Bipolar Solid-State Battery Cell

Abstract

The present invention relates to a bipolar solid-state battery cell comprising a plurality of electrochemical units arranged in a stack such that adjacent electrochemical units share an electronic conductor, wherein the plurality of stacked electrochemical units are arranged in series, the bipolar solid-state battery cell comprising: a cathode current collector; a first electrochemical unit comprising a first catholyte layer, a first solid electrolyte, and a first electronic conductor; x second electrochemical units, x being 0 to 8, each comprising a second catholyte layer, a second solid electrolyte, and a second electronic conductor; a third electrochemical unit comprising a third catholyte layer and a third solid electrolyte; an anode current collector; and an electrical insulating layer. The present invention further relates to a bipolar solid-state battery comprising a stack of at least two bipolar solid-state battery cells.

Description

Technical Field

[0001] The present invention relates to a bipolar solid battery cell, in particular to a bipolar solid battery cell comprising a plurality of stacked electrochemical units. The present invention further relates to a bipolar solid battery comprising a plurality of stacked bipolar solid battery cells.

Background Art

[0002] Secondary batteries have been known for quite a long time. In the search for secondary batteries with high energy density and high output power, bipolar batteries have been developed. In particular, bipolar lithium-ion secondary batteries, or bipolar lithium-ion batteries for short, have attracted much attention.

[0003] A bipolar battery cell comprises a stack of electrochemical units arranged in series. To achieve such a stack, bipolar electrodes are used between an external cathode and an external anode, wherein an electrolyte is present between the cathode and an adjacent bipolar electrode, between each adjacent bipolar electrode, and between the anode and an adjacent bipolar electrode.

[0004] EP1487034 discloses a bipolar battery comprising bipolar electrodes and an electrolyte layer. A bipolar electrode comprises a current collector, a positive electrode layer formed on one surface of the current collector, and a negative electrode layer formed on the other surface of the current collector. The bipolar electrodes are laminated sequentially to provide series connection through the electrolyte layers, forming a stack structure. The positive electrode layers, negative electrode layers and electrolyte layers are potted in a resin portion. The resin portion of the battery provides protection against vibration and impact during operation of a vehicle battery, and renders the battery water-resistant, heat-resistant, air-tight and electrolyte-resistant.

[0005] The drawbacks of these bipolar battery elements include limited power density and energy density, requiring large stacks to achieve sufficient power density. As a result, a significant amount of heat is generated during use, particularly within the electrochemical cell at the center of the stack. This heat tends to accumulate within the battery element, causing electrolyte degradation, such as oxygen release, which poses safety risks and limits the lifespan of the bipolar battery element. A further drawback is that the resin portion used as the embedding material is known to provide insufficient protection in the event of overvoltage in the battery. Furthermore, when using liquid electrolytes, there is a risk of electrolyte leakage, which also poses a safety risk.

[0006] US2009017371 discloses a power storage device comprising multiple electrolyte layers stacked with electrode elements interposed therebetween. To address the difficulty of heat dissipation, the multiple electrolyte layers include an electrolyte layer provided at a first position in the stacking direction and an electrolyte layer provided at a second position different from the first position, so that the head radiation is lower at the second position than at the first position. The electrolyte layer at the second position has a higher tolerance value than the electrolyte layer at the first position. The electrolyte may be a solid electrolyte containing particles, where the particle density at the second position is lower than the particle density at the first position.

[0007] The drawbacks of these bipolar batteries are their complex setup and the need for different electrolyte layer compositions. Furthermore, bipolar batteries remain limited in power density and energy density, and their safety, especially during use, is restricted.

[0008] US2008118826 discloses a lithium-ion battery comprising cell elements including a cathode, an anode, and an electrolyte layer between the cathode and the anode. The electrolyte layer comprises an arrangement of insulating particles with a plurality of intervening spaces between them, the electrolyte occupying at least a portion of the intervening spaces.

[0009] US2009269665 discloses a bipolar battery having an inorganic solid electrolyte for providing a power storage device that can prevent a decrease in the energy efficiency of the power storage device and can avoid fluctuations in temperature distribution.

[0010] JP2019140024 discloses a method for laminating a solid electrolyte layer based on sulfides and oxides in a bipolar all-solid-state battery stack.

[0011] The aforementioned drawback of bipolar batteries is that they tend to be overcharged and / or overvoltaged, which limits their safety. [Overview of the project]

[0012] An objective of the present invention is to overcome one or more of the aforementioned drawbacks. An objective of the present invention is to provide a bipolar solid-state battery element and a bipolar solid-state battery having high power density. A further objective of the present invention is to provide a bipolar solid-state battery element and a bipolar solid-state battery with improved safety compared to bipolar solid-state battery elements and bipolar solid-state batteries of the art.

[0013] According to a first aspect of the present invention, a bipolar solid-state battery cell is provided, as shown in the accompanying claims.

[0014] A bipolar solid-state battery cell includes multiple electrochemical units. These electrochemical units are arranged in a stack such that adjacent electrochemical units share an electronic conductor. Preferably, the stacked electrochemical units are arranged in series.

[0015] A bipolar solid-state battery cell includes a cathode current collector. The cathode current collector may be any cathode current collector known in the art. Preferably, the cathode current collector contains or is substantially made of aluminum.

[0016] The bipolar solid battery cell further includes a first electrochemical unit. The first electrochemical unit is a first Cassolite It includes a (catholyte) layer, a first solid electrolyte, and a first electron conductor.

[0017] First Cassolite The layer contains a first active material. The first active material may be any active material known in the art.

