Dual function capacitor design for bipolar battery pack and method of manufacturing same

Abstract

A bipolar solid state battery cell includes a plurality of battery cells, where each cell includes a separator, an anode disposed on a first side of the separator, and a cathode disposed on a second side of the separator; wherein the second side is disposed opposite the first side. The anode is in electrical communication with the anode current collector and the cathode is in electrical communication with the cathode current collector. A capacitor wall is disposed parallel to at least one outer surface of the anode or cathode, wherein the capacitor wall includes a capacitor active material.

Description

Technical Field

[0001] The present disclosure relates to bifunctional capacitor electrode designs and methods of making the same for gel-assisted bipolar batteries. Background Art

[0002] Polymer barriers are used in gel-assisted bipolar solid-state batteries to avoid possible leakage of the gel electrolyte, especially at high temperatures. Polymer barriers are passive components in these solid-state batteries and thus occupy valuable space in the battery while performing no active function.

[0003] Figure 1 1 is a diagram of a bipolar solid-state battery cell 100, which includes a plurality of individual cells 101A, 101B, 101C, 101D, ..., 100n-1, etc. Each of the plurality of individual cells 101A, 101B, 101C, 101D, ..., 100n-1, etc. includes an anode 104A, 104B, 104C, 104D, ..., 104n-1, a cathode 108A, 108B, 108C, 108D, ..., 108n-1, and a solid electrolyte 106A, 106B, 106C, 106D, ..., 106n-1. Each individual cell has an anode current collector and a cathode current collector 102A, 102B, 102C, 102D, 102E, ..., 102n, which collects the current generated in each individual cell. The solid electrolyte 106A, 106B, 106C, 106D, ..., 106n-1 is a gel electrolyte. Each of the plurality of individual cells 101A, 101B, 101C, 101D, ..., 101n-1, etc. has a blocking portion 202 and 204 that blocks gel leakage from the individual cell. The blocking portions 202 and 204 include a polymer and prevent the gel electrolyte from leaking from the individual cell.

[0004] However, as described above, polymer barriers 202 and 204 are passive components. They take up space but cannot perform positive energy generation functions, thereby reducing the energy generation capacity of the battery. Therefore, it is desirable to replace the polymer barriers with components that generate energy and improve the battery cell capacity. Summary of the invention

[0005] The bipolar solid-state battery cell comprises a plurality of battery cells, wherein each cell comprises a separator, an anode disposed on a first side of the separator, and a cathode disposed on a second side of the separator; wherein the second side is disposed opposite the first side. The anode is electrically connected to an anode current collector, and the cathode is electrically connected to a cathode current collector. A capacitor wall is disposed parallel to at least one outer surface of the anode or cathode; wherein the capacitor wall comprises a capacitor active material.

[0006] In one embodiment, the capacitor wall is separated from at least one outer surface of the anode or cathode by an air gap.

[0007] In another embodiment, the thickness of the air gap is up to 0.1 mm.

[0008] In yet another embodiment, the capacitor wall has a wall thickness of 3 to 100 mm.

[0009] In yet another embodiment, the capacitor wall contacts at least one outer surface of the anode or cathode.

[0010] In yet another embodiment, the capacitor wall contacts at least two outer surfaces of the anode or cathode.

[0011] In yet another embodiment, the capacitor wall contacts at least one outer surface of the anode or cathode adjacent to the current collector.

[0012] In yet another embodiment, the capacitor wall contacts every surface of the anode or cathode except the surface that contacts the separator.

[0013] In yet another embodiment, the capacitor wall is arranged parallel to at least two outer surfaces of the anode or cathode, and wherein an air gap exists between each of the two outer surfaces of the anode or cathode and the capacitor wall.

[0014] In yet another embodiment, the capacitor walls contact every surface of the anode and cathode except the surfaces of the anode and cathode that contact the separator.

[0015] In yet another embodiment, the capacitor walls are arranged symmetrically about the partition.

[0016] In yet another embodiment, the capacitor walls are arranged asymmetrically with respect to the partition.

[0017] In yet another embodiment, the capacitor wall further comprises a conductive additive, a polymer binder, and a solid electrolyte.

[0018] In one embodiment, a method of making a battery cathode or anode having a capacitor wall includes: placing a slurry containing a capacitor active material on a separator so that the slurry surface is parallel to at least one outer surface of the anode or cathode. Drying the slurry to form a capacitor wall.

[0019] In one embodiment, the capacitor wall further comprises a conductive additive, a polymer binder, and a solid electrolyte.

[0020] In yet another embodiment, the capacitor active material is present in an amount of 50 to 99% by weight, the conductive additive is present in an amount of up to 30% by weight, the polymer binder is present in an amount of up to 20% by weight, and the solid electrolyte is present in an amount of up to 30% by weight, based on the total weight of the capacitor wall.

[0021] In another embodiment, the manufacturing method includes unwinding the separator from a first roll and winding it onto a second roll. Disposing the slurry is performed between unwinding and winding.

[0022] In yet another embodiment, the placement of the slurry on the separator is performed continuously.

[0023] In yet another embodiment, the capacitor wall is separated from at least one outer surface of the anode or cathode by an air gap.

[0024] In yet another embodiment, the capacitor wall contacts at least one outer surface of the anode or cathode.

[0025] The present invention may also include the following aspects.

[0026] 1. A bipolar solid-state battery cell comprising a plurality of battery cells, wherein each battery cell comprises:

[0027] Partitions;

[0028] an anode disposed on a first side of the separator;

[0029] an anode current collector in electrical communication with the anode;

[0030] a cathode disposed on a second side of the separator; wherein the second side is disposed opposite the first side;

[0031] a cathode current collector in electrical communication with the cathode;

[0032] A capacitor wall is disposed parallel to at least one outer surface of the anode or cathode; wherein the capacitor wall comprises a capacitor active material.

[0033] 2. The battery of claim 1 , wherein the capacitor wall is separated from the at least one outer surface of the anode or the cathode by an air gap.

[0034] 3. A battery according to Option 2, wherein the thickness of the air gap is up to 0.1 mm.

[0035] 4. The battery according to claim 1, wherein the capacitor wall has a wall thickness of 3 to 100 mm.

