Anode electrode for battery cell comprising lithium aluminum layer and lithium metal layer

Abstract

The present application relates to an anode electrode for a battery cell comprising a lithium aluminum layer and a lithium metal layer. A battery cell includes C cathode electrodes, where each of the C cathode electrodes includes a cathode active material layer disposed on a cathode current collector, S separators, and A anode electrodes, where A, C, and S are integers greater than 1. Each of the A anode electrodes includes an anode active material layer disposed on an anode current collector. The anode active material layer includes a lithium metal layer and a lithium aluminum layer disposed on a separator-facing side of the lithium metal layer.

Description

Anode electrode for battery packs, comprising a lithium aluminum layer and a lithium metal layer. Technical Field

[0001] This disclosure relates to battery packs, and more specifically to battery packs including an anode electrode having a lithium aluminum layer and a lithium metal layer. Background Technology

[0002] The information provided in this section is intended to provide a general overview of the background of this disclosure. The work of the currently named inventors described in this section, and the aspects of the specification that may not have been otherwise identified as prior art at the time of filing, are not expressly or impliedly acknowledged as prior art to this disclosure.

[0003] Electric vehicles (EVs), such as battery electric vehicles (BEVs), hybrid electric vehicles, and / or fuel cell vehicles, include one or more electric motors and a battery pack system comprising one or more battery cells, modules, and / or packs. A power control system is used to control the charging and / or discharging of the battery pack system during charging and / or driving.

[0004] The battery pack includes a cathode electrode, an anode electrode, and a separator. The cathode electrode includes a layer of cathode active material disposed on a cathode current collector. The anode electrode includes a layer of anode active material disposed on an anode current collector. Summary of the Invention

[0005] A battery pack includes C cathode electrodes, S separators, and A anode electrodes, wherein each of the C cathode electrodes includes a cathode active material layer disposed on a cathode current collector, and A, C, and S are integers greater than 1. Each of the A anode electrodes includes an anode active material layer disposed on an anode current collector. The anode active material layer includes a lithium metal layer and a lithium aluminum layer disposed on the lithium metal layer facing the separator side.

[0006] Among other features, an in-situ lithium-aluminum film is formed by arranging the aluminum layer adjacent to the lithium metal layer to form a lithium-aluminum layer. The lithium-aluminum layer comprises 80.0% to 99.99% by weight of lithium-aluminum. The thickness of the lithium-aluminum layer is 2 μm to 25 μm, and the thickness of the lithium metal layer is 20 μm to 50 μm.

[0007] Among other features, the cathode active material layer comprises a cathode active material and a solid electrolyte. The S separators comprise a solid electrolyte. The cathode active material is selected from layered oxides, olivine-type oxides, monoclinic oxides, spinel-type oxides, lithium hydroxyphosphorus iron oxide, sulfur, Li₂S, and combinations thereof. The cathode active material includes a coating selected from LiNbO₃, Li₃PO₄, and combinations thereof.

[0008] Among other features, the solid electrolyte is selected from pseudo-binary sulfides, pseudo-ternary sulfides, pseudo-quaternary sulfides, oxide-based solid electrolytes, metal-doped or aiovalent oxides, nitride-based solid electrolytes, halide-based solid electrolytes, hydride-based solid electrolytes, borate-based solid electrolytes, and combinations thereof.

[0009] Among other features, the battery pack comprises a liquid-based battery pack, and the S separators comprise polymer-based separator layers. The liquid electrolyte comprises one or more lithium salts and one or more solvents. The one or more lithium salts are selected from lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium bis(trifluoromethane)sulfonylimide, lithium bis(fluorosulfonylimide), and combinations thereof. The one or more solvents are selected from alkyl carbonates, esters, γ-lactones, chain ethers, cyclic ethers, and / or combinations thereof.

[0010] Among other features, the battery pack includes semi-solid-state battery packs. The battery pack also includes all-solid-state battery packs. The anode active material layer further includes an anodic aluminum oxide layer formed on an aluminum layer adjacent to the aluminum layer prior to in-situ lithiation.

[0011] Among other features, the anodic active material layer accounts for 0.01% to 10% by weight of the anodic aluminum oxide layer.

