ABSTRACT
Abstract
A bipolar capacitor-assisted solid-state battery is disclosed that includes a plurality of electrochemical battery unit cells, each of which includes a negative electrode, a positive electrode, and a lithium ion-conductive electrolyte-containing separator disposed between the negative electrode and the positive electrode. The lithium ion-conductive electrolyte-containing separator of each electrochemical battery unit cell comprises a solid-state electrolyte material, and, additionally, at least one negative electrode of the electrochemical battery unit cells or at least one positive electrode of the electrochemical battery unit cells includes a capacitor material. The bipolar capacitor-assisted solid-state battery further includes a bipolar current collector disposed between a negative electrode of one electrochemical battery unit cell and a positive electrode of an adjacent electrochemical battery unit cell. A method for manufacturing the disclosed bipolar capacitor-assisted solid-state battery is also disclosed.
Description
INTRODUCTION
Lithium ion batteries are a class of batteries that reversibly exchange lithium ions between opposed electrodes disposed on opposite sides of an electrolyte-containing separator. Solid-state lithium ion batteries include solid electrodes and an ionically-conductive solid electrolyte disposed between the electrodes. These types of batteries are different from more conventional battery architectures in which a microporous polymer with an infiltrated liquid electrolyte is positioned between the electrodes to facilitate ionic transport. Solid-state batteries have the potential to achieve higher energy densities and to operate within a wider temperature window than current lithium ion batteries that utilize a free liquid electrolyte. Eliminating the need to use a free-flowing liquid electrolyte, which typically includes a non-aqueous solvent and a dissolved lithium salt for lithium ion mobility, may also desired in certain battery applications.
The use of lithium ion batteries may be limited in certain applications as a result of low energy density and insufficient power capability, particularly for high power and low voltage applications such as an under-hood start-up battery for a motor vehicle. Under-hood start-up batteries also must be able to function well at cold temperatures. The ability of a battery to deliver high power for a short duration at cold temperatures is often specified in cold-cranking amps or some other metric. For instance, to have confidence that a battery will be able to move engine cylinders and start a vehicle unassisted at cold temperatures, some specifications require a battery to deliver 6 kW of power for 0.5 seconds at â30° C. The present disclosure helps improve the power density of solid-state lithium ion batteries to improve their cold-cranking performance.
SUMMARY OF THE DISCLOSURE
A bipolar capacitor-assisted solid-state battery according to one embodiment of the present disclosure includes a negative end plate current collector, a positive end plate current collector, and a plurality of electrochemical battery unit cells positioned between the negative end plate current collector and the positive end plate current collector. Each of the electrochemical battery unit cells includes a negative electrode, a positive electrode, and a lithium ion-conductive electrolyte-containing separator disposed between the negative electrode and the positive electrode. The lithium ion-conductive electrolyte-containing separator of each electrochemical battery unit cell comprises a solid-state electrolyte material and does not include a free liquid electrolyte. Additionally, at least one negative electrode of the electrochemical battery unit cells or at least one positive electrode of the electrochemical battery unit cells includes a capacitor material. The bipolar capacitor-assisted solid-state battery also includes a plurality of bipolar current collectors. Each of the plurality of bipolar current collectors is disposed between a negative electrode of one electrochemical battery unit cell and a positive electrode of an adjacent electrochemical battery unit cell.
The bipolar capacitor-assisted solid-state battery of the aforementioned embodiment may include additional features or be further defined. For instance, in one implementation, the negative electrode of at least one electrochemical battery unit cell may comprise a mixture of active negative electrode material particles, solid-state electrolyte material particles, and capacitor material particles, and the capacitor material particles may be comprised of a supercapacitor material. In another implementation, the negative electrode of each electrochemical battery unit cell may comprise the mixture of active negative electrode material particles, solid-state electrolyte material particles, and capacitor material particles. Still further, in another implementation, the positive electrode of at least one electrochemical battery unit cell may comprise a mixture of active positive electrode material particles, solid-state electrolyte material particles, and capacitor material particles, and the capacitor material particles may be comprised of a supercapacitor material. And, in another implementation, the positive electrode of each electrochemical battery unit cell may comprise the mixture of active positive electrode material particles, solid-state electrolyte material particles, and capacitor material particles.
As another example, and in another implementation of the capacitor-assisted solid-state battery, the negative electrode of at least one electrochemical battery unit cell may comprises a mixture of active negative electrode material particles, solid-state electrolyte material particles, and capacitor material particles, with the capacitor material particles in the negative electrode being comprised of a supercapacitor material, and additionally the positive electrode of at least one electrochemical battery unit cell may comprises a mixture of active positive electrode material particles, solid-state electrolyte material particles, and capacitor material particles, with the capacitor material particles of the positive electrode also being comprised of a supercapacitor material. In another implementation, the negative electrode of each electrochemical battery unit cell may comprise the mixture of active negative electrode material particles, solid-state electrolyte material particles, and capacitor material particles, and the positive electrode of each electrochemical battery unit cell may comprise the mixture of active positive electrode material particles, solid-state electrolyte material particles, and capacitor material particles.