[0036] 5. The battery of claim 1 , wherein the capacitor wall contacts at least one outer surface of the anode or cathode.

[0037] 6. The battery of claim 1, wherein the capacitor wall contacts at least two outer surfaces of the anode or cathode.

[0038] 7. The battery of claim 1, wherein the capacitor wall contacts at least one outer surface of the anode or cathode adjacent to the current collector.

[0039] 8. The battery according to claim 1, wherein the capacitor wall contacts every surface of the anode or cathode except a surface contacting the separator.

[0040] 9. The battery according to claim 1, wherein the capacitor wall is arranged parallel to at least two outer surfaces of the anode or cathode, and wherein an air gap exists between each of the two outer surfaces of the anode or cathode and the capacitor wall.

[0041] 10. The battery according to claim 8, wherein the capacitor wall contacts every surface of the anode and the cathode except for the surface of the anode and the cathode contacting the separator.

[0042] 11. The battery according to claim 1, wherein the capacitor wall is arranged symmetrically with respect to the separator.

[0043] 12. The battery according to claim 1, wherein the capacitor wall is arranged asymmetrically with respect to the separator.

[0044] 13. The battery according to claim 1, wherein the capacitor wall further comprises a conductive additive, a polymer binder and a solid electrolyte.

[0045] 14. A method of making a battery cathode or anode having a capacitor wall, the method comprising:

[0046] disposing a slurry containing a capacitor active material on a separator so that a surface of the slurry is parallel to at least one outer surface of the anode or the cathode; and

[0047] The slurry is dried to form the capacitor wall.

[0048] 15. The method according to claim 14, wherein the capacitor wall further comprises a conductive additive, a polymer binder and a solid electrolyte.

[0049] 16. A method according to embodiment 15, wherein the capacitor active material is present in an amount of 50-99% by weight, the conductive additive is present in an amount of up to 30% by weight, the polymer binder is present in an amount of up to 20% by weight, and the solid electrolyte is present in an amount of up to 30% by weight, based on the total weight of the capacitor wall.

[0050] 17. The method according to embodiment 14 further comprises: unwinding the separator from the first roller and winding it onto the second roller; wherein the slurry is arranged between unwinding and winding.

[0051] 18. The method according to claim 14, wherein the arranging of the slurry on the separator is performed continuously.

[0052] 19. The method of claim 14, wherein the capacitor wall is separated from the at least one outer surface of the anode or the cathode by an air gap.

[0053] 20. The method of claim 14, wherein the capacitor wall contacts at least one outer surface of the anode or the cathode.

[0054] The above features and advantages and other features and advantages of the present disclosure are apparent from the following detailed description taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Other features, advantages and details are presented by way of example only in the following detailed description, which refers to the accompanying drawings, in which:

[0056] Figure 1 is a schematic diagram of a prior art battery cell including a polymer barrier for preventing electrolyte leakage;

[0057] Figures 2A-2D are top views of various exemplary embodiments of bipolar solid-state battery cells;

[0058] Figure 3A is a side view of features of a cathode in a single cell of a bipolar solid-state battery cell;

[0059] Figure 3B is a side view of features of an anode in a single cell of a bipolar solid-state battery cell;

[0060] Figure 4A is a schematic diagram of forming a capacitor wall during a continuous process; and

[0061] Figure 4B is a top view of a bipolar electrode before and after forming the capacitor wall during a continuous process. DETAILED DESCRIPTION

[0062] The following description is merely exemplary in nature and is not intended to limit the present disclosure, its application, or uses. It should be understood that throughout the drawings, corresponding reference numerals indicate the same or corresponding parts and features.

[0063] Disclosed herein is a bifunctional bipolar electrode for a bipolar solid-state battery containing gel. In the battery, the bifunctional bipolar electrode uses a capacitor material that acts as both a power facilitating portion and a "sealed barrier" at the edge of the electrode due to its excellent power response and high electrolyte absorption capacity. The capacitor material facilitates current collection from the anode and cathode, and can facilitate current transfer to and from the current collector. The capacitor material and the capacitor wall formed therefrom are conductive. It can also absorb solid gel electrolyte, especially at high temperatures, thereby preventing leakage when the stable gel electrolyte structure breaks down or begins to flow. The design eliminates the use of a passive polymer barrier, which, as described above, only takes up space in the solid-state battery to prevent leakage.

[0064] The capacitor material is used as a wall (which will be referred to hereinafter as a "capacitor wall") to surround the electrodes in the cells of the battery pack of various configurations described in detail in the following figures.

[0065] Figures 2A-2D is a cross-sectional top view depicting an exemplary embodiment in which a capacitor wall surrounds an electrode material. Figures 2A-2D Described as cross-sectional top views, they could also be side views of the cells of the battery pack. In other words, Figures 2A-2D The battery pack shown in can be turned to its side, and the cross-sectional view is substantially the same. In some embodiments, the capacitor wall does not directly contact the electrode (anode or cathode) material and is separated from the side surfaces of these electrode materials by an air gap. In this arrangement, the capacitor wall is only parallel to the side surfaces of the electrode material and is separated from the side surfaces by an air gap. It does not contact the electrode material at any point on the surface of the electrode material.

[0066] In some other embodiments, the capacitor wall does not directly contact the electrode (anode or cathode) material and is separated from the side surfaces of these electrode materials by air gaps, but it does contact the electrode material along the bottom surface of the electrode material. In other embodiments, the capacitor wall directly contacts the electrode (anode or cathode) material at its side surfaces and along its bottom surface.

[0067] In one embodiment, in each individual cell of the bipolar solid-state battery cell, the capacitor wall is parallel to at least one external surface of the anode or cathode and is separated from at least one external surface of the anode or cathode by an air gap. In another embodiment, in each individual cell of the bipolar solid-state battery cell, there are at least two capacitor walls, each capacitor wall is parallel to at least one external surface of the anode or cathode and is separated from at least one external surface of the anode or cathode by an air gap.

[0068] In yet another embodiment, there are at least two capacitor walls, each parallel to the outer surface of the anode in each individual cell, and there are at least two capacitor walls, each parallel to the outer surface of the cathode in each cell. The at least two capacitor walls may each contact the outer wall of the anode, or may be separated from the outer wall of the anode by an air gap. The at least two capacitor walls may each contact the outer wall of the cathode, or may be separated from the outer wall of the cathode by an air gap.