[0012] A method for manufacturing an anode electrode for a battery pack includes providing an aluminum foil layer; providing a lithium metal layer; providing an anode current collector; disposing the aluminum foil layer on the lithium metal layer, wherein the aluminum foil layer is in-situ lithiated by the lithium metal layer to form a lithium-aluminum layer; disposing the aluminum foil layer and the lithium metal layer on the anode current collector to form an anode electrode; and disposing the anode electrode in the battery pack.

[0013] Among other features, the method includes forming an anodized aluminum layer on the aluminum foil layer before arranging the aluminum foil layer on the lithium metal layer. The lithium aluminum layer comprises 80.0% to 99.99% by weight of lithium aluminum, the thickness of the lithium aluminum layer is 2 μm to 25 μm, and the thickness of the lithium metal layer is 20 μm to 50 μm.

[0014] Among other features, the battery pack includes A anode electrodes, C cathode electrodes, and S separators arranged in a stacked configuration, where A, C, and S are integers greater than 1. Each of the C cathode electrodes includes a layer of cathode active material disposed on a cathode current collector. The cathode active material comprises a cathode active material and a solid electrolyte. The cathode active material is selected from layered oxides, olivine oxides, monoclinic oxides, spinel oxides, lithium hydroxyphosphorus iron oxide, sulfur, Li₂S, and combinations thereof. The solid electrolyte is selected from pseudo-binary sulfides, pseudo-ternary sulfides, pseudo-quaternary sulfides, oxide-based solid electrolytes, metal-doped or heterovalent oxides, nitride-based solid electrolytes, halide-based solid electrolytes, hydride-based solid electrolytes, borate-based solid electrolytes, and combinations thereof.

[0015] The present invention discloses the following solutions:

[0016] Option 1. A battery pack comprising:

[0017] C cathode electrodes, each of the C cathode electrodes including a layer of cathode active material disposed on a cathode current collector;

[0018] S isolation components; and

[0019] There are A anode electrodes, where A, C, and S are integers greater than 1.

[0020] Each of the A anode electrodes includes an anode active material layer disposed on the anode current collector, and

[0021] The anodic active material layer includes a lithium metal layer and a lithium aluminum layer disposed on the side of the lithium metal layer facing the separator.

[0022] Option 2. The battery pack according to Option 1, wherein the lithium-aluminum layer is formed in situ by arranging the aluminum layer adjacent to the lithium metal layer to form the lithium-aluminum layer.

[0023] Option 3. The battery pack according to Option 1, wherein:

[0024] The lithium-aluminum layer comprises 80.0% to 99.99% by weight of lithium-aluminum.

[0025] The thickness of the lithium-aluminum layer is 2 μm to 25 μm.

[0026] The thickness of the lithium metal layer is 20 μm to 50 μm.

[0027] Option 4. The battery pack according to Option 1, wherein:

[0028] The cathode active material layer includes a cathode active material and a solid electrolyte;

[0029] The S isolation components include solid electrolytes.

[0030] Option 5. The battery pack according to Option 4, wherein the cathode active material is selected from layered oxides, olivine oxides, monoclinic oxides, spinel oxides, lithium hydroxyphosphorus iron oxide, sulfur, Li2S and combinations thereof.

[0031] Option 6. The battery pack according to Option 5, wherein the cathode active material comprises a coating selected from LiNbO3, Li3PO4 and combinations thereof.

[0032] Option 7. The battery pack according to Option 4, wherein the solid electrolyte is selected from pseudo-binary sulfides, pseudo-ternary sulfides, pseudo-quaternary sulfides, oxide-based solid electrolytes, metal-doped or heterovalent oxides, nitride-based solid electrolytes, halide-based solid electrolytes, hydride-based solid electrolytes, borate-based solid electrolytes, and combinations thereof.

[0033] Option 8. The battery pack according to Option 1, wherein:

[0034] The battery pack includes liquid-based battery cells, and

[0035] The S isolation elements include polymer-based isolation element layers.

[0036] Option 9. The battery pack according to Option 8, further comprising a liquid electrolyte, the liquid electrolyte comprising one or more lithium salts and one or more solvents.

[0037] Option 10. The battery pack according to Option 9, wherein the one or more lithium salts are selected from lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium bis(trifluoromethane)sulfonylimide, lithium bis(fluorosulfonyl)imide, and combinations thereof.

