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Ohmically modulated battery — Ec Power, Llc (US9692087B2)

Ec Power, Llc · Google Patents

Google Patents · Patents · License: Open Access

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chao ecpower yangwang

patent, google patents, intellectual property, US9692087B2, Ec Power, Llc, Chao-Yang Wang, en, 2017

ABSTRACT

Abstract

A rechargeable battery whose ohmic resistance is modulated according to temperature is disclosed.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Divisional of U.S. patent application Ser. No. 14/267,648, filed May 1, 2014, which claims the benefit of U.S. Provisional Application No. 61/890,012, filed Oct. 11, 2013, the entire disclosures of which are hereby incorporated by reference herein.

TECHNICAL FIELD

The present invention relates generally to rechargeable batteries, and more particularly, to a rechargeable battery engineered to have more than one internal resistance levels. The internal resistance level changes substantially with temperature. Such batteries can have improved performance and safety and include lithium-ion batteries for electronics, vehicles, and grid energy storage.

BACKGROUND

Energy-dense rechargeable batteries for electronics, transportation and grid energy storage commonly suffer from low performance at low temperatures and safety problems at high temperatures. At low temperatures, especially subfreezing temperatures, rechargeable batteries, especially lithium-ion batteries, exhibit very low power performance and low energy due to sluggish electrochemical kinetics and transport processes occurring in the battery cell. At high temperatures, lithium-ion batteries have a strong tendency to undergo thermal runaway, leading to significant hazards. There is a need for rechargeable batteries with improved performance at low temperatures and/or improved high-temperature safety.

SUMMARY OF THE DISCLOSURE

An advantage of the present disclosure is an ohmically modulated rechargeable battery, such as a lithium ion battery engineered to have two or more internal resistance levels that can change substantially with battery temperature. The ohmic modulation mechanism can be implemented by either active or passive configurations. Advantageously, such batteries can be operated at one internal resistance level over one temperature range and at other internal resistance levels at other temperatures or ranges. The difference between various internal resistance levels can be a factor of two to fifty or higher. Switching between different resistance levels can improve the performance and safety of rechargeable batteries. For example, when the battery temperature rises above a normal operating range, e.g., about 45Â° C. to 55Â° C. or higher, the battery's internal ohmic resistance can increase sharply so that maximum charge/discharge current possible is kept at low levels, which in turn reduces the internal heat generation substantially. The combination of much lower maximum possible current and much lower internal heat generation rate promotes battery safety at high temperatures.

These and other advantages are satisfied, at least in part, by a rechargeable battery comprising 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 , wherein the value of R 2 at about 2Â° C. below T 1 is at least twice the value of R 1 at T 1 or the value of R 2 at about 2Â° C. above T 2 is at least twice the value of R 1 at T 2 . The rechargeable battery can have additional resistance levels, e.g., a third resistance level (R 3 ) associated with a third temperature (T 3 ) or over a third temperature range (T 3 , T 4 ), and so forth. Advantageously, the value of R 2 at about 2Â° 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 2Â° 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 .

In certain aspects of the present disclosure, a rechargeable battery includes terminals for operating the battery at R 1 , e.g., a positive and a negative terminal for operating the battery at R 1 , at least one high resistance terminal for operating the battery at R 2 ; and a switch that activates R 2 when the temperature of the battery is outside of either T 1 or T 2 . The high resistance terminal can be electrically connected to at least one resistor sheet within a cell of the battery or between cells of the battery. Embodiments of such a battery include wherein the at least one resistor sheet is configured to have two tabs, with one tab electrically connected to other electrode tabs in the battery to form a low-resistance terminal, and the other tab of the at least one resistor sheet forming the at least one high-resistance terminal or wherein the at least one resistor sheet is the same as either or both of the two metal current collectors used in a battery cell, or a portion of the two metal current collectors.

For example, the rechargeable battery can include one or more resistor sheets embedded within stacks or jelly-rolls of electrode-separator sheets of a conventional battery and three terminals for operating the battery. The terminals allow operation of the battery at a low-resistance level R 1 or at a high-resistance level R 2 . The three terminals can include either of one positive and two negative terminals or two positive terminals and one negative terminal. The former configuration is preferred. The two same-polarity terminals can further be connected by a switch that is self-activated thermally or driven by a temperature controller such that the battery switches between the terminals for operating the battery at R 1 and the terminals for operating the battery at R 2 , when the battery temperature exceeds a critical value.

