ABSTRACT
Abstract
Rechargeable batteries, charging methods and systems for fast charging of the battery under all environmental temperatures and without causing battery degradation are disclosed. A charging control system for charging a rechargeable battery can include an ohmically modulated battery, a temperature sensor configured to monitor a temperature of the battery: a switch that can electrically engage the battery to a source of electrical current through either a low-resistance terminal or a high-resistance terminal of the battery: and a controller electrically connected to the temperature sensor and the switch and that can receive input from the temperature sensor and is programmed to determine whether to electrically engage the battery to the source of electrical current through either the low-resistance terminal or the high-resistance terminal through the switch based on input from the temperature sensor.
Description
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Application No. 62/029,865 filed Jul. 28, 2014, the entire disclosure of which is hereby incorporated by reference herein.
TECHNICAL FIELD
The present invention generally relates to systems and methods of charging batteries at low temperatures and in particular to fast charging batteries below normal operating temperatures of the batteries.
BACKGROUND
Rechargeable batteries for electronics, transportation and grid energy storage commonly have poor charge acceptance and suffer from excessively long charge time, especially at subfreezing temperatures, due to sluggish electrochemical kinetics and transport processes occurring in the battery cell. Charging batteries at reasonable rates in cold weathers are either impossible to carry out or incur much shortened battery life. For example, the biggest problem for charging lithium-ion batteries at low temperatures is the lithium plating in the graphitic anode. The deposited lithium reacts quickly with the electrolyte leading to irreversible capacity loss. Furthermore, the metallic lithium grows in dendrite form, creating the possibility of penetrating separator and shorting the cell internally. To avoid lithium plating, lithium-ion batteries are charged at very low rate (C/10 or less) at low temperatures, which requires tremendous amount of time to be fully charged.
The long charging time poses a great disadvantage to energy storage solutions, especially electric vehicles (EV). Compared to traditional gasoline-powered vehicles whose fuel tank can be filled up in less than five minutes under all conditions, EV requires hours to get a full recharge in cold weathers. Fast charging is essential to enable public charge stations and battery-powered electric vehicles.
Because of high sensitivity of battery charge acceptance to temperature, charging time can be reduced by heating rechargeable batteries to a near room-temperature range suitable for fast charging. Conventional battery heating systems, however, heat the battery externally by using convective air/liquid heating or thermal jackets, where heat slowly propagates from the exterior into the electrochemical reaction interface inside the battery. Such processes suffer from long heating time and significant heat loss to the surroundings.
Accordingly, a continuing need exists to reduce the charging time of a rechargeable battery without deleteriously affecting the battery.
SUMMARY OF THE DISCLOSURE
An advantage of the present disclosure is a charging control system for charging an ohmically modulated rechargeable battery and methods for its operation. Such a system can be included in an electrically powered vehicle, e.g., an electric vehicle (EV), hybrid electric vehicle (HEV), and plug-in hybrid electric vehicle (PHEV).
These and other advantages are satisfied, at least in part, by a charging control system for charging an ohmically modulated rechargeable battery comprising: a temperature sensor configured to monitor a temperature of the battery; a switch that can electrically engage the battery to a source of electrical current through either a low-resistance terminal or a high-resistance terminal of the battery, or both; and a controller electrically connected to the temperature sensor and the switch and that can receive input from the temperature sensor and is programmed to determine whether to electrically engage the battery to the source of electrical current through either the low-resistance terminal or the high-resistance terminal through the switch based on input from the temperature sensor. The system can include additional components, individually or in combination, such as one or more of a current sensor electrically connected to the battery and capable of measuring current flowing through the battery and/or one or more voltage sensors such as a voltage sensor electrically connected to the low-resistance terminal of the battery; and a voltage sensor electrically connected to the high-resistance terminal voltage of the battery. With the additional sensors, the controller can receive inputs from the additional sensors and is programmed to determine whether to electrically engage the battery to the source of electrical current through either the low-resistance terminal or the high-resistance terminal through the switch based on inputs from some or all of the sensors. The system can also include a generator electrically connected to the battery and capable of charging the battery. The generator can be used to capture kinetic energy, such as in regenerative braking in vehicles, and charge the battery with such energy.
Another aspect of the present disclosure includes a method of charging an ohmically modulated rechargeable battery. The method comprises: charging the battery under a low temperature charging protocol (LTCP) when the battery is in a high resistance mode; and charging the battery under a second protocol when the battery is in a low resistance mode.
Embodiments of the LTCPs include charging the battery under constant voltage, and/or at a constant current (I) and/or at a constant charging power (P) and combinations thereof. In one embodiment of the present disclosure, the LTCP includes: (i) charging the battery at either a constant voltage or a constant charging power (P); and (ii) followed by charging the battery at a constant current. Charging the battery at the constant current can occur when the charging current reaches or exceeds a predetermined maximum charge current (I max ). Further, the constant voltage can be determined from either the low-resistance terminal voltage V LoR and/or the voltage of the battery. The LTCP also can include charging the battery under a pulse voltage and/or pulse power and/or pulse current and combinations thereof. LTCPs can further include charging the battery in the high resistance mode when a temperature of the battery is below a predetermined level T CG1 , e.g. wherein T CG1 is a value between 5° C. and 25° C., and charging the battery in the low resistance mode when the temperature of the battery is equal to or above T CG1 .
Embodiments of charging the battery under the second protocol, i.e., in the low resistance mode, include charging the battery under a constant current, constant voltage protocol, wherein the constant current is about 1 C or higher and the constant voltage is about V set , wherein V set is a predetermined voltage. Advantageously, the protocol can include charging the battery in the low resistance mode when the temperature of the battery is equal to or above a predetermined level T CG1 , e.g., wherein T CG1 is a value between 5° C. and 25° C.
Another aspect of the present disclosure includes a method of charging an ohmically modulated rechargeable battery with regenerative energy, the method comprising: charging the battery under a regenerative charging protocol (RCP) when the battery is in a high resistance mode, e.g., when the temperature of the battery is below a predetermined charge value (T CG1 ); and charging the battery under a second protocol when the battery is in a low resistance mode, e.g., when the temperature of the battery is above T CG1 . Advantageously, the current applied to charge the battery under either RCP or the second protocol is converted from kinetic energy.
