Negative electrode supported solid electrolyte membrane

Abstract

A negative electrode for a battery cell, a battery cell, and a method of forming a negative support electrolyte separator. The negative electrode includes a negative current collector including a first surface and a negative supporting electrolyte separator disposed on the first surface. The anode support electrolyte separator includes at least one electrolyte selected from the group consisting of: a) yLi2S (100-y-x) P2S5 xP2O5, where y is in the range of 70 to 80 mol%, and x is in the range of 1 to 10 mol%, b) Li10MP2S12, where M is at least one of Si, Ge, and Sn, and c) argyrodite. In addition, the negative electrode support electrolyte separator has a thickness in the range of 1 [mu] m to 100 [mu] m.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to negative electrodes for battery cells, and in particular to negative electrodes that support solid-state electrolyte separators. BACKGROUND

[0002] Electric and hybrid electric vehicle technology is enabled by the development and deployment of rechargeable secondary batteries that provide energy for the vehicle powertrain. Secondary batteries include lithium-ion batteries, which typically include one or more battery cells, each battery cell including a positive electrode, a negative electrode, a separator, and an electrolyte. The positive electrode provides a source of lithium ions and determines the capacity and average voltage of the battery. The negative electrode stores and releases lithium ions received from the positive electrode when energy is needed. The separator, which is typically a polymeric film or sheet, prevents the positive and negative electrodes from coming into contact, which would cause a short circuit in the battery, and the electrolyte provides a medium for lithium ions to cross between the positive and negative electrodes. In some systems, a solid-state electrolyte can be used in place of the separator, which is a solid material that acts as an ion conductor, specifically a lithium ion conductor, that also blocks the passage of electrons, thereby preventing a short circuit in the battery cell. The use of a solid-state electrolyte as a separator can also eliminate the need for a separate electrolyte.

[0003] Typically, lithium-ion batteries are assembled as follows: a positive electrode, a separate separator, and a negative electrode are stacked together, the stack is placed into a package and forms a battery cell, an electrolyte is added to the battery cell, and multiple battery cells are connected together. The separate separator is a self-supporting structure and typically has a thickness of 100 microns or more. Reducing the thickness of the self-supporting separator increases the energy density of the battery cell. Reducing the thickness of the separator can also reduce the self-supporting ability of the separator.

[0004] To reduce the thickness of the separator and the battery cell, efforts have been made to support the separator by depositing the separator directly onto the negative or positive electrode and using a solid-state electrolyte as the separator. However, lithium metal negative electrodes are typically not compatible with the casting process commonly used to deposit the separator onto the negative electrode. Positive electrode-supported separators are more compatible with the casting process used to deposit the separator onto the positive electrode. Additionally, the thickness of the positive separator is in the range of 20 microns to 50 microns. However, the negative electrode typically has a relatively larger area than the positive electrode, which results in the negative electrode overhanging the positive electrode. This design is prone to edge shorting because the overhang on the negative electrode can contact the positive electrode. While one solution is to increase the surface area of the positive electrode, it is desirable to develop a separator that can be deposited directly onto the negative electrode.

[0005] Accordingly, while the existing separators achieve their intended purpose, there is a need for new and improved negative electrode and separator designs. SUMMARY

[0006] According to various aspects, this disclosure relates to a negative electrode for a battery cell. The negative electrode includes a negative current collector and a negative electrode supporting electrolyte membrane, the negative current collector including a first surface, and the negative electrode supporting electrolyte membrane disposed on the first surface. The negative electrode supporting electrolyte membrane includes at least one electrolyte selected from the following compositions: a) yLi₂S·(100-yx)P₂S₅·xP₂O₅, wherein y is in the range of 70 mol% to 80 mol%, and x is in the range of 1 mol% to 10 mol%, b) Li 10 MP2S 12 M is at least one of Si, Ge and Sn, and c) silver-germanium sulfide has the following composition: A 12-m-x + (M m+ Y4 2- )Y 2-x 2- X x - , where A + =Li + Cu + Ag + M m+ =Si 4+ 、Ge 4+ Sn 4+ P 5+ As 5+ ;Y 2- =O 2- S 2- Se 2- Te 2- ;X - =Cl - ,Br - I - And 0≤x≤2. In addition, the negative electrode supporting electrolyte membrane has a thickness ranging from 1 micrometer to 100 micrometers.

[0007] In the above embodiment, the negative electrode supporting electrolyte membrane includes a second surface that defines a second region, wherein the second region is larger than a third region defined by a third surface of the adjacent positive electrode.

[0008] In any of the above embodiments, the negative electrode supporting electrolyte membrane contacts the first surface of the negative electrode current collector.

[0009] Alternatively, the negative electrode may further include a negative electrode that contacts the first surface, wherein the negative electrode includes a fourth surface that defines a fourth region, and the negative electrode supports the electrolyte membrane in contact with the fourth surface.

[0010] In the above embodiments, the negative electrode includes one or more active negative electrode materials selected from the group consisting of: silicon, silicon-carbon composites, hard carbon, graphite, and silicon oxide (SiO2). x (where x is 1 or 2) and lithium titanate (LTO). In other embodiments, the negative electrode comprises silicon with a thickness ranging from 1 micrometer to 50 micrometers.

[0011] In any of the above embodiments, the electrolyte is yLi₂S·(100-yx)P₂S₅·xP₂O₅, wherein y is in the range of 70 mol% to 80 mol%, x is in the range of 1 mol% to 10 mol%, and the electrolyte is present in the range of 50 wt% to 99 wt% of the total weight of the negative electrode supporting electrolyte membrane, and the negative electrode supporting electrolyte membrane further includes an electrolyte binder, which is present in the range of 1 wt% to 50 wt% of the total weight of the negative electrode supporting electrolyte membrane. In other embodiments, the electrolyte binder includes one or more binders selected from the group consisting of: styrene-butadiene rubber (SBR), hydrogenated nitrile rubber (HNBR), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polytetrafluoroethylene (PTFE), and lithium salt of polytetrafluoroethylene-perfluoro(3-oxa-4-pentenesulfonic acid) copolymer.

[0012] In any of the above embodiments, the negative electrode supporting electrolyte membrane further includes one or more liquid electrolyte diluents selected from the group consisting of: 1,1,2,2-tetrafluoroethylene 2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,2-trifluoroethyl) ether (BTFE), tris(2,2,2-trifluoroethyl) orthoformate (TFEO), fluorobenzene (FB), 1,2-difluorobenzene (DFB), bis(2,2-difluoroethyl) ether (BDE), ethyl 1,1,2,2-tetrafluoroethyl ether (ETE), hexafluoroisopropyl methyl ether (HFME), 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether, ethyl 1 1,2,3,3,3-Hexafluoropropyl ether, methyl nonafluorobutyl ether (mixture of isomers), difluoromethyl 2,2,3,3-tetrafluoropropyl ether, 1H,1H,5H-octafluoropentyl 1,1,2,2-tetrafluoroethyl ether (OTE), 1,1,2,3,3,3-hexafluoropropyl-2,2,2-trifluoroethyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane, fluoromethyl 1,1,1,3,3,3-hexafluoroisopropyl ether, 1,1,2,3,3,3-hexafluoropropylmethyl ether, methyl 2,2,3,3,3-pentafluoropropyl ether and methyl 1,1,2,2-tetrafluoroethyl ether.

