Anodeless solid state battery and method of manufacturing a battery

Abstract

An anode-free solid state battery includes a cathode layer containing transient anode elements and a bare current collector that does not contain non-transient anode material and is configured to receive transient anode elements thereon. The battery also includes a solid state electrolyte layer defining a void and disposed between the current collector and the cathode layer. The battery additionally includes a gel within the solid state electrolyte and within the cathode layer to saturate the electrolyte void and form a gelled solid state electrolyte layer, a coated cathode layer, and facilitate ionic conduction of anode elements between the cathode layer, the solid state electrolyte layer, and the current collector. Charging the battery causes anode elements to diffuse from the cathode layer onto the current collector via the gelled solid state electrolyte layer. Discharging the battery returns anode elements to the cathode layer via the gelled solid state electrolyte layer. The anode-free solid state battery is manufactured using a particular method.

Description

Technical Field

[0001] This invention relates to anode-free solid-state battery packs and methods for manufacturing such battery packs. Background Technology

[0002] This disclosure relates to an anode-free solid-state battery pack and a method for manufacturing the battery pack.

[0003] Electrochemical energy storage devices, such as lithium-ion battery packs, can be used to power a variety of items, including toys, consumer electronics, and motor vehicles. Typically, a battery pack includes two electrodes, an electrolyte assembly, and / or a separator. One of the two electrodes usually acts as the positive electrode or cathode, while the other acts as the negative electrode or anode. Such battery packs may also include various terminals and packaging materials. Electrochemical battery packs can be broadly classified into primary battery packs and secondary battery packs. Primary battery packs, also known as disposable battery packs, are intended to be used until their charge is depleted, after which they can be easily replaced with a new battery pack. Secondary battery packs, often called rechargeable battery packs, employ specific chemical compositions that allow such battery packs to be repeatedly charged and reused, thus offering advantages in terms of economy, environmental friendliness, and ease of use compared to disposable battery packs.

[0004] Rechargeable battery packs can be in solid, liquid, or solid-liquid hybrid form. A separator and / or electrolyte can be disposed between the negative and positive electrodes. The electrolyte, used to conduct lithium ions between the electrodes, and similar to the electrodes, can be in solid, liquid, or solid-liquid hybrid form. In the case of a solid-state battery pack, it includes a solid electrolyte layer disposed between solid electrodes, which physically separates the solid electrodes, eliminating the need for separate separators. Specifically, rechargeable lithium-ion battery packs operate by reversibly transferring lithium ions back and forth between the negative and positive electrodes. For example, during charging of the battery pack, lithium ions can move from the positive electrode to the negative electrode and in the opposite direction during discharging.

[0005] Compared to battery packs using liquid electrolytes, solid-state battery packs typically offer advantages such as longer storage life, lower self-discharge rates, simpler packaging and thermal management, and the ability to operate over a wider temperature window. For example, solid-state electrolytes are generally non-volatile and non-flammable, allowing such batteries to cycle under more demanding conditions without potential degradation or thermal runaway. However, solid-state battery packs generally have lower power capacity and limited energy density compared to battery packs using liquid electrolytes. Summary of the Invention

[0006] Anode-free solid-state battery packs include a cathode layer having a matrix cathode material comprising transient anolyte elements. The anode-free solid-state battery pack also includes an exposed current collector characterized by the absence of non-transient anolyte material and configured to receive transient anolyte elements thereon during battery pack charging. The battery pack further includes a solid electrolyte layer defining voids and disposed between the exposed current collector and the cathode layer. The battery pack also includes a gel located within each of the solid electrolyte layer and the cathode layer. The gel thus disposed is configured to impregnate the voids in the solid electrolyte layer to form a gelled solid electrolyte layer, coat the matrix cathode material, and facilitate ion conduction of anolyte elements between the cathode layer, the solid electrolyte layer, and the exposed current collector. Charging of the battery pack involves extracting anolyte elements from the cathode layer, diffusing the anolyte elements via the gelled solid electrolyte layer, and depositing the anolyte elements onto the exposed current collector to form transient anolyte material. Discharging of the battery pack returns the anolyte elements from the current collector to the cathode layer via the gelled solid electrolyte layer.

[0007] The anode-free solid-state battery pack of this topic can be a lithium-ion battery pack and can include multiple bipolar stacked battery cells, such that each internal cathode layer is arranged adjacent to an internal current collector.

[0008] The exposed current collector may be an outer current collector arranged on the outer battery pack and configured as a single layer of copper foil.