In yet another implementation of the capacitor-assisted solid-state battery, the negative electrode of at least one electrochemical battery unit cell may comprise a base portion and a coating overlying the base portion. The base portion may comprise a mixture of active negative electrode material particles and solid-state electrolyte material particles, and the coating may comprise capacitor material particles comprised of a supercapacitor material. Likewise, in another implementation, the negative electrode of each electrochemical battery unit cell may comprise the base portion and the coating overlying the base portion. Still further, in another implementation of the capacitor-assisted solid-state batter, the positive electrode of at least one electrochemical battery unit cell may comprise a base portion and a coating overlying the base portion. The base portion may comprise a mixture of active positive electrode material particles and solid-state electrolyte material particles, and the coating may comprise capacitor material particles comprised of a supercapacitor material. Moreover, in another implementation, the positive electrode of each electrochemical battery unit cell may comprise the base portion and the coating overlying the base portion.
In yet another implementation of the capacitor-assisted solid-state battery, the negative electrode of at least one electrochemical battery unit cell may comprise a base portion and a coating overlying the base portion, and the positive electrode of at least one electrochemical battery unit cell may comprise a base portion and a coating overlying the base portion. The base portion of the negative electrode may comprise a mixture of active negative electrode material particles and solid-state electrolyte material particles, and the coating of the negative electrode may comprise capacitor material particles comprised of a supercapacitor. Similarly, the base portion of the positive electrode may comprise a mixture of active positive electrode material particles and solid-state electrolyte material particles, and the coating of the positive electrode may comprise capacitor material particles comprised of a supercapacitor material. In another implementation, the negative electrode of each electrochemical battery unit cell may comprise a base portion and a coating overlying the base portion, and the positive electrode of each electrochemical battery unit cell may comprise a base portion and a coating overlying the base portion. The base portion of the negative electrodes may comprise a mixture of active negative electrode material particles and solid-state electrolyte material particles, and the coating of the negative electrodes may comprise capacitor material particles comprised of a supercapacitor material. Similarly, the base portion of the positive electrodes may comprise a mixture of active positive electrode material particles and solid-state electrolyte material particles, and the coating of the positive electrodes may comprise capacitor material particles comprised of a supercapacitor material.
In various implementations of the capacitor-assisted solid-state battery, the solid-state electrolyte material that comprises the lithium ion-conductive electrolyte-containing separator of each electrochemical battery unit cell may be an inorganic solid. In other implementations, the at least one negative electrode of the electrochemical battery unit cells or the at least one positive electrode of the electrochemical battery unit cells may comprise capacitor material particles intermixed with active electrode material particles and solid-state electrolyte material particles. Furthermore, the at least one negative electrode of the electrochemical battery unit cells or the at least one positive electrode of the electrochemical battery unit cells may include a base portion and a coating that overlies the base portion, with the base portion comprising a mixture of active electrode material particles and solid-state electrolyte particles and the coating comprising capacitor material particles. In other implementations, a voltage between 5 V and 200 V may be established across the negative end plate current collector and the positive end plate current collector when the battery is fully charged.
A method of manufacturing a bipolar capacitor-assisted solid-state battery according to one embodiment of the present disclosure includes several steps. One step involves producing a bipolar electrode of the bipolar capacitor-assisted solid-state battery. This step may include (i) forming a first electrode onto one side of a bipolar current collector, with the first electrode being composed as either a negative electrode or a positive electrode; (ii) forming a second electrode onto the bipolar current collector on a side of the bipolar current collector opposite from the side onto which the first electrode is formed, with the second electrode being composed as either a negative electrode or a positive electrode, whichever is opposite from that of the first electrode, and with at least the first electrode, the second electrode, or both the first electrode and the second electrode including a capacitor material; and (iii) forming a lithium ion-conductive electrolyte-containing separator onto the first electrode, the second electrode, or both the first electrode and the second electrode, with the lithium ion-conductive electrolyte-containing separator comprising a solid-state electrolyte material and being devoid of a free liquid electrolyte. Another step of the method involves stacking the bipolar electrode with one or more other bipolar electrodes to form the bipolar capacitor-assisted solid-state battery.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an idealized cross-sectional view of a bipolar capacitor-assisted solid-state battery according to one embodiment of the present disclosure;
FIG. 2 is a partial magnified view of the positive electrode of one of the electrochemical battery unit cells of the battery shown in FIG. 1 , wherein the positive electrode includes a mixture of active positive electrode material particles, capacitor material particles, and solid-state electrolyte material particles;
FIG. 3 is a partial magnified view of the negative electrode of one of the electrochemical battery unit cells of the battery shown in FIG. 1 , wherein the negative electrode includes a mixture of active negative electrode material particles and solid-state electrolyte material particles;
FIG. 4 is an idealized cross-sectional view of a bipolar capacitor-assisted solid-state battery according to another embodiment of the present disclosure;
FIG. 5 is an idealized cross-sectional view of a bipolar capacitor-assisted solid-state battery according to yet another embodiment of the present disclosure;
FIG. 6 is an idealized cross-sectional view of a bipolar capacitor-assisted solid-state battery according to still another embodiment of the present disclosure;
FIG. 7 is an idealized cross-sectional view of a bipolar capacitor-assisted solid-state battery according to yet another embodiment of the present disclosure;
FIG. 8 is a cross-sectional view of a bipolar capacitor assisted solid-state battery according to still another embodiment of the present disclosure;
FIG. 9 is a schematic illustration of a method for making a bipolar capacitor-assisted solid-state battery according to various embodiments of the present disclosure; and
FIG. 10 is a schematic illustration of another method for making a bipolar capacitor-assisted solid-state battery according to various embodiments of the present disclosure.