[0013] In any of the above embodiments, the negative electrode supporting electrolyte membrane further includes one or more room-temperature ionic liquids selected from the group consisting of: 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMIM-TFSI), 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMIM-TFSI), N-propyl-N-methylpyrrolidine bis(trifluoromethanesulfonyl)imide (PYR13TFSI), 1-butyl-1- Methylpyrrolidine bis(trifluoromethanesulfonyl)imine (PYR14TFSI), 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imine (EMIM-FSI), 1-butyl-3-methylimidazolium bis(fluorosulfonyl)imine (BMIM-FSI), N-propyl-N-methylpyrrolidine bis(fluorosulfonyl)imine (PYR13-FSI) and 1-butyl-1-methylpyrrolidine bis(fluorosulfonyl)imine (PYR14-FSI).

[0014] In any of the above embodiments, the negative electrode supporting electrolyte membrane comprises one or more solvated ionic liquid electrolytes selected from the group consisting of: lithium triethylene glycol dimethyl ether bis(trifluoromethanesulfonyl)imide (Li[G3]TFSI), lithium tetraethylene glycol dimethyl ether bis(trifluoromethanesulfonyl)imide (Li[G4]TFSI), lithium triethylene glycol dimethyl ether bis(fluorosulfonyl)imide (Li[G3]FSI), lithium tetraethylene glycol dimethyl ether bis(fluorosulfonyl)imide (Li[G4]FSI), lithium triethylene glycol dimethyl ether bis(pentafluoroethenesulfonyl)imide (lithium triglyme bis(pentafluoroethenesulfonyl)imide, Li[G3]BETI), lithium tetraethylene glycol dimethyl ether bis(pentafluoroethenesulfonyl)imide (lithium tetraglyme bis(pentafluoroethenesulfonyl)imide, Li[G4]BETI), lithium triethylene glycol dimethyl ether lithium cyclic-TFSI derivative 1,2,3-dithiazolidine-4,4,5,5-tetrafluoro-1,1,3,3-tetraoxide, Li[G3]CTFSI), lithium tetraethylene glycol dimethyl ether lithium cyclic-TFSI derivative 1,2,3-dithiazolidine-4,4,5,5-tetrafluoro-1,1,3,3-tetraoxide, Li[G3]CTFSI, lithium tetraethylene glycol dimethyl ether lithium cyclic-TFSI derivative 1,2,3-dithiazolidine-4,4,5,5-tetrafluoro-1,1,3,3-tetraoxide, lithium tetraglyme cyclic-TFSI derivative 1,2,3-dithiazolidine-4,4,5,5-tetrafluoro-1,1,3,3-tetraoxide, Li[G4]CTFSI), lithium triethylene glycol dimethyl ether perchlorate (Li[G3]ClO4), lithium tetraethylene glycol dimethyl ether perchlorate (Li[G4]ClO4), lithium triethylene glycol dimethyl ether tetrafluoroborate (Li[G3]BF4) and lithium tetraethylene glycol dimethyl ether tetrafluoroborate (Li[G4]BF4).

[0015] According to various additional aspects, this disclosure relates to a battery cell for use in a vehicle battery. In an embodiment, the battery cell includes any of the aforementioned negative electrode electrodes. In an embodiment, the battery cell includes: a negative current collector including a first surface; a negative electrode supporting electrolyte separator disposed on the first surface, the negative electrode supporting electrolyte separator including a second surface defining a second region; and a positive electrode adjacent to the second surface of the negative electrode supporting electrolyte separator, the positive electrode including a third surface defining a third region. The second region is larger than the third region, and the negative electrode supporting electrolyte separator includes a hanger extending beyond the third region of the positive electrode. Additionally, the negative electrode supporting electrolyte separator has a thickness in the range of 1 micrometer to 100 micrometers. Furthermore, the negative electrode supporting electrolyte separator includes at least one of the following electrolyte compositions: a) yLi₂S·(100-yx)P₂S₅·xP₂O₅, wherein y is in the range of 70 mol% to 80 mol%, and x is in the range of 1 mol% to 10 mol%; b) Li 10 MP2S 12 M is at least one of Si, Ge, and Sn; and c) silver-germanium sulfide, which has the following composition: A 12-m-x + (M m+ Y4 2- )Y 2-x 2- X x - , where A + =Li + Cu + Ag + M m+ =Si 4+ 、Ge 4+ Sn 4+ P 5+ As 5+ ;Y 2- =O 2- S 2- Se 2- Te 2- ;X - =Cl - ,Br - I - ;0≤x≤2, the silver-germanium sulfide is present in the range of 50% to 99% by weight of the total weight of the negative electrode supporting electrolyte membrane; and the electrolyte binder is present in the range of 1% to 50% by weight of the total weight of the negative electrode supporting electrolyte membrane.

[0016] In the above implementation scheme, the negative electrode supporting electrolyte membrane contacts the negative electrode current collector.

[0017] Alternatively, the battery cell may also include a negative electrode comprising silicon and a fourth surface defining a fourth region, the negative electrode contacting a first surface of a negative electrode current collector, and the fourth surface of a negative electrode supporting an electrolyte separator contacting the negative electrode.

[0018] In any of the above embodiments, the overhang is in the range of 1 mm to 2 mm.

[0019] In any of the above embodiments, the negative current collector is a bipolar current collector.

[0020] In any of the above embodiments, the battery cell further includes a positive current collector and the positive electrode contacts the positive current collector.

[0021] In any of the above embodiments, the positive electrode includes an active positive electrode material, a positive electrode electrolyte, and a positive electrode binder. The active positive electrode material is present in the range of 64% to 98.5% by weight of the total positive electrode weight, the positive electrode binder is present in the range of 1% to 9% by weight of the total positive electrode weight, and the positive electrode electrolyte is present in the range of 10% to 17% by weight of the total positive electrode weight. In addition, the active positive electrode material includes one or more active positive electrode materials selected from the following: lithium iron phosphate (LFP), sulfur (S), iron sulfide (FeS2) and lithium sulfide (Li2S), the positive electrode binder includes one or more positive electrode binders selected from the group consisting of: styrene-butadiene rubber (SBR), hydrogenated nitrile rubber (HNBR), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polytetrafluoroethylene (PTFE), polyethylene oxide (PEO) and polytetrafluoroethylene-perfluoro(3-oxa-4-pentenesulfonic acid) copolymer lithium salt, and the positive electrode electrolyte includes yLi2S·(100-yx)P2S5·xP2O5, wherein y is in the range of 70 mol% to 80 mol% and x is in the range of 1 mol% to 10 mol%.

[0022] In any of the above embodiments, the negative electrode supporting electrolyte membrane comprises a room-temperature ionic liquid, which is selected from one or more of the following room-temperature ionic liquids: 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMIM-TFSI), 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMIM-TFSI), N-propyl-N-methylpyrrolidine bis(trifluoromethanesulfonyl)imide (PYR13TFSI), 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, etc. The following are listed: 1-ethyl-3-methylpyrrolidone bis(fluorosulfonyl)imine (PYR14TFSI), 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imine (EMIM-FSI), 1-butyl-3-methylimidazolium bis(fluorosulfonyl)imine (BMIM-FSI), N-propyl-N-methylpyrrolidone bis(fluorosulfonyl)imine (PYR13-FSI) and 1-butyl-1-methylpyrrolidone bis(fluorosulfonyl)imine (PYR14-FSI).