[0018] Preferably, the first Cassolite The layer further comprises an electron-conducting compound and / or an ionic-conducting compound. Cassolite The layer may further contain a binder. The electron-conducting compound, ion-conducting compound, and optional binder may be as known in the art.

[0019] Preferably, the first solid electrolyte includes or substantially consists of alkali metals, alkaline earth metals, transition metals, or combinations thereof. Preferred examples of alkali metals include, but are not limited to, lithium and sodium. For example, the first solid electrolyte may be Li7La3Zr2O 12 (LLZO) may be included or substantially derived from it. Preferred examples of alkaline earth metals include, but are not limited to, magnesium. Preferred examples of transition metals include, but are not limited to, aluminum.

[0020] Preferably, the first electronic conductor comprises or consists substantially of steel, steel alloy, titanium, titanium alloy, fired glass-like carbon (also known as vitreous carbon or glassy carbon under registered trademark) or a combination of two or more thereof. Non-limiting examples of steel include stainless steel, carbon steel and A36.

[0021] Optionally, the first electrochemical unit further comprises a first anode layer. The first anode layer may be any anode layer known in the art. Preferably, when present, the first anode layer comprises or consists substantially of an alkali metal, an alkaline earth metal, a transition metal, graphite, silicon, carbide, or a combination of two or more thereof.

[0022] The bipolar solid battery cell further comprises x second electrochemical units. Preferably, x is 0 to 20, for example 0 to 15, preferably 0 to 10, more preferably 0 to 8, for example 0 to 5, or 0 to 1. As will be understood, when x is 0, the bipolar solid battery cell comprises two electrochemical units, namely the first and third electrochemical units, while the bipolar solid battery cell does not comprise any second electrochemical unit.

[0023] Each of the second electrochemical units, when present (i.e., when x is 1 to 8), individually comprises a second Cassolite layer, a second solid electrolyte, and a second electronic conductor.

[0024] The second Cassolite layer comprises a second active material. The second active material is preferably as described hereinabove with reference to the first active material. Preferably, the second Cassolite layer further comprises an electronically conductive compound and / or an ionically conductive compound. The second CassoliteThe layer may further comprise a binder. The electronically conductive compound, the ionically conductive compound and the optional binder may be as known in the art.

[0025] When the bipolar solid battery cell comprises at least two second electrochemical units (i.e., x is 2 to 8), the second electrochemical units may have the same or different (second) Cassolite layers. It will be understood that each individual Cassolite layer of the second electrochemical unit may be the same as or different from the first Cassolite layer of the first electrochemical unit.

[0026] Preferably, the second solid electrolyte is as described hereinabove with reference to the first solid electrolyte. When the bipolar solid battery cell comprises two or more second electrochemical units (i.e., x is 2 to 8), the second electrochemical units may have the same or different (second) solid electrolytes. It will be understood that each individual solid electrolyte of the second electrochemical units may be the same as or different from the first solid electrolyte of the first electrochemical unit.

[0027] Preferably, the second electronic conductor is as described hereinabove with reference to the first electronic conductor. When the bipolar solid battery cell comprises two or more second electrochemical units (i.e., x is 2 to 8), the second electrochemical units may have the same or different (second) electronic conductors. It will be understood that each individual electronic conductor of the second electrochemical units may be the same as or different from the first electronic conductor of the first electrochemical unit.

[0028] Optionally, if present (i.e., x is between 1 and 8), the second electrochemical unit may further include a second anode layer. If the solid battery cell includes two or more second electrochemical units (i.e., x is between 2 and 8), some or all of the second electrochemical units may include a second anode layer. Preferably, if present, each second anode layer is individually as described above with respect to the optional first anode layer herein.

[0029] If a bipolar solid battery cell contains two or more second electrochemical units (i.e., x is 2 to 8), the second electrochemical units may have the same or different second anode layers. If x is 1 to 8, it will be understood that whether one or more second electrochemical units contain a second anode layer is independent of whether the first electrochemical unit contains an anode layer. It will also be understood that each anode layer of a second electrochemical unit, if present, may be the same as or different from the first anode layer of the first electrochemical unit.

[0030] The bipolar solid battery cell further includes a third electrochemical unit. Cassolite It includes a layer and a third solid electrolyte.

[0031] Third Cassolite The layer contains a third active material. The third active material is preferably as described herein with respect to the first active material. Preferably the third Cassolite The layer further comprises an electron-conducting compound and / or an ion-conducting compound. Third Cassolite The layer may further contain a binder. The electron-conducting compound, ion-conducting compound, and optional binder may be as known in the art.

[0032] Preferably, the third solid electrolyte is as described above with respect to the first solid electrolyte in this specification. It will be understood that the solid electrolyte of the third electrochemical unit may be the same as or different from the solid electrolyte of the second electrochemical unit when x is 1 to 8.

[0033] Optionally, the third electrochemical unit further comprises a third anode layer. Preferably, if present, the third anode layer is as described herein with respect to the optional first and / or optional second anode layers. It will be understood that, if present, the anode layer of the third electrochemical unit may be the same as or different from the anode layer of the first electrochemical unit and / or the second electrochemical unit if present, when x is 1 to 8.

[0034] A bipolar solid-state battery cell further includes an anode current collector. The anode current collector may be any anode current collector known in the art. Preferably, the anode current collector contains or is substantially derived from copper.

[0035] A bipolar solid battery cell further includes an electrical insulating layer. Preferably, the electrical insulating layer is arranged to electrically withstand the voltage of the bipolar solid battery cell during use.

