The present disclosure relates generally to the field of lithium ion batteries and battery modules. More specifically, the present disclosure relates to lithium ion batteries that use lithium titanate oxide (LTO) as the anode active material.
This section is intended to introduce the reader to various aspects of art that may be related to various aspects of the present disclosure, which are described below. This discussion is believed to be helpful in providing the reader with background information to facilitate a better understanding of the various aspects of the present disclosure. Accordingly, it should be understood that these statements are to be read in this light, and not as admissions of prior art.
A vehicle that uses one or more battery systems for providing all or a portion of the motive power for the vehicle can be referred to as an xEV, where the term “xEV” is defined herein to include all of the following vehicles, or any variations or combinations thereof, that use electric power for all or a portion of their vehicular motive force. For example, xEVs include electric vehicles (EVs) that utilize electric power for all motive force. As will be appreciated by those skilled in the art, hybrid electric vehicles (HEVs), also considered xEVs, combine an internal combustion engine propulsion system and a battery-powered electric propulsion system, such as 48 volt or 130 volt systems. The term HEV may include any variation of a hybrid electric vehicle. For example, full hybrid systems (FHEVs) may provide motive and other electrical power to the vehicle using one or more electric motors, using only an internal combustion engine, or using both. In contrast, mild hybrid systems (MHEVs) disable the internal combustion engine when the vehicle is idling and utilize a battery system to continue powering the air conditioning unit, radio, or other electronics, as well as to restart the engine when propulsion is desired. The mild hybrid system may also apply some level of power assist, during acceleration for example, to supplement the internal combustion engine. Mild hybrids are typically 96 V to 130 V and recover braking energy through a belt or crank integrated starter generator. Further, a micro-hybrid electric vehicle (mHEV) also uses a “Stop-Start” system similar to the mild hybrids, but the micro-hybrid systems of a mHEV may or may not supply power assist to the internal combustion engine and operates at a voltage below 60 V. For the purposes of the present discussion, it should be noted that mHEVs typically do not technically use electric power provided directly to the crankshaft or transmission for any portion of the motive force of the vehicle, but an mHEV may still be considered as an xEV since it does use electric power to supplement a vehicle's power needs when the vehicle is idling with internal combustion engine disabled and recovers braking energy through an integrated starter generator. In addition, a plug-in electric vehicle (PEV) is any vehicle that can be charged from an external source of electricity, such as wall sockets, and the energy stored in the rechargeable battery packs drives or contributes to drive the wheels. PEVs are a subcategory of EVs that include all-electric or battery electric vehicles (BEVs), plug-in hybrid electric vehicles (PHEVs), and electric vehicle conversions of hybrid electric vehicles and conventional internal combustion engine vehicles.
xEVs as described above may provide a number of advantages as compared to more traditional gas-powered vehicles using only internal combustion engines and traditional electrical systems, which are typically 12 V systems powered by a lead acid battery. For example, xEVs may produce fewer undesirable emission products and may exhibit greater fuel efficiency as compared to traditional internal combustion vehicles and, in some cases, such xEVs may eliminate the use of gasoline entirely, as is the case of certain types of EVs or PEVs.
As technology continues to evolve, there is a need to provide improved power sources, particularly battery modules, for such vehicles. For example, it may be desirable to improve the power density, the low temperature performance, the high temperature performance, and/or the calendar life of lithium ion battery modules in order to effectively meet the power demands of an xEV. Further, it may also be desirable to improve efficiency during the manufacture of such lithium ion battery modules in order to reduce manufacturing time, reduce costs, improve robustness, and improve yields.
A summary of certain embodiments disclosed herein is set forth below. It should be understood that these aspects are presented merely to provide the reader with a brief summary of these certain embodiments and that these aspects are not intended to limit the scope of this disclosure. Indeed, this disclosure may encompass a variety of aspects that may not be set forth below.
The present disclosure relates to a battery module including a lithium ion battery cell having a cathode with a cathode active layer and an anode with an anode active layer. The anode active layer includes at least one polyvinylidene fluoride (PVDF) binder, a conductive carbon, and a secondary lithium titanate oxide (LTO), wherein the secondary LTO includes secondary LTO particles having an average particle size (D50) greater than 2 micrometers (μm).