[0023] According to another aspect, this disclosure relates to a method for forming a negative electrode supported electrolyte membrane. The method includes forming a slurry of an electrolyte and an electrolyte binder in an electrolyte solvent, coating the slurry onto one of a) a first surface of a negative electrode current collector and b) a second surface of the negative electrode, drying the slurry to form a negative electrode supported electrolyte membrane, and calendering the negative electrode supported electrolyte membrane. The at least one electrolyte comprises a composition selected from the group consisting of: a) yLi₂S·(100-yx)P₂S₅·xP₂O₅, wherein y is in the range of 70 mol% to 80 mol%, x is in the range of 1 mol% to 10 mol%, b) Li 10 MP2S 12 M is at least one of Si, Ge and Sn, and c) silver-germanium sulfide has the following composition: A 12-m-x + (M m+ Y4 2- )Y 2-x 2- X x - , where A + =Li + Cu + Ag + M m+ =Si 4+ 、Ge 4+ Sn 4+ P 5+ As 5+ ;Y 2- =O 2- S 2- Se 2- Te 2- ;X -=Cl - ,Br - I - And 0≤x≤2. In addition, the negative electrode supporting electrolyte membrane has a thickness ranging from 1 micrometer to 100 micrometers. Attached Figure Description

[0024] The accompanying drawings described herein are for illustrative purposes only and are not intended to limit the scope of this disclosure in any way.

[0025] Figure 1 A vehicle and a powertrain including a secondary battery, according to an embodiment of this disclosure, are shown.

[0026] Figure 2A A battery according to an embodiment of this disclosure is shown.

[0027] Figure 2B A pouch-shaped or prismatic battery cell according to an embodiment of this disclosure is shown.

[0028] Figure 2C A cylindrical battery cell according to an embodiment of the present disclosure is shown.

[0029] Figure 2D A coin battery cell according to an embodiment of the present disclosure is shown.

[0030] Figure 3A Building blocks for a bipolar battery cell design according to an embodiment of this disclosure are shown.

[0031] Figure 3B A bipolar battery cell design according to an embodiment of this disclosure is shown.

[0032] Figure 4A A side view of a battery cell stack according to an embodiment of the present disclosure is shown.

[0033] Figure 4B This is a front view of a battery cell stack according to an embodiment of this disclosure.

[0034] Figure 5 A method for forming a negative electrode-supported solid electrolyte or semi-solid electrolyte according to an embodiment of the present disclosure is shown.

[0035] Figure 6 A method for coating a negative electrode with a solid electrolyte or a semi-solid electrolyte according to an embodiment of the present disclosure is shown.

[0036] Figure 7 A side view of a conventional battery cell stack including a self-supporting polymer separator is shown.

[0037] Figure 8 A side view of the positive electrode supporting the solid electrolyte membrane is shown.

[0038] Figure 9 The capacity (mAh) change of a conventional battery cell with a polymer separator is shown over 80 cycles, where the y-axis represents capacity and the x-axis represents the number of cycles.

[0039] Figure 10 The diagram shows the change in capacity (mAh) of a battery cell including a negative electrode-supported solid electrolyte separator over 80 cycles, where the y-axis represents capacity and the x-axis represents the number of cycles. Detailed Implementation

[0040] The following description is merely exemplary in nature and is not intended to limit this disclosure, its application, or its uses. Furthermore, it is not intended to be bound by any express or implied theory presented in the foregoing background, summary of the invention, or the following detailed description. It should be understood that throughout the drawings, corresponding reference numerals denote similar or corresponding parts and features.

[0041] Reference will now be made in detail to several embodiments of this disclosure illustrated in the accompanying drawings. Wherever possible, the same or similar reference numerals are used in the drawings and description to refer to the same or similar parts or steps. The drawings are simplified and not drawn to scale.

[0042] This disclosure relates to a negative electrode supporting an electrolyte separator and a method for forming such a separator. In various aspects, the negative electrode, including the supporting electrolyte separator, is incorporated into a battery cell and a secondary battery, such as a prismatic battery cell, a pouch battery cell, a cylindrical battery cell, or a coin-shaped battery cell. These batteries can then be used in electric or hybrid electric vehicles.

[0043] As used herein, the term "vehicle" is not limited to automobiles. While this document primarily describes the technology in conjunction with electric vehicles and hybrid electric vehicles, the technology is not limited to electric vehicles and hybrid electric vehicles. These concepts can be used in a variety of applications, such as those related to components used in motorcycles, mopeds, locomotives, aircraft, ships, and other vehicles, as well as other applications using batteries (e.g., consumer electronics, building power banks, portable power stations for powering remote work sites, emergency backup power supplies, and permanent power stations associated with buildings and equipment), all of which can be powered by, for example, solar or wind turbine systems, power lines, and fuel generators (e.g., gasoline, propane, kerosene, or diesel generators), as well as standard engines.

[0044] Figure 1A vehicle 100 including a propulsion system 120 is shown. The propulsion system 120 typically includes an electric motor 124 and a secondary battery 126 for powering the electric motor 124. Furthermore, in many embodiments of the propulsion system 120, the propulsion system 120 includes an inverter 128 for converting power from DC (direct current) supplied by the battery 126 to AC (alternating current) used by the electric motor 124. The inverter 128 may be included in a power electronics module 130, which includes, for example, transistors and diodes, for switching power from DC to AC and vice versa.

[0045] The controller 132 is connected to the inverter 128 and is programmed to control and manage the operation of the electric motor 124 and related hardware including the inverter 128. The electric motor 124 is connected to the transmission (drive unit) 136 and the drivetrain 138, which transmits mechanical power and rotation to the wheels 140 of the vehicle 100. The controller 132 includes one or more processors and tangible, non-transitory memory 134. A combustible fuel-powered engine may also be included in the propulsion system of the hybrid electric vehicle.

[0046] Referring again to electric motor 124, which is powered by battery 126, electric motor 124 includes a stator 142 and a rotor 144 arranged together with the stator 142. The stator 142 is the stationary part of electric motor 124. The stator 142 provides a rotating magnetic field, and the stationary magnetic field of rotor 144 attempts to align with this rotating magnetic field, causing rotor 144 to rotate in a so-called "electric" mode. In other applications, the rotating field of rotor 144 (caused by physical rotation) generates current in stator 142—this mode of operation is called "generating" mode, and electric motor 124 used in this manner is called generator. In traction motor vehicle applications, electric mode provides motion to vehicle 100. When the vehicle is stationary, generating mode takes some energy recovered from braking and stores it back in vehicle battery 126.