Another embodiment of the disclosure includes a rechargeable battery having one or more resistor sheets interposed between tabs of a battery cell, or subgroups of tabs of a battery, or tabs of multiple battery cells. This construction has the benefit that Joule heating generated on resistors is isolated from active materials and electrolytes of battery cells.

Another embodiment of the disclosure includes a rechargeable battery having one or more electrodes containing one or more positive temperature coefficient (PTC) materials. The PTC material can be included with the conducting agent mixed with electrode slurries, or a thin coating on the surface of active electrode materials, or an interfacial coating interposed between the active electrode materials and current-collecting foil, or a coating onto tabs before being connected together. The PTC materials of the present disclosure exhibit orders-of-magnitude resistance increases above certain temperatures, e.g., above about 80Â° C., thereby further enhancing battery safety. The nonlinear behavior of PTC materials advantageously causes a substantial increase in internal resistance above certain temperatures, which can be reversed upon lowering of the battery temperature.

Another embodiment of the disclosure includes a rechargeable battery having one or more electrodes containing one or more thermally expandable polymers as a binder in making electrodes, or a binder in making a conductive glue for the interface between active materials and current-collecting foil, or a pore filler for porous electrodes. These polymers expand dramatically upon heating, thereby creating large increase in electrical resistance when used as binders or large increase in ionic resistance when used as pore fillers (due to restricting pore volume and increasing pore tortuosity for ion transport). Both results in a dramatic increase in battery resistance as the battery temperature become sufficiently high.

Another aspect of the present disclosure includes a rechargeable battery having a multi-level profile of battery resistance with step changes at more than one threshold temperature. Such a profile can provide multiple layers of defense.

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. 1 shows a resistance characteristic of an ohmically modulated battery (OMB) according to an embodiment of the present disclosure where the battery resistance is modulated to have a sharp increase in internal resistance at a threshold temperature T 2 in order to minimize the potential for thermal runaway and to promote battery safety.

FIGS. 2A-2D are schematic illustrations of a step-by-step mechanism of an OMB with a 10-times jump in battery resistance at threshold temperature T 2 according to an embodiment of the present disclosure.

FIGS. 3A, 3B and 3C show graphs illustrating the relationship of internal resistance as a function of temperature of an ohmically modulated rechargeable battery according to embodiments of the present disclosure. FIG. 3A illustrates the internal resistance vs. temperature relationship of an OMB as a bathtub profile and FIG. 3B illustrates the internal resistance vs. temperature relationship of an OMB as a step function. FIG. 3C is a chart showing the percent change in internal resistance over the change in temperature (dR/R/dT) for the resistance levels and temperatures associated with OMB according to an embodiment of the present disclosure.

FIG. 4 shows the internal resistance vs. temperature relationship of an OMB according to an embodiment of the present disclosure where the battery resistance increases to another level R 3 around at a third temperature T 3 .

FIG. 5 is a schematic showing construction of an OMB 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. 6 illustrates another OMB composed of one resistor sheet embedded in the middle of a stack of electrode-separator assembly according to an embodiment of the present disclosure.

FIGS. 7A-7D show four designs of resistor sheets with two tabs. One tab is electrically connected or welded to all tabs of negative electrode sheets to form LoR(â) terminal, and the other connected to the HiR(â) terminal. 7 A: two tabs located on the same side of the sheet separated by a small cut in the middle to control the resistance path between the two tabs. 7 B: two tabs are located on the opposite side. 7 C: two tabs are located on the same side toward the outer edges. 7 D: two tabs on the opposite side toward the outer edges.

FIG. 8 illustrates a resistor sheet interposed between tabs of two electrodes of a battery cell according to an embodiment of the present disclosure.

FIG. 9 shows 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. 10 illustrates a pair of jelly rolls sandwiching one resistor sheet/foil before inserting into a hard case or being packaged into a pouch cell, according to an embodiment of the present disclosure.