The present disclosure also relates to a method of manufacturing a lithium ion battery cell that includes forming a slurry having a solvent, a conductive carbon, at least one binder, and a secondary LTO active material, wherein the secondary LTO active material includes secondary LTO particles having an average particle size (D50) greater than 2 μm. The method includes depositing the slurry onto the surface of a metal to form the active layer of an anode and assembling the lithium ion battery cell using the anode.
The present disclosure further relates to a lithium ion battery cell that includes an electrode stack with a cathode having a cathode active layer and an anode having at least 5 milligrams (mg) of anode active layer per square centimeter (cm2) of anode. The anode active layer includes at least one polyvinylidene fluoride (PVDF) binder, a conductive carbon, and a secondary lithium titanate oxide (LTO), wherein the secondary LTO includes secondary LTO particles having an average particle size (D50) greater than 2 μm.
Various aspects of this disclosure may be better understood upon reading the following detailed description and upon reference to the drawings in which:
One or more specific embodiments will be described below. In an effort to provide a concise description of these embodiments, not all features of an actual implementation are described in the specification. It should be appreciated that in the development of any such actual implementation, as in any engineering or design project, numerous implementation-specific decisions must be made to achieve the developers' specific goals, such as compliance with system-related and business-related constraints, which may vary from one implementation to another. Moreover, it should be appreciated that such a development effort might be complex and time consuming, but would nevertheless be a routine undertaking of design, fabrication, and manufacture for those of ordinary skill having the benefit of this disclosure.
The battery systems described herein may be used to provide power to various types of electric vehicles (xEVs) and other high voltage energy storage/expending applications (e.g., electrical grid power storage systems). Such battery systems may include one or more battery modules, each battery module having a number of battery cells (e.g., lithium ion (Li-ion) electrochemical cells) arranged to provide particular voltages and/or currents useful to power, for example, one or more components of an xEV.
As used herein, an “anode” refers to an electrode of a lithium ion battery cell that includes an active layer disposed on a surface of a metal layer (e.g., an aluminum strip or plate). As used herein, an “anode active layer” or an “active layer of an anode” refers to a film that is deposited on the surface of the metal layer to facilitate the electrochemistry of the lithium ion battery cell, wherein the anode active layer includes an LTO anode active material. As used herein, “anode loading” or “loading of an anode” refers to the weight (e.g., in milligrams) of the active layer per unit area (e.g., in cm2) of a surface (e.g., a side) of the anode, understanding that the active layer is generally deposited onto each side of the anode at the described level of loading. As used herein, “anode active material” or “active material of an anode” refers to a lithium titanate oxide (LTO) material that is part of the active layer of an anode of a lithium ion battery. As used herein, a “stack” or an “electrode stack” refers to a multi-layered structure within the battery cell that includes a number of alternating cathode and anode layers (with separating layers disposed between) that stores electrical energy within the battery cell. For example, the stack of the battery cell may be implemented in the form of a stack of cathode and anode plates, or in the form of a “jelly-roll” having continuous cathode and anode strips that are aligned and rolled together about a common axis (e.g., using a mandrel) to yield a multi-layered structure. As used herein, “average particle size” refers to D50 in terms of particle size distribution (PSD) nomenclature, which is the average particle diameter by mass. Charge and discharge rates may be described herein in terms of C-rates (i.e., 1 C, 5 C, 10 C), wherein the number indicates the amount of charge (in coulombs) per second passing into or out of the battery cell.
Lithium titanate oxide (LTO) offers many advantages as an anode active material for lithium ion battery cells. For example, LTO-based lithium ion batteries generally demonstrate excellent charge acceptance, superior performance at low temperature, and good cycle life. Further, due the relatively high voltage of LTO (e.g., approximately 1.55 V relative to lithium metal), LTO lacks lithium plating issues experienced by other anode active materials during the charge process. However, it is presently recognized that LTO suffers from poor processability, which contributes difficulty, time, and cost to the manufacture of the anode and the battery cell. Further, it is also presently recognized that, at least in part due to this poor processability, the electrical properties of LTO-based lithium ion battery cells suffers when the loading of the anode is relatively high (e.g., greater than 5 mg/cm2).