[0038] Option 11. The battery pack according to Option 9, wherein one or more solvents are selected from alkyl carbonates, esters, γ-lactones, chain ethers, cyclic ethers and / or combinations thereof.

[0039] Option 12. The battery pack according to Option 1, wherein the battery pack includes a semi-solid-state battery pack.

[0040] Option 13. The battery pack according to Option 1, wherein the battery pack includes an all-solid-state battery pack.

[0041] Option 14. The battery pack according to Option 2, wherein the anode active material layer further includes an anodic aluminum oxide layer formed on an aluminum layer adjacent to the aluminum layer prior to in-situ lithiation.

[0042] Option 15. The battery pack according to Option 14, wherein the anode active material layer accounts for 0.01% to 10% by weight of the anode aluminum oxide layer.

[0043] Option 16. A method for manufacturing an anode electrode for a battery pack, comprising:

[0044] Provide aluminum foil layer;

[0045] Provides a lithium metal layer;

[0046] Provide anode current collector;

[0047] An aluminum foil layer is arranged on a lithium metal layer, wherein the aluminum foil layer is lithiated in situ by the lithium metal layer to form a lithium aluminum layer.

[0048] An aluminum foil layer and a lithium metal layer are arranged on the anode current collector to form the anode electrode; and

[0049] The anode electrode is placed inside the battery pack.

[0050] Option 17. The method according to Option 16 further includes forming an anodized aluminum layer on the aluminum foil layer before arranging the aluminum foil layer on the lithium metal layer.

[0051] Option 18. The method according to Option 16, wherein:

[0052] The lithium-aluminum layer comprises 80.0% to 99.99% by weight of lithium-aluminum.

[0053] The thickness of the lithium-aluminum layer is 2 μm to 25 μm.

[0054] The thickness of the lithium metal layer is 20 μm to 50 μm.

[0055] Option 19. The method according to Option 16, wherein the battery pack includes A anode electrodes, C cathode electrodes and S spacers arranged in a stacked manner, wherein A, C and S are integers greater than 1.

[0056] Option 20. A battery pack for an automotive battery pack, comprising:

[0057] C cathode electrodes, each of the C cathode electrodes including a layer of cathode active material disposed on a cathode current collector;

[0058] S isolation components; and

[0059] There are A anode electrodes, where A, C, and S are integers greater than 1.

[0060] Each of the A anode electrodes includes a layer of anolyte active material disposed on the anode current collector.

[0061] The anode active material layer includes a lithium metal layer and a lithium-aluminum layer disposed on the side of the lithium metal layer facing the separator.

[0062] The lithium-aluminum layer comprises 80.0% to 99.99% by weight of lithium-aluminum, the thickness of the lithium-aluminum layer is 2 μm to 25 μm, and the thickness of the lithium metal layer is 20 μm to 50 μm.

[0063] The further applicability of this disclosure will become apparent from the detailed description, claims, and drawings. The detailed description and specific embodiments are intended to be illustrative only and are not intended to limit the scope of this disclosure. Attached Figure Description

[0064] This disclosure will be more fully understood from the detailed description and the accompanying drawings, in which:

[0065] Figure 1 is a side cross-sectional view of an example of a battery pack according to the present disclosure, comprising C cathode electrodes, A anode electrodes (including a lithium aluminum layer, a lithium metal layer and an anode current collector) and S separators.

[0066] Figure 2 is a more detailed side cross-sectional view of an example of a battery pack including an anode electrode according to the present disclosure, the anode electrode including a lithium aluminum layer, a lithium metal layer and an anode current collector;

[0067] Figure 3 is a diagram showing an example of an aluminum foil according to the present disclosure and an X-ray diffraction pattern of the aluminum foil after contact with a lithium foil;

[0068] Figure 4 is a side cross-sectional view of an example of a liquid-based battery pack according to the present disclosure, including an anode electrode comprising a lithium aluminum layer, a lithium metal layer, and an anode current collector.

[0069] Figure 5 is a side cross-sectional view of an example of a semi-solid-state battery pack including an anode electrode according to the present disclosure, the anode electrode including a lithium aluminum layer, a lithium metal layer and an anode current collector.