[0069] In another embodiment, there is a capacitor wall that contacts at least every outer surface of the anode or cathode, except for the surface of the anode or cathode that contacts the separator. In one embodiment, the capacitor walls may be distributed symmetrically about the separator. In another embodiment, the capacitor walls may be distributed asymmetrically about the separator.

[0070] Figure 2A A top view of an exemplary bipolar solid-state battery cell 300 including a plurality of individual cells 301A, 301B, 301C, ..., 300n-1, etc. is described. Each of the plurality of individual cells 301A, 301B, 301C, ..., 300n-1, etc. includes an anode 303A, 303B, 303C, ..., 303n, a cathode 305A, 305B, 305C, 305D, ..., 305n-1, and a separator 304A, 304B, 304C, ..., 304n-1. Each individual cell has an associated current collector 302A, 302B, 302C, 302D, ..., 302n that collects the current generated in each cell. Each current collector includes an anode current collector and a cathode current collector. For example, current collector 302A (which contacts anode 303A) includes anode current collector 302A2 and cathode current collector 302A1. Current collectors 302B, 302C, 302D, ..., 302n similarly each have an anode current collector and a cathode current collector. Anode current collector and cathode current collector are usually in contact with each other. In one embodiment, anode current collector and cathode current collector are in direct contact with each other. In another embodiment, during the manufacture of current collector, anode current collector and cathode current collector form a single unit. A single unit with cathode and anode current collector is referred to as a cladding current collector. In some embodiments, anode current collector and cathode current collector are in contact with each other via a thin (e.g., less than 5 microns thick) conductive layer, and the conductive layer comprises a material different from anode current collector and cathode current collector.

[0071] Separators 304A, 304B, 304C, 304D, ..., 304n-1 prevent contact between anode material and cathode material. Each of the plurality of cells 301A, 301B, 301C, ..., 301n-1, etc. has capacitor walls 306 and 308 disposed on opposite sides, which prevent gel from leaking from the cell. The capacitor walls 306 and 308 are made of a capacitor material composition, which will be described in detail later.

[0072] Figures 2A-2D are cross-sectional top views depicting different arrangements of capacitor walls 306 and 308 in battery 301A, and the details of these different arrangements will be explained using only a single battery 301A (of each figure) as reference. Figures 2A-2D In each of the remaining single cells 301B, 301C, ..., etc., each has the same structure as the single cell 301A, so for the sake of brevity, their respective structures are not described in detail. The structures will be referenced in the remaining single cells 301B, 301C, ..., etc., and will be explained only when there are substantial differences.

[0073] Now refer to it again Figure 2A , a single cell 301A includes two sets of capacitor walls 306 and 308, which are arranged on opposite sides thereof parallel to the side surfaces of the anode 303A and the cathode 305A. The capacitor wall 306 is divided into two parts 306A and 306B separated by a separator 304A, and the capacitor wall 308 arranged along the opposite side surfaces (of the anode 303A and the cathode 305A) is also divided into two parts 308A and 308B separated by the separator 304A. Air gaps 310 and 312 separate the capacitor walls 306 and 308 from the side surfaces of the anode 303A and the cathode 305A, respectively. Referring to Figure 3A and 3B Air gaps 310 and 312 are discussed in more detail. Figure 3A and 3B is along Figure 2A Individual top view portions taken at sections MM′ and NN′ in FIG.

[0074] Figure 3AA side view portion of cathode 305A taken along section MM′ is depicted. Cathode 305A is separated from capacitor walls 306B, 306B1, 308B, and 308B1 by air gaps 310, 311, 312, and 313. Cathode 305A is in direct contact with cathode current collector 302B1 and is in electrical communication therewith. Cathode current collector 302B1 is in electrical communication with cathode tab 402 located outside battery 301A. The cathode tabs of each battery in the battery pack can be connected together to terminals (not shown). Cathode 305A is therefore surrounded on all sides by capacitor walls 306B, 306B1, 308B, and 308B1, but does not directly contact these capacitor walls. It should be noted that in Figure 3A Only capacitor walls 306B1 and 308B1 and air gaps 311 and 313 are visible in the cross-sectional view of Figure 3A shows a cross-sectional side view of a single cell 301A, and Figure 2A Only the cross-sectional top view is shown.) Circular section LL' shows an enlarged view of the air gaps 310 and 311 between the cathode 305A and the capacitor walls 306B and 306B1.

[0075] from Figure 3A It can be seen that cathode 305A has a D 1 and D 2 The outer dimensions of cathode 305A (ie, the side of cathode 305A has a length D 1 and D 2 In one embodiment, D 1 Can be equal to D 2 , in which case the cross-sectional area of ​​cathode 305A will be square. In another embodiment, D 1 Not equal to D 2 , in which case the cross-sectional area of ​​cathode 305A will be rectangular. 1 and D 2 Independent of each other. Expected D 1 and D 2 50 to 500 mm. 1 and d 2 The air gaps 310 and 311 of thickness d may have a thickness of up to 0.1 mm, preferably 0.01 to 0.1 mm. 1 and d 2 can be independent of each other and can be the same or different from each other.

[0076] Opposing capacitor walls 306B and 308B each have a 3 denoted by D, while the opposing capacitor walls 306B1 and 308B1 each have a thickness denoted by D 4 Indicates the thickness. D 3 and D 4It should be noted that the thickness D 3 and D 4 are independent of each other and have a value between 3 and 100 mm. In one embodiment, it is desired that d 1 and d 2 In another embodiment, it is expected that D 3 and D 4 are equal to each other.

[0077] Figure 3B A side cross-sectional view of anode 303A is depicted, taken along section NN'. In a manner similar to that discussed above with respect to the cathode, anode 303A is separated from capacitor walls 306A, 306A1, 308A, and 308A1 by an air gap. Figure 3B The size of the air gap, the size of the sides of the anode 303A and the thickness of the capacitor wall are shown in FIG. Figure 3A The anode 303A contacts the anode current collector 302A2. The anode current collector 302A2 is in electrical communication with the anode tab 403. The anode tabs 403 from each cell in the battery pack may be connected together to a terminal (not shown).