[0047] refer to Figure 2A , 2B 2C, 2D, 3A, and 3B illustrate methods for designing electric vehicles 100 (e.g., Figure 1 An embodiment of a secondary battery 126 powered by an electric vehicle 100 is shown. As described above, the secondary battery 126 is understood as a rechargeable battery that can discharge when a load is applied and recharge when an external power source is applied. (See reference...) Figure 2A , 2BIn 2C and 2D configurations, battery 126 is shown connected to a load 148, such as electric motor 124. However, other loads 148 include various systems in vehicle 100, such as climate control systems and infotainment systems. Battery 126 includes one or more battery cells 150 assembled together. Battery cells 150 can be, for example, pouch-shaped, prismatic, cylindrical, or coin-shaped, which will be discussed further below. Reference Figure 2B , 2C In the 2D configuration, during discharge, when a load 148 is applied to the battery 126, Li+ ions move from the negative electrode 158 to the positive electrode 156 through the separator 160, which also provides the electrolyte 162. Equivalent electrons (e-) move from the positive electrode 156 to the negative electrode 158 through circuit 146, providing voltage to the load 148. During charging, when an external voltage is applied, Li+ ions move from the positive electrode 156 to the negative electrode 158 through the negative electrode-supporting electrolyte separator 160 and can be embedded in the negative electrode 158.

[0048] Each battery cell has 150 cells, such as... Figure 2B , 2C As shown in 2D, it typically includes a positive current collector 152, a positive electrode 156 disposed on the positive current collector 152, a negative current collector 154, a negative electrode 158 disposed on the negative current collector 154, and a negative electrode supporting electrolyte membrane 160 located between the positive electrode 156 and the negative electrode 158. Although below... Figure 2B to Figure 2D The diagram illustrates a unipolar solid-state battery cell arrangement, including a positive current collector 152, a positive electrode 156, a negative current collector 154, a negative electrode 158, and a solid electrolyte separator 160 for each cell of the battery cell 150. However, it should be understood that alternative arrangements can also be used, such as battery cells 150 including positive electrodes 156 disposed on both sides of the positive current collector 152 and negative electrodes 158 disposed on both sides of the negative current collector 154, as well as arrangements including multiple stacks of positive current collectors 152, positive electrodes 156, negative current collectors 154, negative electrodes 158, and a negative electrode supporting electrolyte separator 160, and arrangements including bipolar battery cell designs. Figure 3A and 3B Further details are provided below.

[0049] In the implementation plan, Figure 2BThe battery cell 150 is configured as either a pouch cell or a prismatic cell. In either design with multiple positive electrodes 156 and multiple negative electrodes 158, a negative electrode supporting electrolyte separator 160 is disposed between the positive electrodes 156 and the negative electrodes 158. In the pouch cell, tabs 164 are welded to the positive current collector 152 and the negative current collector 154, and the cover 166 is in the form of a flexible film pouch made of aluminum or other materials. On the other hand, the prismatic cell includes terminals connected to the positive current collector 152 and the negative current collector 154, and the cover 166 is formed of a relatively rigid shell, typically in the form of a cuboid. The tabs 164 or terminals from the multiple battery cells 150 are connected to the positive current collector 152, for example, via a busbar 168 (see...). Figure 2A ) or other electrical connections together, from multiple battery cells 150 to the tabs 164 or terminals of the negative current collector 154, for example via bus 169 (see Figure 2A (or other electrical connections) are connected together.

[0050] or, Figure 2C The battery cell 150 is configured as a cylindrical battery cell 150. In this design, the positive current collector 152, the negative current collector 154, the positive electrode 156, the negative electrode 158, and one or more negative electrode supporting electrolyte membranes 160 are in the form of long strips, which are rolled into cylinders or jelly rolls. Similar to prismatic batteries, the cover 166 is formed of a relatively rigid shell of aluminum or other materials. The tabs 164 are welded to the positive current collector 152 and the negative current collector 154. The tabs 164 connecting the multiple battery cells 150 to the positive current collector 152 are, for example, via bus 168 (see...). Figure 2A ) or other electrical connections are made together, and the multiple battery cells 150 are connected to the tabs 164 or terminals of the negative current collector 154, for example, via bus 169 (see Figure 2A (or other electrical connections) are connected together.

[0051] In other alternative embodiments, the battery cell 150 is encapsulated in a coin cell, such as... Figure 2D As shown. In this design, the positive current collector 152, the negative current collector 154, the positive electrode 156, the negative electrode 158, and the negative electrode supporting electrolyte membrane 160 are in the form of a disc, which are sandwiched together in a coin package forming a cover 166, which includes a lid 170 and a can 172. A spring washer 174 may be included between the positive current collector 152 and the lid 170.

[0052] The bipolar battery cell design includes battery cells 150 connected in series. Each battery cell 150 includes one or more bipolar current collectors. Each current collector includes a positive electrode 156 deposited on one side of the current collector and a negative electrode 158 deposited on the other side. The use of the bipolar design further increases energy density because the packaging of individual battery cells can be eliminated, and the number of connections between battery cells can be reduced as current flows through the entire battery stack. Now turning to... Figure 3A , Figure 3A Embodiments of building blocks 300, 302, and 304 for forming bipolar battery cells are shown. Building block 300 includes a positive electrode 156 deposited on a first side 306 of a bipolar current collector 308, a negative electrode 158 deposited on a second side 310 of the bipolar current collector 308, and a negative electrode supporting electrolyte membrane 160 deposited on a surface 312 of the negative electrode 158 opposite to the bipolar current collector 308. Building block 302 includes a positive electrode 156 deposited on the first side 306 of the bipolar current collector 308, and building block 304 includes a negative electrode 158 deposited on the second side 310 of the bipolar current collector 308 and a negative electrode supporting electrolyte membrane 160 deposited on a surface 312 of the negative electrode 158 opposite to the current collector 308. Building blocks 300, 302, and 304 are arranged to form stacks of positive electrode 156 and negative electrode 158, including a negative electrode supporting electrolyte membrane 160 between the positive electrode 156 and negative electrode 158, and a bipolar current collector 308 between each stack of positive electrode 156, negative electrode supporting electrolyte membrane 160, and negative electrode 158. Figure 3B As shown in the implementation scheme, multiple bipolar cell units can be encapsulated within a single cover 166, similar to the above reference. Figure 2A , 2B Packages described in 2C and 2D. The bipolar current collector 308 is provided with... Figure 2A to Figure 2D , Figure 4A and Figure 4B The negative current collector 154 and the positive current collector 152 are shown.

[0053] The above and further references Figure 4A and Figure 4BIn various types of battery cells 150, a negative electrode supporting electrolyte membrane 160 is supported on and in contact with the surface 403 of the negative electrode 158, which is opposite to the surface 405 of the negative electrode 158 that contacts the surface 407 of the negative electrode current collector 154. Alternatively, as further discussed herein, the negative electrode supporting electrolyte membrane 160 contacts the surface of the negative electrode current collector 154. In any embodiment, the negative electrode supporting electrolyte membrane 160 is disposed on the surface 407 of the negative electrode current collector 154. In an embodiment, the negative electrode supporting electrolyte membrane 160 covers the entire surface 403 of the negative electrode 158. Furthermore, regions 402 and 406 of the negative electrode 158 surface 403 and the negative electrode supporting electrolyte membrane 160 are selected to be larger than and larger than the region 404 of the positive electrode 156 to which the negative electrode supporting electrolyte membrane 160 will be adjacent, respectively. Additionally, region 402 of the negative electrode 158 exhibits the same characteristics as region 406 of the negative electrode supporting electrolyte membrane 160. This creates a droop 408, namely, an overlapping region 413 of the negative electrode 158 and the negative electrode supporting electrolyte membrane 160, which overlaps and extends beyond the region 404 and periphery 411 presented by the surface 415 of the positive electrode 156. The width 409 of the droop 408 ranges from 1 mm to 2 mm, including all values ​​and ranges therein. In an embodiment, the width 409 of the droop 408 is consistent around the entire periphery 411 of the positive electrode 156. Alternatively, the width 409 of the droop 408 varies around the periphery 411 of the positive electrode 156. However, it should be understood that if the negative electrode 158 and the negative electrode supporting electrolyte membrane 160 bend and contact the negative electrode 156, the droop is wide enough at any location around the periphery 411 of the positive electrode 156 to separate the positive electrode 156 from the negative electrode 158. If the overhang 408 folds and contacts the positive electrode 156, the presence of the negative electrode supporting electrolyte membrane 160 at the overhang 408 prevents a short circuit, because the membrane 160, rather than the negative electrode 158, will contact the positive electrode 156. Regions 402, 404, and 406 are defined along a direction generally perpendicular to the thickness 410 of the stack, and surfaces 403, 405, and 417 are generally vertical.