[0070] Figure 6A illustrates a method for forming the anode electrode of a battery pack according to the present disclosure;

[0071] Figure 6B is a side cross-sectional view of another example of a battery pack according to the present disclosure, including the anode electrode of Figure 6A.

[0072] Figure 7A is a graph showing an example of voltage and specific capacity during the initial formation of ASSLMB without a LiAl layer at 0.1C and 25°C;

[0073] Figure 7B is a graph showing an example of voltage and specific capacity of ASSLMB having a LiAl layer during initial formation at 0.1C and 25°C according to the present disclosure;

[0074] Figure 7C is a graph showing an example of how the discharge capacity changes with the number of cycles during cycling at 0.1C and 25°C;

[0075] Figure 8A is a graph showing examples of voltage and specific capacity during the initial formation of battery packs with and without LiAl layers at 0.05C and 25°C;

[0076] Figure 8B is a graph illustrating examples of the voltage and capacity of battery packs with and without LiAl layers during charge and discharge at 0.5C and 25°C according to the present disclosure; and

[0077] Figure 8C is a graph showing examples of how the capacity retention of battery packs with and without LiAl layers changes with the number of cycles during cycling at 0.5C and 25°C.

[0078] In the accompanying drawings, reference numerals may be reused to designate similar and / or identical elements. Detailed Implementation

[0079] Although the battery pack according to this disclosure is shown in the context of an electric vehicle, the battery pack can be used in stationary applications and / or other applications.

[0080] All-solid-state lithium metal battery packs (ASSLMBs) are emerging as important energy storage candidates for enhanced thermal stability and increased energy density. The solid electrolyte undergoes reductive decomposition and forms a passivated solid electrolyte interface (SEI) layer upon direct contact with the lithium metal layer. This passivated SEI layer continues to grow during cycling, reducing the effective contact area and potentially accelerating the growth of dendritic lithium. Furthermore, factors such as uneven lithium plating / stripping behavior and physical defects can promote the growth of dendritic lithium, leading to internal short circuits.

[0081] The battery pack according to this disclosure includes an anode electrode comprising a lithium aluminum (LiAl) layer formed in situ via a spontaneous reaction between an aluminum layer and a lithium metal layer. The LiAl layer is lithium-philic and has a low interfacial energy relative to lithium metal. The LiAl layer reduces the interfacial resistance, allowing Li... + The flux is uniform, and uniform Li nucleation is regulated. Therefore, the electrochemical performance of ASSLMB, which includes a LiAl layer, suppresses the initial lithium dendrite growth and achieves stable battery cycling.

[0082] Referring now to Figure 1, the battery pack 10 includes C cathode electrodes 20, A anode electrodes 40, and S spacers 32 arranged in a predetermined order within the battery pack stack 12, where C, S, and A are integers greater than zero. In some instances, the vehicle 11 includes a battery pack module or battery pack 13 comprising the battery pack 10. The battery pack stack 12 is arranged within a housing 50. The C cathode electrodes 20-1, 20-2, ..., 20-C include a cathode active material layer 24 on one or both sides of the cathode current collector 26. The A anode electrodes 40-1, 40-2, ..., 40-A include an anode active material layer 42 (including a LiAl layer and a lithium metal layer, as further described below) arranged on the anode current collector 46. In some instances, the LiAl layer is formed in situ by arranging an aluminum layer on the lithium metal layer. In other instances, the LiAl layer is formed prior to its arrangement adjacent to the lithium metal layer.

[0083] During charging / discharging, A anode electrodes 40 and C cathode electrodes 20 exchange lithium ions. In some instances, the cathode active material layer 24 includes a coating comprising one or more active materials applied to the current collector, a solid electrolyte (for solid and semi-solid battery packs), one or more conductive additives, and / or one or more binder materials.

[0084] In some instances, the cathode current collector 26 comprises metal foil, metal mesh, perforated metal, three-dimensional (3D) metal foam, and / or expanded metal. In some instances, the current collector is made of one or more materials selected from stainless steel, aluminum, and / or alloys thereof. External tabs 28 and 48 are connected to the current collectors of the cathode and anode electrodes, respectively, and may be arranged on the same side or different sides of the battery pack stack 12. External tabs 28 and 48 are connected to the terminals of the battery pack cells.