[0078] Figure 2B A top view of an exemplary bipolar solid-state battery cell 300 is depicted, comprising a plurality of individual cells 301A, 301B, 301C, ..., 300n-1, etc., wherein a capacitor wall 312A1 is located between an anode 303A and a current collector pair 302A, and wherein a capacitor wall 312A2 is located between a cathode 305A and a current collector pair 302B. Figure 2B In the arrangement shown, the capacitor wall surrounds the anode and cathode by: a) being in direct contact with one side surface of the anode and one side of the cathode; and b) being separated from the other side surfaces of the anode and cathode by an air gap. The remainder of the arrangement of the bipolar solid-state battery cell 300 is similar to Figure 2A The same as described in and will not be described in detail here.

[0079] Reference now Figure 2B , capacitor walls 312A1 and 312A2 are arranged perpendicular to Figure 2A The surfaces of capacitor walls 306 and 308 are shown in direct contact with anode 303A and cathode 305A. Capacitor walls 306A and 306B are separated from anode 303A and cathode 305A by air gap 310, while capacitor side walls 308A and 308B are separated from anode 303A and cathode 305A by air gap 312. Capacitor walls 312A1 and 312A2 are separated from capacitor walls 306A, 306B, 308A, and 308B by air gaps 310 and 312.

[0080] Figure 2C A top view of an exemplary bipolar solid-state battery cell 300 including a plurality of battery cells 301A, 301B, 301C, ..., 300n-1, etc. is described, wherein a capacitor wall 312A1 is located between an anode 303A and a current collector pair 302A, and wherein a capacitor wall 312A2 is located between a cathode 305A and a current collector pair 302B. In this embodiment, capacitor walls 312A1 and 312A2 are in direct contact with capacitor walls 306A, 306B, 308A, and 308B. Capacitor wall 312A1 contacts capacitor wall 306A at a first end 314A1 of capacitor wall 312A1. It contacts capacitor wall 308A at a second end 314A2 of capacitor wall 312A1, wherein second end 314A2 is opposite to first end 314A1. Capacitor wall 312A2 contacts capacitor wall 306B at a first end 316A1 of capacitor wall 312A2. It contacts capacitor wall 308B at a second end 316A2 of capacitor wall 312A2, wherein second end 316A2 is opposite to first end 316A1. Figure 2C In the arrangement shown, capacitor walls 306A and 306B are separated from anode 303A and cathode 305A by air gap 310. Capacitor walls 308A and 308B are separated from anode 303A and cathode 305A by air gap 312.

[0081] Figure 2D Another top view of an exemplary bipolar solid-state battery cell 300 including a plurality of individual cells 301A, 301B, 301C, ..., 300n-1, etc. is shown, wherein the capacitor wall 312A1 is located between the anode 303A and the current collector pair 302A, and wherein the capacitor wall 312A2 is located between the cathode 305A and the current collector pair 302B. In this embodiment, as previously described, Figure 2C As described, capacitor wall 312A1 contacts capacitor walls 306A and 308A at its ends, while capacitor wall 312A2 contacts capacitor walls 306B and 308B at its ends. In this embodiment, there is no air gap between capacitor walls 306A and 306B and anode 303A or between capacitor walls 308A and 308B and cathode 305A. Therefore, the capacitor walls partially surround the anode and cathode and directly contact each of the anode and cathode on three sides.

[0082] exist Figure 2B , 2CIn a variation of the embodiment shown in FIG. 2D or FIG. 3D , for each cell in the bipolar solid-state battery cell 300, the capacitor walls 312A1 and 312A2 may only exist in the anode or cathode, but not in both the anode and cathode. In other words, the capacitor walls may be arranged symmetrically or asymmetrically about the separator. This embodiment is not described herein, but can be easily understood by a person skilled in the art. For example, in Figure 2B , 2C In 2D, battery 301A may have capacitor walls 312A1, 306A, 306B, 308A, and 308B, but may not have capacitor wall 312A2, while battery 301B may have capacitor walls 312A1, 306A, 306B, 308A, and 308B. Figure 2B , 2C Or all capacitor walls are arranged as described in the embodiment shown in 2D.

[0083] In another embodiment regarding asymmetry, the capacitor walls on opposite sides of the separator can have different thicknesses from one another. For example, all of the capacitor walls on one side of the separator can have a greater thickness than those on the other side of the separator. In yet another embodiment, the capacitor walls on opposite sides of the separator can have different compositions from one another. For example, the capacitor walls on one side of the separator can have a first composition, while the capacitor walls on the other side can have a second composition, wherein the second composition is different from the first composition.

[0084] The following paragraphs describe in detail the Figure 2A , 2B , 2C or 2D. Figure 2A The bipolar solid-state battery cell 300 shown in FIG. 1 describes the materials in detail, but can also be applied to Figure 2B , 2C or the battery pack cells shown in 2D.

[0085] Now see again Figure 2A , anode current collector 302A2 comprises copper, and cathode current collector 302A1 comprises aluminum. Capacitor walls 306A, 306B, 308A, and 308B include capacitor active material, conductive additives, polymer binder, and solid electrolyte.

[0086] Capacitor active materials used in the capacitor wall include carbonaceous materials (e.g., activated carbon, graphene, single-walled carbon nanotubes, multi-walled carbon nanotubes, or combinations thereof), metal oxides (e.g., MOx, where M is a metal, and where M=Co, Ni, Nb, or combinations thereof), metal sulfides (e.g., TiS 2, CuS, NiS or a combination thereof), intrinsically conductive polymers (e.g., polyaniline, polyacetylene, polythiophene, polypyrrole or a combination thereof) or a combination thereof. The capacitor active material is present in an amount of 50 to 99, preferably 55 to 95, more preferably 60 to 90 weight percent (wt%) based on the total weight of the capacitor wall. Some of the carbonaceous materials listed above are described in detail below. They are also used as conductive additives in the capacitor wall.

[0087] Conductive additives used in capacitor walls include conductive additives. The conductive additives preferably include conductive carbonaceous materials. Examples of conductive carbonaceous materials include carbon nanotubes, carbon black, activated carbon, graphene, graphite, graphite oxide, carbon fibers, etc. or combinations thereof.