[0054] In addition, refer to Figure 2A to Figure 4BAs shown, the positive current collector 152, negative current collector 154, and bipolar current collector 308 are formed of conductive materials. In one embodiment, the positive current collector 152 comprises aluminum. Alternatively or additionally, the positive current collector 152 may comprise copper-clad aluminum and stainless steel. In one embodiment, the negative current collector 154 comprises copper. Alternatively or additionally, the negative current collector comprises one or more of nickel, stainless steel, and titanium. In one embodiment, the bipolar current collector 308 comprises one or more of the following materials: aluminum, copper-clad aluminum, stainless steel, copper, nickel, and titanium. Current collectors 152, 154, and 308 are shown in the form of foil; however, it should be understood that other forms, such as meshes, may be presented. In one embodiment, the foil current collector is impermeable. The positive current collector 152 has a thickness 412 in the range of 5 micrometers to 50 micrometers (inclusive of all values ​​and ranges therein, e.g., in the range of 5 micrometers to 25 micrometers). The negative current collector 154 has a thickness 414 ranging from 4 micrometers to 50 micrometers (inclusive of all values ​​and ranges therein, e.g., from 4 micrometers to 25 micrometers). The bipolar current collector 308 has a thickness ranging from 5 micrometers to 50 micrometers (inclusive of all values ​​and ranges therein). In an embodiment, either or both current collectors include surface roughening, thereby increasing the surface area of ​​the current collectors.

[0055] The positive electrode 156 includes lithium ions (Li... +The source can undergo reversible insertion or intercalation of lithium ions, thereby determining, for example, the battery capacity and average voltage. In embodiments, the positive electrode includes an active positive electrode material, a binder, an optional positive electrode electrolyte, and an optional conductive filler. The active positive electrode material includes one or more of the following: lithium iron phosphate (LFP), sulfur (S), iron sulfide (FeS2), and lithium sulfide (Li2S). In embodiments, the active positive electrode material further includes carbon black, wherein the carbon black is present in a range from 0.1% by weight to 40% by weight (inclusive) of the total weight of the active positive electrode material, wherein the total weight percentage is 100%, and the remaining weight percentage includes the aforementioned active positive electrode material. The binder includes one or more of the following positive electrode binders: styrene-butadiene rubber (SBR), hydrogenated nitrile butadiene rubber (HNBR), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polytetrafluoroethylene (PTFE), polyethylene oxide (PEO), and polytetrafluoroethylene-perfluoro(3-oxa-4-pentenesulfonic acid) copolymer lithium salt. The positive electrode electrolyte includes yLi₂S·(100-yx)P₂S₅·xP₂O₅ (LPSO), wherein y is in the range of 70 mol% to 80 mol% (inclusive), and x is in the range of 1 mol% to 10 mol% (inclusive). The conductive filler includes one or more of the following: metal wire, metal oxide, carbon nanotubes, carbon black, graphite sheets, graphite nanoparticles, graphite nanosheets, and combinations thereof. In one embodiment, the active positive electrode material is present in the range of 64% to 98.5% by weight (inclusive) of the total weight of the positive electrode, the positive electrode binder is present in the range of 1% to 9% by weight (inclusive) of the total weight of the positive electrode, optionally, the positive electrode electrolyte is present in the range of 10% to 17% by weight (inclusive) of the total weight of the positive electrode, and optionally, the conductive filler is present in the range of 0.5% to 25% by weight (inclusive) of the total weight of the positive electrode, wherein the total weight of the positive electrode is equal to 100%. In another embodiment, the active positive electrode material, the positive electrode binder, and the conductive filler are deposited on the positive electrode 156 in the form of a slurry deposited on the positive electrode current collector 152. The slurry is formed from a liquid (e.g., toluene, anisole, N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), dimethylformamide (DMF), or acetonitrile (MeCN).

[0056] The positive electrode 156 has a thickness 416 ranging from 80 micrometers to 500 micrometers (inclusive of all values ​​and ranges therein, such as 110 micrometers). When the positive electrode material is formed on one side of the positive electrode current collector 152, the positive electrode 157, comprising both the positive electrode current collector 152 and the positive electrode 156, has a thickness 418 ranging from 85 micrometers to 550 micrometers (inclusive of all values ​​and ranges therein). When the positive electrode material is formed on both sides of the positive electrode current collector 152, the positive electrode 157 has a thickness ranging from 165 micrometers to 1,050 micrometers (inclusive of all values ​​and ranges therein for both positive electrode 157 sides, such as 205 micrometers to 500 micrometers).

[0057] The negative electrode 158 comprises an active negative electrode material that can undergo reversible lithium-ion insertion or intercalation at a lower electrochemical potential than the positive electrode 156, resulting in an electrochemical potential difference between the negative electrode 158 and the positive electrode 156. Active negative electrode materials include silicon, silicon-carbon composites, hard carbon (non-graphitized carbon), graphite, and silicon oxide (SiO₂). x The negative electrode is formed by vapor deposition of a negative electrode active material onto a negative electrode current collector 154 via physical or chemical vapor deposition (where x is 1 or 2) and one or more of lithium titanate (LTO). Alternatively, the negative electrode can be formed by forming a coating on the negative electrode current collector 154 using a deposition process such as a slurry-based process, hot roll forming, extrusion, or additive manufacturing. In one embodiment, the negative electrode 158 has a thickness 420 in the range of 10 micrometers to 150 micrometers (inclusive). In a preferred embodiment, the negative electrode is silicon deposited by physical vapor deposition, having a thickness in the range of 1 micrometer to 100 micrometers (inclusive, e.g., 14 micrometers to 15 micrometers). The combined negative electrode 158 and negative electrode current collector 154 provide a negative electrode 159 having a thickness 422 in the range of 1 micrometer to 200 micrometers (inclusive).

[0058] In an alternative embodiment, the negative electrode 158 is initially omitted and formed on the negative electrode current collector 154 during the first charging cycle due to in-situ electroplating of lithium metal. In this embodiment, the negative electrode supporting electrolyte membrane 160 is disposed on and in contact with the negative electrode current collector 154 prior to the first charging cycle. This embodiment is referred to as "negative electrode-free".