[0009] The exposed current collector may be part of an intermediate current collector arranged between individual battery cells and configured as a clad foil having a copper layer and an aluminum layer, such that the aluminum layer is arranged between the copper layer and the cathode layer.

[0010] The battery pack may also include polymer blocker elements configured to encapsulate and seal the gel and solid electrolyte within the battery pack.

[0011] The polymer barrier element may have a thickness of 2-200 micrometers. The material of the polymer barrier element may include at least one of hot melt adhesive, polyethylene resin or polypropylene resin, silicone (e.g., polyamide or epoxy resin), and acrylic resin or acrylic rubber, isocyanate adhesive, acrylic adhesive or cyanoacrylate adhesive.

[0012] In a lithium-ion battery pack, the matrix cathode material may include at least one of olivine, multi-anion cathode, lithium transition metal oxide (e.g., rock salt layered oxide, spinel), cathode material with surface coated and / or doped with lithium transition metal oxide, and low-voltage cathode material (e.g., lithium metal oxide / sulfide or lithium sulfide).

[0013] The cathode layer material may additionally include a conductive additive having at least one of carbon black, graphite, graphene, graphene oxide, acetylene black, and carbon nanofibers / nanotubes.

[0014] The matrix cathode material and / or the solid electrolyte layer may additionally include an adhesive material having at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), styrene rubber (SBR), nitrile rubber (NBR), and styrene-ethylene-butadiene-styrene copolymer (SEBS).

[0015] The gel may comprise polymeric constituent materials and a liquid electrolyte. A method for manufacturing an anode-free solid-state battery pack (e.g., a lithium-ion battery pack) is also disclosed. Specifically, the method includes arranging a solid electrolyte layer and a cathode layer adjacent to each other, wherein the solid electrolyte layer defines voids and is combined with a gel precursor containing a solvent. The method further includes forming a gel within the solid electrolyte layer and the cathode layer to thereby form a gelled solid electrolyte layer and coating the matrix cathode material. The method additionally includes arranging an exposed current collector against the gelled solid electrolyte layer, the exposed current collector being characterized by being free of non-transient anode material and configured to receive transient anode elements thereon during battery pack charging.

[0016] The present invention discloses the following technical solutions:

[0017] 1. An anode-free solid-state battery pack, comprising:

[0018] The cathode layer has a matrix cathode material containing transient anodic elements;

[0019] An exposed current collector, characterized in that it does not contain non-transient anode material and is configured to receive the transient anode element thereon during battery pack charging;

[0020] A solid electrolyte layer, defining a void and disposed between the current collector and the cathode layer; and

[0021] A gel, located within each of the solid electrolyte and the cathode layer, is configured to permeate the voids in the solid electrolyte layer to form a gelled solid electrolyte layer, coat the matrix cathode material, and promote ion conduction of the anodic element between the cathode layer, the solid electrolyte layer, and the exposed current collector.

[0022] in:

[0023] The charging of the battery pack involves extracting the anode element from the cathode layer, diffusing the anode element through the gelled solid electrolyte layer, and reversibly depositing the anode element onto the exposed current collector to form a transient anode material; and

[0024] The discharge of the battery pack returns the anode element from the current collector to the cathode layer via the gelled solid electrolyte layer.

[0025] 2. The anode-free solid-state battery pack according to technical solution 1, wherein the anode-free solid-state battery pack comprises a plurality of bipolar stacked battery cells.

[0026] 3. The anode-free solid-state battery pack according to technical solution 2, wherein the exposed current collector is an outer current collector arranged on the outer battery pack cells and configured as a single layer of copper foil.

[0027] 4. The anode-free solid-state battery pack according to technical solution 2, wherein the exposed current collector is part of an intermediate current collector, the intermediate current collector is arranged between individual battery cells and configured as a cladding foil having a copper layer and an aluminum layer, such that the aluminum layer is arranged between the copper layer and the cathode layer.

[0028] 5. The anode-free solid-state battery pack according to technical solution 1, further comprising a polymer barrier element configured to encapsulate and seal the gel and the solid electrolyte within the battery pack.

[0029] 6. The anode-free solid-state battery pack according to technical solution 5, wherein the material of the polymer blocking element includes at least one of hot melt adhesive, polyethylene resin or polypropylene resin, silicone, and acrylic resin or acrylic rubber, isocyanate adhesive, acrylic adhesive or cyanoacrylate adhesive.