Embodiments of the RCP include charging the battery by applying a charging current to the battery in voltage controlled form or in power P controlled form or in current controlled for or combinations thereof. The voltage controlled form, power P controlled form and current controlled form can be either a constant value or a function of time. In one embodiment of the present disclosure, the RCP includes (i) charging the battery by applying a charging current to the battery in voltage controlled form or in power P controlled form, (ii) followed by charging the battery at a constant current; wherein the voltage controlled form is determined either at the low-resistance terminal voltage V LoR (t) of the battery or at the voltage of the battery V(t). Charging under the second protocol when the battery is in the low resistance mode can include a constant current-constant voltage protocol, for example. RCPs can further include charging the battery in the high resistance mode when a temperature of the battery is below a predetermined level T CG1 , e.g. wherein T CG1 is a value between 5° C. and 25° C., and charging the battery in the low resistance mode when the temperature of the battery is equal to or above T CG1 .
Additional advantages of the present invention will become readily apparent to those skilled in this art from the following detailed description, wherein only the preferred embodiment of the invention is shown and described, simply by way of illustration of the best mode contemplated of carrying out the invention. As will be realized, the invention is capable of other and different embodiments, and its several details are capable of modifications in various obvious respects, all without departing from the invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
BRIEF DESCRIPTION OF THE DRAWINGS
Reference is made to the attached drawings, wherein elements having the same reference numeral designations represent similar elements throughout and wherein:
FIG. 1A is a schematic showing construction of an ohmically modulated battery having several resistor sheets/foils embedded within a stack of electrode-separator assemblies, one high-resistance negative terminal HiR(â) and one low-resistance negative terminal LoR(â), one positive terminal (+), and a thermally activated switch connecting the HiR(â) and LoR(â) terminals, according to an embodiment of the present disclosure.
FIG. 1B is a schematic of a three-terminal ohmically modulated battery in a prismatic configuration according to an embodiment of the present disclosure
FIG. 1C is a schematic of a four-terminal ohmically modulated battery wherein two tabs of a resistor sheet form two HiR(â) terminals independently from the LoR(â) terminal, according to an embodiment of the present disclosure.
FIG. 2 is a schematic showing construction of a twin-cell battery module with one resistor sheet/foil between the two cells, i.e. outside each cell casing without direct contact with battery electrolyte according to an embodiment of the present disclosure.
FIG. 3A is a circuit diagram depicting a battery charging control system, according to an embodiment of the present disclosure.
FIG. 3B is another circuit diagram depicting a battery charging control system, according to another embodiment of the present disclosure
FIG. 4 is a flowchart illustrating a method for charging OMB using battery charging control system according to an embodiment of the present disclosure.
FIG. 5 is a flowchart illustrating a method (CV LoR -CC) for low temperature charging according to an embodiment of the present disclosure.
FIG. 6 is a flowchart illustrating a method (CV-CC) for low temperature charging as according to an embodiment of the present disclosure.
FIG. 7 is a flowchart illustrating a method (CC) for low temperature charging according to an embodiment of the present disclosure.
FIG. 8 is a flowchart illustrating a method (CP-CC) for low temperature charging according to an embodiment of the present disclosure.
FIG. 9 is a flowchart illustrating a method (PV) for low temperature charging according to an embodiment of the present disclosure.
FIG. 10 is a flowchart illustrating a method (PC) for low temperature charging according to an embodiment of the present disclosure.
FIG. 11 is a diagram depicting regenerative charging system, according to an embodiment of the present disclosure.
FIG. 12 is a flowchart illustrating a method for regenerative charging of OMB using regenerative charging system, according to an embodiment of the present disclosure.
FIG. 13 is a flowchart illustrating a method (V LoR -CC) for regenerative charging according to an embodiment of the present disclosure.
FIG. 14 is a flowchart illustrating a method (V-CC) for regenerative charging according to an embodiment of the present disclosure.
FIG. 15 is a flowchart illustrating a method (C-CV LoR ) for regenerative charging according to an embodiment of the present disclosure.
FIG. 16 is a flowchart illustrating a method (P-CC) for regenerative charging according to an embodiment of the present disclosure.
FIGS. 17A and 17B are graphs showing the results of charging an ohmically modulated battery according to an embodiment of the present disclosure. The charging protocols employed a CV LoR -CC low temperature charging combined with CC-CV normal charging (CV LoR 4V CC I max when T<T CG1 , CC 2.5 C, CV 4.1V when Tâ¥T CG1 ).
FIGS. 18A, 18B and 18C are graphs showing the results of charging an ohmically modulated battery according to an embodiment of the present disclosure. The charging protocols employed a PV low temperature charging combined with CC-CV normal charging (PV 6.8Vâ0.4V when T<T CG1 , CC 2.5 C, CV 4.1V when Tâ¥T CG1 ).
FIGS. 19A, 19B and 19C are graphs showing the results of charging an ohmically modulated battery according to an embodiment of the present disclosure. The charging protocols employed a PC low temperature charging combined with CC-CV normal charging (PC±3.2 C when T<T CG1 , CC 2.5 C, CV 4.1V when Tâ¥T CG1 ).
FIGS. 20A, 20B and 20C are graphs showing the results of comparing charging a conventional Li-ion battery with that of an OMB using a PC-CCCV charging protocol.
FIGS. 21A, 21B and 21C are graphs showing the results of comparing regenerative charging of a conventional Li-ion battery with that of an OMB using a C-CV LoR charging protocol.
DETAILED DESCRIPTION OF THE DISCLOSURE
Ohmically Modulated Battery
Rechargeable batteries have been engineered to substantially increase the internal resistance of the battery at low temperatures, e.g., at temperatures below the normal operating temperature of the particular battery. Such batteries have been disclosed for example in co-pending U.S. patent application Ser. No. 14/267,648, filed May 1, 2014, and PCT/US2014/059729, filed Oct. 8, 2014, both entitled Ohmically Modulated Battery, the entire disc
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Application No. 62/029,865 filed Jul. 28, 2014, the entire disclosure of which is hereby incorporated by reference herein.
TECHNICAL FIELD
The present invention generally relates to systems and methods of charging batteries at low temperatures and in particular to fast charging batteries below normal operating temperatures of the batteries.