With the forgoing in mind, present embodiments are directed toward LTO anode active materials, as well as electrode and battery cell designs, that enable the manufacture of lithium ion battery cells having excellent discharge power and charge power (e.g., up to 8800 Watts per liter (W/L)), and are suitable for use with xEVs, such as the micro-hybrid xEVs mentioned above. To address the aforementioned processability problems of LTO, present embodiments involve the use of secondary LTO particulate materials to enable the practical manufacture of LTO anodes having relatively high loading (e.g., greater than approximately 5 mg/cm2), which enables the manufacture of LTO batteries with secondary LTO particles that have improved electrical properties (e.g., higher energy and higher power density) compared to LTO battery cells made using primary LTO particles. As set forth below, compared to LTO cell with primary particles, LTO cells with secondary LTO particles can have significantly higher anode loading without significant performance losses. Additionally, in certain embodiments, the disclosed LTO anodes with secondary LTO particles enable the production of LTO battery cells having lower impedance, better high temperature performance, and improved calendar life when compared to LTO cells with primary particles.
As used herein, LTO refers to any lithium titanium-based oxide (e.g., Li4Ti5O12) having a spinel structure. As such, an LTO material generally includes lithium, titanium, and oxygen, and, in certain embodiments, may include other dopant atoms as well. As used herein, “primary LTO” refers to a LTO material that comprises single grains (e.g., individual crystals) of LTO. The average particle size of the primary LTO particles in a primary LTO is less than approximately 2 μm (e.g., between approximately 1 μm and approximately 1.5 μm). In contrast, as used herein, “secondary LTO” refers to a LTO material that comprises secondary LTO particles, which may be formed by agglomerating (e.g., sintering) primary LTO particles into larger particles having a secondary (e.g., spherical) morphology. As such, the average particle size of the secondary LTO particles in a secondary LTO is greater than approximately 2 μm (e.g., between approximately 2 μm and 20 μm). Additionally, 99% or more of the secondary LTO particles of a secondary LTO, as used herein, have a diameter less than 60 μm. Since a secondary LTO is formed via the agglomeration of a primary LTO, a secondary LTO may be described herein according to the size of the secondary LTO particles (e.g., D50 of the secondary LTO particles), according to the size of the primary LTO particles used to form the secondary LTO particles (e.g., D50 of the primary LTO particles before agglomeration), or combinations thereof.
It may be appreciated that the electrical performance enabled by the disclosed secondary LTO active materials, as discussed below, is believed to be unexpected considering other methods for manufacturing LTO anodes teach against using having agglomerates or aggregates of primary LTO particles present in the anode active layer, as this has been previously observed to decrease electrical performance of the resulting battery cell. However, herein we disclose a number of secondary LTO materials made of agglomerated primary LTO particles having dimensions (e.g., primary and secondary particle sizes) and morphologies (e.g., secondary morphologies) that enable the disclosed advantages over certain primary LTO active materials in terms of processability, electrical performance, design freedom, and/or cost.
With the foregoing in mind, present embodiments relating to secondary LTO materials, anode designs, and battery cell designs may be applied in any number of energy expending systems (e.g., vehicular contexts and stationary power contexts). To facilitate discussion, embodiments of the battery modules described herein are presented in the context of advanced battery modules (e.g., lithium ion battery modules) employed in xEVs. To help illustrate,
As discussed above, it would be desirable for a battery system 12 to be largely compatible with traditional vehicle designs. Accordingly, the battery system 12 may be placed in a location in the vehicle 10 that would have housed a traditional battery system. For example, as illustrated, the vehicle 10 may include the battery system 12 positioned similarly to a lead-acid battery of a typical combustion-engine vehicle (e.g., under the hood of the vehicle 10). Furthermore, as will be described in more detail below, the battery system 12 may be positioned to facilitate managing temperature of the battery system 12. For example, in some embodiments, positioning a battery system 12 under the hood of the vehicle 10 may enable an air duct to channel airflow over the battery system 12 and cool the battery system 12.