DETAILED DESCRIPTION
The present disclosure is directed to a bipolar capacitor-assisted solid-state battery of the lithium ion variety and a method of making the battery. The disclosed battery seeks to achieve good and reliable energy capacity and power density so that the battery can function effectively under cold cranking conditions. To achieve this functionality, a capacitor material is incorporated into at least one of the electrodes of at least one of the electrochemical battery unit cells of the battery along with an active electrode material and a solid-state electrolyte material. The capacitor material is a supercapacitor material that can store charge electrostatically (non-electrochemically); that is, the supercapacitor stores at least some charge on its surface as an electric double layer in conjunction with the solid electrolyte material and, therefore, can absorb and de-absorb ions rather quickly in comparison to the active electrode material, which reacts electrochemically with the mobile ions and only stores lithium faradaically within its bulk structure. While the capacitor material demonstrates relatively fast rate capabilities compared to the active electrode material, it tends to possess less reversible capacity to store charge. To that end, the discharge kinetics of the capacitor material can enhance the power density of the battery, but the lower charge storage capacity of the capacitor material may restrict energy density. The energy density losses that may be attributed to the capacitor material can, however, be mitigated by a bipolar battery architecture.
The capacitor material is hybridized with the active electrode material and the solid-state electrolyte material of one or both of the electrodes within each unit cell of the bipolar solid-state battery. In particular, and in one embodiment, the solid-state battery includes one or more unit cells in which at least one of the negative electrode (anode on discharge) or the positive electrode (cathode on discharge) includes a mixture of particles that contains active electrode material particles (either active positive or active negative), capacitor material particles, and solid-state electrolyte material particles. In another embodiment, the solid-state battery includes one or more unit cells in which at least one of the negative electrode or the positive electrode includes (i) a base portion containing mixture of particles that comprises active electrode material particles and solid-state electrolyte material particles and (ii) a coating of capacitor material particles over the base portion. In each case, the capacitor material particles supplement the discharge/charge kinetics of the active electrode particles to improve the power performance of the battery.
By employing a bipolar battery architecture and striking the appropriate balance between the fast charging/discharging capacitor material and the higher-capacity active electrode material, as h
INTRODUCTION
Lithium ion batteries are a class of batteries that reversibly exchange lithium ions between opposed electrodes disposed on opposite sides of an electrolyte-containing separator. Solid-state lithium ion batteries include solid electrodes and an ionically-conductive solid electrolyte disposed between the electrodes. These types of batteries are different from more conventional battery architectures in which a microporous polymer with an infiltrated liquid electrolyte is positioned between the electrodes to facilitate ionic transport. Solid-state batteries have the potential to achieve higher energy densities and to operate within a wider temperature window than current lithium ion batteries that utilize a free liquid electrolyte. Eliminating the need to use a free-flowing liquid electrolyte, which typically includes a non-aqueous solvent and a dissolved lithium salt for lithium ion mobility, may also desired in certain battery applications.
The use of lithium ion batteries may be limited in certain applications as a result of low energy density and insufficient power capability, particularly for high power and low voltage applications such as an under-hood start-up battery for a motor vehicle. Under-hood start-up batteries also must be able to function well at cold temperatures. The ability of a battery to deliver high power for a short duration at cold temperatures is often specified in cold-cranking amps or some other metric. For instance, to have confidence that a battery will be able to move engine cylinders and start a vehicle unassisted at cold temperatures, some specifications require a battery to deliver 6 kW of power for 0.5 seconds at â30° C. The present disclosure helps improve the power density of solid-state lithium ion batteries to improve their cold-cranking performance.
SUMMARY OF THE DISCLOSURE
A bipolar capacitor-assisted solid-state battery according to one embodiment of the present disclosure includes a negative end plate current collector, a positive end plate current collector, and a plurality of electrochemical battery unit cells positioned between the negative end plate current collector and the positive end plate current collector. Each of the electrochemical battery unit cells includes a negative electrode, a positive electrode, and a lithium ion-conductive electrolyte-containing separator disposed between the negative electrode and the positive electrode. The lithium ion-conductive electrolyte-containing separator of each electrochemical battery unit cell comprises a solid-state electrolyte material and does not include a free liquid electrolyte. Additionally, at least one negative electrode of the electrochemical battery unit cells or at least one positive electrode of the electrochemical battery unit cells includes a capacitor material. The bipolar capacitor-assisted solid-state battery also includes a plurality of bipolar current collectors. Each of the plurality of bipolar current collectors is disposed between a negative electrode of one electrochemical battery unit cell and a positive electrode of an adjacent electrochemical battery unit cell.
The bipolar capacitor-assisted solid-state battery of the aforementioned embodiment may include additional features or be further defined. For instance, in one implementation, the negative electrode of at least one electrochemical battery unit cell may comprise a mixture of active negative electrode material particles, solid-state electrolyte material particles, and capacitor material particles, and the capacitor material particles may be comprised of a supercapacitor material. In another implementation, the negative electrode of each electrochemical battery unit cell may comprise the mixture of active negative electrode material particles, solid-state electrolyte material particles, and capacitor material particles. Still further, in another implementation, the positive electrode of at least one electrochemical battery unit cell may comprise a mixture of active positive electrode material particles, solid-state electrolyte material particles, and capacitor material particles, and the capacitor material particles may be comprised of a supercapacitor material. And, in another implementation, the positive electrode of each electrochemical battery unit cell may comprise the mixture of active positive electrode material particles, solid-state electrolyte material particles, and capacitor material particles.