[0085] Referring now to Figure 2, an example of ASSLMB 100 is shown. The cathode electrode 120 includes a cathode active material layer 124 disposed on a cathode current collector 126. In some examples, the cathode active material layer 124 includes a cathode active material 162 and a solid electrolyte 164. In some examples, the cathode active material layer 124 also includes conductive fillers and / or binders.

[0086] The separator layer 132 (including solid electrolyte 164, conductive filler, and / or binder) is disposed adjacent to the cathode electrode 120. In some embodiments, the anode electrode 140 includes an in-situ lithiated aluminum layer to form a lithium aluminum (LiAl) layer 144 on the lithium metal layer 142. In other embodiments, the anode electrode 140 includes a lithium aluminum layer 144 formed prior to being disposed on the lithium metal layer 142.

[0087] An aluminum layer or a pre-formed lithium-aluminum layer 144 and a lithium metal layer 142 are disposed on an anode current collector 146 (e.g., a copper foil layer). If used, the aluminum layer (e.g., Al foil) spontaneously reacts in situ with the lithium metal layer 142 (e.g., Li foil) to form the lithium-aluminum layer 144. In some instances, the aluminum layer reacts with the lithium metal layer 142 at 25°C for 24 hours to form the lithium-aluminum layer 144 without any electrochemical treatment.

[0088] In some examples, the lithium-aluminum layer 144, after in-situ formation, contains 80.0% to 99.99% by weight (e.g., 99.7% LiAl) of LiAl. In some examples, the thickness of the lithium-aluminum layer 144 is 2 μm to 25 μm. In some examples, the thickness of the lithium-aluminum layer 144 is 5 μm to 10 μm. In some examples, the thickness of the lithium metal layer 142 is 20 μm to 50 μm. In some examples, the thickness of the lithium metal layer 142 is 25 μm to 35 μm.

[0089] Referring now to Figure 3, the X-ray diffraction patterns of the aluminum foil before and after contact with the lithium foil are shown. The aluminum foil (α phase, face-centered cubic (fcc)) spontaneously transforms into LiAl (β phase, cubic), which can be confirmed by standard data on LiAl crystals from the Inorganic Crystal Structure Database (ICSD). Furthermore, the aluminum foil expands in a direction perpendicular to the electrode / electrolyte interface, which reduces physical defects at the interface and / or suppresses the formation of voids. Based on the above, the lithium-aluminum layer 144 suppresses lithium dendrite growth and / or maintains a stable interface for ASSLMB.

[0090] The lithium-aluminum layer 144 is lithium-philic, with a low interface energy to Li, which can reduce the interface resistance and allow Li to... + The flux is uniform, and uniform Li nucleation is regulated. The lithium-aluminum layer 144 also protects the lithium metal layer 142 from direct contact with the sulfide solid electrolyte (if used), which mitigates side reactions.

[0091] Referring now to Figures 4 and 5, the lithium-aluminum layer 144 can also be used in liquid-based battery packs and semi-solid-state lithium metal battery packs. In Figure 4, the liquid-based battery pack 300 includes a cathode electrode 320 having a cathode active material layer 124 and a cathode current collector 126. The cathode active material layer 124 includes a cathode active material 162, a liquid electrolyte 310, conductive fillers, and / or binders. The separator layer 332 includes a polymer-based separator layer (and liquid electrolyte 310). The anode electrode 140 includes a lithium-aluminum layer 144 (pre-formed or in-situ formed), a lithium metal layer 142, and an anode current collector 146.

[0092] In some instances, the liquid electrolyte 310 comprises one or more lithium salts dissolved in one or more organic solvents. In some instances, the concentration of the lithium salt is greater than 1 mole (M). In some instances, the one or more lithium salts are selected from lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium bis(trifluoromethane)sulfonylimide, lithium bis(fluorosulfonylimide), and combinations thereof. In some instances, the solvent is selected from alkyl carbonates, esters, γ-lactones, chain ethers, cyclic ethers, and / or combinations thereof.