A more detailed view of the battery system 12 is described in
In other words, the battery system 12 may supply power to components of the vehicle's electrical system, which may include radiator cooling fans, climate control systems, electric power steering systems, active suspension systems, auto park systems, electric oil pumps, electric super/turbochargers, electric water pumps, heated windscreen/defrosters, window lift motors, vanity lights, tire pressure monitoring systems, sunroof motor controls, power seats, alarm systems, infotainment systems, navigation features, lane departure warning systems, electric parking brakes, external lights, or any combination thereof Illustratively, in the depicted embodiment, the energy storage component 14 supplies power to the vehicle console 20 and the ignition system 16, which may be used to start (e.g., crank) the internal combustion engine 22.
Additionally, the energy storage component 14 may capture electrical energy generated by the alternator 18 and/or the electric motor 21. In some embodiments, the alternator 18 may generate electrical energy while the internal combustion engine 22 is running More specifically, the alternator 18 may convert the mechanical energy produced by the rotation of the internal combustion engine 22 into electrical energy. Additionally or alternatively, when the vehicle 10 includes an electric motor 21, the electric motor 21 may generate electrical energy by converting mechanical energy produced by the movement of the vehicle 10 (e.g., rotation of the wheels) into electrical energy. Thus, in some embodiments, the energy storage component 14 may capture electrical energy generated by the alternator 18 and/or the electric motor 21 during regenerative braking. As such, the alternator and/or the electric motor 21 are generally referred to herein as a regenerative braking system.
To facilitate capturing and supplying electric energy, the energy storage component 14 may be electrically coupled to the vehicle's electric system via a bus 24. For example, the bus 24 may enable the energy storage component 14 to receive electrical energy generated by the alternator 18 and/or the electric motor 21. Additionally, the bus may enable the energy storage component 14 to output electrical energy to the ignition system 16 and/or the vehicle console 20. Accordingly, when a 12 volt battery system 12 is used, the bus 24 may carry electrical power typically between 8-18 volts.
Additionally, as depicted, the energy storage component 14 may include multiple battery modules. For example, in the depicted embodiment, the energy storage component 14 includes a lithium ion (e.g., a first) battery module 25 and a lead-acid (e.g., a second) battery module 26, which each includes one or more battery cells. In other embodiments, the energy storage component 14 may include any number of battery modules. Additionally, although the lithium ion battery module 25 and lead-acid battery module 26 are depicted adjacent to one another, they may be positioned in different areas around the vehicle. For example, the lead-acid battery module 26 may be positioned in or about the interior of the vehicle 10 while the lithium ion battery module 25 may be positioned under the hood of the vehicle 10.
In some embodiments, the energy storage component 14 may include multiple battery modules to utilize multiple different battery chemistries. For example, when the lithium ion battery module 25 is used, performance of the battery system 12 may be improved since the lithium ion battery chemistry generally has a higher coulombic efficiency and/or a higher power charge acceptance rate (e.g., higher maximum charge current or charge voltage) than the lead-acid battery chemistry. As such, the capture, storage, and/or distribution efficiency of the battery system 12 may be improved.
To facilitate controlling the capturing and storing of electrical energy, the battery system 12 may additionally include a control module 27. More specifically, the control module 27 may control operations of components in the battery system 12, such as relays (e.g., switches) within energy storage component 14, the alternator 18, and/or the electric motor 21. For example, the control module 27 may regulate amount of electrical energy captured/supplied by each battery module 25 or 26 (e.g., to de-rate and re-rate the battery system 12), perform load balancing between the battery modules 25 and 26, determine a state of charge of each battery module 25 or 26, determine temperature of each battery module 25 or 26, control voltage output by the alternator 18 and/or the electric motor 21, and the like.