As another example, and in another implementation of the capacitor-assisted solid-state battery, the negative electrode of at least one electrochemical battery unit cell may comprises a mixture of active negative electrode material particles, solid-state electrolyte material particles, and capacitor material particles, with the capacitor material particles in the negative electrode being comprised of a supercapacitor material, and additionally the positive electrode of at least one electrochemical battery unit cell may comprises a mixture of active positive electrode material particles, solid-state electrolyte material particles, and capacitor material particles, with the capacitor material particles of the positive electrode also being comprised of a supercapacitor material. In another implementation, the negative electrode of each electrochemical battery unit cell may comprise the mixture of active negative electrode material particles, solid-state electrolyte material particles, and capacitor material particles, and the positive electrode of each electrochemical battery unit cell may comprise the mixture of active positive electrode material particles, solid-state electrolyte material particles, and capacitor material particles.
In yet another implementation of the capacitor-assisted solid-state battery, the negative electrode of at least one electrochemical battery unit cell may comprise a base portion and a coating overlying the base portion. The base portion may comprise a mixture of active negative electrode material particles and solid-state electrolyte material particles, and the coating may comprise capacitor material particles comprised of a supercapacitor material. Likewise, in another implementation, the negative electrode of each electrochemical battery unit cell may comprise the base portion and the coating overlying the base portion. Still further, in another implementation of the capacitor-assisted solid-state batter, the positive electrode of at least one electrochemical battery unit cell may comprise a base portion and a coating overlying the base portion. The base portion may comprise a mixture of active positive electrode material particles and solid-state electrolyte material particles, and the coating may comprise capacitor material particles comprised of a supercapacitor material. Moreover, in another implementation, the positive electrode of each electrochemical battery unit cell may comprise the base portion and the coating overlying the base portion.
In yet another implementation of the capacitor-assisted solid-state battery, the negative electrode of at least one electrochemical battery unit cell may comprise a base portion and a coating overlying the base portion, and the positive electrode of at least one electrochemical battery unit cell may comprise a base portion and a coating overlying the base portion. The base portion of the negative electrode may comprise a mixture of active negative electrode material particles and solid-state electrolyte material particles, and the coating of the negative electrode may comprise capacitor material particles comprised of a supercapacitor. Similarly, the base portion of the positive electrode may comprise a mixture of active positive electrode material particles and solid-state electrolyte material particles, and the coating of the positive electrode may comprise capacitor material particles comprised of a supercapacitor material. In another implementation, the negative electrode of each electrochemical battery unit cell may comprise a base portion and a coating overlying the base portion, and the positive electrode of each electrochemical battery unit cell may comprise a base portion and a coating overlying the base portion. The base portion of the negative electrodes may comprise a mixture of active negative electrode material particles and solid-state electrolyte material particles, and the coating of the negative electrodes may comprise capacitor material particles comprised of a supercapacitor material. Similarly, the base portion of the positive electrodes may comprise a mixture of active positive electrode material particles and solid-state electrolyte material particles, and the coating of the positive electrodes may comprise capacitor material particles comprised of a supercapacitor material.
In various implementations of the capacitor-assisted solid-state battery, the solid-state electrolyte material that comprises the lithium ion-conductive electrolyte-containing separator of each electrochemical battery unit cell may be an inorganic solid. In other implementations, the at least one negative electrode of the electrochemical battery unit cells or the at least one positive electrode of the electrochemical battery unit cells may comprise capacitor material particles intermixed with active electrode material particles and solid-state electrolyte material particles. Furthermore, the at least one negative electrode of the electrochemical battery unit cells or the at least one positive electrode of the electrochemical battery unit cells may include a base portion and a coating that overlies the base portion, with the base portion comprising a mixture of active electrode material particles and solid-state electrolyte particles and the coating comprising capacitor material particles. In other implementations, a voltage between 5 V and 200 V may be established across the negative end plate current collector and the positive end plate current collector when the battery is fully charged.