[0059] As described above, the negative electrode-supported electrolyte membrane 160 is sandwiched or at least partially surrounded between the positive electrode 156 and the negative electrode 158, thereby preventing the positive electrode 156 from contacting the negative electrode 158. The negative electrode-supported electrolyte membrane 160 includes an electrolyte that provides a medium for lithium ions to pass through between the positive electrode 156 and the negative electrode 158, while still electrically insulating the positive electrode 156 from the negative electrode 158, thereby preventing short circuits. The negative electrode-supported electrolyte membrane 160 is at least one of a solid electrolyte or a semi-solid electrolyte.

[0060] Solid electrolytes are understood to be electrolytes that exhibit a solid state of matter. The negative electrode supported solid electrolyte membrane 160 comprises a sulfide solid electrolyte, such as a lithium-phosphorus-sulfur (LPS) electrolyte or a lithium-phosphorus-sulfur-oxygen (LPSO) electrolyte. In an embodiment, the negative electrode supported solid electrolyte membrane 160 comprises one or more of the following electrolyte compositions: yLi₂S·(100-yx)P₂S₅·xP₂O₅ (LPSO), wherein y is in the range of 70 mol% to 80 mol% (inclusive), and x is in the range of 1 mol% to 10 mol% (inclusive), Li 10 MP2S 12 (LPS), where M is at least one of Si, Ge, and Sn, and silver-germanium sulfide has the following formula: A 12-m-x + (M m+ Y4 2- )Y 2-x 2- X x - , where A + =Li + Cu + Ag + M m+ =Si 4+ 、Ge 4+ Sn 4+ P 5+ As 5+ ;Y 2- =O 2- S 2- Se 2- Te 2- ;X - =Cl - ,Br - I -And 0 ≤ x ≤ 2, for example, Li6PS5Cl. The electrolyte composition is present in the range of 50% to 99% by weight (inclusive) of the total weight of the negative electrode supporting solid electrolyte membrane 160. Furthermore, the negative electrode supporting solid electrolyte membrane 160 includes an electrolyte binder present in the range of 1% to 50% by weight (inclusive) of the total weight of the solid electrolyte membrane. The electrolyte binder includes one or more of the following binders: styrene-butadiene rubber (SBR), hydrogenated nitrile rubber (HNBR), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polytetrafluoroethylene (PTFE), polytetrafluoroethylene-perfluoro(3-oxa-4-pentenesulfonic acid) copolymer lithium salt, and combinations thereof. Furthermore, in an embodiment, the solid electrolyte and electrolyte binder are deposited on the negative electrode 158 as a slurry in which the electrolyte and binder are mixed in a solution of the binder and binder solvent. The binder solvent is selected from one or more of the following solvents: toluene, alkanes, anisole, and organophosphates. In this embodiment, the solid electrolyte is present in the slurry at a concentration ranging from 28% to 60% by weight (inclusive of all values ​​and increments) of the total slurry weight. The electrolyte binder is present in the solution at a concentration ranging from 0.4% to 18% by weight (inclusive of all values ​​and ranges) of the total solution weight. The negative electrode-supported solid electrolyte membrane 160 has a thickness 424 ranging from 1 micrometer to 100 micrometers (inclusive of all values ​​and ranges). Furthermore, the porosity of the negative electrode-supported solid electrolyte membrane 160 is in the range of 1% to 50% of the total volume typically defined by the periphery of the negative electrode-supported solid electrolyte membrane 160, inclusive of all values ​​and ranges.

[0061] In other or alternative embodiments, the negative electrode supporting electrolyte membrane 160 comprises a semi-solid electrolyte. As understood herein, the semi-solid electrolyte comprises a solid matrix including the negative electrode supporting solid electrolyte membrane, the negative electrode supporting solid electrolyte membrane having a liquid electrolyte injected into the gaps in the solid matrix, and in some cases, the semi-solid electrolyte is described as a gel. In embodiments, the semi-solid electrolyte comprises a solvated ionic liquid electrolyte. Solvated ionic liquid electrolytes include one or more of the following: lithium triethylene glycol dimethyl ether bis(trifluoromethanesulfonyl)imide (Li[G3]TFSI), lithium tetraethylene glycol dimethyl ether bis(trifluoromethanesulfonyl)imide (Li[G4]TFSI), lithium triethylene glycol dimethyl ether bis(fluorosulfonyl)imide (Li[G3]FSI), lithium tetraethylene glycol dimethyl ether bis(fluorosulfonyl)imide (Li[G4]FSI), lithium triethylene glycol dimethyl ether bis(pentafluoroethylenesulfonyl)imide (Li[G3]BETI), lithium tetraethylene glycol dimethyl ether bis(pentafluoroethylenesulfonyl)imide (Li[G4]BETI), lithium triethylene glycol dimethyl ether bis(pentafluoroethylenesulfonyl)imide (Li[G4]BETI), lithium triethylene glycol dimethyl ether bis(pentafluoroethylenesulfonyl)imide (Li[G4]BETI), lithium triethylene glycol dimethyl ether bis(pentafluoroethylenesulfonyl)imide (Li[G4]BETI), lithium triethylene glycol dimethyl ether bis(pentafluoroethylenesulfonyl)imide (Li[G4]BETI), lithium triethylene glycol dimethyl ether bis(pentafluoroethylenesulfonyl)imide (Li[G3]TFSI ...4]BETI), lithium triethylene glycol dimethyl ether bis(pentafluoroethylenesulfonyl)imide (Li[G3]TFSI), lithium triethylene glycol dimethyl ether bis(pentafluoroethylenesulfonyl)imide Lithium dimethyl ether cyclic-TFSI derivatives 1,2,3-dithiazolyl-4,4,5,5-tetrafluoro-1,1,3,3-tetraoxide (Li[G3]CTFSI), lithium dimethyl ether cyclic-TFSI derivatives 1,2,3-dithiazolyl-4,4,5,5-tetrafluoro-1,1,3,3-tetraoxide (Li[G4]CTFSI), lithium triethylene glycol dimethyl ether perchlorate (Li[G3]ClO4), lithium tetraethylene glycol dimethyl ether perchlorate (Li[G4]ClO4), lithium triethylene glycol dimethyl ether tetrafluoroborate (Li[G3]BF4), and lithium tetraethylene glycol dimethyl ether tetrafluoroborate (Li[G4]BF4). Semi-solid electrolytes are formed by applying a solvated ionic liquid electrolyte to a solid electrolyte membrane supporting the negative electrode. The solvated ionic liquid electrolyte permeates into the gaps in the solid matrix, which can be assisted by applying a vacuum. A solvated ionic liquid electrolyte may be applied before or prior to assembling the negative electrode supporting electrolyte membrane into the battery cell. If applied prior to assembly, excess solvated ionic liquid electrolyte is removed prior to assembly. The negative electrode supporting semi-solid electrolyte membrane 160 has a thickness 424 ranging from 1 micrometer to 100 micrometers (inclusive).

