (Cu).
In some variations, the sacrificial current collector may include one or more of chromium (Cr), iron (Fe), tin (Sn), lead (Pb), zinc (Zn), aluminum (Al), lithium (Li), lithium (Li) alloy, magnesium aluminum alloy (MgAl), magnesium titanium (MgTi), calcium magnesium (CaMg), lithiated silica oxide, conductive polymer, or conductive polymer composites.
In some variations, the sacrificial electrode may be disposed within a cavity at a center of a jellyroll formed by winding a first layer of material comprising the positive electrode, a second layer of material comprising the negative electrode, and a third layer of material comprising a separator interposed between the first layer of material and the second layer of material.
In some variations, the first material comprising the sacrificial electrode may be coated on a first portion of the second material comprising the negative current collector while a third material comprising the negative electrode is coated on a second portion of the second material comprising the negative current collector.
In some variations, the first material comprising the sacrificial electrode may be mixed with a third material comprising the negative electrode to form a mixture that is coated on the second material comprising the negative current collector.
In some variations, the battery cell may further include: an auxiliary electrode configured to receive metal ions depleted from the sacrificial electrode by the decomposing of the sacrificial electrode.
In some variations, a third material comprising the auxiliary electrode may be coated on a first portion of a fourth material comprising the positive current collector and a fifth material comprising the positive electrode is coated on a second portion of the fourth material comprising the positive current collector.
In some variations, the auxiliary electrode may include one or more of cobalt oxide (CoO), nickel oxide (NiO), copper oxide (CuO), iron oxide, manganese oxide (MnO2), tin oxide (e.g., SnO, SnO2, and/or the like), iron sulfide (FeS), or nickel phosphorus (NiP).
In some variations, the positive electrode may include one or more of high nickel lithium nickel manganese cobalt oxide, doped lithium nickel oxide, doped or pure lithium manganese oxide, lithium iron, vanadium phosphate, doped or pure lithium cobalt oxide (LiCoO2), lithium vanadium oxide, or lithium fluorine.
In some variations, the negative electrode may include one or more of silicon, silicon oxide, graphite, carbon, tin, tin oxide, germanium, nitrates, or lithium titanium oxide.
In some variations, the positive current collector and/or the negative current collector may be formed from a porous material.
In some variations, the porous material includes one or more of an expanded metal foil, a perforated foil, or a composite carbon-based foil.
In some variations, the battery cell may be a prismatic battery cell or a cylindrical battery cell.
In some variations, the battery cell may further include: an electrolyte; a separator interposed between the positive electrode and the negative electrode; a case enclosing the positive electrode coupled with the positive current collector, the negative electrode coupled with the negative current collector, the separator, and the electrolyte; a positive tab coupled with the positive electrode and welded to a header of the battery cell; and a negative tab coupled with the negative electrode and welded to the case.
In some variations, the battery cell may further include a solid electrolyte interphase (SEI) stabilizer.
In some variations, the solid electrolyte interphase (SEI) stabilizer may include a fluorine-based compound.
In some variations, the first material of the sacrificial electrode may be welded on to a surface of the second material of the negative electrode.
In some variations, the first material of the sacrificial electrode may be welded to one or more ends of the second material of the negative electrode.
In some variations, the sacrificial electrode may be formed by spraying the first material onto a first surface of the negative current collector and/or a second surface of a case of the battery cell.
In some variations, the sacrificial electrode may be coupled to the negative electrode by being coupled to a metallic case of the battery cell that is coupled to the negative electrode.
The details of one or more variations of the subject matter described herein are set forth in the accompanying drawings and the description below. Other features and advantages of the subject matter described herein will be apparent from the description and drawings, and from the claims. While certain features of the currently disclosed subject matter are described for illustrative purposes, it should be readily understood that such features are not intended to be limiting. The claims that follow this disclosure are intended to define the scope of the protected subject matter.
The accompanying drawings, which are incorporated in and constitute a part of this specification, show certain aspects of the subject matter disclosed herein and, together with the description, help explain some of the principles associated with the disclosed implementations. In the drawings,
When practical, similar reference numbers denote similar structures, features, or elements.
A metal ion battery cell, such as a lithium (Li) ion battery cell, may be over discharged when the metal ion battery cell is discharged beyond a minimum voltage. Subjecting a conventional metal ion battery cell to an over discharge (or deep discharge) may destabilize the metal ion battery cell. For example, when a conventional metal ion battery cell is discharged to a low-voltage state or a zero-voltage state, the solid electrolyte interphase (SEI) present within the metal ion battery cell may begin to decompose. The solid electrolyte interphase (SEI) may prevent electrolyte decomposition and sustain electrochemical reactions within the metal ion battery cell by enabling the transport of metal ions (e.g., lithium (Li) ions and/or the like) while blocking the transport of electrons and further reaction between the electrolyte and negative electrode. As such, a degraded solid electrolyte interphase (SEI) may contribute to an irreversible capacity loss at the metal ion battery cell. Moreover, a metal ion battery cell with a degraded solid electrolyte interphase (SEI) may exhibit a higher impendence and is thus able to provide less power to its load because more power is being dissipated as heat by the internal resistance of the metal ion battery cell.
Discharging a conventional metal ion battery cell to a low-voltage state or a zero-voltage stage may also cause the negative current collector of the metal ion battery cell to undergo an anodic corrosion, which depletes metal ions from the negative current collector. Metal ions from the negative current collector may dissolve into the electrolyte of the metal ion battery cell, travel through the separator, and accumulate on the positive electrode of the metal ion battery cell. Meanwhile, during a subsequent recharging of the battery cell, the depleted metal ions may again dissolve into the electrolyte before being deposited on the surface of the negative electrode. The resulting change in the internal morphology of the metal ion battery cell, which includes metal dendrites formed by the accumulation of metal ions on the negative electrode, may degrade the capacity of the metal ion battery cell. Moreover, an internal short circuit may develop within the metal ion battery cell when the metal dendrites formed on the surface of the negative electrode puncture the separator and come in contact with the positive electrode of the metal ion battery cell.