[0036] Preferably, the electrical insulating layer is provided on the outer surface of the cathode current collector and / or the outer surface of the anode current collector. Preferably, the electrical insulating layer is provided on the outer surface of the cathode current collector. Preferably, and / or, the electrical insulating layer is provided on the outer surface of the anode current collector.

[0037] In this disclosure, the “outer surface” of the layers of a bipolar solid battery cell means the surface facing outwards from the battery cell, i.e., the surface opposite to the surface facing the solid electrolyte.

[0038] Preferably, the electrical insulating layer comprises or substantially comprises a polymer, a ceramic material, or a combination of two or more thereof.

[0039] Preferably, but not limited to, the polymer is selected from the group consisting of polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, cellulose, viscose, natural rubber, and synthetic rubber.

[0040] Preferably, but not limited to, the ceramic material is selected from the group consisting of glass, metal oxides, metal nitrides, porcelain, and mica. A preferred example of a metal oxide is alumina. A preferred example of a metal nitride is boron nitride.

[0041] A second aspect of the present invention provides a bipolar solid-state battery as shown in the accompanying claims.

[0042] A bipolar solid battery comprises or substantially comprises at least two bipolar solid battery cells. The bipolar solid battery cells are stacked. Preferably, at least one, preferably all, of the at least two bipolar solid battery cells are according to a first aspect of the present disclosure.

[0043] Preferably, at least two, preferably one, cathode current collectors of at least two bipolar solid battery cells are electronically coupled together, particularly by coupling to the cathode tab. This preferably allows for easy coupling of the cathode current collector's electronic circuitry, particularly to external electronic circuitry (i.e., outside or outside the battery cell).

[0044] Similarly, and preferably, at least two anode current collectors of at least two bipolar solid battery cells, preferably one each, are electronically coupled together, particularly by coupling to anode tabs. This preferably allows for easy coupling of the anode current collector's electronic circuitry, particularly to external electronic circuitry (i.e., outside or outside the battery cell).

[0045] The advantages of the bipolar solid-state battery cells of this disclosure include, but are not limited to, improved functionality due to the stacking of multiple electrochemical cells, improved safety, reduced or even minimized risk of thermal runaway, and thereby improved battery cell components, particularly Cassolite This includes protecting the anode (if present) and / or the electrolyte. Safety is further improved by reducing the risk of leakage of harmful gases released from the chemical reactions of battery components.

[0046] A further advantage of the bipolar solid battery cells of this disclosure is that multiple bipolar SSB cells can be stacked, thereby making it possible to obtain a bipolar solid battery with increased safety compared to existing SSBs. The increased safety is achieved, but is not limited to, by ensuring protection against thermal runaway, particularly under overvoltage or overcharge conditions. [Brief explanation of the drawing]

[0047] Aspects of the present invention will be described in more detail with reference to the accompanying drawings, where the same reference numerals illustrate the same features. [Figure 1] Figures 1-9 schematically illustrate the bipolar solid-state battery cells described herein. [Figure 2] Figures 1-9 schematically illustrate the bipolar solid-state battery cells described herein. [Figure 3] Figures 1-9 schematically illustrate the bipolar solid-state battery cells described herein. [Figure 4] Figures 1-9 schematically illustrate the bipolar solid-state battery cells described herein. [Figure 5] Figures 1-9 schematically illustrate the bipolar solid-state battery cells described herein. [Figure 6]Figures 1-9 schematically illustrate the bipolar solid-state battery cells described herein. [Figure 7] Figures 1-9 schematically illustrate the bipolar solid-state battery cells described herein. [Figure 8] Figures 1-9 schematically illustrate the bipolar solid-state battery cells described herein. [Figure 9] Figures 1-9 schematically illustrate the bipolar solid-state battery cells described herein. [Figure 10] Figure 10 schematically shows the bipolar solid battery described herein. [Modes for carrying out the invention]

[0048] Figure 1 schematically shows a bipolar solid-state battery cell 1 described herein. The bipolar solid-state battery cell 1 includes a cathode current collector 2, a first electrochemical unit 3a, a third electrochemical unit 3b, and an anode current collector 8. The bipolar solid-state battery cell 1 does not include any second electrochemical unit, i.e., x is 0.

[0049] Preferably, the anode current collector 8 is as described above herein. Preferably, the cathode current collector 2 is as described above herein.

[0050] Preferably, and as known in the art, the cathode current collector 2 extends from the bipolar solid battery cell 1. In other words, the cathode current collector 2 preferably has a portion that extends or protrudes from the stack including the first electrochemical unit 3a and the third electrochemical unit 3b. This can be achieved by providing the cathode current collector 2 having a surface area larger than, for example, the surface area of ​​the components of the first electrochemical unit 3a, as known in the art. As known, such extension or protrusion allows for easy connection or coupling of the cathode current collector 2 to any electronic circuit (not shown), to which the anode current collector 8 is also preferably connected or coupled. Such electronic circuits include, in particular, any external electronic circuits, i.e., electronic circuits outside or outside the battery cell.

[0051] Preferably, and as known in the art, the anode current collector 8 extends from the bipolar solid battery cell 1. In other words, the anode current collector 8 preferably has a portion that extends or protrudes from the stack including the first electrochemical unit 3a and the third electrochemical unit 3b. This can be achieved by providing the anode current collector 8 having a surface area larger than, for example, the surface area of ​​the components of the third electrochemical unit 3b, as known in the art. As known, such extension or protrusion allows for easy connection or coupling of the anode current collector 8 to any electronic circuit (not shown) to which the cathode current collector 2 is also preferably connected or coupled. Such electronic circuits include, in particular, any external electronic circuits, i.e., electronic circuits outside or outside the battery cell.