[0062] In an optional embodiment, the negative electrode supporting electrolyte membrane 160, comprising one or more solvated liquid electrolytes, further comprises at least one of a liquid electrolyte diluent and a room-temperature ionic liquid. The liquid electrolyte diluent comprises a fluorinated ether electrolyte. The fluorinated ether electrolyte comprises one or more of the following: 1,1,2,2-tetrafluoroethylene 2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,2-trifluoroethyl) ether (BTFE), tris(2,2,2-trifluoroethyl) orthoformate (TFEO), fluorobenzene (FB), 1,2-difluorobenzene (DFB), bis(2,2-difluoroethyl) ether (BDE), ethyl 1,1,2,2-tetrafluoroethyl ether (ETE), hexafluoroisopropyl methyl ether (HFME), 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether, ethyl 1,1,2,3,3,3-hexafluoropropyl Ethers, methyl nonafluorobutyl ether (mixture of isomers), difluoromethyl 2,2,3,3-tetrafluoropropyl ether, 1H,1H,5H-octafluoropentyl 1,1,2,2-tetrafluoroethyl ether (OTE), 1,1,2,3,3,3 hexafluoropropyl-2,2,2-trifluoroethyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane, fluoromethyl 1,1,1,3,3,3-hexafluoroisopropyl ether, 1,1,2,3,3,3-hexafluoropropylmethyl ether, methyl 2,2,3,3,3-pentafluoropropyl ether and methyl 1,1,2,2-tetrafluoroethyl ether. Liquid electrolyte diluents and solvated ionic liquid electrolytes help increase the contact between the solid electrolyte membrane and the positive and negative electrodes by filling the gaps formed during the deposition of the positive electrode 156 and negative electrode 158 on the positive electrode current collector 152 and negative electrode current collector 154, respectively. Room temperature ionic liquids are understood as ionic systems that exhibit a liquid state at room temperature. Room temperature ionic liquids include one or more of, for example, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imine (EMIM-TFSI), 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imine (BMIM-TFSI), N-propyl-N-methylpyrrolidine bis(trifluoromethanesulfonyl)imine (PYR13TFSI), 1-butyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imine, etc. The electrolytes are 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (PYR14TFSI), 1-butyl-3-methylimidazolium bis(fluorosulfonyl)imide (BMIM-FSI), N-propyl-N-methylpyrrolidine bis(fluorosulfonyl)imide (PYR13-FSI), and 1-butyl-1-methylpyrrolidine bis(fluorosulfonyl)imide (PYR14-FSI). In embodiments, the ratio of at least one of the liquid electrolyte and room-temperature ionic liquid to at least one of the solid electrolyte and semi-solid electrolyte is in the range of 1 volume part to 1 volume part to 5 volume parts to 1 volume part, including all values ​​and ranges therein.

[0063] Turn now Figure 5 ,refer to Figure 2A to Figure 4B This describes an embodiment of a method for forming a negative electrode supporting electrolyte. Method 500 includes mixing one or more electrolytes, one or more electrolyte binders, and one or more binder solvents at block 502 to form a slurry. In an embodiment, the slurry is mixed at a temperature ranging from 21°C to 25°C for a time ranging from 10 minutes to 30 minutes. At block 504, the slurry is coated onto the negative electrode and allowed to dry. In an embodiment, drying is performed at a temperature ranging from 60°C to 150°C, for example, at 80°C for a period ranging from 1 hour to 48 hours. Figure 6 The coating 602 deposited on the negative electrode 154 is shown. Return to Figure 5 At block 506, a coating 602 is calendered under a pressure greater than 100 MPa (e.g., in the range of 100 MPa to 600 MPa, including all values ​​and ranges therein). At block 508, optionally, at least one of a solvated ionic liquid electrolyte, a liquid electrolyte diluent, and a room-temperature ionic liquid is applied to the negative electrode support electrolyte membrane 160, allowing liquid permeation into the negative electrode support electrolyte membrane 160, which can be done with vacuum assistance and removing any excess liquid. At block 510, the negative electrode, including the negative electrode support electrolyte membrane 160, is assembled into a battery cell 150. As an alternative to optional block 508, at block 512, optionally, after the battery cell 150 is assembled and sealed, at least one of a solvated ionic liquid electrolyte, a liquid electrolyte diluent, and a room-temperature ionic liquid is added to the battery cell 150.

[0064] Comparative Example

[0065] Three 2032 coin cells were formed using a conventional polymer separator, a positive electrode supported solid electrolyte separator, and a negative electrode supported solid electrolyte separator. They are respectively as follows: Figure 7 , 8 All three battery cells 700, 800, and 400 shown in Figure 4 include an aluminum positive current collector 152, a copper negative current collector 154, and a silicon negative electrode 158 with an energy density of 4.4 mAh / cm². The positive electrode 156 of all three battery cells comprises 6 parts by weight of Li₂S and carbon black (wherein Li₂S is present at 70% by weight of the total active positive electrode material, and carbon black is present at 30% by weight of the total active positive electrode material), 2.5 parts by weight of LPSO₄·70Li₂S·25P₂S₅·5P₂O₅, 1 part by weight of carbon black, and 0.5 parts by weight of hydrogenated nitrile rubber. The positive electrode is applied at a load of 2 to 3 mg / cm².

[0066] Turn now Figure 7 The figure shows a conventional battery cell 700, which includes a conventional polymer separator 760 formed from an ENTEK ultra-high molecular weight polyethylene (UHMWPE) silica molten separator. Figure 8 A battery cell 800 including a positive electrode supported solid electrolyte membrane is shown. The positive electrode supported solid electrolyte membrane 860 comprises LPSO 70Li2S·25P2S5·5P2O5 and is applied as a 25-micron film to the positive electrode. The negative electrode supported solid electrolyte membrane 160, as... Figure 4A As shown, this includes LPSO applied to the negative electrode as a 25-micron film.

[0067] Figure 9 The diagram shows the capacity (mAhh) degradation of a conventional battery cell 700 over 80 cycles (shown on the x-axis) with a charging rate of C / 10 (10 hours of charging) and a discharging rate of C / 10 (10 hours of discharging). Figure 10 The diagram illustrates the capacity (mAhh) decay (shown on the y-axis) of a battery cell 400, including a negative electrode-supported solid electrolyte membrane 160, over 80 cycles (shown on the x-axis, line A) and discharge (line B), with a charge rate of C / 10 (10 hours of charging) and a discharge rate of C / 10 (10 hours of discharging). As shown, neither battery exhibits significant capacity decay over 80 cycles. The battery cell including a positive electrode-supported solid electrolyte suffers from edge short circuits, thus hindering the measurement of capacity as a function of charge / discharge cycles.

[0068] The electrolyte, battery cell, secondary battery, and manufacturing method described herein offer numerous advantages. These advantages include, for example, preventing short circuits in the battery cell caused by contact between the negative and positive electrodes. These advantages also include providing a negative electrode material that is mechanically robust enough for the calendering process used in the deposition of the negative electrode supporting the electrolyte separator. These advantages also include the ability to reduce separator thickness to increase battery energy density. Furthermore, these advantages include the ability to apply this technology to both monopolar and bipolar battery cell designs.

[0069] As used herein, the term "controller" and related terms (e.g., microcontroller, control module, module, control, control unit, processor, and similar terms) refer to one or more combinations of relevant non-transient memory components in the form of application-specific integrated circuits (ASICs), field-programmable gate arrays (FPGAs), electronic circuits, central processing units (e.g., microprocessors), and memory and storage devices (read-only, programmable read-only, random access, hard disk drives, etc.). Controller 132 may also consist of multiple controllers electrically connected to each other. Controller 132 may interconnect with additional systems and / or controllers of vehicle 100, thereby allowing controller 132 to access data such as the speed, acceleration, braking, and steering angle of vehicle 100.