BACKGROUND
Rechargeable batteries for electronics, transportation and grid energy storage commonly have poor charge acceptance and suffer from excessively long charge time, especially at subfreezing temperatures, due to sluggish electrochemical kinetics and transport processes occurring in the battery cell. Charging batteries at reasonable rates in cold weathers are either impossible to carry out or incur much shortened battery life. For example, the biggest problem for charging lithium-ion batteries at low temperatures is the lithium plating in the graphitic anode. The deposited lithium reacts quickly with the electrolyte leading to irreversible capacity loss. Furthermore, the metallic lithium grows in dendrite form, creating the possibility of penetrating separator and shorting the cell internally. To avoid lithium plating, lithium-ion batteries are charged at very low rate (C/10 or less) at low temperatures, which requires tremendous amount of time to be fully charged.
The long charging time poses a great disadvantage to energy storage solutions, especially electric vehicles (EV). Compared to traditional gasoline-powered vehicles whose fuel tank can be filled up in less than five minutes under all conditions, EV requires hours to get a full recharge in cold weathers. Fast charging is essential to enable public charge stations and battery-powered electric vehicles.
Because of high sensitivity of battery charge acceptance to temperature, charging time can be reduced by heating rechargeable batteries to a near room-temperature range suitable for fast charging. Conventional battery heating systems, however, heat the battery externally by using convective air/liquid heating or thermal jackets, where heat slowly propagates from the exterior into the electrochemical reaction interface inside the battery. Such processes suffer from long heating time and significant heat loss to the surroundings.
Accordingly, a continuing need exists to reduce the charging time of a rechargeable battery without deleteriously affecting the battery.
SUMMARY OF THE DISCLOSURE
An advantage of the present disclosure is a charging control system for charging an ohmically modulated rechargeable battery and methods for its operation. Such a system can be included in an electrically powered vehicle, e.g., an electric vehicle (EV), hybrid electric vehicle (HEV), and plug-in hybrid electric vehicle (PHEV).
These and other advantages are satisfied, at least in part, by a charging control system for charging an ohmically modulated rechargeable battery comprising: a temperature sensor configured to monitor a temperature of the battery; a switch that can electrically engage the battery to a source of electrical current through either a low-resistance terminal or a high-resistance terminal of the battery, or both; and a controller electrically connected to the temperature sensor and the switch and that can receive input from the temperature sensor and is programmed to determine whether to electrically engage the battery to the source of electrical current through either the low-resistance terminal or the high-resistance terminal through the switch based on input from the temperature sensor. The system can include additional components, individually or in combination, such as one or more of a current sensor electrically connected to the battery and capable of measuring current flowing through the battery and/or one or more voltage sensors such as a voltage sensor electrically connected to the low-resistance terminal of the battery; and a voltage sensor electrically connected to the high-resistance terminal voltage of the battery. With the additional sensors, the controller can receive inputs from the additional sensors and is programmed to determine whether to electrically engage the battery to the source of electrical current through either the low-resistance terminal or the high-resistance terminal through the switch based on inputs from some or all of the sensors. The system can also include a generator electrically connected to the battery and capable of charging the battery. The generator can be used to capture kinetic energy, such as in regenerative braking in vehicles, and charge the battery with such energy.
Another aspect of the present disclosure includes a method of charging an ohmically modulated rechargeable battery. The method comprises: charging the battery under a low temperature charging protocol (LTCP) when the battery is in a high resistance mode; and charging the battery under a second protocol when the battery is in a low resistance mode.
Embodiments of the LTCPs include charging the battery under constant voltage, and/or at a constant current (I) and/or at a constant charging power (P) and combinations thereof. In one embodiment of the present disclosure, the LTCP includes: (i) charging the battery at either a constant voltage or a constant charging power (P); and (ii) followed by charging the battery at a constant current. Charging the battery at the constant current can occur when the charging current reaches or exceeds a predetermined maximum charge current (I max ). Further, the constant voltage can be determined from either the low-resistance terminal voltage V LoR and/or the voltage of the battery. The LTCP also can include charging the battery under a pulse voltage and/or pulse power and/or pulse current and combinations thereof. LTCPs can further include charging the battery in the high resistance mode when a temperature of the battery is below a predetermined level T CG1 , e.g. wherein T CG1 is a value between 5° C. and 25° C., and charging the battery in the low resistance mode when the temperature of the battery is equal to or above T CG1 .
Embodiments of charging the battery under the second protocol, i.e., in the low resistance mode, include charging the battery under a constant current, constant voltage protocol, wherein the constant current is about 1 C or higher and the constant voltage is about V set , wherein V set is a predetermined voltage. Advantageously, the protocol can include charging the battery in the low resistance mode when the temperature of the battery is equal to or above a predetermined level T CG1 , e.g., wherein T CG1 is a value between 5° C. and 25° C.
Another aspect of the present disclosure includes a method of charging an ohmically modulated rechargeable battery with regenerative energy, the method comprising: charging the battery under a regenerative charging protocol (RCP) when the battery is in a high resistance mode, e.g., when the temperature of the battery is below a predetermined charge value (T CG1 ); and charging the battery under a second protocol when the battery is in a low resistance mode, e.g., when the temperature of the battery is above T CG1 . Advantageously, the current applied to charge the battery under either RCP or the second protocol is converted from kinetic energy.
Embodiments of the RCP include charging the battery by applying a charging current to the battery in voltage controlled form or in power P controlled form or in current controlled for or combinations thereof. The voltage controlled form, power P controlled form and current controlled form can be either a constant value or a function of time. In one embodiment of the present disclosure, the RCP includes (i) charging the battery by applying a charging current to the battery in voltage controlled form or in power P controlled form, (ii) followed by charging the battery at a constant current; wherein the voltage controlled form is determined either at the low-resistance terminal voltage V LoR (t) of the battery or at the voltage of the battery V(t). Charging under the second protocol when the battery is in the low resistance mode can include a constant current-constant voltage protocol, for example. RCPs can further include charging the battery in the high resistance mode when a temperature of the battery is below a predetermined level T CG1 , e.g. wherein T CG1 is a value between 5° C. and 25° C., and charging the battery in the low resistance mode when the temperature of the battery is equal to or above T CG1 .