FIG. 11 is a schematic illustrating an unfolded jelly roll contained in a pouch cell wherein the positive electrode sheet has a number of closely spaced tabs welded together to form the positive terminal (+), and the negative electrode sheet has some closely spaced tabs welded together to form a low-resistance terminal LoR(â) as well as a far-away tab forming the high-resistance terminal HiR(â), according to an embodiment of the present disclosure. The LoR(â) terminal is connected with the HiR(â) terminal by a thermally activated switch.

FIG. 12 illustrates a different design of an unfolded jelly roll with both the positive and negative electrode sheets featuring a number of closely spaced tabs and a far-away tab, respectively, according to an embodiment of the present disclosure. This design has four terminals outside the cell casing, i.e. two positive, LoR(+) and HiR(+), and two negative, LoR(â) and HiR(â). The two switches on both sides provide more than two levels of internal resistance according to the battery temperature and switching algorithms.

FIGS. 13, 14 and 15 illustrate flat jelly roll electrode assemblies having one or more resistor sheets according to the embodiment of the present disclosure.

FIGS. 16A-16B compare electrical current and cell temperature responses in external shorting experiments of an OMB constructed according to an embodiment of the present disclosure with a conventional Li-ion battery (LiB). FIG. 16A compares the shorting current responses of the OMB with the conventional LiB. FIG. 16B compares the battery temperature responses of the OMB with the conventional LiB.

DETAILED DESCRIPTION OF THE DISCLOSURE

The present disclosure relates to a rechargeable battery that can modulate its internal resistance according to temperature. 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 levels that can change substantially with battery temperature.

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 2Â° C. below T 1 is at least twice the value of R 1 at T 1 or the value of R 2 at about 2Â° C. above T 2 is at least twice the value of R 1 at T 2 . Advantageously, the value of R 2 at about 2Â° 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 2Â° 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 .

In an embodiment an ohmically modulated rechargeable battery, the rate of the change in internal resistance over the change in temperature

(

dR R

â¢

â¢ dT

)

is greater than 10% per degree of Celsius in temperature, e.g. greater than 20%, 30%, 40%, or 50% per degree of Celsius in temperature, but less than 200,000% per degree of Celsius in temperature, e.g., less than 100,000%, 50,000% per degree of Celsius in temperature. In one aspect of the present disclosure, the rate of the change

CROSS-REFERENCE TO RELATED APPLICATIONS

TECHNICAL FIELD

BACKGROUND

SUMMARY OF THE DISCLOSURE

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. 6 illustrates another OMB composed of one resistor sheet embedded in the middle of a stack of electrode-separator assembly according to an embodiment of the present disclosure.

FIG. 8 illustrates a resistor sheet interposed between tabs of two electrodes of a battery cell according to an embodiment of the present disclosure.

FIGS. 13, 14 and 15 illustrate flat jelly roll electrode assemblies having one or more resistor sheets according to the embodiment of the present disclosure.

DETAILED DESCRIPTION OF THE DISCLOSURE

In an embodiment an ohmically modulated rechargeable battery, the rate of the change in internal resistance over the change in temperature

(

dR R

â¢

â¢ dT

)

(

dR R

â¢

â¢ dT

)

is between about 50% but smaller than 5,000% per degree of Celsius in temperature. Conventional Li-ion batteries do not change internal resistance by more than a few percent for every degree of Celsius and cannot substantially change to another internal resistance level other than by a short circuit or separator shutdown, which results in a change rate of internal resistance likely much higher than 500,000%. Battery internal resistance R can be measured using standard DC or AC methods at discrete temperatures, and then the derivative dR/dT can be calculated from an R vs. T curve.

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, nickel-manganese-cobalt, 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 5Â° C. or in subfreezing environments (temperatures less than about 0Â° C., e.g., less than about â10 or â20Â° 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 Î©cm 2 to about 200 Î©cm 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.