[0093] Referring now to Figure 5, the semi-solid-state battery pack 400 includes a cathode electrode 420, which includes a cathode active material layer 124 disposed on a cathode current collector 126. The cathode active material layer 124 includes a cathode active material 162, a solid electrolyte 164, a liquid electrolyte 310, a conductive filler, and / or a binder. The separator layer 432 includes a solid electrolyte, a conductive filler, and / or a binder (and the liquid electrolyte 310). The anode electrode 140 includes a lithium aluminum layer 144 (pre-formed or in-situ formed), a lithium metal layer 142, and an anode current collector 146.

[0094] Referring now to Figure 6A, another method for forming the anode electrode of a battery pack cell is shown. An aluminum layer 510 is coated with an anodic aluminum oxide (AAO) layer 514. The aluminum layer 510 and the anodic aluminum oxide layer 514 are laminated onto a lithium metal layer 520 to form a lithium aluminum layer 524. In some examples, the anodic aluminum oxide accounts for 0.01% to 10% by weight of the aluminum layer 510 and the anodic aluminum oxide layer 514.

[0095] Referring now to Figure 6B, another example of the ASSLMB 600 is shown. The cathode electrode 120 includes a cathode active material layer 124 disposed on a cathode current collector 126. The cathode active material layer 124 includes a cathode active material 162, a solid electrolyte 164, conductive fillers, and / or binders. An insulating layer 132 (including the solid electrolyte 164, conductive fillers, and / or binders) is disposed adjacent to the cathode electrode 120. The anode electrode 540 includes a lithium aluminum layer 524, a lithium metal layer 520, and an anode current collector 146.

[0096] In some instances, the cathode electrode is prepared using a wet coating process, a dry film process, a dry powder coating process, and / or other suitable processes. In some instances, the cathode active material layer comprises 30% to 98% by weight of cathode active material, 1% to 50% by weight of solid electrolyte, 1% to 30% by weight of conductive filler, and / or 0.1% to 10% by weight of binder.

[0097] In some instances, the cathode active material includes layered oxides (e.g., LiMeO2), olivine-type oxides (e.g., LiFePO4), monoclinic oxides (e.g., Li3Me2(PO4)3), spinel-type oxides (e.g., LiMe2O4), lithium iron phosphate (e.g., LiFeSO4F and / or LiFePO4F), wherein Me is a transition metal (e.g., Co, Ni, Mn, Fe, Al, V or combinations thereof), sulfur, Li2S, or combinations thereof. In some instances, the cathode active material includes coatings (e.g., LiNbO3 and Li3PO4).

[0098] In some instances, the adhesive is selected from polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), nitrile rubber (NBR), styrene-ethylene-butene-styrene copolymer (SEBS), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polyethylene oxide (PEO), polyacrylonitrile (PAN), polyacrylic acid (PAA), styrene-butadiene-styrene copolymer (SBS), and combinations thereof.

[0099] In some instances, the solid electrolytes in Figures 2, 5, and 6B are selected from pseudo-binary sulfides, pseudo-ternary sulfides, pseudo-quaternary sulfides, oxide-based solid electrolytes, metal-doped or heterovalent oxides, nitride-based solid electrolytes, halide-based solid electrolytes, hydride-based solid electrolytes, borate-based solid electrolytes, and combinations thereof.

[0100] Examples of pseudo-binary sulfides include the Li2S-P2S5 system (Li3PS4, Li7P3S) 11 and Li 9.6 P3S 12 The following systems are also mentioned: Li2S-SnS2 (Li4SnS4), Li2S-SiS2, Li2S-GeS2, Li2S-B2S3, Li2S-Ga2S3, Li2S-P2S3, and Li2S-Al2S3.

[0101] Examples of pseudo-ternary sulfides include the Li₂O-Li₂S-P₂S₅ system, the Li₂S-P₂S₅-P₂O₅ system, the Li₂S-P₂S₅-GeS₂ system, and (Li 3.25 Ge 0.25 P 0.75 S4 and Li 10 GeP2S 12), Li2S-P2S5-LiX system (where X = F, Cl, Br, I), (Li6PS5Br, Li6PS5Cl, Li7P2S8I and Li4PS4I), Li2S-As2S5-SnS2 system, (Li 3.833 Sn 0.833 As 0.166 The following systems were mentioned: Li₂S-P₂S₅-Al₂S₃, Li₂S-Liₓ-SiS₂ (where X = F, Cl, Br, I), 0.4LiI-0.6Li₄SnS₄, and Li₂S₃. 11 Si2PS 12 Examples of pseudo-quaternary sulfides include the Li₂O-Li₂S-P₂S₅-P₂O₅ system, Li… 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 Li7P 2.9 Mn 0.1 S 10.7 I 0.3 and Li 10.35 [Sn 0.27 Si 1.08 ]P 1.65 S 12 .