A method of manufacturing a bipolar capacitor-assisted solid-state battery according to one embodiment of the present disclosure includes several steps. One step involves producing a bipolar electrode of the bipolar capacitor-assisted solid-state battery. This step may include (i) forming a first electrode onto one side of a bipolar current collector, with the first electrode being composed as either a negative electrode or a positive electrode; (ii) forming a second electrode onto the bipolar current collector on a side of the bipolar current collector opposite from the side onto which the first electrode is formed, with the second electrode being composed as either a negative electrode or a positive electrode, whichever is opposite from that of the first electrode, and with at least the first electrode, the second electrode, or both the first electrode and the second electrode including a capacitor material; and (iii) forming a lithium ion-conductive electrolyte-containing separator onto the first electrode, the second electrode, or both the first electrode and the second electrode, with the lithium ion-conductive electrolyte-containing separator comprising a solid-state electrolyte material and being devoid of a free liquid electrolyte. Another step of the method involves stacking the bipolar electrode with one or more other bipolar electrodes to form the bipolar capacitor-assisted solid-state battery.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an idealized cross-sectional view of a bipolar capacitor-assisted solid-state battery according to one embodiment of the present disclosure;
FIG. 2 is a partial magnified view of the positive electrode of one of the electrochemical battery unit cells of the battery shown in FIG. 1 , wherein the positive electrode includes a mixture of active positive electrode material particles, capacitor material particles, and solid-state electrolyte material particles;
FIG. 3 is a partial magnified view of the negative electrode of one of the electrochemical battery unit cells of the battery shown in FIG. 1 , wherein the negative electrode includes a mixture of active negative electrode material particles and solid-state electrolyte material particles;
FIG. 4 is an idealized cross-sectional view of a bipolar capacitor-assisted solid-state battery according to another embodiment of the present disclosure;
FIG. 5 is an idealized cross-sectional view of a bipolar capacitor-assisted solid-state battery according to yet another embodiment of the present disclosure;
FIG. 6 is an idealized cross-sectional view of a bipolar capacitor-assisted solid-state battery according to still another embodiment of the present disclosure;
FIG. 7 is an idealized cross-sectional view of a bipolar capacitor-assisted solid-state battery according to yet another embodiment of the present disclosure;
FIG. 8 is a cross-sectional view of a bipolar capacitor assisted solid-state battery according to still another embodiment of the present disclosure;
FIG. 9 is a schematic illustration of a method for making a bipolar capacitor-assisted solid-state battery according to various embodiments of the present disclosure; and
FIG. 10 is a schematic illustration of another method for making a bipolar capacitor-assisted solid-state battery according to various embodiments of the present disclosure.
DETAILED DESCRIPTION
The present disclosure is directed to a bipolar capacitor-assisted solid-state battery of the lithium ion variety and a method of making the battery. The disclosed battery seeks to achieve good and reliable energy capacity and power density so that the battery can function effectively under cold cranking conditions. To achieve this functionality, a capacitor material is incorporated into at least one of the electrodes of at least one of the electrochemical battery unit cells of the battery along with an active electrode material and a solid-state electrolyte material. The capacitor material is a supercapacitor material that can store charge electrostatically (non-electrochemically); that is, the supercapacitor stores at least some charge on its surface as an electric double layer in conjunction with the solid electrolyte material and, therefore, can absorb and de-absorb ions rather quickly in comparison to the active electrode material, which reacts electrochemically with the mobile ions and only stores lithium faradaically within its bulk structure. While the capacitor material demonstrates relatively fast rate capabilities compared to the active electrode material, it tends to possess less reversible capacity to store charge. To that end, the discharge kinetics of the capacitor material can enhance the power density of the battery, but the lower charge storage capacity of the capacitor material may restrict energy density. The energy density losses that may be attributed to the capacitor material can, however, be mitigated by a bipolar battery architecture.
The capacitor material is hybridized with the active electrode material and the solid-state electrolyte material of one or both of the electrodes within each unit cell of the bipolar solid-state battery. In particular, and in one embodiment, the solid-state battery includes one or more unit cells in which at least one of the negative electrode (anode on discharge) or the positive electrode (cathode on discharge) includes a mixture of particles that contains active electrode material particles (either active positive or active negative), capacitor material particles, and solid-state electrolyte material particles. In another embodiment, the solid-state battery includes one or more unit cells in which at least one of the negative electrode or the positive electrode includes (i) a base portion containing mixture of particles that comprises active electrode material particles and solid-state electrolyte material particles and (ii) a coating of capacitor material particles over the base portion. In each case, the capacitor material particles supplement the discharge/charge kinetics of the active electrode particles to improve the power performance of the battery.
By employing a bipolar battery architecture and striking the appropriate balance between the fast charging/discharging capacitor material and the higher-capacity active electrode material, as hybridized together, the solid-state battery can deliver high power for short durations over a wide operating window as needed for a variety of high power, low voltage applications. The disclosed bipolar capacitor-assisted solid-state battery is thus a strong candidate to replace the lead-acid battery that has been used for many years as an under-hood start-up battery for a motor vehicle. Other battery applications outside of automotive applications are of course possible as well.
A bipolar capacitor-assisted solid- state battery 10 according to one embodiment of the present disclosure is shown schematically in FIGS. 1-3 . The battery 10 includes a plurality electrochemical battery unit cells 12 that are stacked in a stacking dimension 14 oriented normal to a centerplane 15 of the battery 10 that lies parallel to the plane of each cell 12 . Each of the electrochemical battery unit cells 12 includes a negative electrode 16 , a positive electrode 18 , and an electrolyte-containing separator 20 that physically separates and electrically isolates the electrodes
16 , 18 from each other while permitting lithium ions to migrate back-and-forth between the electrodes
16 , 18 . The plurality of electrochemical battery unit cells 12 includes at least a first end unit cell 121 and a second end unit cell 123 . And, if additional electrochemical battery unit cells 12 are present, one or more interior unit cells 125 are positioned between the first and second end unit cells 121 , 123 . Anywhere from one to fifty interior unit cells 125 may be included in the battery 10 .