Instability at low-voltage or zero-voltage is detrimental for applications in which the metal ion battery cell may be subject to long term storage. For example, even in the absence of active use, the voltage of the metal ion battery cell may diminish due to self-discharge, power consumption by a battery management system, and/or parasitic loads. In other cases, imbalances in a serially connected cluster of metal ion battery cells may inadvertently over discharge one or more of the metal ion battery cells in the cluster. Some measures, such as pre-lithiating the negative electrode of a lithium (Li) ion battery cell, merely counteract the loss of lithium that occurs during the manufacturing process. However, conventional pre-lithiation techniques, such as applying a lithium powder to the surface of the negative electrode, render the negative electrode highly reactive and thus require an inert manufacturing environment (e.g., dry room). Moreover, despite the manufacturing complexity and safety hazards, pre-lithiating the negative electrode of a lithium-ion battery cell does not protect the negative electrode from anodic corrosion when the lithium-ion battery cell is in a low-voltage or a zero-voltage state for an extended period. For example, the lithium-ion battery cell may be pre-lithiated with less than 20% additional lithium in order to compensate for the lithium that is lost during the initial charge and discharge cycle. Pre-lithiating the lithium ion battery cell with more lithium that what could be lost during the first charge and discharge cycle may run the risk of converting the lithium ion battery cell into a lithium metal battery cell. However, pre-lithiating the lithium-ion battery cell with only the lithium that could be lost during the initial charge and discharge cycle leaves the negative current collector unprotected once the residual lithium is consumed. As such, pre-lithiating the lithium ion battery cell alone is not sufficient to protect the negative electrode from corrosion after the initial charge and discharge cycle.
In some implementations of the current subject matter, a metal ion battery cell may include one or more sacrificial electrodes configured to improve the stability of the metal ion battery cell in a low-voltage state or a zero-voltage state. For example, the one or more sacrificial electrodes may be formed from a first material having a lower decomposition voltage than a second material forming the negative current collector of the metal ion battery cell. In one example where the negative current collector of the metal ion battery cell is formed from copper (Cu), the sacrificial electrodes may be formed from one or more of zinc (Zn), aluminum (Al), lithium (Li), a lithium (Li) alloy, an oxide, and/or the like.
In some implementations of the current subject matter, the one or more sacrificial electrodes may be incorporated into the metal ion battery cell by being electrically coupled the negative electrode but not the positive electrode of the metal ion battery cell. For example, the one or more sacrificial electrodes may be coupled with the negative electrode of the metal ion battery cell or a metal case of the metal ion battery cell in cases where the metal case of the metal ion battery cell is coupled with the negative electrode. The sacrificial electrodes may prevent a decomposition of the negative current collector and/or the solid electrolyte interphase (SEI) when the metal ion battery cell is in a low-voltage state or a zero-voltage state. For instance, when the metal ion battery cell is in a low-voltage state or a zero-voltage state, the sacrificial electrodes may decompose instead of the negative current collector and/or the solid electrolyte interphase (SEI), thereby preserving the negative current collector and thus the internal morphology of the metal ion battery cell. Even in cases where the dissolved sacrificial electrodes accumulate on the surface of the positive electrode (during the discharging of the battery cell) or on the surface of the negative electrode (during the recharging of the battery cell), the materials forming the sacrificial electrodes may accumulate more uniformly and are thus resistant to forming dendrites on the surfaces of the electrodes. As such, the sacrificial electrodes may preserve the morphology of the battery cell, thus maintaining the capacity and cycle life of the metal ion battery cell even when the metal ion battery cell is discharged to a low-voltage state or a zero-voltage state such as when the metal ion battery cell is subjected to long term storage.
In some implementations of the current subject matter, the metal ion battery cell may include one or more porous current collectors. For example, the negative current collector and/or the positive current collector of the metal ion battery cell may be formed from a porous material such as an expanded metal foil, a perforated foil, or a composite carbon-based foil (e.g., carbon fiber, graphene, and/or the like). The one or more sacrificial electrodes may be incorporated in the metal ion battery cell in a variety of manner including, for example, by being disposed in a center a cylindrical or flat jellyroll formed by winding the positive electrode, negative electrode, and separator of the metal ion battery cell. Alternatively and/or additionally, the sacrificial electrode may be coated on a negative current collector of the metal ion battery cell. The porosity of the current collectors may reduce diffusion length by several orders of magnitude at least because metal ions from the sacrificial electrodes are able to diffuse across the layers of current collectors and electrodes rather than being forced to diffuse along the length of the current collectors and electrodes.
In some implementations of the current subject matter, the battery cell 100 may include one or more sacrificial electrodes such as, for example, the sacrificial electrode 130. In the example shown in
In some implementations of the current subject matter, the sacrificial electrode 130 may be coupled with the negative electrode 116 of the battery cell 100. Alternatively, as is shown in
Referring to
In some implementations of the current subject matter, the sacrificial electrode 130 may improve the stability of the battery cell 100 in a low-voltage or a zero-voltage state, which may occur when the battery cell 100 is discharged beyond a minimum voltage. For example, the sacrificial electrode 130 may be formed from a first material having a lower decomposition voltage than a second material forming the negative current collector of the battery cell 100. In one example where the negative current collector of the metal ion battery cell is formed from copper (Cu), the sacrificial electrode 130 may be formed from zinc (Zn), aluminum (Al), lithium (Li), a lithium (Li) alloy, an oxide, and/or the like. The sacrificial electrode 130 may also include lithiated silicon (Si), pre-lithiated graphite I, lithium titanate oxide (LTO), lithium tin oxide (LiSnO2), and/or the like.
In some implementations of the current subject matter, the sacrificial electrode 130 may decompose, for example, through oxidation, when the battery cell 100 is in a low-voltage state or a zero-voltage state. The sacrificial electrode 130 may decompose instead of the negative current collector and/or the solid electrolyte interphase (SEI) of the battery cell 100, thus preserving the capacity and cycle life of the battery cell 100 even when the battery cell 100 is discharged to a low-voltage state or a zero-voltage state such as when the battery cell 100 is subjected to long term storage.