[0052] The electrical insulating layer 9 is provided on the surface of the cathode current collector 2 opposite to the surface facing the first electrochemical unit 3a.

[0053] Preferably, when two or more bipolar solid battery cells 1 are stacked to obtain a bipolar solid battery, the electrical insulating layer 9 can electrically insulate adjacent bipolar solid battery cells 1. In other words, the electrical insulating layer 9 is Below a predetermined threshold, From one bipolar solid battery cell 1 to an adjacent bipolar solid battery cell 1 No current flows. It can be prepared in that way.

[0054] Preferably, the threshold is defined by the thickness of the electrical insulating layer 9 and its relative permittivity. As is known, the relative permittivity is defined by the material(s) from which the electrical insulating layer 9 is composed.

[0055] Preferably, the thickness of the electrical insulation layer 9 is selected according to the characteristic voltage values ​​defined by the electrochemical units (3a, 3b, and 4 (not shown in Figure 1)) of the bipolar solid battery cell 1, and according to the set voltage values ​​that define the safe operating conditions of the bipolar solid battery cell 1.

[0056] Preferably, the material, dielectric constant, and / or thickness of the electrical insulation layer 9 are selected to ensure that the level of electrical insulation required for the bipolar solid battery cell 1 to avoid damage to the electrochemical unit is sufficient. Thus, the electrical insulation layer 9 shall be considered an adjustable dielectric breakthrough circuit element. Preferably, the dielectric constant, material, and / or thickness are selected so that the electrical insulation layer 9 matches a desired dielectric breakthrough voltage.

[0057] Preferably, when the total charge voltage of the bipolar solid battery cell 1 exceeds a certain value, the electrical insulating layer 9 enters a dielectric breakthrough state. Preferably, in this dielectric breakthrough state, the electrical insulating layer 9 becomes electrically conductive. As a result, the electrical insulating layer 9 in the dielectric breakthrough state allows current to bypass the electrochemical units 3a and 3b (and 4 (not present in Figure 1)), thereby avoiding damage to the electrochemical units 3a, 3b, and 4 (not present in Figure 1).

[0058] In other words, the electrical insulating layer 9 can preferably be considered to function as a Zehner diode. Under normal operating conditions, the electrical insulating layer 9 acts as an insulator. Under extreme conditions, particularly when overvoltage and / or overcurrent occurs, the electrical insulating layer 9 becomes electrically conductive, thereby preventing thermal runaway. Preferably, thermal runaway is prevented by bypassing energy through an operated short circuit involving the electrical insulating layer 9. As a result, electrical energy is preferably, Cassolite , it is not absorbed by the anode (if present; not shown in Figure 1) and / or electrolytes, thereby avoiding damage to them.

[0059] Preferably, the electrical insulation layer 9 protects adjacent bipolar solid battery cells stacked in the bipolar solid battery from overvoltages greater than 1x the normal charging voltage of the bipolar solid battery cells, for example, at least 1.1x, at least 1.2x, at least 1.25x, at least 1.5x, at least 1.75x, or at least 2x. In particular, the electrical insulation layer 9 is provided so that the bipolar solid battery, including a stack of at least two bipolar solid battery cells, is deemed safe by UN38 testing.

[0060] The first electrochemical unit 3a is the first Cassolite It includes layer 5a, a first solid electrolyte 6a, and a first electron conductor 7.

[0061] Preferably, the first Cassolite Layer 5a is as described herein above. Preferably, the first Cassolite Layer 5a is the first Cassolite Based on the total weight of layer 5a, the first active material is contained in an amount of 50% to 100% by weight.

[0062] Preferably, the first solid electrolyte 6a is as described above herein.

[0063] Preferably, the first electron conductor 7 is as described herein. Preferably, the first electron conductor 7 is provided to restrict, and even substantially block, the movement of ions between the first 3a and third 3b electrochemical units. In other words, the electron conductor preferably provides ion resistance while ensuring electron conductivity between adjacent electrochemical units 3a and 3b. As a result, because of the electron conductivity between adjacent electrochemical units 3a and 3b, the first 3a and third 3b electrochemical units of the bipolar solid battery cell 1 are considered to be connected in series.

[0064] The third electrochemical unit 3b is the third Cassolite It comprises layer 5c and a third solid electrolyte 6c. Preferably, the third Cassolite Layer 5c is as described above herein. Preferably, the third solid electrolyte 6c is as described above herein.

[0065] Preferably, the third Cassolite Layer 5c is the third Cassolite Based on the total weight of layer 5c, it contains 50% to 100% by weight of the third active material.

[0066] Figure 2 shows another bipolar solid battery cell 100 according to the present disclosure. The bipolar solid battery cell 100 comprises a cathode current collector 2, a first electrochemical unit 3a, a third electrochemical unit 3b, and an anode current collector 8, all of which are preferably as described herein.

[0067] The bipolar solid battery cell 100 further includes an electrical insulating layer 9. The electrical insulating layer 9 is provided on the side or surface of the anode current collector 8 opposite to the side or surface adjacent to the third electrochemical unit 3b. The electrical insulating layer 9 is preferably as described herein.

[0068] Figure 3 shows yet another bipolar solid battery cell 101 according to the present disclosure. The bipolar solid battery cell 101 comprises a cathode current collector 2, a first electrochemical unit 3a, a third electrochemical unit 3b, and an anode current collector 8, all preferably as described herein.