[0088] Carbon nanotubes include single-walled carbon nanotubes (SWNT), double-walled carbon nanotubes (DWNT), multi-walled carbon nanotubes (MWNT) or a combination thereof, and have a diameter of 2 to 100 nanometers, preferably 10 to 50 nanometers. Their length is 20 to 10,000 nanometers, preferably 200 to 5000 nanometers. It is desirable that the aspect ratio is greater than 10, preferably greater than 50, and more preferably greater than 100.

[0089] Carbon black with a high surface area is preferably used for electrodes. Carbon black (subtypes are acetylene black, channel black, furnace black, lamp black and thermal black) is a material produced by the incomplete combustion of coal and coal tar, vegetable matter or petroleum products (including fuel oil, fluid catalytic cracking tar and ethylene cracked in limited supply of air). Carbon black is a form of subcrystalline carbon that has a high surface area to volume ratio, although less than that of activated carbon. The surface area is 50-1000m 2 / gm of carbon black may be used in the slurry, which is used to form the electrode.

[0090] Activated carbon, also known as activated charcoal, is a carbon with a surface area of ​​more than 3,000 m 2 / gm carbon form. It can be used in combination with other conductive carbon-containing elements listed herein. An example of carbon black or activated carbon that can be used in the electrode forming slurry is Keltjen TM Black or Super P.

[0091] Graphene is an allotrope of carbon consisting of a single layer of atoms arranged in a hexagonal lattice nanostructure. The graphene added to the slurry can be in the form of individual graphene sheets or in the form of multiple loosely connected graphene sheets. Each atom in the graphene sheet is connected to its three nearest neighbors by σ bonds and delocalized π bonds, which contribute to a valence band that extends across the sheet. This is the same type of bonding seen in carbon nanotubes and polycyclic aromatic hydrocarbons, as well as in fullerenes and glassy carbon. The valence band is contacted by a conduction band, making graphene a semimetal with unusual electronic properties that are best described by theories for massless relativistic particles.

[0092] Graphite particles can also be used in conductive compositions. Graphite is a natural manifestation of pure carbon with a hexagonal crystal structure arranged in several parallel levels, called graphene layers. In simple terms, a graphite particle contains multiple graphene sheets arranged parallel to each other. This anisotropic structure gives graphite special properties, such as electrical conductivity along the layers or a specific strength. It is extremely heat-resistant, with a sublimation point of over 3,800°C, high thermal conductivity and chemical inertness.

[0093] Graphite oxide (GO), sometimes called graphene oxide, graphite oxide or graphitic acid, is a compound of carbon, oxygen and hydrogen in variable ratios obtained by treating graphite with strong oxidants and acids to decompose additional metals. The bulk product of maximum oxidation is a yellow solid with a C:O ratio between 2.1:1 and 2.9:1, which retains the layer structure of graphite, but with much larger and irregular spacing. The bulk material disperses spontaneously in alkaline solutions or can be dispersed by ultrasonic treatment in polar solvents to produce monomolecular sheets, similar to graphene and is called graphene oxide, i.e., graphite in a single layer form. Graphene oxide sheets exist in the form of strong paper-like materials, films, thin films and composites, and can be used in electrode-forming slurries used to prepare electrodes.

[0094] Carbon fibers have a diameter of 5 to 10 microns and are primarily composed of carbon atoms. They may be greater than 1000 microns in length, preferably greater than 10,000 microns. The carbon fibers are prepared by stretching pitch or polyacrylonitrile polymer fibers under high pressure and at temperatures exceeding 1500° C., preferably at temperatures above 2200° C. Carbon fibers are different from carbon nanotubes and do not have concentrically arranged cylindrical graphene sheets. Carbon fibers typically include high aspect ratio graphene sheets arranged in a configuration parallel to one another.

[0095] The above carbon nanotubes, carbon black, activated carbon, graphene sheets, graphite particles, graphite oxide particles or combinations thereof may be used alone or in any combination to form a conductive network in the capacitor wall. In an exemplary embodiment, carbon nanotubes are generally used in the largest amount when compared to other carbon-containing ingredients.

[0096] Capacitor walls 306A, 306B, 308A, and 308B may contain up to 30% by weight, preferably less than 20% by weight, and more preferably less than 10% by weight of conductive additives based on the total weight of the capacitor walls. In one embodiment, if conductive additives are present, the capacitor walls may contain 1% by weight or more, preferably 2% by weight or more of conductive additives.

[0097] Capacitor walls 306A, 306B, 308A, and 308B may include a binder that helps maintain the capacitor walls in a monolithic form and prevents materials used in the capacitor walls from dispersing during the manufacturing process. The binder is preferably a polymer binder that promotes adhesion of the capacitor active material particles, conductive additives, and optional solid electrolyte. The polymer binder promotes shape retention of the capacitor walls. The polymer binder typically comprises an organic polymer. Examples of organic polymers include poly(tetrafluoroethylene) (PTFE), styrene butylene styrene copolymer (SEBS), styrene butadiene styrene copolymer (SBS), acrylonitrile butadiene rubber (NBR), styrene-butadiene rubber (SBR), poly(propylene carbonate) PPC, sodium carboxymethylcellulose (CMC), poly(vinylidene fluoride) (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP), polyacrylonitrile (PAN), poly(vinylidene fluoride-co-chlorotrifluoroethylene) (P(VDF-CTFE)), poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TeFE)), poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) terpolymer (P(VDF-TrFE-CFE)) or combinations thereof. In a preferred embodiment, the polymer binder for the active layer is a poly(vinylidene fluoride-hexafluoropropylene) copolymer. The polymer binder has a weight average molecular weight of 5,000 to 1,000,000 g / mole, preferably 50,000 to 750,000 g / mole, more preferably 75,000 to 500,000 g / mole, as measured using gel permeation chromatography with polystyrene standards.

[0098] The polymer binder is present in an amount of at most 20% by weight, preferably at most 10% by weight, more preferably at most 1% by weight, based on the total weight of the capacitor wall.

[0099] Capacitor walls 306A, 306B, 308A, and 308B may also include a solid electrolyte. The solid electrolyte may be a sulfide solid electrolyte, an oxide-based solid electrolyte, a metal-doped or asymmetrically substituted oxide solid electrolyte, a nitride-based solid electrolyte, a halide-based solid electrolyte, a hydride-based solid electrolyte, or a combination thereof.