[0102] Examples of halide-based sulfide electrolytes include Li3YCl6, Li3InCl6, Li3YBr6, LiI, and Li2CdC. 14 Li2MgC 14 Li2Cd 14 Li2Zn 14 And Li3OCl. Examples of hydride-based sulfide electrolytes include LiBH4, LiBH4-LiX (X = Cl, Br or I), LiNH2, Li2NH, LiBH4-1iNH2 and Li3AIH6.

[0103] Examples of oxide-based solid electrolytes include garnet-type electrolytes (e.g., Li7La3Zr2O). 12 ), perovskite type (e.g., Li), 3x La 2 / 3-x TiO3), NASICON type (e.g., Li) 1.4 Al 0.4 Ti 1.6 (PO4)3 and Li 1+x Al x Ge 2-x (PO4)3), LISICON type (e.g., Li 2+2x Zn 1-x GeO4).

[0104] Examples of metal-doped or anisovalently substituted oxide solid electrolytes include Al, Nb, or Sb-doped Li7La3Zr2O 12 Ga-substituted Li7La3Zr2O 12 LiSn2P3O substituted with Cr and V 12 Al-substituted perovskites, Li 1+x+ y Al x Ti 2-x Si y P 3-y O 12 Examples of nitride-based solid electrolytes include Li3N, Li7PN4, and LiSi2N3. Examples of borate-based solid electrolytes include Li2B4O7 and Li2O-B2O3-P2O5.

[0105] In some instances, the separator layer 132 comprises 20% to 100% by weight of a solid electrolyte, 0% to 30% by weight of a filler, and 0% to 20% by weight of a binder. In some instances, the filler for the separator layer 132 is selected from oxide particles (e.g., SiO2, Al2O3, TiO2, and ZrO2), polymer backbones (e.g., polypropylene (PP), polyethylene (PE), lithium salts (e.g., LiTFSI, LiBF4), and combinations thereof.

[0106] In some examples, the adhesive material is selected from polyvinylidene fluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), nitrile rubber (NBR), styrene-ethylene-butene-styrene copolymer (SEBS), polyethylene oxide (PEO), polyvinylpyrrolidone (PVP), polyvinyl alcohol, polyacrylic acid (PAA), and combinations thereof. In some examples, the thickness of the spacer layer ranges from 5 μm to 200 μm.

[0107] In some instances, the separator layer of the liquid-based battery pack shown in Figure 4 has a porosity of 30% to 80%. In some instances, the porosity is 45% to 60%. In some instances, the separator layer comprises a material selected from polyolefins, cellulose, polyvinylidene fluoride (PVDF), porous polyimide, ceramic coating materials, and high-temperature stable polymer-based materials.

[0108] Examples of polyolefin spacers include polyacetylene, polypropylene (PP), polyethylene (PE), bilayer (PP-PE), and trilayer (PP-PS-PP). Examples of ceramic-coated spacers include SiO2-coated PE. Examples of high-temperature stable polymer-based spacers include nonwoven materials based on polyimide (Pl) nanofibers, nano-sized Al2O3 and poly(lithium 4-styrene sulfonate) coated polyethylene films, SiO2-coated polyethylene (PE), copolyimide-coated polyethylene, polyetherimide (PEI) spacers (e.g., bisphenol A-phthalic anhydride (BPADA) and p-phenylenediamine), foamed polytetrafluoroethylene reinforced polyvinylidene fluoride-hexafluoropropylene spacers, sandwich structure PVDF / PMIA / PVDF nanofiber spacers, and combinations thereof.