[0069] The bipolar solid battery cell 101 further includes a first electrical insulating layer 9 provided on the side of the cathode current collector 2 opposite to the side adjacent to the first electrochemical unit 3a. The bipolar solid battery cell 101 further includes a second electrical insulating layer 9 provided on the side of the anode current collector 8 opposite to the side adjacent to the third electrochemical unit 3b. The electrical insulating layer 9 is preferably as described herein.

[0070] By providing electrical insulating layers 9 on both (opposite) sides of the bipolar solid battery cell 101 (and thus providing two electrical insulating layers 9), each electrical insulating layer 9 can preferably be thinner than when a single electrical insulating layer 9 is provided when the bipolar solid battery cells 101 are stacked to obtain a bipolar solid battery, because each electrical insulating layer 9 contributes to the electrical insulation of the (adjacent) bipolar solid battery cells 101 of the bipolar solid battery.

[0071] Figure 4 shows a bipolar solid battery cell 102 according to yet another embodiment of the present invention. The bipolar battery cell 102 includes an electrical insulating layer 9 provided on the surface of the cathode current collector 2 adjacent to the first electrochemical unit 3a and on the surface of the cathode current collector 2 opposite to it. The bipolar solid battery cell 102 further includes a third electrochemical unit 3b and an anode current collector 8. Preferably, each of the electrical insulating layer 9, the anode current collector 8 and the cathode current collector 2 is as described herein.

[0072] The first electrochemical unit 3a is the first CassoliteIt comprises 5a, a first solid electrolyte 6a, a first anode layer 10a, and a first electron conductor 7. The first anode layer 10a is preferably provided between the first solid electrolyte 6a and the first electron conductor 7. Preferably the first Cassolite 5a, the first solid electrolyte 6a, the first anode layer 10a, and the first electron conductor 7 are as described herein.

[0073] The third electrochemical unit 3b is the third Cassolite It comprises 5c, a third solid electrolyte 6c, and a third anode layer 10c. The third anode layer 10c is preferably provided between the third solid electrolyte 6c and the anode current collector 8. Preferably the third Cassolite Each of 5c, the third solid electrolyte 6c, and the third anode layer 10c is as described herein.

[0074] Preferably, the first 10a and / or third 10c anode layers include or substantially consist of a metal layer. The metal of the metal layer may be the same as or different from one of the metals contained in the cathode, for example, one of the metals contained in the cathode active material. For example, if the cathode contains lithium, the anode layer is preferably a metal layer containing or substantially consisting of lithium. For example, the anode layer may be a lithium foil that is optionally doped or substituted with aluminum.

[0075] Alternatively, and more preferably, the anode may include an intercalation anode or This is essentially what will happen from now on. Examples of appropriate intercalation electrodes, not limited to those shown in the graph, Li4Ti5O 12 This includes, or a combination thereof.

[0076] Alternatively, and also preferably, the anode layers of the first 10a and / or third 10c include or substantially consist of a conversion electrode. Preferably, the conversion electrode includes or substantially consists of an oxide, nitride, sulfide, or a combination of two or more thereof. Not limited examples of oxides include LiVO2 and SnO2. Not limited examples of nitrides include vanadium nitride (VN) and molybdenum nitride (δ-MoN). Not limited examples of sulfides include tin sulfide (SnS x ) and vanadium sulfide (VS2 and VS4) are included.

[0077] Preferably, the anode layers of the first 10a and / or third 10c may be provided by means known in the art, for example by providing a film, sheet or foil, or by depositing the layer by known methods, such as sputtering and plasma deposition.

[0078] Figure 5 shows a bipolar solid battery cell 103 according to yet another embodiment of the present invention. The bipolar battery cell 103 includes an electrical insulating layer 9 provided on the surface of the anode current collector 8 adjacent to the third electrochemical unit 3b and on the surface of the anode current collector 8 opposite to it. The bipolar solid battery cell 103 further includes a first electrochemical unit 3a and a cathode current collector 2. Preferably, each of the electrical insulating layer 9, the anode current collector 8 and the cathode current collector 2 is as described herein.

[0079] The first 3a and third 3b electrochemical units are preferably as described herein with respect to the bipolar solid battery cell 102 of Figure 4, and each includes the first 10a and third 10c anode layers, respectively.

[0080] Figure 6 shows a bipolar solid battery cell 104 according to yet another embodiment of the present invention. The bipolar battery cell 104 includes an electrical insulating layer 9 provided on the surface of the cathode current collector 2 opposite to the surface of the cathode current collector 2 adjacent to the first electrochemical unit 3a. The bipolar battery cell 104 further includes a second electrical insulating layer 9 provided on the surface of the anode current collector 8 opposite to the surface of the anode current collector 8 adjacent to the third electrochemical unit 3b.

[0081] Preferably, each of the electrical insulating layer 9, the anode current collector 8, and the cathode current collector 2 is as described herein. Preferably, the first 3a and third 3b electrochemical units are as described herein with respect to the bipolar solid battery cell 102 of Figure 4, and therefore include the first 10a and third 10c anode layers, respectively.

[0082] Figure 7 shows a bipolar solid battery cell 105 according to a further embodiment of the present invention. The bipolar battery cell 105 includes an electrical insulating layer 9 provided on the surface of the cathode current collector 2 adjacent to the first electrochemical unit 3a and on the surface of the cathode current collector 2 opposite to it. The bipolar solid battery cell 105 further includes a third electrochemical unit 3b and an anode current collector 8.