Referring again to
In some implementations of the current subject matter, the battery cell 100 may include a primer layer that is permeable to metal ion diffusion. For example, the primer layer may include a polymer capable of absorbing electrolyte in order to provide ionic conductivity for faster diffusion of metal ions from the sacrificial electrode 130. This primer layer may further facilitate the manufacturing of the battery cell 100, particularly where the battery cell 100 includes porous current collectors. For instance, during the coating process in which slurries forming the positive electrode 114 and/or the negative electrode 116 are coated onto the corresponding current collectors, the primer layer may block the pores present in the current collectors and thus prevent the slurries from leaking through the pores during the coating process. The primer layer may also contain one or more protective components or materials configured to respond to excessive voltage, pressure, and/or temperature at the battery cell 100.
Referring again to
In some implementations of the current subject matter, the sacrificial electrode 130 may be formed by spraying the one or more materials (e.g., a metal, metal alloy, and/or the like) forming the sacrificial electrode 130 onto a surface of the negative current collector and/or the interior surface of the case 120 (if the sacrificial electrode 130 is coupled with the negative electrode 116 through the case 120). Metal spraying is a process in which molten metal (or metal alloy) is sprayed onto a surface to form a coating. For example, molten metal (or metal alloy) may be subjected to a blast of compressed air, which has the joint effect of creating tiny droplets of metal and projecting them towards the surface to be coated. The end result is a solid metal coating on the surface of the current collector and/or the interior surface of the case 120. The thickness of the metal coating may depend on the quantity of layers applied. For instance, the sacrificial electrode 130 may be formed by spraying one or more layers of aluminum (Al), which forms a good, hard barrier but may become passive in mildly corrosive conditions, or zinc (Zn), which forms a poor barrier to erosion or mechanical damage will almost always behave sacrificially. In some instances, the sacrificial electrode 130 may be formed by spraying one or more layers of a metal alloy, such as an aluminum-zinc-indium (Al—Zn—In) alloy, which exhibits the respective advantages of aluminum (Al) and zinc (Zn). The alloy may be heavily aluminum-based (e.g., 95% aluminum (Al)) such that the alloy is much less dense than zinc (Zn) (e.g., 40% the density of zinc (Zn). The sacrificial reaction may involve the loss of three electrons as with pure aluminum (Al) but the aluminum-zinc-indium (Al—Zn—In) alloy is much harder than pure aluminum (Al), which is already harder than zinc (Zn). The inclusion of small quantities of zinc (Zn) and indium (In) keeps the alloy sacrificial in the corrosive environment of the battery cell 100 (e.g., in the presence of chloride ions).
In some implementations of the current subject matter, the battery cell 100 may also include one or more sacrificial electrodes, such as the sacrificial electrode 130 disposed in a cavity 135 at a center of the jellyroll 110. The cavity 135 may be formed within the jellyroll 110 by winding the separator 112, the positive electrode 114, and the negative electrode 116. For example, the jellyroll 110 may be formed by winding the separator 112, the positive electrode 114, and the negative electrode 116 around a mandrel. Removing the mandrel then forms the cavity 135 for the insertion of the sacrificial electrode 130. Alternatively, the separator 112, the positive electrode 114, and the negative electrode 116 may be wound around the sacrificial electrode 130.
In some implementations of the current subject matter, the sacrificial electrode 130 may be coupled with the negative electrode 116 of the battery cell 100. For example, in the example shown in
Although not shown in
In some implementations of the current subject matter, the sacrificial electrode 130 may be coupled with the negative electrode 116 of the battery cell 100. In the examples of the jellyroll 110 shown in
Referring now to
In some example embodiments, the second material forming the sacrificial electrode 130 may include one or more metals and/or metal alloys. Examples of the second material include lithium salts and other compounds with a lower decomposition voltage than the metal forming the negative electrode (e.g., lithium (Li), sodium (Na), magnesium (Mg), aluminum (Al), and/or the like). For example, the second material may include one or more of chromium (Cr), iron (Fe), tin (Sn), lead (Pb), aluminum (Al), lithiated silica oxide (e.g., Li2Si2O5, Li2SiO3, LiSiO4, Li2O, Li12Si3, Li13Si4, LiSnO3, and/or the like), magnesium aluminum alloy (MgAl), magnesium titanium (MgTi), calcium magnesium (CaMg), zinc (Zn), and magnesium (Mg) based alloys, and some potential conductive polymers or composites that have low decomposition voltage than Copper (Cu). Examples of conductive polymers include polyacetylene (PA), polyaniline (PANI), polypyrrole (PPy), polythiophene (PTH), poly(para-phenylene) (PPP), poly(phenylenevinylene) (PPV), and polyfuran (PF).
In some implementations of the current subject matter, the current collector 520 may be a porous current collector. That is, the current collector 520 may be a metallic foil (e.g., a copper (Cu) foil, an aluminum (Al) foil, and/or the like) having a plurality of pores, which shorten a diffusion pathway of metal ions (e.g., lithium (Li) ions and/or the like) by at least providing a passageway through the current collector 520. To further illustrate,
Referring to
Nevertheless, the porosity of the current collector 520 may also render the current collector 520 penetrable to other substances including, for example, the slurries forming the electrode material 510. Accordingly, in the example shown in
In some implementations of the current subject matter, the primer layer 530 may further include one or more protective components and/or materials configured to respond to an excessive voltage, pressure, and/or temperature. For example, the primer layer 530 may include a positive temperature coefficient material (e.g., polyethylene (PE) and carbon black, polyvinylidene fluoride (PVDF) and carbon black, an inorganic conductive ceramic (e.g., barium titanium oxide (BaTiO3) and/or the like) and polyethylene (PE)) whose conductivity is inversely proportional to the temperature of the battery cell 100. Alternatively, the primer layer 530 may include a material that responds to an excessive voltage, pressure, and/or temperature by creating a nonconductive gap between the current collector 520 and one or more layers of the electrode material 510. For instance, the primer layer 530 may generate a gas and/or a liquid that further transitions to a gas when exposed to an excessive voltage, pressure, and/or temperature. The gas may generate the nonconductive gap by at least causing a delamination between the electrode material 510 and the current collector 520. Alternatively and/or additionally, the gas and/or the liquid may generate the nonconductive gap by at least decomposing at least a portion of the electrode material 510.