Additional advantages of the present invention will become readily apparent to those skilled in this art from the following detailed description, wherein only the preferred embodiment of the invention is shown and described, simply by way of illustration of the best mode contemplated of carrying out the invention. As will be realized, the invention is capable of other and different embodiments, and its several details are capable of modifications in various obvious respects, all without departing from the invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
BRIEF DESCRIPTION OF THE DRAWINGS
Reference is made to the attached drawings, wherein elements having the same reference numeral designations represent similar elements throughout and wherein:
FIG. 1A is a schematic showing construction of an ohmically modulated battery having several resistor sheets/foils embedded within a stack of electrode-separator assemblies, one high-resistance negative terminal HiR(â) and one low-resistance negative terminal LoR(â), one positive terminal (+), and a thermally activated switch connecting the HiR(â) and LoR(â) terminals, according to an embodiment of the present disclosure.
FIG. 1B is a schematic of a three-terminal ohmically modulated battery in a prismatic configuration according to an embodiment of the present disclosure
FIG. 1C is a schematic of a four-terminal ohmically modulated battery wherein two tabs of a resistor sheet form two HiR(â) terminals independently from the LoR(â) terminal, according to an embodiment of the present disclosure.
FIG. 2 is a schematic showing construction of a twin-cell battery module with one resistor sheet/foil between the two cells, i.e. outside each cell casing without direct contact with battery electrolyte according to an embodiment of the present disclosure.
FIG. 3A is a circuit diagram depicting a battery charging control system, according to an embodiment of the present disclosure.
FIG. 3B is another circuit diagram depicting a battery charging control system, according to another embodiment of the present disclosure
FIG. 4 is a flowchart illustrating a method for charging OMB using battery charging control system according to an embodiment of the present disclosure.
FIG. 5 is a flowchart illustrating a method (CV LoR -CC) for low temperature charging according to an embodiment of the present disclosure.
FIG. 6 is a flowchart illustrating a method (CV-CC) for low temperature charging as according to an embodiment of the present disclosure.
FIG. 7 is a flowchart illustrating a method (CC) for low temperature charging according to an embodiment of the present disclosure.
FIG. 8 is a flowchart illustrating a method (CP-CC) for low temperature charging according to an embodiment of the present disclosure.
FIG. 9 is a flowchart illustrating a method (PV) for low temperature charging according to an embodiment of the present disclosure.
FIG. 10 is a flowchart illustrating a method (PC) for low temperature charging according to an embodiment of the present disclosure.
FIG. 11 is a diagram depicting regenerative charging system, according to an embodiment of the present disclosure.
FIG. 12 is a flowchart illustrating a method for regenerative charging of OMB using regenerative charging system, according to an embodiment of the present disclosure.
FIG. 13 is a flowchart illustrating a method (V LoR -CC) for regenerative charging according to an embodiment of the present disclosure.
FIG. 14 is a flowchart illustrating a method (V-CC) for regenerative charging according to an embodiment of the present disclosure.
FIG. 15 is a flowchart illustrating a method (C-CV LoR ) for regenerative charging according to an embodiment of the present disclosure.
FIG. 16 is a flowchart illustrating a method (P-CC) for regenerative charging according to an embodiment of the present disclosure.
FIGS. 17A and 17B are graphs showing the results of charging an ohmically modulated battery according to an embodiment of the present disclosure. The charging protocols employed a CV LoR -CC low temperature charging combined with CC-CV normal charging (CV LoR 4V CC I max when T<T CG1 , CC 2.5 C, CV 4.1V when Tâ¥T CG1 ).
FIGS. 18A, 18B and 18C are graphs showing the results of charging an ohmically modulated battery according to an embodiment of the present disclosure. The charging protocols employed a PV low temperature charging combined with CC-CV normal charging (PV 6.8Vâ0.4V when T<T CG1 , CC 2.5 C, CV 4.1V when Tâ¥T CG1 ).
FIGS. 19A, 19B and 19C are graphs showing the results of charging an ohmically modulated battery according to an embodiment of the present disclosure. The charging protocols employed a PC low temperature charging combined with CC-CV normal charging (PC±3.2 C when T<T CG1 , CC 2.5 C, CV 4.1V when Tâ¥T CG1 ).
FIGS. 20A, 20B and 20C are graphs showing the results of comparing charging a conventional Li-ion battery with that of an OMB using a PC-CCCV charging protocol.
FIGS. 21A, 21B and 21C are graphs showing the results of comparing regenerative charging of a conventional Li-ion battery with that of an OMB using a C-CV LoR charging protocol.
DETAILED DESCRIPTION OF THE DISCLOSURE
Ohmically Modulated Battery
Rechargeable batteries have been engineered to substantially increase the internal resistance of the battery at low temperatures, e.g., at temperatures below the normal operating temperature of the particular battery. Such batteries have been disclosed for example in co-pending U.S. patent application Ser. No. 14/267,648, filed May 1, 2014, and PCT/US2014/059729, filed Oct. 8, 2014, both entitled Ohmically Modulated Battery, the entire disclosure of both of which are hereby incorporated by reference herein.
As used herein the terms ohmic modulation of a rechargeable battery or an ohmically modulated rechargeable battery refer to a rechargeable battery engineered to have more than one internal resistance level that can change substantially with battery temperature. This deliberate ohmic modulation can be engineered either actively or passively.
An advantage of such rechargeable batteries is that the internal resistance of the battery can change substantially when the battery temperature falls below a predetermined level. The high internal resistance of the battery creates heat within the battery to warm the battery. Preferably the internal resistance of the battery becomes high enough to rapidly warm the battery by tens of degree Celsius within seconds or within up to a few minutes. After the battery temperature reaches a desired level, the high internal resistance is deactivated allowing the battery to operate at a low-resistance mode, e.g., as low as in conventional batteries, thereby enabling the battery to deliver high power and energy despite being in a low temperature environment.