[0100] The solid electrolyte generally comprises a pseudo binary sulfide, a pseudo ternary sulfide, a pseudo quaternary sulfide or a combination thereof. Examples of pseudo binary sulfides include Li 2 SP 2 S 5 System (such as Li 3 PS 4 , Li 7 P 3 S 11 and Li 9.6 P 3 S 12 )、Li 2 S-SnS 2 System (such as Li 4 S N 4 )、Li 2 S-SiS 2 System, Li 2 S-GeS 2 System, Li 2 SB 2 S 3 System, Li 2 S-Ga 2 S 3 System, Li 2 SP 2 S 3 System, Li 2 S-Al 2 S 3 Examples of pseudo-ternary sulfides include Li 2 O-Li 2 SP 2 S 5 System, Li 2 SP 2 S 5 -P 2 O 5 System, Li 2 SP 2 S 5 -GeS 2 System (such as Li 3.25 Ge 0.25 P 0.75 S 4 and Li 10 G 2 S 12 )、Li 2 SP 2 S 5 -LiX system (wherein X = F, Cl, Br or I, examples of which include Li 6 PS 5 Br, Li 6PS 5 Cl, L 7 P 2 S 8 I and Li 4 PS 4 I), Li 2 S-As 2 S 5 -SnS 2 System (such as Li 3.833 Sn 0.833 As 0.166 S 4 )、Li 2 SP 2 S 5 -Al 2 S 3 System, Li 2 S-LiX-SiS 2 (where X = F, Cl, Br or I, examples of which include 0.4LiI·0.6Li 4 S N 4 and Li 11 Si 2 PS 12 Sulfide-based solid electrolytes include Li 2 SP 2 S 5 System, Li 2 SP 2 S 5 -MO X System, Li 2 SP 2 S 5 -MS x system, LGPS (Li 10 G 2 S 12 ), sulfide crystalline lithium superion conductor (Li 3.25 Ge 0.25 P 0.75 S 4 )、Li 3.4 Si 0.4 P 0.6 S 4 , Li 10 G 2 S 11.7 O 0.3 , silver lithium (e.g., Li 6 PS 5 X (X = Cl, Br, or I), Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3)、Li 9.6 P 3 S 12 , Li 7 P 3 S 11 , Li 9 P 3 S 9 O 3 , Li 10.35 Ge 1.35 P 1.65 S 12 , Li 10.35 Si 1.35 P 1.65 S 12 , Li 9.81 Sn 0.81 P 2.19 S 12 , Li 10 (Si 0.5 Ge 0.5 ) 2 S 12 , Li 10 (Ge 0.5 Sn 0.5 ) 2 S 12 , Li 10 (Si 0.5 Sn 0.5 ) 2 S 12 , Li 3.833 Sn 0.833 As 0.166 S 4 )、LiI-Li 4 S N 4 , Li 4 S N 4 or a combination thereof.

[0101] Oxide-based solid electrolytes include garnets (e.g. Li 7 La 3 Zr 2 O 12 ), perovskites (such as Li 3x La 2 / 3- x TiO 3 )、NASICON (such as Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 and Li 1+x Al x Ge 2-x (PO4 ) 3 ), LISICON (such as Li 2+2x Zn 1- x GeO 4 ) or a combination thereof.

[0102] Metal-doped or alivalently substituted oxide solid electrolytes can also be used in the capacitor wall. Examples include Al (or Nb)-doped Li 7 La 3 Zr 2 O 12 , Sb-doped Li 7 La 3 Zr 2 O 12 , Li substituted by Ga 7 La 3 Zr 2 O 12 , Cr and V substituted LiSn 2 P 3 O 12 , Al-substituted perovskite, Li 1+x+y Al x Ti 2-x Si y P 3-y O 12 or a combination thereof.

[0103] Nitride-based solid electrolytes such as Li 3 N.Li 7 PN 4 、LiSi 2 N 3 or a combination thereof, can also be used in capacitor walls.

[0104] Hydride-based solid electrolytes, such as LiBH 4 , LiBH 4 -LiX (X = Cl, Br or I), LiNH 2 , Li 2 NH, LiBH 4 -LiNH 2 , Li 3 AlH 6 or a combination thereof may also be used in the capacitor wall.

[0105] Halide-based solid electrolytes, such as LiI, Li 3 InCl 6 , Li 2 CdCl 4 , Li 2 MgCl 4, Li 2 CdI 4 , Li 2 ZnI 4 , Li 3 OCl or a combination thereof can also be used in the capacitor wall.

[0106] Borate-based solid electrolytes such as Li 2 8 4 O 7 , Li 2 OB 2 O 3 -P 2 O 5 Or a combination thereof may also be used in the capacitor wall. Based on the total weight of the cathode active layer 108, the amount of the solid electrolyte that can be used in the capacitor wall is up to 50% by weight, preferably less than 30% by weight, and more preferably less than 15% by weight. In one embodiment, based on the total weight of the cathode active layer 108, the solid electrolyte may be used in the cathode active layer in an amount of 1% by weight or more, preferably 2% by weight or more.

[0107] Cathode 305A (see Figure 2A , 2B , 2C or 2D) comprises a cathode active material, a conductive additive, a binder and a solid electrolyte.

[0108] The cathode active material comprises lithium cobalt oxide (LCO, sometimes referred to as "lithium cobaltate" or "lithium cobaltite", a variant of which is LiCoO 2 ); lithium nickel manganese cobalt oxide (NMC, with a variant chemical formula of LiNiMnCo); lithium manganese oxide (LMO, with a variant chemical formula of LiMn 2 O 4 , Li 2 MnO 3 Lithium nickel cobalt aluminum oxide (LiNiCoAlO 2 and its variants as NCA) and lithium titanate oxide (LTO, a variant formula is Li 4 Ti 5 O 12 ); lithium iron phosphate (LFP, a variant of which is LiFePO 4 ), lithium nickel cobalt aluminum oxide (its variant as NCA) and other similar materials, spinel (LiMn 2 O 4 、LiNi 0.5 Mn 1.5 O 4 ), polyanion cathode (LiV2 (PO 4 ) 3 ) and other lithium transition metal oxides. The above-mentioned surface-coated and / or doped cathode materials, such as LiNbO 3 Coated LiMn 2 O 4 and Al-doped LiMn 2 O 4 Low voltage cathode materials such as lithiated metal oxides / sulfides (e.g., LiTiS 2 ), lithium sulfide and sulfur.