The negative electrode and positive electrode of the battery cell may be formed by punching sheets of electrode material into appropriately shaped and/or sized pieces (702). For instance, sheets of positive electrode material and/or negative electrode material may be punched into appropriately shaped and/or sized pieces using an electrode tab. The negative electrode and the positive electrode of the battery cell may be dried (704). For example, the positive electrode of the battery cell may be dried at 125° C. for 10 hours while the negative electrode of the battery cell may be dried at 140° C. for 10 hours.
A layer of separator may be interposed between the positive electrode and the negative electrode to form a sheet (706). For instance, a layer of separate may be laminated the positive electrode and the negative electrode of the battery cell to form a sheet. The sheet including the separator interposed between the positive electrode and the negative electrode may be wound to form a jellyroll with one or more sacrificial electrodes and/or auxiliary electrodes (708). In some implementations of the current subject matter, the sacrificial electrode may be disposed inside a cavity of the battery cell. For example, the sheet including the separator interposed between the positive electrode and the negative electrode may be wound around a mandrel. The mandrel may be removed from the center of the jellyroll to form the cavity for the insertion of the sacrificial electrode. Alternatively, the sacrificial electrode may be coated on a surface of the negative current collector of the battery cell. For instance, the first material corresponding to the negative electrode and the second material corresponding to the sacrificial electrode be coated alternately onto the surface of the third material corresponding to the negative current collector of the battery cell. Meanwhile, the first material corresponding to the positive electrode and the second material corresponding to the auxiliary electrode may be coated alternately onto the surface of the third material corresponding to the positive current collector of the battery cell. With either configuration, the sacrificial electrode may be coupled with the negative electrode of the battery cell but not the positive electrode of the battery cell such that the sacrificial electrode may decompose to preserve the negative current collector and the solid electrolyte interphase (SEI) at the negative electrode of the battery cell when the battery cell is discharged to a low-voltage state or a zero-voltage state.
The jellyroll may be placed in a case (710). For instance, the flat jellyroll formed in operation 708 may be placed inside a metallic (e.g., aluminum (Al)) case. The jellyroll may be dried inside the case (712). For example, the flat jellyroll inside the case may be dried at 70° C. for 10 hours. The case may be filled with electrolyte and sealed to complete the assembly of the battery cell (714).
The assembled battery cell may be aged (716). For instance, the battery cell formed in operation 714 can be aged for 36 hours. The assembled and aged battery cell may be activated (718). For example, the battery cell may be activated by undergoing a formation process in which the battery cell is subject to a controlled charge and discharge cycle configured to activate the chemical components of the battery cell. This formation process may require the battery cell to be charged by being exposed to a gradually increasing current instead of a constant current such that the buildup of voltage within the battery cell is gradual.
The positive electrode of Sample Cell I may be formed by dissolving a certain quantity of polyvinylidene difluoride (PVDF) in N-methylpyrrolidone (NMP) to prepare an 8% polymer solution. A certain quantity of carbon black may be added to the 8% polymer solution and mixed for 30 minutes at 6500 revolutions-per-minute to form a slurry. A certain quantity of high nickel lithium nickel manganese cobalt oxide may be added the slurry and mixed for 30 minutes at 6500 revolutions-per-minute with additional N-methylpyrrolidone (NMP) added for adjusting the viscosity to achieve a flowable slurry. The flowable slurry may be coated onto an aluminum (Al) foil (e.g., 15-μm aluminum foil) using an automatic coating machine with the first heat zone set to approximately 80° C. and the second heat zone set to approximately 130° ° C. to evaporate the N-methylpyrrolidone (NMP). The positive electrode of Sample Cell I may then be formed by compressing the aluminum (Al) foil coated with the slurry to a target thickness and cutting to a target width (e.g., 56 millimeters). A positive tab may be welded to a mass free zone, for example, at the center of the positive electrode.
The negative electrode of Sample Cell I may be formed by dissolving a certain quantity of binder in deionized water and then a conductive additive is added and mixed for 30 minutes at 6500 revolutions-per-minute. Silicon (Si)/Silica oxide (SiO) and a carbon composite may be added to the resulting solution and mixed for 60 minutes at 6500 revolutions-per-minute. Additional water may be added to adjust the viscosity and form a flowable slurry. The slurry may then be coated on to a copper (Cu) foil (e.g., 9-μm thick copper foil) using an automatic coater. The negative electrode of Sample Cell I may be formed by compressing the copper (Cu) foil coated with the slurry to a target thickness and cutting to a target width (e.g., 58 millimeters). Zinc (Zn) foil (e.g., (˜0.025-millimeter zinc foil) corresponding to the sacrificial electrode may be welded (e.g., by ultrasonic welding) to the header or tail of the mass free zone (or negative current collector Cu foil) of negative electrode depending on the desired configuration of Sample Cell I. One or more negative tabs may be welded to the mass free zone of the negative electrode of Sample Cell I.
The jellyroll of Sample Cell I may be formed by winding the positive electrode, the separator, and the negative electrode using, for example, a winding machine. The jellyroll may be inserted into a case which may be, for example, a metal case, a soft pouch, and/or the like. One of the negative tabs may be welded to the case while the positive tab may be welded to the header of Sample Cell I, for example, by laser welding. The unfinished Sample Cell I may be dried at 80° ° C. for at least 12 hours before the dried Sample Cell I is filled with electrolyte and crimped. Sample Cell I may be aged for 24 hours at room temperature and before undergoing a formation process. For example, the average open circuit voltage (OCV) and impedance of Sample Cell I at 1 kilohertz (KHz) may be ˜0.70 volts and ˜19 milliohms respectively. Sample Cell I may be formed by being charged at C/40 with 300 milliampere hours (mAh) and then to 4.2V at the relatively high rate before being aged for 7 days at room temperature.