The negative electrode 16 , the positive electrode 18 , and the separator 20 of each unit cell 12 are in the form of component battery layers that have opposed major faces. The component battery layers are typically rectangularly-shaped layers of consolidated particles that have porosities of, typically, 15% or less, but other geometrical shapes are also possible. The major faces of the battery component layersâwhich define a thickness of the electrodes
16 , 18 and the separator 20 âprovide the active surface areas of the component battery layers. Indeed, the electrodes
16 , 18 and the separator 20 are pressed together and overlap such that the opposed major faces of adjacent battery component layers make interfacial contact with each other, as shown generally in FIG. 1 . The negative and positive electrodes
16 , 18 are sized to provide a specified capacity while the separator 20 is sized to maintain separation of the electrodes
14 , 16 . In certain applications, the negative electrode 16 has a thickness ranging from 5 μm to 1000 μm, the positive electrode 18 has a thickness ranging from 5 μm to 1000 μm, and the separator 20 has a thickness ranging from 3 μm to 150 μm.
The plurality of electrochemical battery unit cells 12 are stacked so that the negative and positive electrodes
16 , 18 of the several unit cells 12 alternate along the stacking dimension 14 from an outwardly-facing positive electrode 181 of the first unit end cell 121 to an outwardly facing negative electrode 161 of the second end unit cell 123 . The negative and positive electrodes
16 , 18 within each electrochemical battery cell 12 are separated by the electrically insulating (i.e., non-electrically conductive) separator 20 , while the negative and positive electrodes
16 , 18 of adjacent electrochemical battery unit cells 12 are separated by a bipolar current collector 22 . To that end, the outwardly-facing positive electrode 181 of the first unit end cell 121 and the negative electrode 16 of the same cell 121 are separated by a separator 20 , while the negative electrode 16 of the first unit end cell 121 and the positive electrode 18 of the next adjacent unit cell 12 are separated by a bipolar current collector 22 , and so on. Each of the bipolar current collectors 22 is electrically insulated from each other by the separator 20 located outward of the negative electrode 16 positioned against one of its major faces and the separator located outward of the positive electrode 18 positioned against the other of its major face.
The electrochemical battery unit cells 12 are stacked between a positive end plate current collector 24 and a negative end plate current collector 26 . The positive end plate current collector 24 is interfacially disposed against the outwardly-facing positive electrode 181 of the first unit end cell 121 , and, likewise, the negative end plate current collector 26 is interfacially disposed against the outwardly facing negative electrode 161 of the second end unit cell 123 . The electrochemical battery unit cells 12 are thus electrically connected to each other in series with the positive end plate current collector 24 and the negative end plate current collector 26 serving as positive and negative terminals, respectively, of the battery 10 . The positive end plate current collector 24 and the negative end plate current collector 26 may be electrically connected to an external circuit 28 that routes current through a load device 30 . The external circuit 28 may also be electrically connected to a power source 32 that can reverse the current within the battery 10 to increase the voltage of the cells 12 and thereby charge the battery 10 .
When the negative electrodes 16 are lithiated and charged, a voltage is established across the negative end plate current collector 24 and the positive end plate current collector 26 . This voltage may range from 5 V to 200 V, or more narrowly from 8 V to 20 V when the negative electrodes 16 are fully charged depending on the electrode materials used. The voltage may of course be greater or lesser than this range by increasing or decreasing on the number of interior unit cells 125 . To discharge the battery 10 and deliver current to the load device 30 , the external circuit 28 is closed, causing the negative electrodes 16 to spontaneously release lithium ions and free electrons. In each cell 12 , the released lithium ions migrate through the adjacent separator 20 to the positive electrode 18 within the same electrochemical battery unit cell 12 . This migration of lithium ions is represented by arrows 34 . The free electrons, however, move in the opposite direction, and are conducted through the adjacent bipolar current collector 22 to the positive electrode 18 of the adjacent electrochemical battery unit cell 12 . This conductive movement of the electrons is represented by arrows 36 . In this way, the electrons move from one electrochemical battery unit cell 12 to another, while that movement of electrons is balance by the migration of lithium ions in the opposite direction within each of the cells 12 themselves. The electrons that reach the negative end plate current collector 24 are ultimately directed through the external circuit and delivered to the positive end plate current collector 26 , as represented by arrows 38 , thereby supplying current to the load device 30 . The serial connections of the electrochemical unit cells 12 enables the battery 10 to exhibit a high voltage simply by stacking together the appropriate number of cells 12 .
Unlike the operation of a monopolar battery architectureâa battery design in which a metal current collector is sandwiched between to electrodes of the same polarity; that is, between two negative electrodes or two positive electrodesâthe bipolar configuration of the battery 10 results in electron and lithium ion flow normal to the confronting major faces of the electrodes
16 , 18 or, in other words, parallel to the stacking dimension 14 , as opposed to in a direction along the planes of the electrodes
16 , 18 . This results in more uniform current and potential distributions over the major surfaces of the electrodes
16 , 18 . As a result, the cell-to-cell serial connections exhibit relative low electrical resistance, which minimizes heat generation and associated energy losses. The bipolar battery architecture is thus better able to preserve the power and energy densities of the several electrochemical battery unit cells 12 compared to a prismatic battery architecture, which is particularly helpful here since the inclusion of the capacitor material in the negative and/or positive electrodes
16 , 18 of the electrochemical battery unit cells 12 may result in an energy density sacrifice to the battery 10 compared to a scenario in which a capacitor material is not present.