The rechargeable battery of the present disclosure can also be configured to switch to a high internal resistance once the battery's internal temperature exceeds the high end of the normal operating range, e.g. above T 2 . Temperatures that exceed the normal operating range depend upon several factors including the battery type. Such high end temperatures include, for example, above about 45Â° C., such as above about 50Â° C., 60Â° C., 70Â° C. and as high as about 130Â° C. Such higher internal temperatures can occur during abuse or a faulty event. The high internal resistance causes much enlarged cell voltage overshoot in the cell overcharge case, thus greatly facilitating early detection and shutdown of external charging systems before the cell enters a thermal runaway condition. In a short circuit case, for example, the higher internal resistance will release battery energy at a slower and controlled rate, thereby slowing down the rate of the cell temperature rise and protecting the cell from thermal runaway. This high internal resistance feature at the high end of the normal temperature range can facilitate the inherent safety of the battery.

An advantage of the ohmically modulated battery of the present disclosure is that the internal resistance of the battery can jump sharply when the battery temperature reaches a threshold point T 2 , as shown in FIG. 1 . The resistance jump quickly suppresses the discharge/charge current and then significantly reduces the internal heat generation. This can be illustrated as shown in FIG. 2 . As shown in the figure, with a 10-times jump in battery resistance at threshold temperature T 2 ( FIG. 2 a ) leads to a significant drop in current ( FIG. 2 b ) and heat generation ( FIG. 2 c ) which in turn slows the rate of temperature rise ( FIG. 2 d ). The increased battery resistance at T 2 reduces the rate of battery temperature rise, thereby minimizing or avoiding thermal runaway and promoting battery safety under any abuse conditions. T 2 is preferably set in at a temperature having a value within a range between about 45Â° C. and about 130Â° C., e.g. within a range between about 60Â° C. and about 100Â° C.

The ohmically modulated battery is not limited to having a resistance jump at the threshold temperature T 2 for high-temperature safety, it can also have a resistance increase occurring at a low temperature T 1 at or around subzero temperatures so as to generate internal heat and provide high power output when operated at subfreezing ambient temperatures. It is preferred for a single rechargeable battery to be configured to have a high internal resistance at both low and high temperatures, e.g., R 2 changes both below T 1 and above T 2 . Such a rechargeable battery can then have both high power at low temperatures and high safety at high temperatures.

An example of an idealized resistance to temperature relationship of such a rechargeable battery having two resistance levels is schematically illustrated in FIGS. 3A and 3B . FIG. 3A illustrates the internal resistance vs. temperature relationship of an OMB as a bathtub profile and FIG. 3B illustrates the internal resistance vs. temperature relationship of an OMB as a step function. In these figures, the battery's internal resistance is modulated to a high level below a low temperature T 1 in order to rapidly warm up the battery and hence provide high power output at below operating temperatures and the battery's internal resistance is modulated to a high level above a high temperature T 2 to provide significantly improved safety at high temperatures.

As shown in the figures, during a normal operating temperature range, e.g., T 1 <T<T 2 , where T 1 is about 0Â° C. and T 2 is about 50Â° C., for example, the battery exhibits a low internal resistance (R 1 ) similar to the internal resistance experienced in a conventional rechargeable battery, e.g., such as a Li-ion battery. However, outside this operating temperature range, the internal resistance of the battery jumps to a higher level (R 2 ) where R 2 is preferably at least 2 to 5 times R 1 , e.g., at least 10, 20 or as high as 50 times the value of R 1 , when the value for R 2 is determined within about 2Â° C. of T 1 and/or T 2 .

FIG. 3C is a chart showing the percent change in internal resistance over the change in temperature

(

dR R

â¢

â¢ dT

)

for the resistance levels and temperatures associated with OMB according to an embodiment of the present disclosure. In this figure, the percent change in internal resistance over the change in temperature

(

dR R

â¢

â¢ dT

)

is over 10% and 70% per Â° C. Battery resistance R is measured by standard DC or AC methods at various discrete temperatures. Subsequently, dR/dT is calculated by taking the derivative of the R vs. T relationship.

In another aspect of the present disclosure, the OMB can include a third level of internal resistance (R 3 ) when the battery reaches a third temperature (T 3 ). Preferably, the value of R 3 changes abruptly or sharply above T 3 , e.g. the value of R 3 at about 2Â° C. above T 3 is at least twice, e.g. at least 5, 10, 20 times or higher, the value of R 2 at T 3 . In one aspect of the present disclosure, T 3 is a temperature having a value within a range between about 80Â° C. and about 130Â° C.