Sample Cell I may be tested for its capacity, direct current resistance (DCR), and cycle life before and after zero-voltage exposure. To test Sample Cell I for its capacity and direct current resistance (DCR), Sample Cell I may be rested for 2 hours before being charged at a constant current and constant voltage (CC-CV) at C/5 to 4.4 volts until C/20. Once charged, Sample Cell I may be rested for 10 minutes before being discharged at a constant current (CCD) at C/2 for 5 minutes to approximately 95% state of charge (SOC). A first voltage measurement V1 and current measurement I1 may be made 10 seconds prior to the end of the discharge. Sample Cell I may again be subjected to a constant current discharge (CCD) at C/5 for 1 minute before a second voltage measurement V2 and current measurement I2 may be made 10 seconds into the second discharge. The direct current resistance (DCR) of Sample Cell I at 95% state of charge (SOC) may correspond to DCR95% SOC=|(V2−V1)/(I2−I1)|.
Sample Cell I may again be subjected to a constant current discharge (CCD) at C/2 for 54 minutes to reach approximately a 50% state of charge (SOC). A third voltage measurement V2 and current measurement I3 may be performed 10 seconds prior to the end the discharge. Sample Cell I may be subjected to constant current discharge (CCD) at C/5 for 1 minute before a fourth voltage measurement V4 and current measurement I4 is performed 10 seconds into this discharge. The direct current resistance of Sample Cell I at 50% state of charge (SOC) may correspond to DCR50% SOC=|(V4−V3)/(I4−I3)|.
Sample Cell I may be subjected again to a constant current discharge (CCD) at C/2 for 36 minutes to reach approximately a 20% state of charge (SOC). A fifth voltage measurement V5 and current measurement I5 may be performed 10 seconds prior to the end of this discharge. Sample Cell I may then be subjected to a constant current discharge (CCD) at C/5 for 1 minute before a sixth voltage measurement V6 and current measurement I6 is performed approximately 10 seconds into this discharge. The direct current resistance (DCR) of Sample Cell I at 20% state of charge may correspond to DCR20% SOC=|(V6−V5)/(I6−I5)|. The discharge capacity/energy, coulombic/energy efficiency, and direct current resistance (DCR) of Sample Cell I may be recorded.
The cycle life at 40% depth of discharge (DOD) for Sample Cell I may be determined by the first resting Sample Cell I for 2 hours. Sample Cell I may be charged at a constant current and constant voltage (CC-CV) at C/5 to 4.4 volts until <C/20. The charged Sample Cell I may be subjected to a constant current discharge (CCD) at C/1.5 for 35 minutes to reach a 40% depth of discharge (DOD). At this point, Sample Cell I may again be charged at a constant current at C/2.25 for 65 minutes before being discharged at a constant current. The charging and discharging of Sample Cell I may be repeated until Sample Cell I exhibits an end-of-discharge voltage (EODV) of 2.5 volts. The capacity of Sample Cell I at 20° C. and its direct current resistance (DCR) may be tested every 200 cycles.
The cycle life at 100% depth of discharge (DOD) for Sample Cell I may be determined by the first resting for 2 hours. Sample Cell I may be charged at a constant current and constant voltage (CC-CV) at C/3 to 4.4 volts until <C/20, rested for 10 minutes, discharged at a constant current (CCD) at C/5 to 2.5 volts, and rested for 30 minutes. Sample Cell I may be repeated charged and discharged until Sample Cell I is at 80% capacity.
The response of Sample Cell I to zero-voltage exposure (ZVE) may be determined by measuring the initial 20° C. capacity and direct current resistance (DCR) of Sample Cell I. Sample Cell I may then be discharged at a constant current and constant voltage (CC-CV) at C/5 to 4.4 volts until <C/20, rested for 10 minutes, discharged at a constant current (CCD) at C/5 to 2.5 volts, rested for 30 minutes, discharged at a constant current (CCD) at C/5 to 0 volts, and further discharged 20 ohms while at 0 volts for 7 days. Thereafter, Sample Cell I may be charged at a constant current and constant voltage (CC-CV) to 3.8 volts at C/5 before being rested for 24 hours. The 20° C. capacity and direct current resistance (DCR) of Sample Cell I may be determined at this point. Table 1 below depicts a comparative analysis of the capacity and direct current resistance (DCR) of Sample Cell I before and after zero-voltage exposure (ZVE).
Sample Cell II is a baseline battery cell without a sacrificial electrode to preserve its capacity and cycle life while Sample Cell II is in a low-voltage state or zero-voltage state. The positive electrode of Sample Cell II may in the same manner as the positive electrode of Sample Cell I, which includes dissolving a certain quantity of polyvinylidene difluoride (PVDF) in N-methylpyrrolidone (NMP) to prepare an 8% polymer solution. A certain quantity of carbon black may be added to the 8% polymer solution and mixed for 30 minutes at 6500 revolutions-per-minute to form a slurry. A certain quantity of high nickel lithium nickel manganese cobalt oxide may be added the slurry and mixed for 30 minutes at 6500 revolutions-per-minute with additional N-methylpyrrolidone (NMP) added for adjusting the viscosity to achieve a flowable slurry. The flowable slurry may be coated onto an aluminum (Al) foil (e.g., 15-μm aluminum foil) using an automatic coating machine with the first heat zone set to approximately 80° C. and the second heat zone set to approximately 130° ° C. to evaporate the N-methylpyrrolidone (NMP). The positive electrode of Sample Cell II may then be formed by compressing the aluminum (Al) foil coated with the slurry to a target thickness and cutting to a target width (e.g., 56 millimeters). A positive tab may be welded to a mass free zone, for example, at the center of the positive electrode.