[0030] 7. The anode-free solid-state battery pack according to technical solution 1, wherein the anode-free solid-state battery pack is a lithium-ion battery pack, wherein the matrix cathode material includes at least one of olivine, multi-anion cathode, lithium transition metal oxide, cathode material with surface coated and / or doped with lithium transition metal oxide, and low-pressure lithiated metal oxide / sulfide or lithium sulfide.

[0031] 8. The anode-free solid-state battery pack according to technical solution 7, wherein the material of the cathode layer further includes a conductive additive having at least one of carbon black, graphite, graphene, graphene oxide, acetylene black and carbon nanofibers / nanotubes.

[0032] 9. The anode-free solid-state battery pack according to technical solution 1, wherein at least one of the matrix cathode material and the solid electrolyte layer further comprises an adhesive material having at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), styrene rubber (SBR), nitrile rubber (NBR), and styrene-ethylene-butene-styrene copolymer (SEBS).

[0033] 10. The anode-free solid-state battery pack according to technical solution 1, wherein the gel comprises a polymeric material and a liquid electrolyte.

[0034] 11. A method for manufacturing an anode-free solid-state battery pack, the method comprising:

[0035] Arrange the following layers adjacent to each other:

[0036] A solid electrolyte layer defining voids and combined with a gel precursor containing a solvent, such that the gel precursor permeates the voids; and

[0037] The cathode layer has a matrix cathode material containing transient anodic elements;

[0038] A gel is formed within the solid electrolyte layer and the cathode layer to thereby form a gelled solid electrolyte layer and coat the matrix cathode material; and

[0039] An exposed current collector is disposed against the gelled solid electrolyte layer, the exposed current collector being characterized by being free of non-transient anode material and being configured to receive the transient anode element thereon during battery charging, wherein the gel thus formed promotes ion conduction of the anode element between the cathode layer, the solid electrolyte layer and the exposed current collector;

[0040] Make:

[0041] The charging of the battery pack involves extracting the anode element from the cathode layer, diffusing the anode element through the gelled solid electrolyte layer, and reversibly depositing the anode element onto the exposed current collector to form a transient anode material; and

[0042] The discharge of the battery pack returns the anode element from the current collector to the cathode layer via the gelled solid electrolyte layer.

[0043] 12. The method according to technical solution 11, wherein stacking the exposed current collector, the cathode layer and the solid electrolyte relative to each other comprises constructing a battery pack of multiple bipolar stacks.

[0044] 13. The method according to technical solution 12 further includes arranging the exposed current collector on the outer battery pack cell, wherein the exposed current collector is an outer current collector configured as a single layer of copper foil.

[0045] 14. The method according to technical solution 12, further comprising arranging the exposed current collector between individual battery cells, wherein the exposed current collector is part of an intermediate current collector configured as having a cladding foil having a copper layer and an aluminum layer, further comprising arranging the intermediate current collector such that the aluminum layer is disposed between the copper layer and the cathode layer.

[0046] 15. The method according to technical solution 11 further includes arranging polymer barrier elements to encapsulate and seal the gel and the solid electrolyte within the battery pack.

[0047] 16. The method according to technical solution 15, wherein the material of the polymer blocking element includes at least one of hot melt adhesive, polyethylene resin or polypropylene resin, silicone, and acrylic resin or acrylic rubber, isocyanate adhesive, acrylic adhesive or cyanoacrylate adhesive.

[0048] 17. The method according to technical solution 11, wherein the anode-free solid-state battery pack is a lithium-ion battery pack, wherein the matrix cathode material includes at least one of olivine, multi-anion cathode, lithium transition metal oxide, cathode material with surface coated and / or doped with lithium transition metal oxide, and low-pressure lithiated metal oxide / sulfide or lithium sulfide.

[0049] 18. The method according to claim 17, wherein the material of the cathode layer further includes a conductive additive having at least one of carbon black, graphite, graphene, graphene oxide, acetylene black, and carbon nanofibers / nanotubes.

[0050] 19. The method according to technical solution 11, wherein at least one of the matrix cathode material and the solid electrolyte layer further comprises an adhesive material having at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), styrene rubber (SBR), nitrile rubber (NBR), and styrene-ethylene-butene-styrene copolymer (SEBS).

[0051] 20. The method according to claim 11, wherein the formed gel comprises a polymeric constituent material and a liquid electrolyte, the method further comprising loading a gel precursor having the polymeric constituent material, the liquid electrolyte and a solvent onto the solid electrolyte before arranging the solid electrolyte and the cathode layer adjacent to each other, and wherein forming the gel comprises evaporating the solvent from the gel precursor after the solid electrolyte and the cathode layer have been arranged adjacent to each other.