[0083] The first electrochemical unit 3a is preferably the first Cassolite The material comprises 5a, a first electrolyte 6a, and a first electron conductor 7, which are preferably as described herein.

[0084] The third electrochemical unit 3b is preferably the third Cassolite It comprises 5c and a third electrolyte 6c, which are preferably as described herein.

[0085] The bipolar solid battery cell 105 further includes one second electrochemical unit 4, i.e., x = 1. The second electrochemical unit 4 is second CassoliteIt comprises 5b, a second solid electrolyte 6b, and a second electron conductor 11. Preferably, the second Cassolite 5b and the second solid electrolyte 6b are as described herein. Preferably, the second electron conductor 11 is as described herein, and in particular with respect to the first electron conductor 7 is as described herein.

[0086] Preferably, the first electron conductor 7 of the first electrochemical unit 3a is provided to restrict, and even substantially block, the movement of ions between the first 3a and the second 4 electrochemical unit. In other words, the first electron conductor 7 preferably provides ionic resistance while ensuring electron conductivity between adjacent electrochemical units 3a and 4.

[0087] Preferably, the second electron conductor 11 of the second electrochemical unit 4 is provided to restrict, and even substantially block, the movement of ions between the second 4 and the third 3b electrochemical unit. In other words, the second electron conductor 11 preferably provides ionic resistance while ensuring electron conductivity between adjacent electrochemical units 4 and 3b.

[0088] Figure 8 shows a bipolar solid-state battery cell 106 according to a further embodiment of the present invention. The bipolar battery cell 106 includes an electrical insulating layer 9 provided on the surface of the cathode current collector 2 adjacent to the first electrochemical unit 3a and on the surface of the cathode current collector 2 opposite to it. The bipolar solid-state battery cell 106 further includes a third electrochemical unit 3b and an anode current collector 8. The first 3a and third 3b electrochemical units are preferably as described above herein with respect to the bipolar solid-state battery cell 105 of Figure 7.

[0089] The bipolar solid battery cell 106 further includes two second electrochemical units 4, i.e., x = 2. Each of the second electrochemical units 4 is preferably a second Cassolite It comprises 5b, a second solid electrolyte 6b, and a second electron conductor 11. Preferably, the second Cassolite5b, the second solid electrolyte 6b, and the second electron conductor 11 are as described herein, individually.

[0090] Preferably, the second electron conductor 11 of the first second electrochemical unit 4 is provided to restrict, and even substantially block, the movement of ions between adjacent second electrochemical units 4. Preferably, the second electron conductor 11 of the second second electrochemical unit 4 is provided to restrict, and even substantially block, the movement of ions between the second 4 and the third 3b electrochemical unit.

[0091] Figure 9 shows a bipolar solid battery cell 107 according to yet another embodiment of the present invention. The bipolar battery cell 107 includes an electrical insulating layer 9 provided on the surface of the anode current collector 8 adjacent to the third electrochemical unit 3b and on the surface of the anode current collector 8 opposite to it. The bipolar solid battery cell 106 further includes a first electrochemical unit 3a and a cathode current collector 2.

[0092] The first electrochemical unit 3a is preferably the first Cassolite The material comprises 5a, a first electrolyte 6a, a first anode layer 10a, and a first electron conductor 7, which are preferably as described herein.

[0093] The third electrochemical unit 3b is preferably the third Cassolite It comprises 5c, a third electrolyte 6c, and a third anode layer 10c, which are preferably as described herein.

[0094] The bipolar solid battery cell 107 further includes one second electrochemical unit 4, i.e., x = 1. The second electrochemical unit 4 is second Cassolite It comprises 5b, a second solid electrolyte 6b, a second anode layer 10b, and a second electron conductor 11. Preferably, the second Cassolite 5b, the second solid electrolyte 6b, the second anode layer 10b, and the second electron conductor 11 are as described herein.

[0095] Figure 10 shows a bipolar solid battery 200 according to the present disclosure. The bipolar solid battery 200 includes a stack of two bipolar solid battery cells 107. The presence of the electrical insulation layer 9 enables each bipolar solid battery cell 107 to function safely, as described above herein.

[0096] The cathode current collector 2 of the bipolar solid battery cell 107 preferably extends or protrudes from the stack containing the first 3a, second 4, and third 3b electrochemical units. This allows for easy coupling with one another. As shown in Figure 10, the cathode current collector 2 of the bipolar solid battery cell 107 is electronically coupled by cathode tabs 12.

[0097] The anode current collector 8 of the bipolar solid battery cell 107 preferably extends or protrudes from the stack containing the first 3a, second 4, and third 3b electrochemical units. This allows for easy coupling with one another. As shown in Figure 10, the anode current collector 8 of the bipolar solid battery cell 107 is electronically coupled by the anode tab 13.

[0098] Preferably, the cathode current collector 2 extends or protrudes in a first direction, and the anode current collector 8 extends or protrudes in a second direction different from the first direction. This allows for easy connection of the cathode current collector 2 to the cathode tab 12 and the anode current collector 8 to the anode tab 13. [Examples]

[0099] Example 1 A bipolar solid-state battery cell 102 was fabricated according to the schematic presentation in Figure 4 (i.e., x is 0).

[0100] An aluminum sheet was used for the cathode current collector 2. Copper foil was used for the anode current collector 8.

[0101] First 5a and third 5c Cassolite It contained NMC as the active material, carbon nanotubes (CNTs) as the electron-conducting compound, and LLZO as the ion-conducting compound.

[0102] The solid electrolytes of the first 6a and third 6c contained LLZO. 25 μm thick lithium foil was provided as the anode layers of the first 10a and third 10c. The first electron conductor 7 was 8 μm thick stainless steel foil.