Preferably, the rechargeable battery can comprise one level of internal resistance (R 1 ) over a temperature range of the battery between a first temperature (T 1 ) and a second temperature (T 2 ), and a second level of internal resistance (R 2 ) outside of either T 1 or T 2 . Preferably the value of R 2 changes abruptly, such as in a step function, or changes sharply, such as in a continuous but rapid change in resistance, below around T 1 and/or at above around T 2 . For example, the value of R 2 at about 2° C. below T 1 is at least twice the value of R 1 at T 1 or the value of R 2 at about 2° C. above T 2 is at least twice the value of R 1 at T 2 . Advantageously, the value of R 2 at about 2° C. below T 1 is at least twice to fifty times the value of R 1 at T 1 and the value of R 2 at about 2° C. above T 2 is at least twice to fifty times the value of R 1 at T 2 . The ohmic modulation of the battery is advantageously reversible, i.e., the internal resistance can switch back from R 2 to R 1 between T 1 and T 2 . Embodiments of the present disclosure include wherein the value of R 2 /R 1 is between and including 2 to 500, e.g., the value of R 2 /R 1 is between and including 2 to 100, or 2 to 50, when the value of R 2 is determined at about 2° C. below T 1 and R 1 is determined at T 1 . Additional or alternative embodiments include wherein the value of R 2 /R 1 is between and including 2 to 500, e.g., the value of R 2 /R 1 is between and including 2 to 100, or 2 to 50, when the value of R 2 is determined at about 2° C. above T 2 and R 1 is determined at T 2 . The ohmic modulation of the battery is advantageously reversible, i.e., the internal resistance can switch back from R 2 to R 1 between T 1 and T 2 .
As used herein the terms rechargeable battery or battery are used to represent any rechargeable electrochemical energy storage device that contains one or more electrochemical cells. The basic elements of a battery cell include an anode electrode coated on a current collector, a separator, a cathode electrode coated on another current collector and an electrolyte.
The battery configuration of the present disclosure can be applied to a variety of batteries such as, but not limited to, lithium-ion, lithium-polymer, lead-acid, nickel-metal hydride, lithium-sulfur, lithium-air and all solid-state batteries. Such batteries are useful for transportation, aerospace, military, and stationary energy storage applications.
In an embodiment of the present disclosure, a rechargeable battery can have at least two levels of internal resistance which depend on the battery's temperature. As used herein the temperature of the battery can be the internal temperature or external surface temperature of the battery. The rechargeable battery of the present embodiment can be configured to operate at a higher resistance level when the internal temperature of the battery is below an optimum temperature, e.g. below T 1 , thereby heating the battery and improving battery performance. For example, when the battery's internal temperature is below a normal range, e.g. below normal operating temperatures such as below about 5° C. or in subfreezing environments (temperatures less than about 0° C., e.g., less than about â10 or â20° C.), the internal resistance of the battery becomes several-fold higher than when the battery operates in the normal temperature range (e.g. in the range of from about 40 Ωcm 2 to about 200 Ωcm 2 ). As a result, there is much intensified internal heating (as the battery's heat generation is proportional to its internal resistance), which leads to rapid rise of the battery's internal temperature. This in turn quickly improves power and energy output of the battery while operating in subfreezing environments.
A rechargeable battery of the present disclosure can include the conventional components of a rechargeable battery and additionally include one or more components to modulate the internal resistance of the battery.
For example, an ohmically modulated rechargeable battery can include at least one negative terminal and at least one positive terminal for operating the battery at R 1 , e.g. at a low internal resistance level (LoR), above T 1 . The ohmically modulated battery can also include at least one high resistance terminal for operating the battery at R 2 , e.g. at a high internal resistance level (HiR), when the battery temperature is below T 1 . The high resistance terminal can either be an additional negative terminal (i.e., a HiR (â)) or an additional positive terminal (i.e., a HiR(+)).
Such a rechargeable battery can include a switch that switches the resistance levels of the battery. For example the switch can engage the low resistance terminals of the battery, e.g., LoR (â) and/or LoR (+), to operate the battery when the temperature of the battery is above T 1 , and can engage one or more high resistance terminal, e.g., HiR(â) and/or HiR(+), when the battery temperature is below T 1 .
The switch of the present disclosure can be composed of an electromechanical relay and a temperature controller, or a solid-state relay with a temperature sensor, a power MOSFET with a temperature sensor, or a high-current switch with a temperature sensor. Alternatively, the switch connecting LoR(â) and HiR(â) terminals can be carried out by a controller having an electric circuit and a cell temperature sensor in a battery management system.
In an embodiment of the present disclosure, the rechargeable battery includes at least one resistor sheet that is electrically connected to the high resistance terminal. The at least one resistor sheet can be located either inside a battery cell (exposed to the electrolyte), or outside and between two battery cells, or a combination of some resistor sheets inside cells and some resistor sheets outside and between cells. The resistor sheet configured with a cell of the battery can be integrally part of the current collector of an electrode of the cell of the battery
As used herein, a resistor sheet is a material that has a lower conductivity (higher electrical resistance) relative to the battery current-collecting foils and, when activated during battery operation, causes a significant increase in the internal electrical resistance of the battery. The resistor sheet preferably has a resistance in units of Ohm equal to the numerical value of between 0.1 to 5 divided by the battery's capacity in Amp-hours (Ah), e.g. between about 0.5 to 2 divided by the battery's capacity in Ah. For example the resistor sheet for a 20 Ah battery is preferably between about 0.005 Ohm (0.1 divided by 20) to about 0.25 Ohm (5 divided by 20), e.g. between about 0.025 Ohm (0.5 divided by 20) to about 0.1 Ohm (2 divided by 20).
The resistor sheets of the present disclosure can be any metal that is stable when exposed to battery electrolytes and within the electrochemical voltage window of a rechargeable battery when the resistor sheet is exposed to such an environment. Such resistor sheets can be made of graphite, highly ordered pyrolytic graphite (HOPG), stainless steel, nickel, chrome, nichrome, copper, aluminum, titanium, or combinations thereof. If used outside battery cells and between two adjacent cells in a module, the resistor sheets do not need to be anti-corrosive and thus additional materials are available for use as resistor sheets of the present disclosure. The resistor sheet of the present disclosure preferably is flat with large surface area in good contact with adjacent battery components and has a thickness between about 1 and about 150 micrometers with a preferred range of about 5 to about 60 micrometers. Resistor sheets that have large electrical resistance, high thermal conductivity, and small heat capacity are useful for certain embodiments of the present disclosure.