Accordingly, the control module 27 may include one or processor 28 and one or more memory 29. More specifically, the one or more processor 28 may include one or more application specific integrated circuits (ASICs), one or more field programmable gate arrays (FPGAs), one or more general purpose processors, or any combination thereof. Additionally, the one or more memory 29 may include volatile memory, such as random access memory (RAM), and/or non-volatile memory, such as read-only memory (ROM), optical drives, hard disc drives, or solid-state drives. In some embodiments, the control module 27 may include portions of a vehicle control unit (VCU) and/or a separate battery control module. Furthermore, as depicted, the lithium ion battery module 25 and the lead-acid battery module 26 are connected in parallel across their terminals. In other words, the lithium ion battery module 25 and the lead-acid module 26 may be coupled in parallel to the vehicle's electrical system via the bus 24.
The lithium ion battery modules 25 described herein, as noted, may include a number of lithium ion electrochemical battery cells electrically coupled to provide particular currents and/or voltages to provide power to the xEV 10.
As discussed below, in certain embodiments, the battery cell 30 may be designed to have a particular set of dimensions that enable a particular power density to be achieved. The pouch battery cell 30 of
As mentioned above, present embodiments utilize a secondary LTO as an anode active material. Nine different LTO materials are presented in Table 1. More specifically, Table 1 indicates the type (i.e., primary or secondary LTO), particle size distribution (PSD) data, and Brunauer-Emmett-Teller (BET) surface area analysis data for each of these LTO materials. Additionally,
In particular, the SEM image of
As illustrated in the SEM images of
To further illustrate differences between the LTO anode 52 made using primary LTO and the LTO anode 64 made using secondary LTO,
With the foregoing in mind, it is presently recognized that the morphology of the secondary LTO substantially affects the processability of the secondary LTO during anode manufacturing, as well as the eventual electrical performance of LTO battery cell. For example, it is presently recognized that, when the secondary LTO has a medium secondary particle size and a small primary particle size, the electrical performance and the processability of the secondary LTO are substantially better. By specific example, for a secondary LTO, when the average particle size of the secondary LTO particles is less than 12 μm (e.g., less than 10 μm, or approximately 6 μm) and the average particle size of the primary LTO particles (i.e., the average particle size of the agglomerated primary LTO particle grains within the secondary LTO particles) is less than 500 nm (e.g., less than 250 nm, or approximately 100 nm), excellent processability and electrical performance may be achieved. For example, the secondary LTO illustrated in
Coin battery cells were produced using a number of different secondary LTO materials (i.e., LTO1, LTO2, LTO5, LTO6, and LTO7) as well as different primary LTO materials (i.e., LTO3 and LTO4), and the coin battery cells were subsequently electrically evaluated for comparison. A representative portion of the electrical performance data for different LTO active materials is illustrated in
Furthermore, as illustrated by the graph 88 of
The graph 92 of
The graph 94 of
The graph 96 of
It is also presently recognized that the relative ratio of components in the active layer 66 of the disclosed anodes 64 also affect the electrical performance of the resulting battery cell 30. For example, the graphs 98 and 100 of
It is also presently recognized that the negative-to-positive capacity ratio (N/P) affects the electrical performance of the resulting battery cell 30. For example,
It is presently recognized that, as illustrated by the graph 120 in
As illustrated by the graph 122 in
As mentioned above, the loading of the LTO anode active material (i.e., milligrams of active layer per square centimeter of anode) also affects the electrical performance of the resulting battery cell 30. For example, the graph 140 of
Manufacturing LTO Anode
The process 150 illustrated in
As illustrated in
After the second period of time is complete, the slurry may then be degassed (block 164) using vacuum and/or inert gas bubbling. In certain embodiments, the mixer may continue to provide planetary mixing to the mixture throughout the degassing represented by block 164. Subsequently, the degassed slurry may be deposited (block 166) onto the surface of a metal foil to form the active layer of an anode. For example, the degassed slurry may be deposited onto the surface of an aluminum metal foil, for example, using a die coating or reverse roll coating process, to form the active layer 66 of a LTO anode 64. Finally, the LTO anode 64 formed in block 166 may be used to construct (block 168) a lithium ion battery cell 30 capable of providing the electrical performance described above.