FIG. 4 illustrates a rechargeable battery having three resistance levels. As shown in the figure, the rechargeable battery has three internal resistance levels that are operated at different temperatures. After the battery temperature passes a higher threshold point T 3 , the battery is operated at a third level of resistance R 3 . Such a battery provides a double defense mechanism for the battery and improves the safety of the battery at elevated temperatures.

Advantageously, the rechargeable battery of the present disclosure can be readily configured with conventional rechargeable battery components with minimal modification in certain embodiments. In general terms, a conventional battery, such as a lithium-ion battery, includes sheets of one or more anode electrodes, separators and cathode electrodes either stacked up or wound in a jelly roll that are packaged in a pouch cover or hard case. Then the pouch or case is filled with an electrolyte. The cathode active materials can include lithium cobalt oxide, lithium iron phosphate, lithium manganese oxide, lithium nickel-cobalt-manganese oxides, lithium-rich layered oxides, or their mixtures. Anode active materials can include graphite, silicon, silicon alloys, lithium metal, lithium alloys such as lithium titanate, their mixtures, etc.

For example, a conventional lithium-ion battery includes a positive electrode, a negative electrode, a separator, a positive electrode current collector, a negative electrode current collector, an electrolyte and a battery cover or can. The positive electrode coated on one current collecting foil (e.g. Al foil) and the negative electrode coated on another current collecting foil (e.g. Cu foil) are stacked or wound with a separator interposed in-between, and an electrolyte solution in which an electrolyte is dissolved in a solvent is impregnated in the separator and the two porous electrodes.

Both positive and negative electrodes include afore-described active materials, binders and conducting agents if necessary. Common binders include PVDF (Polyvinylidene fluoride) and styrene-butadiene rubber (SBR) and sodium salt of carboxymethyl cellulose (CMC). Conducting agents are usually carbon-based and mixed with the active materials to increase the electrode conductivity.

Lithium salts such as LiPF 6 , LiBF 4 , etc. can be used singly or in combination as the electrolyte. Chained carbonate, annular carbonate, annular ester, nitrile compounds and the like can be used as the solvent used to dissolve the lithium salts. Specific examples thereof include ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), propylene carbonate (PC), diethyl carbonate, dimethoxyethane, etc. In addition, a polymer-gel electrolyte or a solid electrolyte can be used as the electrolyte.

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 of the present disclosure 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), between T 1 and T 2 and 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 outside of either T 1 or T 2 . 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 between T 1 and T 2 , and can engage one or more high resistance terminal, e.g., HiR(â) and/or HiR(+), when the battery temperature is outside of either T 1 or T 2 .

The switch of the present disclosure can include those activated by thermally sensitive devices such as a glycol-water liquid capsule that expands upon freezing and pushes the switch open, a phase-change material that undergoes phase transition and appreciable volume change at T 1 or T 2 or both, or a bimetal switch, or a solid material whose volume expands appreciably at temperature T 1 or T 2 or both, for example.

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. In addition, 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 similar or lower electrical conductivity relative to an unmodified current-collecting foil of a battery's electrode but causes a significant increase in the internal electrical resistance of the battery when activated during battery operation. 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 sufficiently conductive material 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, for example, graphite, highly ordered pyrolytic graphite (HOPG), stainless steel, nickel, chrome, nichrome, copper, aluminum, titanium, or combinations thereof. If used outside of 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. In certain embodiments, the resistor sheet of the present disclosure is preferably flat with a large surface area so that it can have good contact with adjacent battery components. The resistor sheets of the present disclosure can have a thickness between about 1 micrometer 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 internal resistance mode.

FIGS. 5 and 6 illustrate additional embodiments of the present disclosure. As shown in FIG. 5 , rechargeable battery 110 has several resistor sheets 112 embedded within a stack of electrode-separator assemblies. 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 place 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. 5 features three terminals on the outside of casing 140 , 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 within a normal operating range, defined as between a first temperature T 1 and a second temperature T 2 , 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 goes outside the normal range of T 1 and T 2 , 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 above a normal range, such as above about 45Â° C., the internal resistance of the battery becomes several-fold higher due to the presence of the resistor sheets in the current flow path.