In certain configurations of the present disclosure, the rechargeable battery includes one or more high resistance tabs or terminals and one or more low resistance tabs or terminals. The high resistance terminals electrically connect the one or more resistance sheets and the low resistance tabs or terminals are configured to operate the battery in a low resistance mode.
Advantageously, the rechargeable battery of the present disclosure can be readily configured with conventional rechargeable battery components with minimal modification in certain embodiments, additionally including one or more high resistance terminals connected to one or more resistor sheets, for example. The following figures illustrate certain embodiments of the present disclosure.
FIG. 1A illustrates an embodiment of an ohmically modulated battery. As shown in FIG. 1A , rechargeable battery 110 has several resistor sheets 112 embedded within a stack of electrode-separator assemblies and in contact with the electrolyte. The electrode-separator assemblies include anode electrodes 114 having anode tabs 114 a , separators 116 and cathode electrodes 118 having cathode tabs 118 a . Battery 110 further includes one low-resistance negative terminal LoR(â) 120 and one high-resistance negative terminal HiR(â) 122 , switch 124 and positive terminal (+) 126 .
In this embodiment, each resistor sheet has two tabs ( 112 a , 112 b ), which can be attached by welding. Resistor tab 112 a and anode tabs 114 a of anode electrodes 114 are electrically connected to low-resistance negative terminal LoR(â) 120 to form a low electrical resistance circuit. Resistor tab 112 b is electrically connected to high-resistance negative terminal HiR(â) 122 to form a high electrical resistance level circuit that is activated by switch 124 . Cathode tabs 118 a of cathode electrodes 118 are electrically connected together and to positive terminal 126 . In this particular example, switch 124 is a thermally activated switch that can electrically connect or disconnect LoR(â) terminal 120 and HiR(â) terminal 122 .
The anode-separator-cathode-resistor sheet assembly can be placed in an appropriate package, e.g., in a casing of a pouch cell and filled with electrolyte. In this embodiment, the anode-separator-cathode-resistor sheet assembly is contained in casing 140 . The negative and positive terminals can be electrically connected to an external circuit
128 a and 128 b.
In sum, the rechargeable battery illustrated in FIG. 1A features three terminals on the outside, two negative terminals, LoR(â) and HiR(â), and one positive terminal (+). The two negative terminals, LoR(â) and HiR(â), are further connected by a temperature-sensitive switch immediately outside of the battery. In operation, when the battery temperature is above T 1 , the switch is CLOSED and the battery current bypasses the resistor sheets since current prefers to flow through the low-resistance circuit. In this case, the battery operates between the terminals (+) and LoR(â), exhibiting a low internal resistance. When the battery temperature falls below T 1 , the switch is made OPEN, leaving the terminals (+) and HiR(â) operative. This forces the battery current to flow through the resistor sheets and hence exhibits high internal resistance. For example, when the battery temperature is below a normal range, such as below about 5° C. or in subfreezing environments, the internal resistance of the battery becomes several-fold higher due to the presence of the resistor sheets in the current flow path. Once operated or activated, there is intense internal heating (as the battery's heat generation is proportional to its internal resistance), which leads to rapid rise of the battery temperature to a point that triggers the temperature-sensitive switch to CLOSED. The CLOSED switch immediately enables the LoR(â) terminal to be operative and lowers battery internal resistance. The combination of low internal resistance and high internal temperature substantially improves power and energy output of the battery despite operating in subfreezing environments.
Another embodiment is to place a switch between the positive terminal and HiR(â) terminal of an ohmically modulated battery. When the battery temperature is above T 1 , the switch is OPEN and the battery operates between the positive and LoR(â) terminals and the battery current bypasses the resistor sheets, exhibiting a low internal resistance. When the battery temperature falls below T 1 , the switch is made CLOSED while leaving the positive and LoR(â) terminals at open circuit. This forces the battery current to flow through the resistor sheets and hence rapid internal heating. Once the battery temperature rises to a point, the temperature-sensitive switch is triggered to OPEN.
FIG. 1B shows another, partial illustration of the battery described for FIG. 1A . FIG. 1B shows a three-terminal ohmically modulated battery in a prismatic configuration having cathode electrode 118 and resistor sheet 112 adjacent anode electrode 114 . The cell would further include electrolyte and a separator, which are not shown for illustrative convenience. Cathode electrode 118 includes tab 118 a , resistor sheet 112 includes tabs
112 a and 112 b and anode electrode 114 includes tab 114 a . The battery further includes one low-resistance negative terminal LoR(â) 120 and one high-resistance negative terminal HiR(â) 122 , switch 124 and positive terminal (+) 126 . The elements of the battery shown in FIG. 1B are electrically connected as described for FIG. 1A .
FIG. 1C shows another arrangement for the battery described in FIG. 1A . In this embodiment, the battery is in a prismatic configuration. As shown in FIG. 1C , the ohmically modulated battery can be configured with four terminals, e.g., positive terminal 126 , low resistance negative terminal LoR(â) 121 , and two high resistance terminals HiR(â) 123 , 125 . Resistor sheet 113 includes two tabs ( 113 a , 113 b ) which form two HiR(â) terminals ( 123 , 125 ) which is independent from the LoR(â) terminal 121 . One of the HiR(â) terminals can be connected externally with the LoR(â) terminal, essentially reducing this 4-terminal battery into the 3-terminal battery shown in FIG. 1B . Or, one of the HiR(â) terminals can be electrically connected to one of the HiR(â) terminals from an adjacent cell in a multi-cell battery or module, forming a serially connected plurality of resistor sheets. The plurality of resistor sheets can then be connected into a multi-cell circuit by using only one switch.
While the battery in FIG. 1A is illustrated with three unit cells and two resistor sheets electrically connected in parallel and one switch for activating the battery in the high or low resistance mode, the ohmically modulate rechargeable battery of the present disclosure can have additional modules and/or additional unit cells. The battery can include additional resistor sheets and switches. For example, the battery can comprise more than one module or pack of cells where the cells in the module are adjacent each other and electrically connected to each other in a parallel or in a series arrangement or combinations thereof. The battery can include a plurality of resistor sheets that are electrically connected to each other in series or in parallel and located between adjacent cells in a module and plurality of thermally activated switches to operate the battery in a high or low resistance mode.