In an example embodiment of the process 150 illustrated in
Continuing through the example embodiment, next 2.3 kg of secondary LTO active material (e.g., LTO7) is added to the slurry, as represented by block 158, along with an additional 650 mL of NMP. The slurry then undergoes planetary mixing with strong disperser for 150 min, as represented by block 160. At the 30 minute mark, the mixer is paused and 300 mL of NMP is added to the slurry, as represented by block 162, before the remaining 120 min of mixing/dispersing represented by block 160 are completed. The slurry is subsequently placed under a vacuum as mixing/dispersing continues for an additional 30 minutes to degas the slurry, as represented by block 164.
For this example, the resulting secondary LTO slurry has a total solid ratio of approximately 43% and a viscosity of approximately 1050 centipoise (cps). For comparison, when an example primary LTO slurry is prepared using the process 150 with the substitution of a primary LTO material (e.g., LTO4) in block 158, the total mixing time is approximately 15% longer, and the resulting primary LTO slurry has a lower total solid ratio (i.e., 38%) and a higher viscosity (i.e., 1080 cps). As such, it is presently recognized that the higher solid ratio and the lower viscosity slurry of the secondary LTO slurry enables the slurry to be more easily formed and coated onto the surface of the metal foil, as represented by block 166. Furthermore, as set forth above, the improved processability of the secondary LTO slurry leads to the formation of anodes with high loading (e.g., greater than 5 mg/cm2) and good electrical performance.
With the forgoing in mind, Table 2 includes design parameters for three example embodiments of the pouch battery cell 30, as illustrated in
It may be appreciated that the three example embodiments of the battery cell 30 represented in Table 2 each have different active material loadings (i.e., for both the cathode and anode) and each have a capacity around approximately 8 Ah. To maintain similar capacity while accommodating different active material loadings, the LTO battery cell embodiments represented in Table 2 have an increasing number of layers (i.e., cathode layers, anode layers, separator layers) in the stack with decreasing anode loading. Since the thickness 42 of the pouch battery cell 30, as illustrated in
As illustrated in Table 2, the disclosed secondary LTO active materials enable greater freedom in the design of both anodes 64 and battery cells 30, compared to primary LTO active materials. That is, since the secondary LTO active material enables anode loading beyond 5 mg/cm2, embodiments of the pouch battery cell 30 may be manufactured to provide similar capacity using a smaller stack (e.g., fewer cathode/anode layers, a thinner “jelly-roll” with fewer rolls). Since a fewer cathode/anode layers may be used while maintaining a similar capacity, embodiments of the battery cell 30 with higher anode loading (e.g., greater than 5 mg/cm2) may be cheaper to manufacture and/or may enable a weight reduction for the battery cell 30. Additionally, although a larger stack is used (e.g., greater than 25 anode layers) for the embodiments represented in Table 2 with the lower anode loading, these embodiments also demonstrate higher power density, which may be useful to particular applications involving higher charging/discharging rates. As such, the disclosed secondary LTO materials, anode designs, and battery cell designs enable greater freedom in production of different types of lithium ion of battery cells based on desired cost, dimensions, application, and so forth.
One or more of the disclosed embodiments, alone or on combination, may provide one or more technical effects including the manufacture of battery modules having LTO anodes made using secondary LTO particles. The technical effects and technical problems in the specification are exemplary and are not limiting. It should be noted that the embodiments described in the specification may have other technical effects and can solve other technical problems. The specific embodiments described above have been shown by way of example, and it should be understood that these embodiments may be susceptible to various modifications and alternative forms. It should be further understood that the claims are not intended to be limited to the particular forms disclosed, but rather to cover all modifications, equivalents, and alternatives falling within the spirit and scope of this disclosure.
This application claims priority from and the benefit of U.S. Provisional Application Ser. No. 62/049,902, entitled “LTO ANODE ELECTRODE FOR HIGH LOADING TO ACCOMPLISH HIGH ENERGY AND POWER CELL,” filed Sep. 12, 2014, which is hereby incorporated by reference in its entirety for all purposes.
Number | Date | Country | |
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62049902 | Sep 2014 | US |