[0103] A polyethylene foil having a thickness of 600nm to 800nm ​​is the first Cassolite An electrical insulating layer 9 is provided on the side adjacent to 5a and on the opposite side of the aluminum cathode current collector 2.

[0104] The bipolar solid battery cells were sealed with an air press in an argon atmosphere, with all layers placed on top of each other to prevent contamination.

[0105] The voltage was measured and determined to be 8.4V~8.8V or 4.2V~4.4V on the cathode current collector 2 and electron conductor 7 of the first electrochemical unit 3a, and 4.2V~4.4V on the electron conductor 7 and anode current collector 8 through the third electrochemical unit 3b. <Note> Item 1 A bipolar solid battery cell (1, 100, 101, 102, 103, 104, 105, 106, 107) comprising a plurality of electrochemical units (3a, 3b, 4) arranged in a stack such that adjacent electrochemical units share an electron conductor (7, 11), wherein the bipolar solid battery cell (1, 100, 101, 102, 103, 104, 105, 106, 107) is: - Cathode current collector (2), - A first electrochemical unit (3a) comprising a first catholite layer (5a) containing a first active material, a first solid electrolyte (6a), and a first electron conductor (7), -x second electrochemical units (4), each second electrochemical unit (4) individually comprises a second catholite layer (5b) containing a second active material, a second solid electrolyte (6b), and a second electron conductor (11), - A third electrochemical unit (3b) comprising a third catholite layer (5c) containing a third active material and a third solid electrolyte (6c) - Anode current collector (8) and Includes, The aforementioned stacked electrochemical units (3a, 3b, 4) are arranged in series, and the number x of the second electrochemical unit (4) is between 0 and 8. The bipolar solid battery cells (1, 100, 101, 102, 103, 104, 105, 106, 107) are characterized in that they further include an electrical insulating layer (9) comprising a ceramic material, provided on the outer surface of the cathode current collector (2) and / or the outer surface of the anode current collector (8). Bipolar solid battery cells (1, 100, 101, 102, 103, 104, 105, 106, 107). Section 2 The bipolar solid battery cell according to claim 1 (1, 100, 101, 102, 103, 104, 105, 106, 107), wherein the electrical insulating layer (9) is arranged to be electrically resistant to the voltage of the bipolar solid battery cell during use. Section 3 A bipolar solid battery cell according to any one of the preceding claims (1, 100, 101, 102, 103, 104, 105, 106, 107), wherein the electrical insulating layer (9) further comprises a polymer. Section 4 The bipolar solid battery cell (1, 100, 101, 102, 103, 104, 105, 106, 107) according to claim 3, wherein the polymer is selected from the group consisting of polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, cellulose, viscose, natural rubber, and synthetic rubber. Section 5 A bipolar solid battery cell according to any one of the preceding claims (1, 100, 101, 102, 103, 104, 105, 106, 107), wherein the ceramic material is selected from the group consisting of glass, metal oxide, metal nitride, porcelain, and mica. Section 6 A bipolar solid battery cell according to any one of the preceding claims (1, 100, 101, 102, 103, 104, 105, 106, 107), wherein the first electron conductor (7) and the second electron conductor (11) each include steel, a steel alloy, titanium, a titanium alloy, glassy carbon, or a combination of two or more thereof. Section 7 A bipolar solid battery cell according to any one of the preceding claims (102, 103, 104, 107), wherein the first electrochemical unit (3a) further comprises a first anode layer (10a), and / or the third electrochemical unit (3b) further comprises a third anode layer (10c). Section 8 A bipolar solid battery cell (107) according to any one of the preceding claims, wherein x is 1 to 8, and the second electrochemical unit (4) further comprises, individually, a second anode layer (10b). Section 9 A bipolar solid battery cell (102, 103, 104, 107) according to any one of claims 7 to 8, wherein the anode layer (10a, 10b, 10c) comprises an alkali metal, an alkaline earth metal, a transition metal, graphite, silicon, carbide, or a combination of two or more thereof. Item 10 The first solid electrolyte (6a), the second solid electrolyte (6b) if present, and the third solid electrolyte (6c) are, respectively, alkali metals, alkaline earth metals, transition metals, or combinations thereof, preferably lithium, sodium, magnesium, or aluminum, more preferably Li 7 La 3 Zr 2 O 12 A bipolar solid battery cell (1, 100, 101, 102, 103, 104, 105, 106, 107) according to any one of the preceding claims, including (LLZO). Section 11 A bipolar solid battery cell according to any one of the preceding claims (1, 100, 101, 102, 103, 104, 105, 106, 107), wherein the first catholite layer (5a), if present, the second catholite layer (5b), and the third catholite layer (5c) each further comprises one or more electron-conducting compounds and ion-conducting compounds, respectively. Section 12 A bipolar solid battery (200) comprising a stack of at least two bipolar solid battery cells (1, 100, 101, 102, 103, 104, 105, 106, 107) as described in any one of the preceding claims. Section 13 A bipolar solid battery (200) according to claim 12, wherein one cathode current collector (2) of each of the at least two bipolar solid battery cells (1, 100, 101, 102, 103, 104, 105, 106, 107) is electronically connected to a cathode tab (12). Section 14 A bipolar solid battery (200) according to any one of claims 12 to 13, wherein one anode current collector (8) of each of the at least two bipolar solid battery cells (1, 100, 101, 102, 103, 104, 105, 106, 107) is electronically connected to an anode tab (13). [Explanation of Symbols]