[0109] Other variations of the foregoing may be included. In some embodiments using NMC as the active material, a nickel-rich NMC may be used. For example, in some embodiments, a variant of NMC may be LiNi x Mn y Co (1-x-y) O 2 、LiNi x Mn y Al (1-x-y) O 2 、LiNi x Mn (1-x) O 2 , Li 1+x MO 2 , wherein x is equal to or greater than about 0.7, 0.75, 0.80, 0.85 or greater, and wherein y is less than 0.15, preferably less than 0.1. In some embodiments, NMC811 may be used, wherein in the above formula x is about 0.8 and y is about 0.1.

[0110] The cathode active material is present in the cathode in an amount of 30 to 95% by weight, preferably 40 to 80% by weight, more preferably 45 to 75% by weight, based on the total weight of the cathode.

[0111] The cathode may contain a conductive additive in an amount of up to 30% by weight, preferably up to 20% by weight, preferably up to 10% by weight, based on the total weight of the cathode. If present, the conductive additive may also be present in an amount of 1% by weight or more, preferably 2% by weight or more, based on the total weight of the cathode. The conductive additives listed above may also be used in the cathode and are therefore not listed again for the sake of brevity.

[0112] The cathode may also contain a polymer binder in an amount of up to 20% by weight, preferably up to 15% by weight, preferably up to 10% by weight, based on the total weight of the cathode. If a polymer binder is present, it may also be present in an amount of 1% by weight or more, preferably 2% by weight or more, based on the total weight of the cathode. The cathode may also contain a solid electrolyte in an amount of up to 30% by weight, preferably up to 25% by weight, and preferably up to 10% by weight, based on the total weight of the cathode. If a solid electrolyte is present, it may also be present in an amount of 1% by weight or more, preferably 2% by weight or more, based on the total weight of the cathode. Both the polymer binder and the solid electrolyte used for the cathode may be the same as those listed above for the capacitor wall, so these will not be listed again here.

[0113] Anode 303A (see Figure 2A , 2B , 2C or 2D) includes an anode active material, a conductive additive, a binder and a solid electrolyte.

[0114] Anode active materials include some of the above carbonaceous materials, hard carbon, silicon, silicon mixed with graphite, carbon-coated silicon particles, Li 4 Ti 5 O 12 ; transition metals, such as tin, metal oxides, metal sulfides (such as TiO 2 , FeS, etc.), lithium metal and alloys, or combinations thereof. Exemplary active materials may include graphite, hard carbon, activated carbon, carbon in nanoform, silicon, silicon oxide, carbon-coated silicon nanoparticles, or combinations thereof. In some such embodiments, the anode active material may be intercalated with lithium (e.g., using pre-lithiation methods known in the art).

[0115] Hard carbon is a solid form of carbon that cannot be converted into graphite by heat treatment, even at temperatures as high as 3000°C. Hard carbon is also known as charcoal or non-graphitizable carbon. Hard carbon is made by heating a carbon-containing precursor to about 1000°C in the absence of oxygen. The precursors of hard carbon are polyvinylidene chloride (PVDC), lignin, and sucrose. Other precursors, such as polyvinyl chloride (PVC) and petroleum coke, produce soft carbon or graphitized carbon. Soft carbon can be easily converted into graphite by heating to 3000°C.

[0116] The anode active material is present in the anode in an amount of 30 to 95% by weight, preferably 40 to 80% by weight, more preferably 45 to 75% by weight, based on the total weight of the anode.

[0117] The anode may contain a conductive additive in an amount of up to 30% by weight, preferably up to 20% by weight, preferably up to 10% by weight, based on the total weight of the anode. If present, the conductive additive may also be present in an amount of 1% by weight or more, preferably 2% by weight or more, based on the total weight of the anode. The conductive additives listed above (for the capacitor wall and cathode) may also be used in the anode and are therefore not listed again for brevity.

[0118] The anode may also contain a polymer binder in an amount of up to 20% by weight, preferably up to 15% by weight, preferably up to 10% by weight, based on the total weight of the anode. If a polymer binder is present, it may also be present in an amount of 1% by weight or more, preferably 2% by weight or more, based on the total weight of the anode. The anode may also contain a solid electrolyte in an amount of up to 30% by weight, preferably up to 25% by weight, preferably up to 10% by weight, based on the total weight of the anode. If a solid electrolyte is present, it may also be present in an amount of 1% by weight or more, preferably 2% by weight or more, based on the total weight of the anode. Both the polymer binder and the solid electrolyte used for the anode may be the same as those listed above for the capacitor wall, so these will not be listed again here.

[0119] Partition 304A (see Figure 2A , 2B , 2C or 2D) include electrically insulating polymeric materials and / or ceramic materials. Separator 304A can be a polymer-based separator embedded with a gel electrolyte, a free-standing gel film, or a solid electrolyte layer with or without a gel electrolyte. Polymer sheets with or without a ceramic coating can be used as separators. Examples of polymer sheets include polypropylene or polyethylene sheets. Examples of ceramics that can be used to coat polymer sheets include silicon dioxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), zirconium oxide (ZrO 2 ), titanium dioxide (TiO 2 ) or a combination thereof.

[0120] Examples of other high temperature separators include polyimide (PI) nanofiber-based nonwoven films, nano-sized alumina and poly (lithium 4-styrene sulfonate) coated polyethylene films, silica-coated polyethylene films, polyimide co-coated polyethylene films, polyetherimide (PEI) films, bisphenol-acetone diphthalic anhydride (BPADA) and (p-phenylenediamine) films, expanded polytetrafluoroethylene-reinforced polyvinylidene fluoride-hexafluoropropylene films, sandwich-structured polyvinylidene fluoride / poly (m-phenylene isophthalamide) / polyvinylidene fluoride (PVdF / PMIA / PVdF) nanofiber films or combinations thereof. The thickness of these separators may be 1 to 50 microns.