The negative electrode of Sample Cell II may be formed by dissolving a certain quantity of binder in deionized water and then a conductive additive is added and mixed for 30 minutes at 6500 revolutions-per-minute. Silicon (Si)/silica oxide (SiO) and a carbon composite may be added to the resulting solution and mixed for 60 minutes at 6500 revolutions-per-minute. Additional water may be added to adjust the viscosity and form a flowable slurry. The slurry may then be coated on to a copper (Cu) foil (e.g., 9-μm thick copper foil) using an automatic coater. The negative electrode of Sample Cell I may be formed by compressing the copper (Cu) foil coated with the slurry to a target thickness and cutting to a target width (e.g., 58 millimeters). One or more negative tabs may be welded to the mass free zone of the negative electrode of Sample Cell II. As noted, Sample Cell II is a baseline cell that is formed without the sacrificial electrode present in Sample Cell I.
The jellyroll of Sample Cell II may be formed by winding the positive electrode, the separator, and the negative electrode using, for example, a winding machine. The jellyroll may be inserted into a case which may be, for example, a metal case, a soft pouch, and/or the like. One of the negative tabs may be welded to the case while the positive tab may be welded to the header of Sample Cell II, for example, by laser welding. The unfinished Sample Cell II may be dried at 80° C. for at least 12 hours before the dried Sample Cell II is filled with electrolyte and crimped. Sample Cell II may be aged for 24 hours at room temperature and before undergoing a formation process. For example, the open circuit voltage (OCV) and impedance of Sample Cell II at 1 kilohertz may be ˜0.7 volts and ˜19 milliohms respectively. Sample Cell II may be formed by being charged at C/40 with 300 milliampere hours (mAh) before being aged for 7 days at room temperature.
Sample Cell II may be tested for its capacity, direct current resistance (DCR), and cycle life before and after zero-voltage exposure (ZVE) in the same manner as Sample Cell I. Table 2 below depicts a comparative analysis of the capacity and direct current resistance (DCR) of Sample Cell II before and after zero-voltage exposure (ZVE).
The positive electrode of Sample Cell III may be formed in the same manner as the positive electrode of Sample Cell II, which includes dissolving a certain quantity of polyvinylidene difluoride (PVDF) in N-methylpyrrolidone (NMP) to prepare an 8% polymer solution. A certain quantity of carbon black may be added to the 8% polymer solution and mixed for 30 minutes at 6500 revolutions-per-minute to form a slurry. A certain quantity of high nickel lithium nickel manganese cobalt oxide may be added the slurry and mixed for 30 minutes at 6500 revolutions-per-minute with additional N-methylpyrrolidone (NMP) added for adjusting the viscosity to achieve a flowable slurry. The flowable slurry may be coated onto an aluminum (Al) foil (e.g., 15-μm aluminum foil) using an automatic coating machine with the first heat zone set to approximately 80° C. and the second heat zone set to approximately 130° C. to evaporate the N-methylpyrrolidone (NMP). The positive electrode of Sample Cell III may then be formed by compressing the aluminum (Al) foil coated with the slurry to a target thickness and cutting to a target width (e.g., 56 millimeters). A positive tab may be welded to a mass free zone, for example, at the center of the positive electrode.
The negative electrode of Sample Cell III may be formed in the same manner as the negative electrode of Sample Cell II, which includes dissolving a certain quantity of binder in deionized water and then a conductive additive is added and mixed for 30 minutes at 6500 revolutions-per-minute. Silicon (Si)/silica oxide (SiO) and a carbon composite may be added to the resulting solution and mixed for 60 minutes at 6500 revolutions-per-minute. Additional water may be added to adjust the viscosity and form a flowable slurry. The slurry may then be coated on to a copper (Cu) foil (e.g., 9-μm thick copper foil) using an automatic coater. The negative electrode of Sample Cell III may be formed by compressing the copper (Cu) foil coated with the slurry to a target thickness and cutting to a target width (e.g., 58 millimeters).
Sample Cell III may be assembled in the same manner as Sample Cell II. For example, the jellyroll of Sample Cell III may be formed by winding the positive electrode, the separator, and the negative electrode using, for example, a winding machine. The jellyroll may be inserted into a case which may be, for example, a metal case, a soft pouch, and/or the like. One of the negative tabs may be welded to the case while the positive tab may be welded to the header of Sample Cell III, for example, by laser welding. The unfinished Sample Cell III may be dried at 80° C. for at least 12 hours before the dried Sample Cell III is filled with electrolyte and crimped. Sample Cell III may be aged for 24 hours at room temperature and before undergoing a formation process. For example, the open circuit voltage (OCV) and impedance of Sample Cell III at 1 kilohertz (KHz) may be ˜1.1 volts and ˜23 milliohms respectively. Sample Cell III may be formed at 100 milliamps with 300 milliampere hours and charged to 4.2 volts before being aged for 7 days at room temperature.
The positive electrode of Sample Cell IV may be formed in the same manner as the positive electrode of Sample Cell I, which includes dissolving a certain quality of polyvinylidene difluoride (PVDF) in N-methylpyrrolidone (NMP) to prepare an 8% polymer solution. A certain quantity of carbon black may be added to the 8% polymer solution and mixed for 30 minutes at 6500 revolutions-per-minute to form a slurry. A certain quantity of high nickel lithium nickel manganese cobalt oxide may be added the slurry and mixed for 30 minutes at 6500 revolutions-per-minute with additional N-methylpyrrolidone (NMP) added for adjusting the viscosity to achieve a flowable slurry. The flowable slurry may be coated onto an aluminum (Al) foil (e.g., 15-μm aluminum foil) using an automatic coating machine with the first heat zone set to approximately 80° C. and the second heat zone set to approximately 130° C. to evaporate the N-methylpyrrolidone (NMP). The positive electrode of Sample Cell IV may then be formed by compressing the aluminum (Al) foil coated with the slurry to a target thickness and cutting to a target width (e.g., 56 millimeters). A positive tab may be welded to a mass free zone, for example, at the center of the positive electrode.