In other embodiments of an ohmically modulated battery, a rechargeable battery can be configured by placing one or more resistor sheets outside a cell of the battery. For example, with a battery module including multiple cells, the one or more resistor sheets can be sandwiched between two adjacent cells within the battery module. FIG. 2 illustrates such an embodiment.
As shown in FIG. 2 , battery module 210 includes resistor sheet 212 positioned between two cells
213 a and 213 b . The resistor sheet is preferably positioned between the cells to provide even heating of the cells and battery module, such as interposed tightly between two cells. Each cell includes anode electrodes 214 , separators 216 and cathode electrodes 218 . Battery module 210 further includes one low-resistance negative terminal LoR(â) 220 which is electrically connected to each cell of the module and one high-resistance negative terminal HiR( ) 222 , which is electrically connected to the resistor sheet. The battery module also includes switch 224 and positive terminals (+) 226 a and 226 b . The negative and positive terminals can be electrically connected to an external circuit
228 a and 228 b.
In sum, the rechargeable battery illustrated in FIG. 2 features two-terminal cells in which one terminal (in this embodiment the negative terminal) is electrically connected to a switch which is further electrically connected to a resistor sheet. The rechargeable battery module 210 of FIG. 2 can be operated in the same manner as described for FIG. 1 .
While battery module 210 in FIG. 2 is illustrated as a twin-cell module with one resistor sheet between the two cells, ohmically modulated batteries of the present disclosure can have additional cells and/or modules and/or resistor sheets and/or switches. For example, the battery module can have 4, 5 or 6 cells with one or more resistor sheets positioned between cells and around other positions near the cells. The battery can have additional modules with one or more resistor sheets positioned between modules and around other positions near the modules. The battery can have additional switches to connect the additional resistor sheets or one switch connecting all of the resistor sheets. The cells and/or the module can be electrically connected to each other in a parallel or in a series arrangement or combinations thereof. The resistor sheets can also be electrically connected to each other in series or in parallel.
All afore-described battery designs are applicable to rechargeable batteries such as Li-ion, nickel-metal hydride, lead-acid, etc. Advantageously, the rechargeable battery of the present disclosure can be implemented for all battery chemistries, such as rechargeable lithium ion, nickel-metal hydride, or advanced lithium batteries such as lithium-sulfur, lithium-air batteries or all solid-state batteries, and for all form factors, either pouch, cylindrical, prismatic or angular. The cell structure can accommodate rolled electrode and stacked electrode designs, among others.
Fast Charging at Low Temperatures
Another advantage of ohmically modulated rechargeable batteries is that they can be configured for fast charging at low temperatures. Preferably, the ohmically modulated batteries can be charged within a period of about 20-30 minutes at low temperatures without causing lithium plating or other appreciable degradation. The ohmically modulated battery can also advantageously be charged by regenerative power for simultaneous electric charging and internal heating.
For example in one embodiment of the present disclosure, an ohmically modulated battery can be included in a charging control system. The system can include a temperature sensor configured to monitor a temperature of the battery and a controller electrically connected to the temperature sensor that can receive inputs from the sensor and is programmed to determine whether to charge the battery in a low temperature resistance protocol or another protocol, e.g. a second protocol, based on the input from the temperature sensor.
The system can include additional components, individually or in combination, such as one or more of a voltage sensor electrically connected to the battery, e.g., a voltage sensor electrically connected to either the low-resistance terminal and or the high resistance terminal of the ohmically modulated battery; a current sensor electrically connected to the battery and capable of measuring current flowing through the battery; and/or a generator electrically connected to the battery and capable of charging the battery. The generator can be used to capture kinetic energy, such as in regenerative braking in vehicles, and charge the battery with such energy. With these additional optional components, the controller is capable of receiving inputs from the temperature sensor, the one or more voltage sensors and the current sensor and is capable of determining whether to charge the battery based on said inputs. Advantageously, the controller is further capable of setting the battery to a high resistance level or a low resistance level based on the temperature of the battery in certain embodiments.
In practicing certain embodiments of the present disclosure, an ohmically modulated rechargeable battery can be charged under a low temperature charging protocol (LTCP) when the battery is in a high resistance mode, e.g., when the temperature of the battery is below a predetermined charge temperature (T CG1 ). In addition, the battery can be charged under another or a second protocol (e.g. a normal charging protocol that is used at normal operating temperatures) when the battery is in a low resistance mode. LTCPs include charging the battery under constant voltage, and/or at a constant current (I) and/or at a constant charging power (P) and combinations thereof. In one embodiment of the present disclosure, the LTCP includes: (i) charging the battery at either a constant voltage or a constant charging power (P); and (ii) followed by charging the battery at a constant current. Charging the battery at the constant current can occur when the charging current reaches or exceeds a predetermined maximum charge current (I max ). Further, the constant voltage can be determined from either the low-resistance terminal voltage V LoR and/or the voltage of the battery. The LTCP also can include charging the battery under a pulse voltage and/or pulse power and/or pulse current and combinations thereof. Charging under the second protocol when the battery is in a low resistance mode can include a constant current-constant voltage protocol, for example.
FIG. 3A illustrates a charging control system 600 A that supports fast charging of an ohmically modulated battery at low temperatures in accordance with an embodiment of the present disclosure. Charging control system 600 A includes ohmically modulated battery 601 . In a preferred embodiment, lithium-ion is used as the cell chemistry for battery 601 . However, the control system is applicable to other cell chemistries as well.
As shown in FIG. 3A , battery 601 has one positive terminal (not shown) and two negative terminals
612 and 613 , wherein 612 is the low-resistance negative terminal LoR(â) and 613 is the high-resistance negative terminal HiR(â). Switch 609 is electrically connected to LoR(â) terminal 612 and HiR(â) terminal 613 . LoR(â) terminal 612 is engaged when switch 609 is on, and HiR(â) terminal 613 is engaged when switch 609 is off. Switch 609 is operated by controller 604 in the present embodiment. Battery 601 is connected to charger 602 through switch 610 and to load 603 through switch 611 . Battery 601 is also connected to a current sensor 605 for measuring charging current, a temperature sensor 608 for detecting a temperature of battery 601 , and two voltage sensors
606 and 607 . Voltage sensor 606 is connected to low-resistance negative terminal 612 for monitoring low-resistance terminal voltage V LoR of battery 601 . Voltage sensor 607 is connected to high-resistance negative terminal 613 for measuring the voltage V of battery 601 .