[0109] Referring now to Figures 7A through 7C, the performance of ASSLMB, comprising a solid electrolyte containing Li6PS5Cl and a cathode active material containing NCM721, is shown. In Figure 7A, ASSLMB without a LiAl layer is formed at 0.1C and 25°C and undergoes a short circuit. Figure 7B shows the voltage and specific capacity of ASSLMB with a LiAl layer during initial formation at 0.1C and 25°C. Figure 7C shows ASSLMB with a LiAl layer during cycling at 0.1C and 25°C. The in-situ formed LiAl layer provides protection by effectively suppressing initial lithium dendrite growth and achieving stable battery cycling at 0.1°C.

[0110] Referring now to Figures 8A through 8C, the performance of a liquid-based battery pack comprising a liquid electrolyte containing 1.2 M LiPF6 in carbonate, a polymer separator, and a cathode active material containing lithium iron phosphate (LFP) is shown. Figure 8A shows the voltage and specific capacity during initial formation of the battery pack at 0.05°C and 25°C with and without a LiAl layer at 710°C. Figure 8B shows the voltage and capacity during charge and discharge of the battery pack with and without a LiAl layer at 0.5°C and 25°C. Figure 8C shows the capacity retention of the battery pack with and without a LiAl layer during cycling at 0.5°C and 25°C as a function of cycle number. The in-situ formed LiAl layer improves the cycle stability of the liquid-based lithium metal battery pack at 0.5°C.

[0111] The foregoing description is merely exemplary and is in no way intended to limit this disclosure, its application, or its use. The broad teachings of this disclosure can be implemented in various forms. Therefore, although this disclosure includes specific examples, its true scope should not be limited thereto, as other modifications will become apparent upon examination of the drawings, specification, and the following claims. It should be understood that one or more steps within the method may be performed in a different order (or simultaneously) without altering the principles of this disclosure. Furthermore, although the embodiments are described above as having certain features, any one or more features described with respect to any embodiment of this disclosure may be implemented in any other embodiment and / or combined with features of any other embodiment, even if such combination is not explicitly described. In other words, the embodiments are not mutually exclusive, and substitution of one or more embodiments for each other remains within the scope of this disclosure.

Claims

1. A battery pack comprising: C cathode electrodes, each of the C cathode electrodes including a layer of cathode active material disposed on a cathode current collector; S isolation components; and A anode electrodes, wherein A, C, and S are integers greater than 1, wherein each of the A anode electrodes includes an anode active material layer disposed on an anode current collector, and wherein the anode active material layer includes a lithium metal layer and a lithium aluminum layer disposed on the separator side of the lithium metal layer.

2. The battery pack according to claim 1, wherein, The lithium-aluminum layer is formed in situ by arranging an aluminum layer adjacent to the lithium metal layer to form the lithium-aluminum layer.

3. The battery pack according to claim 1, wherein: The lithium-aluminum layer comprises 80.0% to 99.99% by weight of lithium-aluminum, the thickness of the lithium-aluminum layer is 2 μm to 25 μm, and the thickness of the lithium metal layer is 20 μm to 50 μm.

4. The battery pack according to claim 1, wherein: The cathode active material layer includes a cathode active material and a solid electrolyte; the S isolation components include a solid electrolyte.

5. The battery pack according to claim 4, wherein the cathode active material is selected from layered oxides, olivine oxides, monoclinic oxides, spinel oxides, lithium phosphite, sulfur, Li2S, and combinations thereof.

6. The battery pack according to claim 5, wherein the cathode active material comprises a coating selected from LiNbO3, Li3PO4, and combinations thereof.

7. The battery pack according to claim 4, wherein the solid electrolyte is selected from pseudo-binary sulfides, pseudo-ternary sulfides, pseudo-quaternary sulfides, oxide-based solid electrolytes, metal-doped or heterovalent oxides, nitride-based solid electrolytes, halide-based solid electrolytes, hydride-based solid electrolytes, borate-based solid electrolytes, and combinations thereof.

8. The battery pack according to claim 1, wherein: The battery pack includes a liquid-based battery pack, and the S separators include polymer-based separator layers.

9. The battery pack according to claim 8, further comprising a liquid electrolyte, said liquid electrolyte comprising one or more lithium salts and one or more solvents.

10. The battery pack according to claim 9, wherein the one or more lithium salts are selected from lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium bis(trifluoromethane)sulfonylimide, lithium bis(fluorosulfonyl)imide, and combinations thereof.

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