The negative electrode of Sample Cell IV may be formed in the same manner as the negative electrode of Sample Cell I, which includes dissolving a certain quantity of binder in deionized water and then a conductive additive is added and mixed for 30 minutes at 6500 revolutions-per-minute. Silicon (Si)/silica oxide (SiO) and a carbon composite may be added to the resulting solution and mixed for 60 minutes at 6500 revolutions-per-minute. Additional water may be added to adjust the viscosity and form a flowable slurry. The slurry may then be coated on to a copper (Cu) foil (e.g., 9-μm thick copper foil) using an automatic coater. The negative electrode of Sample Cell IV may be formed by compressing the copper (Cu) foil coated with the slurry to a target thickness and cutting to a target width (e.g., 58 millimeters). A foil of pure zinc (Zn) corresponding to the sacrificial electrode may be welded (e.g., by ultrasonic welding) to the header or tail of the negative electrode depending on the desired configuration of Sample Cell VI. One or more negative tabs may be welded to the mass free zone of the negative electrode of Sample Cell VI.
Sample Cell IV may be assembled in the same manner as Sample Cell I. For example, the jellyroll of Sample Cell IV may be formed by winding the positive electrode, the separator, and the negative electrode using, for example, a winding machine. The jellyroll may be inserted into a case which may be, for example, a metal case, a soft pouch, and/or the like. One of the negative tabs may be welded to the case while the positive tab may be welded to the header of Sample Cell IV, for example, by laser welding. The unfinished Sample Cell IV may be dried at 80° C. for at least 12 hours before the dried Sample Cell IV is filled with electrolyte and crimped. Sample Cell IV may be aged for 24 hours at room temperature and before undergoing a formation process. Referring again to
The positive electrode of Sample Cell V may be formed by dissolving a certain quantity of polyvinylidene difluoride (PVDF) in N-methylpyrrolidone (NMP) to prepare an 8% polymer solution. A certain quantity of carbon black may be added to the 8% polymer solution and mixed for 30 minutes at 6500 revolutions-per-minute to form a slurry. A certain quantity of high nickel lithium nickel manganese cobalt oxide may be added the slurry and mixed for 30 minutes at 6500 revolutions-per-minute with additional N-methylpyrrolidone (NMP) added for adjusting the viscosity to achieve a flowable slurry. The flowable slurry may be coated onto an aluminum (Al) foil (e.g., 15-μm aluminum foil) using an automatic coating machine with the first heat zone set to approximately 80° C. and the second heat zone set to approximately 130° ° C. to evaporate the N-methylpyrrolidone (NMP). The positive electrode of Sample Cell V may then be formed by compressing the aluminum (Al) foil coated with the slurry to a target thickness and cutting to a target width (e.g., 56 millimeters). A positive tab may be welded to a mass free zone, for example, at the center of the positive electrode.
The negative electrode of Sample Cell V may be formed by incorporating a first material having a lower decomposition voltage than a second material of the negative current collector directly into a third material of the negative electrode. The negative electrode of Sample Cell V may be formed by dissolving a certain quantity of binder in deionized water and then a conductive additive is added and mixed for 30 minutes at 6500 revolutions-per-minute. A small amount of Zinc (Zn) powder (e.g., between 1 micrometer and 5 micrometers) (2% in weight in total solid of the negative electrode) may be added to the resulting slurry and mixed at 3000 revolutions-per-minute. Silica (Si)/silica oxide (SiO) and a carbon composite may be added to the zinc (Zn) slurry and mixed for 60 minutes at 6500 revolutions-per-minute to form a flowable slurry with water being added to adjust the viscosity necessary to achieve a smooth coating. The resulting slurry may be coated onto a copper (Cu) foil (e.g., 8-μm thick Cu foil) using an automatic coater. The negative electrode of Sample Cell V may be compressed to a desired thickness and sliced to a target width (e.g., 58 millimeters). One or more negative tabs may be welded to the mass free zone of the negative electrode of Sample Cell V.
The assembly of Sample Cell V includes forming a jellyroll by winding the positive electrode, the separator, and the negative electrode using, for example, a winding machine. The jellyroll may be inserted into a case which may be, for example, a metal case, a soft pouch, and/or the like. One of the negative tabs may be welded to the case while the positive tab may be welded to the header of Sample Cell V, for example, by laser welding. The unfinished Sample Cell V may be dried at 80° ° C. for at least 12 hours before the dried Sample Cell V is filled with electrolyte and crimped. Sample Cell V may be aged for 24 hours at room temperature and before undergoing a formation process. For example, the open circuit voltage (OCV) and impedance of Sample Cell V at 1 KHz may be approximately 0.765 volts and 19 milliohms. Sample Cell V may be formed at C/40 with 300 milliampere hours before being aged for 7 days at room temperature.
The positive electrode of Sample Cell VI may incorporate manganese di-oxide (MnO2) to provide additional protection against the decomposition of the negative current collector when Sample Cell VI undergoes zero-voltage exposure. The positive electrode of Sample Cell VI may be formed by mixing 200 grams of lithium cobalt oxide (LiCoO2) active and 3 grams of JD-600 carbon black into 100 grams of a polyvinylidene difluoride (PVDF) and N-methylpyrrolidone (NMP) binder solution (e.g., an 8% PVDF NMP solution). Manganese di-oxide (MnO2) powder (e.g., 2 grams of MnO2 power) may be added to the resulting slurry and mixed for 30 minutes at 4000 revolutions-per-minute. The viscosity of the slurry may be adjusted by the addition of N-methylpyrrolidone (NMP) before being coated onto an aluminum foil (e.g., 16-μm thick aluminum foil) with a loading of 21 mg/cm2. The solvent may be evaporated using a reverse roll coater before the positive electrode is calendered to a target thickness (e.g., 138 μm) and sliced to desired dimensions (e.g., 56 millimeters wide and 700 millimeters long). A positive tab (e.g., an aluminum (Al) tab) may be welded to a mass free zone, for example, at the center of the positive electrode using an ultrasonic welder.