In this particular embodiment of the battery 10 , and referring now to FIGS. 2 and 3 , the positive electrode 18 of at least one electrochemical battery unit cell 12 , and preferably all of the unit cells 12 , includes a mixture 40 of active positive electrode material particles 42 , solid-state electrolyte material particles 44 , and capacitor material particles 46 . The mixture 40 of particles may also include electrically conductive diluent particles 48 , if desired. The mixture 40 of particles may be bound together by a binder. The positive electrode 18 may comprise anywhere from 40 wt % to 95 wt % of the active positive electrode material particles 42 , anywhere from 2 wt % to 40 wt % of the solid-state electrolyte material particles 44 , anywhere from 0.1 wt % to 35 wt % of the capacitor material particles 46 , anywhere from 1 wt % to 15 wt % of the electrically conductive diluent particles 48 , and anywhere from 0.5 wt % to 10 wt % of the binder. The
various particles
42 , 44 , 46 , 48 may vary in size to promote efficient packing. Typically, however, the
particles
42 , 44 , 46 , 48 have particle sizes, which is a measurement of the largest particle dimension, and an average particle size of the
particles
42 , 44 , 46 may range from 100 nm to 50 μm. Only a few of the capacitor material particles 46 are depicted in FIG. 1 for purposes of indicating the specific electrode(s) that include those particles in this embodiment.
The negative electrode 16 of each electrochemical battery unit cell 12 in this particular embodiment includes a mixture 50 of active negative electrode material particles 52 , solid-state electrolyte material particles 54 , and electrically conductive diluent particles 56 , if desired. The mixture 50 of particles may be bound together by a binder. The negative electrode 16 of each cell 12 may comprises anywhere from 40 wt % to 95 wt % of the active negative electrode material particles 52 , anywhere from 0.5 wt % to 50 wt % of the solid-state electrolyte material particles 54 , anywhere from 0 wt % to 15 wt % of the conductive diluent particles 56 , and anywhere from 0.5 wt % to 10 wt % of the binder. As before, the various particles
52 , 54 , 56 may vary in size to promote efficient packing, with the particles typically having an average particle size ranging from 100 nm to 50 μm.
The active positive electrode material particles 42 and the active negative electrode particles 52 of the positive electrodes 18 and the negative electrodes 16 , respectively, are comprised of an electrochemically active electrode material that can store lithium faradaically. These electrode materials can thus intercalate and deintercalate lithium. The electrode materials of the two types of electrode material particles
42 , 52 are formulated to store lithium at different electrochemical potentials relative to a common reference electrode (typically lithium). Specifically, the electrode material of the active negative electrode particles 52 stores intercalated lithium at a lower electrochemical potential (i.e., a higher energy state) than the electrode material of the active positive electrode material particles 42 . This electrochemical potential difference may range from 2 V to 5 V. As such, lithium ions can be transferred spontaneously from the active negative electrode particles 52 in the negative electrode 16 to the active positive electrode particles 42 in the positive electrode of each cell 12 (discharge phase). The same lithium ions can also be transferred in the reverse direction within each cell 12 by applying a voltage across the battery 10 that is sufficient to overcome the electrochemical potential difference between the electrode materials of the two types of particles 42 , 52 (charge phase).
The electrode material from which the active positive electrode material particles 42 are formed may be a layered lithium transition metal oxide such as lithium cobalt oxide (LiCoO 2 ), a lithium-nickel-manganese-cobalt oxide [Li(Ni X Mn Y Co 1âXâY )O 2 ] (where 0<Xâ¤1 and 0<Yâ¤1), a lithium-nickel-cobalt-aluminum oxide [LiNi 0.8 Co 0.15 Al 0.05 O 2 ], a lithium-nickel-manganese oxide [LiNi X Mn 1âX O 2 ] (where 0<Xâ¤1), or Li 1+X MO 2 (where M comprises Ni, Co, Mn, Cr, Ti, Nb, V, Mg, or Al and 0â¤Xâ¤0.3). The electrode material may also be a spinel oxide such as lithium manganese oxide (LiMn 2 O 4 ) or a lithium-nickel-manganese oxide [LiNi X Mn 2âX O 4 ] (where 0â¤Xâ¤2). Still further, the electrode material may be a lithium polyanion such as lithium-vanadium phosphate [LiV 2 (PO 4 ) 3 ], a lithium-iron-manganese p
CLAIMS
Claims ( 15 )
The invention claimed is:
1. A bipolar capacitor-assisted solid-state battery comprising:
a negative end plate current collector;
a positive end plate current collector;
a plurality of electrochemical battery unit cells positioned between the negative end plate current collector and the positive end plate current collector,
wherein each of the electrochemical battery unit cells including a negative electrode, a positive electrode, and a lithium ion-conductive electrolyte-containing separator disposed between the negative electrode and the positive electrode,
wherein the lithium ion-conductive electrolyte-containing separator of each electrochemical battery unit cell comprises a first solid-state electrolyte material and does not include a free liquid electrolyte,
wherein at least one negative electrode of the electrochemical battery unit cells or at least one positive electrode of the electrochemical battery unit cells includes a capacitor coating comprising a capacitor material and a second solid-state electrolyte material, and
wherein the capacitor material is a pseudocapacitor material selected from the group consisting of: RuO 2 , MnO 2 , NiO, Co 3 O 4 , Co(OH) 2 , Ni(OH) 2 , and combinations thereof; and
a plurality of bipolar current collectors, each of the plurality of bipolar current collectors being disposed between a negative electrode of one electrochemical battery unit cell and a positive electrode of an adjacent electrochemical battery unit cell.