In operation, controller 604 receives information about charging/discharging current signal I (positive for charging, negative for discharging) from current sensor 605 , temperature signal T from temperature sensor 608 , battery low-resistance voltage signal V LoR from voltage sensor 606 and battery voltage signal from voltage sensor 607 . The <figure-callout id="604" label="controller" filenames=
CLAIMS
Claims ( 20 )
What is claimed is:
1. A charging control system for charging an ohmically modulated rechargeable battery comprising:
an ohmically modulated battery comprising at least one negative terminal and at least one positive terminal for operating the battery at a low resistance level and at least one high resistance terminal for operating the battery at a high resistance level through at least one resistor sheet within a cell of the battery or between cells of the battery, wherein the at least one resistor sheet includes two tabs with one tab electrically connected to the at least one high resistance terminal and the other tab electrically connected to either the at least one negative terminal or the at least one positive terminal;
a temperature sensor configured to monitor a temperature of the battery;
a switch that can electrically engage the battery to a source of electrical current through either a low-resistance terminal or the high-resistance terminal of the battery; and
a controller electrically connected to the temperature sensor and the switch and that can receive input from the temperature sensor and is programmed to determine whether to electrically engage the battery to the source of electrical current through either the low-resistance terminal or the high-resistance terminal based on input from the temperature sensor.
2. The charging control system according to claim 1 , further comprising:
a current sensor electrically connected to the battery and capable of measuring current flowing through the battery and/ or a voltage sensor electrically connected to the battery;
wherein the controller can receive inputs from the temperature sensor and the current sensor and/or voltage sensor and is programmed to determine whether to electrically engage the battery to the source of electrical current through either the low-resistance terminal or the high-resistance terminal based on inputs from the sensors.
3. The charging control system according to claim 1 , wherein the switch can electrically engage the high-resistance terminal to the at least one positive terminal of the battery as the low resistance terminal of the battery.
4. The charging control system according to claim 1 , further comprising a generator electrically connected to the battery and capable of charging the battery.
5. An electrically powered vehicle comprising the charging control system of claim 4 .
6. The charging control system according to claim 1 , wherein the ohmically modulated rechargeable battery comprises lithium ion cells.
7. The charging control system according to claim 1 , wherein the at least one resistor sheet is within a cell of the battery.
8. The charging control system according to claim 7 , wherein the at least one resistor sheet comprises nickel, copper, aluminum, or combinations thereof.
9. A method of charging an ohmically modulated rechargeable battery, the method comprising:
charging the battery under a low temperature charging protocol (LTCP) when the battery is in a high resistance mode; and
charging the battery under a second protocol when the battery is in a low resistance mode
wherein the ohmically modulated battery comprises at least one negative terminal and at least one positive terminal forming the low resistance mode of the battery and at least one high resistance terminal forming the high resistance mode of the battery through at least one resistor sheet within a cell of the battery or between cells of the battery, wherein the at least one resistor sheet includes two tabs with one tab electrically connected to the at least one high resistance terminal and the other tab electrically connected to either the at least one negative terminal or the at least one positive terminal.
10. The method according to claim 9 , wherein the LTCP includes: (i) charging the battery at either a constant voltage or a constant charging power (P); and (ii) followed by charging the battery at a constant current; wherein the constant voltage is determined either at the low-resistance terminal voltage V LoR of the battery or at the voltage of the battery.
11. The method according to claim 10 , wherein charging the battery at the constant current occurs when the charging current reaches or exceeds a predetermined maximum charge current (I max ).
12. The method according to claim 9 , wherein the LTCP includes charging the battery by alternatively applying charging and discharging pulse power to the battery.
13. The method according to claim 9 , further comprising charging the battery in the high resistance mode when a temperature of the battery is below a predetermined level T CG1 and charging the battery in the low resistance mode when the temperature of the battery is equal to or above T CG1 .
14. The method according to claim 13 , wherein TCGI is a value between 5° C. and 25° C.
15. The method according to claim 9 , wherein the ohmically modulated rechargeable battery comprises lithium ion cells.
16. The method according to claim 9 , wherein the at least one resistor sheet is within a cell of the battery.
17. The method according to claim 9 , wherein the LTCP includes charging the battery at a constant current (I) in the range of 1Câ¤Iâ¤I max , wherein I max is a predetermined maximum charge current.
18. A charging control system for charging an ohmically modulated rechargeable battery comprising:
an ohmically modulated battery comprising at least one negative terminal and at least one positive terminal forming a low resistance circuit and at least one high resistance terminal electrically connected to a plurality of resistor sheets within cells of the battery or between cells of the battery or a combination thereof forming a high resistance circuit, wherein each resistor sheet of the plurality of resistor sheets has two tabs, one tab forming the electrical connection to the at least one high resistance terminal and the other tab forming an electrical connection to either the at least one negative terminal or the at least one positive terminal;
a temperature sensor configured to monitor a temperature of the battery;
a switch that can electrically engage the battery to a source of electrical current through either a low-resistance terminal or the high-resistance terminal of the battery; and
a controller electrically connected to the temperature sensor and the switch and that can receive input from the temperature sensor and is programmed to determine whether to electrically engage the battery to the source of electrical current through either the low-resistance terminal or the high-resistance terminal based on input from the temperature sensor.
19. The charging control system according to claim 18 , wherein the ohmically modulated rechargeable battery comprises lithium ion cells and the plurality of resistor sheets are within the lithium ion cells.
20. The charging control system according to claim 19 , further comprising:
a current sensor electrically connected to the battery and capable of measuring current flowing through the battery and/ or a voltage sensor electrically connected to the battery;
wherein the controller can receive inputs from the temperature sensor and the current sensor and/or voltage sensor and is programmed to determine whether to electrically engage the battery to the source of electrical current through either the low-resistance terminal or the high-resistance terminal based on inputs from the sensors.
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