[0106] 1 bipolar solid battery cell 2 Cathode current collector 3a First electrochemical unit 3b Third Electrochemical Unit 4. Second Electrochemical Unit 5a First Cassolite layer 5b Second Cassolite layer 5c Third Cassolite layer 6a First solid electrolyte 6b Second solid electrolyte 6c Third solid electrolyte 7. The first electron conductor 8 Anode current collector 9. Electrical insulation layer 10a First anode layer 10b Second anode layer 10c Third anode layer 11. Second electron conductor 12 Cathode tab for external connection 13 Anode tab for external connection 100 bipolar solid-state battery cells 101 Bipolar Solid-State Battery Cells 102 Bipolar Solid-State Battery Cells 103 Bipolar Solid-State Battery Cells 104 Bipolar Solid-State Battery Cells 105 Bipolar Solid State Battery Cells 106 Bipolar Solid State Battery Cells 107 Bipolar Solid-State Battery Cells 200 Bipolar Solid-State Batteries

Claims

1. A bipolar solid battery (200) comprising a stack of at least two bipolar solid battery cells (1, 100, 101, 102, 103, 104, 105, 106, 107), Each bipolar solid battery cell (1, 100, 101, 102, 103, 104, 105, 106, 107) includes a plurality of electrochemical units (3a, 3b, 4) arranged in a stack such that adjacent electrochemical units share an electron conductor (7, 11), and the bipolar solid battery cells (1, 100, 101, 102, 103, 104, 105, 106, 107) are: - Cathode current collector (2), - A first electrochemical unit (3a) comprising a first catholite layer (5a) containing a first active material, a first solid electrolyte (6a), and a first electron conductor (7), - x second electrochemical units (4), each second electrochemical unit (4) individually comprises a second catholite layer (5b) containing a second active material, a second solid electrolyte (6b), and a second electron conductor (11), - A third electrochemical unit (3b) comprising a third catholite layer (5c) containing a third active material and a third solid electrolyte (6c) - Anode current collector (8) and Includes, The aforementioned stacked electrochemical units (3a, 3b, 4) are arranged in series, and the number x of the second electrochemical unit (4) is between 0 and 8. The bipolar solid battery cells (1, 100, 101, 102, 103, 104, 105, 106, 107) further include an electrical insulating layer (9) comprising a ceramic material, provided on the outer surface of the cathode current collector (2) and / or the outer surface of the anode current collector (8), The electrical insulating layer (9) is arranged to be electrically resistant to the voltage of the bipolar solid battery cell during use. The electrical insulating layer (9) is provided such that, when the current level is below a predetermined threshold, no current flows from one bipolar solid battery cell (1, 100, 101, 102, 103, 104, 105, 106, 107) to an adjacent bipolar solid battery cell (1, 100, 101, 102, 103, 104, 105, 106, 107), and the threshold is defined by the thickness and relative permittivity of the electrical insulating layer (9). Bipolar solid-state battery (200).

2. The bipolar solid battery (200) according to claim 1, wherein the electrical insulating layer (9) further comprises a polymer.

3. The bipolar solid battery (200) according to claim 2, wherein the polymer is selected from the group consisting of polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, cellulose, viscose, natural rubber, and synthetic rubber.

4. The bipolar solid battery (200) according to claim 1, wherein the ceramic material is selected from the group consisting of glass, metal oxide, metal nitride, porcelain, and mica.

5. The bipolar solid battery (200) according to claim 1, wherein the first electron conductor (7) and the second electron conductor (11) each include steel, a steel alloy, titanium, a titanium alloy, glassy carbon, or a combination of two or more thereof.

6. The bipolar solid battery (200) according to claim 1, wherein the first electrochemical unit (3a) further comprises a first anode layer (10a), and / or the third electrochemical unit (3b) further comprises a third anode layer (10c).

7. The first anode layer (10a) is provided between the first solid electrolyte (6a) and the first electron conductor (7), The bipolar solid battery (200) according to claim 6, wherein the third anode layer (10c) is provided between the third solid electrolyte (6c) and the anode current collector (8).

8. The bipolar solid battery (200) according to claim 1, wherein x is 1 to 8, and the second electrochemical unit (4) each further comprises a second anode layer (10b).

9. The bipolar solid battery (200) according to claim 8, wherein the second anode layer (10b) is provided between the second solid electrolyte (6b) and the second electron conductor (11).

10. A bipolar solid battery (200) according to any one of claims 6 to 9, wherein the anode layer (10a, 10b, 10c) comprises an alkali metal, an alkaline earth metal, a transition metal, graphite, silicon, carbide, or a combination of two or more thereof.

11. The bipolar solid battery (200) according to claim 1, wherein the first solid electrolyte (6a), the second solid electrolyte (6b), and the third solid electrolyte (6c) each include an alkali metal, an alkaline earth metal, a transition metal, or a combination thereof.

12. The bipolar solid battery (200) according to claim 1, wherein the first catholite layer (5a), the second catholite layer (5b), and the third catholite layer (5c) each further comprises one or more electron-conducting compounds and ion-conducting compounds.

13. The bipolar solid battery (200) according to claim 1, wherein one cathode current collector (2) of each of the at least two bipolar solid battery cells (1, 100, 101, 102, 103, 104, 105, 106, 107) is electronically connected to a cathode tab (12).

14. The bipolar solid battery (200) according to claim 1, wherein one anode current collector (8) of each of the at least two bipolar solid battery cells (1, 100, 101, 102, 103, 104, 105, 106, 107) is electronically connected to an anode tab (13).

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