2. The bipolar capacitor-assisted solid-state battery set forth in claim 1 , wherein the negative electrode of at least one electrochemical battery unit cell comprises a base portion comprising a mixture of active negative electrode material particles and solid-state electrolyte material particles, and the capacitor coating overlays the base portion.
3. The bipolar capacitor-assisted solid-state battery set forth in claim 1 , wherein the negative electrode of each electrochemical battery unit cell comprises a capacitor coating.
4. The bipolar capacitor-assisted solid-state battery set forth in claim 1 , wherein the positive electrode of at least one electrochemical battery unit cell comprises a base portion comprising a mixture of active positive electrode material particles and solid-state electrolyte material particles, and the capacitor coating overlays the base portion.
5. The bipolar capacitor-assisted solid-state battery set forth in claim 1 , wherein the positive electrode of each electrochemical battery unit cell comprises a capacitor coating.
6. The bipolar capacitor-assisted solid-state battery set forth in claim 1 , wherein the negative electrode of at least one electrochemical battery unit cell comprises a capacitor coating overlying a base portion, the base portion of the negative electrode comprising a mixture of active negative electrode material particles and solid-state electrolyte material particles, and
wherein the positive electrode of at least one electrochemical battery unit cell comprises a capacitor coating overlying a base portion, the base portion of the positive electrode comprising a mixture of active positive electrode material particles and solid-state electrolyte material particles.
7. The bipolar capacitor-assisted solid-state battery set forth in claim 1 , wherein the negative electrode of each electrochemical battery unit cell comprises a capacitor coating overlying a base portion, the base portion of the negative electrodes comprising a mixture of active negative electrode material particles and solid-state electrolyte material particles, and
wherein the positive electrode of each electrochemical battery unit cell comprises a capacitor coating overlying the base portion, the base portion of the positive electrodes comprising a mixture of active positive electrode material particles and solid-state electrolyte material particles.
8. The bipolar capacitor-assisted solid-state battery set forth in claim 1 , wherein the first solid-state electrolyte material of the lithium ion-conductive electrolyte-containing separator of each electrochemical battery unit cell comprises an oxide-based inorganic solid, a sulfide-based inorganic solid, a solid polymer, or a combination thereof.
9. The bipolar capacitor-assisted solid-state battery set forth in claim 1 , wherein at least one negative electrode of the electrochemical battery unit cells or at least one positive electrode of the electrochemical battery unit cells includes a base portion portion comprising a mixture of active electrode material particles, solid-state electrolyte particles, and capacitor material particles.
10. The bipolar capacitor-assisted solid-state battery set forth in claim 1 , wherein a voltage between 5 V and 200 V is established across the negative end plate current collector and the positive end plate current collector when the battery is fully charged.
11. A method of manufacturing a bipolar capacitor-assisted solid-state battery, the method comprising:
producing a bipolar electrode of the bipolar capacitor-assisted solid-state battery, which includes:
forming a first electrode onto one side of a bipolar current collector, the first electrode being composed as either a negative electrode or a positive electrode;
forming a second electrode onto the bipolar current collector on a side of the bipolar current collector opposite from the side onto which the first electrode is formed, the second electrode being composed as either a negative electrode or a positive electrode, whichever is opposite from that of the first electrode, and wherein at least the first electrode, the second electrode, or both the first electrode and the second electrode includes a capacitor coating comprising a capacitor material and a first solid-state electrolyte material, wherein the capacitor material is a pseudocapacitor material selected from the group consisting of: RuO 2 , MnO 2 , NiO, Co 3 O 4 , Co(OH) 2 , Ni(OH) 2 , and combinations thereof;
forming a lithium ion-conductive electrolyte-containing separator onto the first electrode, the second electrode, or both the first electrode and the second electrode, the lithium ion-conductive electrolyte-containing separator comprising a second solid-state electrolyte material and being devoid of a free liquid electrolyte;
stacking the bipolar electrode with one or more other bipolar electrodes to form the bipolar capacitor-assisted solid-state battery.
12. The bipolar capacitor-assisted solid-state battery set forth in claim 9 , wherein the at least one negative electrode of the electrochemical battery unit cells or the at least one positive electrode of the electrochemical battery unit cells including the base portion comprising the mixture of active electrode material particles, solid-state electrolyte particles, and capacitor material particles is different from the at least one negative electrode of the electrochemical battery unit cells or the at least one positive electrode of the electrochemical battery unit cells including the capacitor coating comprising the capacitor material and the second solid-state electrolyte material.
13. The bipolar capacitor-assisted solid-state battery set forth in claim 9 , wherein the at least one negative electrode of the electrochemical battery unit cells or the at least one positive electrode of the electrochemical battery unit cells including the base portion comprising the mixture of active electrode material particles, solid-state electrolyte particles, and capacitor material particles is the same as the at least one negative electrode of the electrochemical battery unit cells or the at least one positive electrode of the electrochemical battery unit cells including the capacitor coating comprising the capacitor material and the second solid-state electrolyte material.
14. The bipolar capacitor-assisted solid-state battery set forth in claim 1 , wherein the first solid-state electrolyte material is the same as the second solid-state electrolyte material.
15. The bipolar capacitor-assisted solid-state battery set forth in claim 1 , wherein the first solid-state electrolyte material is different from the second solid-state electrolyte material.
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