The negative electrode of Sample Cell VI may be formed by incorporating a first material having a lower decomposition voltage than a second material of the negative current collector directly into a third material of the negative electrode. The negative electrode of Sample Cell VI may be formed by mixing 200 grams of graphite negative active and 3 grams of carbon black into 150 grams of a carboxymethyl cellulose (CMC) water binder solution (e.g., a 1.5% CMC water solution) and then 50 grams of water and 2 grams of zinc (Zn) powder are added and mixed for 30 minutes at 4000 revolutions-per-minute. A suspension solution (e.g., 8 grams of a styrene-butadiene-rubber (SBR) suspension solution with a 48% solid content) may be added to the slurry with the viscosity adjusted by the addition of water if needed. The resulting slurry may be coated onto a copper (Cu) foil (e.g., 8-μm thick copper foil) with a loading of 10 mg/cm2 before being dried using a reverse roll coater to remove the solvent. The negative electrode may be calendered to a target thickness (e.g., 148 μm) and sliced to desired dimensions (e.g., 58 millimeters wide and 650 millimeters long). One or more negative tabs (e.g., one or more nickel (Ni) tabs) may be welded to a mass free zone of the negative electrode.
The assembly of Sample Cell VI includes forming a jellyroll by winding the positive electrode, the separator, and the negative electrode using, for example, a winding machine. The jellyroll may be inserted into a case which may be, for example, a metal case, a soft pouch, and/or the like. One of the negative tabs may be welded to the case while the positive tab may be welded to the header of Sample Cell VI, for example, by laser welding. The unfinished Sample Cell VI may be dried at 80° C. for at least 48 hours before the dried Sample Cell VI is filled with 5.5 grams of electrolyte and crimped. Sample Cell VI may be aged for 24 hours at room temperature and before undergoing a formation process that includes charging Sample Cell VI at C/50 to 4.2 volts, resting for 10 minutes, and discharging Sample Cell VI at C/5 to 3 volts. A scanning electron microscopy (SEM) analysis of the separator, the positive electrode, and the negative electrode of a battery cell may be performed to demonstrate that a sacrificial electrode preserves the negative current collector of the battery cell from anodic corrosion when the battery cell is discharged to a low-voltage state or a zero-voltage state. Table 3 and graph 1100 depicted in
Table 4 and graph 1125 depicted in
Table 5 and graph 1150 depicted in
Table 6 and graph 1175 depicted in
Commercial 3.5 Ah 18650 cells were tested according to the same testing sequence for zero-voltage exposure (ZVE) in Sample Cells I and II.
The cycle life at 100% depth of discharge (DOD) for Sample Cell VII may be determined by the first resting for 2 hours. Sample Cell VII may be charged at a constant current and constant voltage (CC-CV) at C/3 to 4.2 volts until <C/20, rested for 10 minutes, discharged at a constant current (CCD) at C/5 to 2.5 volts, and rested for 30 minutes. Sample Cell VII may be repeated charged and discharged until ˜80% capacity retention.
The response of Sample Cell VII to zero-voltage exposure (ZVE) may be determined by measuring the initial 20° C. capacity and direct current resistance (DCR) of Sample Cell VII. Sample Cell VII may then be discharged at a constant current and constant voltage (CC-CV) at C/5 to 4.2 volts until <C/20, rested for 10 minutes, discharged at a constant current (CCD) at C/5 to 2.5 volts, rested for 30 minutes, discharged at a constant current (CCD) at C/5 to 0 volts, and further discharged 20 ohms while at 0 volts for 7 days. Thereafter, Sample Cell VII may be charged at a constant current and constant voltage (CC-CV) to 3.8 volts at C/5 before being rested for 24 hours. The 20° C. capacity and direct current resistance (DCR) of Sample Cell VII may be determined at this point.
Table 7 below depicts a comparative analysis of the capacity and direct current resistance (DCR) of Sample Cell VII before and after zero-voltage exposure (ZVE).
In the descriptions above and in the claims, phrases such as “at least one of” or “one or more of” may occur followed by a conjunctive list of elements or features. The term “and/or” may also occur in a list of two or more elements or features. Unless otherwise implicitly or explicitly contradicted by the context in which it used, such a phrase is intended to mean any of the listed elements or features individually or any of the recited elements or features in combination with any of the other recited elements or features. For example, the phrases “at least one of A and B;” “one or more of A and B;” and “A and/or B” are each intended to mean “A alone, B alone, or A and B together.” A similar interpretation is also intended for lists including three or more items. For example, the phrases “at least one of A, B, and C;” “one or more of A, B, and C;” and “A, B, and/or C” are each intended to mean “A alone, B alone, C alone, A and B together, A and C together, B and C together, or A and B and C together.” Use of the term “based on,” above and in the claims is intended to mean, “based at least in part on,” such that an unrecited feature or element is also permissible.
The subject matter described herein can be embodied in systems, apparatus, methods, and/or articles depending on the desired configuration. The implementations set forth in the foregoing description do not represent all implementations consistent with the subject matter described herein. Instead, they are merely some examples consistent with aspects related to the described subject matter. Although a few variations have been described in detail above, other modifications or additions are possible. In particular, further features and/or variations can be provided in addition to those set forth herein. For example, the implementations described above can be directed to various combinations and subcombinations of the disclosed features and/or combinations and subcombinations of several further features disclosed above. In addition, the logic flows depicted in the accompanying figures and/or described herein do not necessarily require the particular order shown, or sequential order, to achieve desirable results. Other implementations may be within the scope of the following claims.
This application claims priority to U.S. Provisional Application No. 63/167,570, entitled “LOW VOLTAGE SACRIFICIAL ELECTRODE” and filed on Mar. 29, 2021, U.S. Provisional Application No. 63/279,019, entitled “LOW VOLTAGE SACRIFICIAL ELECTRODE” and filed on Nov. 12, 2021, and U.S. Provisional Application No. 63/284,438, entitled “LOW VOLTAGE SACRIFICIAL ELECTRODE” and filed on Nov. 30, 2021 the disclosures of which are incorporated herein by reference in their entirety.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2021/065097 | 12/23/2021 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 63284438 | Nov 2021 | US | |
| 63279019 | Nov 2021 | US | |
| 63167570 | Mar 2021 | US |