[0070] The processor may be a custom or commercially available processor, a central processing unit (CPU), a graphics processing unit (GPU), an auxiliary processor among a plurality of processors associated with controller 132, a microprocessor based on semiconductor composite conductors (in the form of a microchip or chipset), a macroprocessor, a combination thereof, or a device typically used to execute instructions.

[0071] The tangible non-transitory memory 134 may include volatile and non-volatile storage devices such as read-only memory (ROM), random access memory (RAM), and keep-alive memory (KAM). KAM is a persistent or non-volatile memory used to store various operational variables when the processor is powered off. The tangible non-transitory memory 134 may be implemented using multiple storage devices, such as PROM (programmable read-only memory), EPROM (electrical PROM), EEPROM (electrically erasable PROM), flash memory, or other electrical, magnetic, optical, or combined storage devices capable of storing data, some of which represents executable instructions for various systems of the vehicle 100 controlled by the controller 132.

[0072] The descriptions in this disclosure are merely exemplary in nature, and changes that do not depart from the spirit and scope of this disclosure are intended to fall within its scope. Such changes should not be considered as departing from the spirit and scope of this disclosure.

Claims

1. A negative electrode for a battery cell, comprising: a negative current collector, the negative current collector comprising a first surface; and a negative support electrolyte separator disposed on the first surface, wherein the negative electrode supports an electrolyte separator comprising at least one electrolyte selected from the group consisting of: a) y Li2S - (100 - y - x) P2S5 - x P2O5, wherein y is in the range of 70 mol% to 80 mol%, x is in the range of 1 mol% to 10 mol%, b) Li 10 MP2S 12 wherein M is at least one of Si, Ge and Sn, and c) argyrodite having a composition of: A1 2-m-x + (M m+ Y4 2- )Y 2-x 2- X x - wherein A + = Li + , Cu + , Ag + ; M m+ = Si 4+ , Ge 4+ , Sn 4+ , P 5+ , As 5+ ; Y 2- = O 2- , S 2- , Se 2- , Te 2- ; X - = Cl - , Br - , I - ; and 0 < x < 2, wherein the negative support electrolyte separator has a thickness in the range of 1 micron to 100 microns.

2. The negative electrode according to claim 1, wherein the negative support electrolyte separator comprises a second surface, the second surface defining a second area, wherein the second area is greater than a third area defined by a third surface of an adjacent positive electrode.

3. The negative electrode according to claim 2, wherein the negative support electrolyte separator contacts the first surface of the negative current collector.

4. The negative electrode of claim 2, further comprising a negative electrode that contacts the first surface, wherein, the negative electrode comprises a fourth surface, the fourth surface defining a fourth area, and the negative support electrolyte separator contacts the fourth surface.

5. The negative electrode according to claim 4, wherein The negative electrode includes one or more active negative electrode materials selected from the group consisting of silicon, silicon-carbon composite, hard carbon, graphite, silicon oxide (SiO x wherein x is 1 or 2) and lithium titanate (LTO).

6. The negative electrode according to claim 1, wherein the electrolyte is yLi2S-(100-y-x)P2S5-xP2O5, wherein y is in the range of 70 mole % to 80 mole %, x is in the range of 1 mole % to 10 mole %, and the electrolyte is present in the range of 50 wt % to 99 wt % of the total weight of the negative support electrolyte separator, and the negative support electrolyte separator further comprises an electrolyte binder present in the range of 1 wt % to 50 wt % of the total weight of the negative support electrolyte separator.

7. The negative electrode according to claim 6, wherein the electrolyte binder comprises one or more binders selected from the group consisting of: styrene butadiene rubber (SBR), hydrogenated nitrile butadiene rubber (HNBR), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polytetrafluoroethylene (PTFE), and polytetrafluoroethylene-perfluoro(3-oxa-4-pentenesulfonic acid) copolymer lithium salt.

8. The negative electrode according to claim 1, wherein the negative support electrolyte separator further comprises one or more liquid electrolyte diluents selected from the group consisting of: 1,1,2,2-tetrafluoroethylene 2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,2-trifluoroethyl) ether (BTFE), tris(2,2,2-trifluoroethyl)orthoformate (TFEO), fluorobenzene (FB), 1,2-difluorobenzene (DFB), bis(2,2-difluoroethyl) ether (BDE), ethyl 1,1,2,2-tetrafluoroethyl ether (ETE), hexafluoroisopropyl methyl ether (HFME), 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether, ethyl 1,1,2,3,3,3-hexafluoropropyl ether, methyl nonafluorobutyl ether (isomer mixture), difluoromethyl 2,2,3,3-tetrafluoropropyl ether, 1H,1H,5H-octafluoropentyl 1,1,2,2-tetrafluoroethyl ether (OTE), 1,1,2,3,3,3 hexafluoropropyl-2,2,2-trifluoroethyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane, fluoromethyl 1,1,1,3,3,3-hexafluoroisopropyl ether, 1,1,2,3,3,3-hexafluoropropyl methyl ether, methyl 2,2,3,3,3-pentafluoropropyl ether, and methyl 1,1,2,2-tetrafluoroethyl ether.

9. The negative electrode of claim 1, wherein, The negative electrode-supporting electrolyte separator further comprises one or more room temperature ionic liquids selected from the group consisting of: 1-ethyl-3- methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM-TFSI), 1-butyl-3- methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIM-TFSI), N-propyl-N- methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (PYR13TFSI), 1-butyl-1- methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (PYR14TFSI), 1-ethyl-3- methylimidazolium bis(fluorosulfonyl)imide (EMIM-FSI), 1-butyl-3-methylimidazolium bis(fluorosulfonyl)imide (BMIM-FSI), N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide (PYR13-FSI), and 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (PYR14-FSI).

10. The negative electrode according to claim 1, wherein The negative electrode-supporting electrolyte separator comprises one or more solvated ionic liquid electrolytes selected from the group consisting of: triethylene glycol dimethyl ether bis(trifluoromethylsulfonyl)imide lithium (Li[G3]TFSI), tetraethylene glycol dimethyl ether bis(trifluoromethylsulfonyl)imide lithium (Li[G4]TFSI), triethylene glycol dimethyl ether bis(fluorosulfonyl)imide lithium (Li[G3]FSI), tetraethylene glycol dimethyl ether bis(fluorosulfonyl)imide lithium (Li[G4]FSI), triethylene glycol dimethyl ether bis(pentafluoroethenesulfonyl)imide lithium (Li[G3]BETI), tetraethylene glycol dimethyl ether bis(pentafluoroethenesulfonyl)imide lithium (Li[G4]BETI), triethylene glycol dimethyl ether lithium cyclic-TFSI derivative 1,2,3-dithiazolidine-4,4,5,5-tetrafluoro-1,1,3,3-tetraoxide (Li[G3]CTFSI), tetraethylene glycol dimethyl ether lithium cyclic-TFSI derivative 1,2,3-dithiazolidine-4,4,5,5-tetrafluoro-1,1,3,3-tetraoxide (Li[G4]CTFSI), triethylene glycol dimethyl ether lithium perchlorate (Li[G3]ClO4), tetraethylene glycol dimethyl ether lithium perchlorate (Li[G4]ClO4), triethylene glycol dimethyl ether lithium tetrafluoroborate (Li[G3]BF4), and tetraethylene glycol dimethyl ether lithium tetrafluoroborate (Li[G4]BF4).

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