FIG. 6 shows another configuration of a rechargeable battery having at least one resistor sheets inserted between a stack of the electrode-separator assemblies for increasing the internal resistance of the battery. In this embodiment, rechargeable battery 210 includes resistor sheet 212 positioned between two electrode- separator assemblies

213 a and 213 b . The resistor sheet is preferably positioned in the middle of the stack of electrodes and can be sandwiched by separators 217 that can be the same or different than separators 216 . Each electrode-separator assembly includes anode electrodes 214 , separators 216 and cathode electrodes 218 . Battery 210 further includes one low-resistance negative terminal LoR(â) 220 , one high-resistance negative terminal HiR(â) 222 , switch 224 and positive terminal (+) 226 .

In this embodiment, resistor sheet 212 has two tabs ( 212 a , 212 b ), which can be attached by welding. Resistor tab 212 a and anode tabs 214 a of anode electrodes 214 are electrically connected to low-resistance negative terminal LoR(â) 220 to form a low electrical resistance circuit. Resistor tab 212 b is electrically connected to high-resistance negative terminal HiR(â) 222 to form a high electrical resistance level circuit that is activated by switch 224 . Cathode tabs 218 a of cathode electrodes 218 are electrically connected together and to positive terminal 226 . In this particular example, switch 224 is a thermally activated switch that can electrically connect or disconnect LoR(â) terminal 220 and HiR(â) terminal 222 .

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 240 . The negative and positive terminals can be electrically connected to an external circuit

228 a and 228 b . The rechargeable battery 210 of FIG. 6 can be operated in the same manner as described for FIG. 5 .

FIGS. 7A-7D illustrate different resistor sheet configurations that can be used in the rechargeable batteries of the present disclosure, including in the configurations shown in FIGS. 5 and 6 . Each resistor sheet, 310 , 320 , 330 , 340 , has two tabs, which can be attached by welding. The tabs on the various resistor sheets can be positioned in various configurations, as shown in FIGS. 7A-7D . These configurations include (a) 2 tabs on the same side ( 311 , 312 ), separated by cut 314 ; (b) 2 tabs on the opposite side of the resistor sheet and located at approximately in the middle of the edge ( 321 , 322 ) and separated by cut 334 ; (c) 2 tabs on the same side but on the outer edges of the resistor sheet ( 331 , 332 ); and (d) 2 tabs on the opposite side of the resistor sheet but on outer edges ( 341 , 342 ). In one embodiment of the present disclosure, one or more of the resistor sheets shown in FIGS. 7A-7D can be used in the configurations of FIG. 5 or 6 . For example, for any resistor sheet in FIGS. 7A-7D , the tabs labeled as Tab 1 can be connected (e.g. welded) with all tabs of the anode electrode sheets in the battery. Together, they form the low-resistance terminal LoR(â) in FIG. 5 or FIG. 6 . Tabs 2 as shown in FIGS. 7A-7D can be welded together to form the high-resistance terminal HiR(â) in either FIG. 5 or FIG. 6 .

Another embodiment of the present disclosure includes a rechargeable battery having one or more resistor sheets interposed between tabs of a battery cell, or subgroups of tabs of a battery, or tabs of multiple battery cells. The design in this embodiment can be used with any conventional rechargeable battery. FIG. 8 illustrates an embodiment of a rechargeable battery having a resistor sheet interposed between tabs of electrodes in a battery cell. This figure shows resistor sheet 812 interposed between tabs

814 a and 816 a of two electrodes, 814 and 816 . Resistor sheet tab 812 a is electrically connected to tabs

814 a and 816 a of electrodes

814 and 816 , e.g., anode electrodes of a cell and to a low-resistance negative terminal LoR(â) (not shown) to form a low electrical resistance circuit. Tab 812 b of the resistor sheet 812 is electrically connected to high-resistance negative terminal HiR(â) (not shown) to form a high electrical resistance level circuit. The rechargeable battery in this embodiment would also include a switch that can electrically connect or disconnect the LoR(â) terminal and the HiR(â) terminal and the battery with this configuration can be operated in the same manner as described for FIG. 5 .