[0121] In another embodiment, separator 306A may be a free-standing gel film having a thickness of 10 to 100 microns, comprising up to 30% by weight of a polymer (e.g., polyacrylonitrile, polyethylene oxide, or polyacrylic acid) mixed with 70 to 90% by weight of a liquid electrolyte. The liquid electrolyte comprises a carbonate solvent (e.g., ethylene carbonate (EC), γ-butyrolactone (GBL), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), propylene carbonate (PC), or a combination thereof) in which a lithium salt (e.g., LiTFSI, LiBOB, LiDFOB, LiFSI, LiBeTi, LiPF 6 , LiBF 4 、LiAsF 6 、LiClO 4 , LiTfO or a combination thereof), and also has additives of vinylene carbonate (VC), vinylene carbonate (VEC), butylene carbonate (BC), fluoroethylene carbonate (FEC), InCl 3 、ZnCl 2 or at least one of a combination thereof.

[0122] In another embodiment, the gel electrolyte can be distributed in the electrode (anode 303A or cathode 305A) and / or in the separation layer 304A. In addition to 50 to 99.9% by weight of the liquid electrolyte, the gel electrolyte can also include 0.1 to 50% by weight of the polymer host. The polymer host can include polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polyethylene oxide (PEO), polypropylene oxide (PPO), polyacrylonitrile (PAN), polymethacrylonitrile (PMAN), polymethyl methacrylate (PMMA) or a combination thereof. Other polymers listed above as polymer binders can also be used. The liquid electrolyte is listed above and is not listed here.

[0123] In a method of making a bipolar solid-state battery cell, a separator having a material capable of serving as an anode on one surface and a material capable of serving as a cathode on an opposing surface is printed with a material that forms a capacitor wall. Figure 4A An exemplary method of making a bipolar solid-state battery cell is described in which a bipolar electrode (a separator 304A having an anode 303A and a cathode 305A disposed on opposing surfaces) is coated with a precursor slurry that forms capacitor walls 306A, 306A1, 308A, and 308A1 (for cells of bipolar solid-state battery cells of equivalent construction, see Figure 3A and 3B ).exist Figure 4A, a sheet including a bipolar electrode is mounted on a first roller 502 and unwound during the process of placing a capacitor electrode slurry thereon. After the capacitor electrode slurry is deposited thereon, the bipolar electrode is unwound from the first roller 502 and wound on a second roller 508. During its travel from the first roller 502 to the second roller 508, the bipolar electrode travels on rollers 504 and 506 that guide it (hold it in place) so that nozzles 602 and 604 can place the capacitor slurry thereon. Nozzle 602 places the slurry for capacitor walls 306B and 308B, while nozzle 604 moves back and forth on the bipolar electrode to deposit the slurry for capacitor walls 306B1 and 308B1. Figure 4B A top view of a bipolar electrode before and after deposition of a slurry for a capacitor wall is depicted. After disposing the slurry for forming the capacitor, the bipolar electrode may be dried to remove any solvent from the bipolar electrode. The bipolar electrode after solvent removal includes a capacitor wall disposed around an anode and a cathode, thereby forming a bipolar solid-state battery cell.

[0124] The composition for forming the capacitor wall is described in detail above. To form the capacitor wall slurry, the above disclosed composition can be mixed with one of the above carbonate solvents to form a slurry. The slurry is then filled into nozzles 602 and 604, and the slurry is discharged from the nozzles to the bipolar electrodes to form the capacitor wall.

[0125] The terms "a" and "an" do not indicate a limitation of quantity, but rather indicate the presence of at least one of the referenced item. The term "or" means "and / or," unless the context clearly indicates otherwise. References to "aspects" throughout the specification mean that a particular element (e.g., feature, structure, step, or characteristic) described in conjunction with that aspect is included in at least one aspect described herein, and may or may not be present in other aspects. In addition, it should be understood that the described elements may be combined in any suitable manner in the various aspects.

[0126] When an element such as a layer, film, region, or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present.

[0127] Unless specified to the contrary herein, all test standards are the most recent standards in effect prior to the filing date of the present application or, if priority is claimed, the filing date of the earliest priority application in which the test standards appear.

[0128] Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.

[0129] Although the above disclosure has been described with reference to exemplary embodiments, it will be appreciated by those skilled in the art that various changes may be made and elements thereof may be replaced with equivalents without departing from the scope of the present invention. In addition, many modifications may be made to adapt specific circumstances or materials to the teachings of the present disclosure without departing from the substantive scope of the present disclosure. It is therefore intended that the present disclosure is not limited to the specific embodiments disclosed, but will include all embodiments falling within its scope.

Claims

1. A bipolar solid-state battery cell comprising a plurality of battery cells, wherein: Each battery includes: Partitions; an anode disposed on a first side of the separator; an anode current collector in electrical communication with the anode; a cathode disposed on a second side of the separator; wherein the second side is disposed opposite the first side; a cathode current collector in electrical communication with the cathode; A capacitor wall is disposed parallel to at least one outer surface of the anode or cathode; wherein the capacitor wall comprises a capacitor active material.

2. The battery according to claim 1, wherein The capacitor wall is separated from the at least one outer surface of the anode or the cathode by an air gap.

3. The battery according to claim 2, wherein The thickness of the air gap is up to 0.1 mm.

4. The battery according to claim 1, wherein The capacitor wall has a wall thickness of 3 to 100 mm.

5. The battery according to claim 1, wherein The capacitor wall contacts at least one outer surface of the anode or cathode.

6. The battery according to claim 1, wherein The capacitor wall contacts at least two outer surfaces of the anode or cathode.

7. The battery according to claim 1, wherein The capacitor wall contacts at least one exterior surface of the anode or cathode adjacent to the current collector.

8. The battery according to claim 1, wherein The capacitor wall contacts every surface of the anode or cathode except the surface contacting the separator.

9. The battery according to claim 1, wherein The capacitor wall is arranged parallel to at least two outer surfaces of the anode or cathode, and an air gap is present between each of the two outer surfaces of the anode or cathode and the capacitor wall.

10. The battery according to claim 8, wherein The capacitor wall contacts each surface of the anode and the cathode except for surfaces of the anode and the cathode contacting the separator.

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