While the battery configuration in FIG. 8 is illustrated with one resistor sheet interposed between two electrodes, additional resistor sheets can be interposed between additional electrodes to form a high resistance internal level of the battery. The use of one or more resistor sheets interposed between tabs of a battery cell has the benefit that Joule heating generated upon activation of the resistor sheet is isolated from the active materials of the electrode and the electrolyte of battery cells, thereby further enhancing battery safety. In one embodiment of the present disclosure, one or more of a resistor sheet shown in FIG. 8 can be used in the configurations of FIG. 5 or 6 .

In other embodiments of the present disclosure, 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. 9 illustrates such an embodiment.

As shown in FIG. 9 , battery module 410 includes resistor sheet 412 positioned between two cells

413 a and 413 b . The resistor sheet is preferably positioned between the cells of the battery module, such as interposed tightly between two cells. Each cell includes anode electrodes 414 , separators 416 and cathode electrodes 418 . Battery module 410 further includes one low-resistance negative terminal LoR(â) 420 which is electrically connected to each cell of

CLAIMS

Claims ( 19 )

What is claimed is:

1. A method of operating a rechargeable battery including at least one negative terminal and at least one positive terminal which forms a low internal resistance level (R 1 ); at least one high resistance terminal electrically connected to at least one resistor sheet within a cell of the battery or between cells of the battery which forms a high internal resistance level (R 2 ); and a switch that electrically connects or disconnects the at least one high resistance terminal with either the at least one positive or the at least one negative terminal having the low internal resistance level, the method comprising activating the switch to operate the battery at R 2 when a temperature of the battery is below a first temperature (T 1 ) or above a second temperature (T 2 ).

2. The method according to claim 1 , wherein T 2 is a temperature having a value within a range between about 45Â° C. and about 130Â° C.

3. The method according to claim 1 , wherein the at least one high resistance terminal for operating the battery at R 2 is an additional negative terminal.

4. The method according to claim 1 , wherein the switch is driven by a temperature sensor for switching between the terminals for operating the battery at R 1 and the terminals for operating the battery at R 2 .

5. The method according to claim 1 , wherein the switch is self-activated thermally for switching between the terminals for operating the battery at R 1 and the terminals for operating the battery at R 2 .

6. The method according to claim 1 , wherein the switch is 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, or a bimetal switch.

7. The method according to claim 1 , wherein the at least one resistor sheet is made of graphite, highly ordered pyrolytic graphite (HOPG), stainless steel, nickel, chrome, nichrome, copper, aluminum, titanium, or combinations thereof.

8. The method according to claim 1 , wherein the at least one resistor sheet 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).

9. The method according to claim 1 , wherein the at least one resistor sheet is sandwiched inside an electrode-separator stack or a jelly roll.

10. The method according to claim 1 , wherein the at least one resistor sheet is located between cells within a battery module.

11. The method according to claim 1 , wherein the battery is a lithium ion battery.

12. The method according to claim 1 , wherein the battery further includes a controller that can switch between operating the battery at R 1 and operating the battery at R 2 .

13. The method according to claim 1 , wherein the battery further includes a temperature sensor for determining the temperature of the battery.

14. The method according to claim 1 , comprising activating the switch to operate the battery at R 2 when the temperature of the battery is below T 1 .

15. The method according to claim 14 , wherein the at least one resistor sheet is within a cell of the battery.

16. The method according to claim 15 , wherein T 1 is about 5Â° C.

17. The method according to claim 1 , comprising activating the switch to operate the battery at R 2 when the temperature of the battery is above T 2 .

18. The method according to claim 17 , wherein T 2 is about 45Â° C.

19. The method according to claim 1 , wherein the value of R 2 at about 2Â° C. below T 1 is 2 to 50 times the value of R 1 at T 1 or the value of R 2 at about 2Â° C. above T 2 is 2 to 50 times the value of R 1 at T 2 .

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2019-06-28

HUE042190T2

( en )

2019-06-28

Ohmically modulated battery — Ec Power, Llc (US9692087B2)

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