[0052] The foregoing features and advantages, as well as other features and advantages, of this disclosure will readily become apparent when taken in conjunction with the accompanying drawings and the appended claims, by the following detailed description of one or more embodiments and one or more preferred modes of implementing the disclosure. Attached Figure Description

[0053] Figure 1 This is a schematic diagram of an energy storage battery for powering a load according to the present disclosure. The energy storage battery is shown as a lithium-ion (Li-ion) battery pack having an exposed current collector, a cathode layer, and a gelled solid electrolyte layer.

[0054] Figure 2A yes Figure 1 The schematic diagram of the energy storage battery shown depicts a solid electrolyte layer directly coated on the cathode layer.

[0055] Figure 2B yes Figure 1 The schematic diagram of the energy storage battery shown depicts a solid electrolyte layer directly coated on the exposed current collector.

[0056] Figure 3 yes Figure 1 The diagram shows a schematic perspective view of a battery pack module embodiment, which has a plurality of batteries having a structure according to this disclosure.

[0057] Figure 4 Based on this disclosure Figure 3 The schematic perspective view of the battery pack module shown illustrates the charging and discharging of the battery pack cells.

[0058] Figure 5 Based on this disclosure Figure 3 The schematic diagram of the battery pack module shown includes polymer barrier elements configured to encapsulate and seal gel and solid electrolyte layers within a single battery pack cell.

[0059] Figure 6 Illustrated manufacturing Figure 1-6 The method for an anode-free solid-state battery pack (e.g., a lithium-ion battery pack) is shown. Detailed Implementation Plan

[0060] Reference Figure 1 The image depicts an energy storage battery pack 10 supplying power to a load device 12. This energy storage battery pack 10 is shown as an anode-free solid-state battery pack. The description "anode-free" herein is intended to mean an electrochemical battery pack characterized by the absence of a permanent anode material, having an anode material deposited thereon during manufacturing. The anode-free battery pack of this subject is configured such that current cannot be received by or supplied through the battery pack before initial charging and the corresponding formation of the anode. The description "solid-state" herein is intended to mean an electrochemical battery pack employing an electrolyte in a non-liquid form. The anode-free solid-state battery pack 10 may specifically be a lithium-ion (Li-ion) battery pack.

[0061] Typically, Li-ion battery packs are rechargeable electrochemical battery packs known for their high specific energy and low self-discharge. Li-ion battery packs can be used to power a variety of items such as toys, consumer electronics, and motor vehicles. Vehicles in this context can include, but are not limited to, commercial vehicles, industrial vehicles, passenger vehicles, aircraft, boats, trains, etc. It is also considered that the vehicles can be mobile platforms, such as airplanes, all-terrain vehicles (ATVs), boats, personal mobility devices, robots, etc., to achieve the purposes of this disclosure. Typically, in a Li-ion battery pack, lithium ions move from the anode (negative electrode) through the electrolyte to the cathode (positive electrode) during discharge and return during charging.

[0062] Typically, the reactants in the electrochemical reactions within a battery pack are the anode and cathode materials. Li-ion battery packs typically use lithium compounds as the material at the positive electrode and graphite at the negative electrode. During discharge, the oxidation half-reaction at the anode produces positively charged lithium ions and negatively charged electrons. The oxidation half-reaction can also produce uncharged material that remains at the anode. Lithium ions move through the electrolyte, and electrons move through external circuitry (including connections to electrical loads or charging devices), then recombine at the cathode (along with the cathode material) in the reduction half-reaction. The electrolyte and external circuitry provide the conductive medium for lithium ions and electrons, respectively, but do not participate in the electrochemical reactions.

[0063] In an electrochemical battery pack, such as battery pack 10, during discharge, electrons flow from the anode to the cathode via an external circuit. Reactions during discharge lower the chemical potential of the battery pack, thus transferring energy from the battery to any point where current consumes its energy, primarily in the external circuit. During charging, the aforementioned reactions and transport occur in the opposite direction: electrons move from the positive electrode to the negative electrode via the external circuit. To charge the battery, the external circuit must provide electrical energy. This energy is then stored in the battery as chemical energy (with some loss). In a typical Li-ion battery pack, both the anode and cathode allow lithium ions to move into and out of their structures via processes called insertion (intercalation) and extraction (deintercalation), respectively.

[0064] Figure 1 The battery pack 10 shown herein, assembled with “bare” current collector 14, is specifically defined as excluding non-transient or permanent anode materials, i.e., characterized by the absence of non-transient or permanent anode materials, such as graphite in a Li-ion battery pack. For example, for corrosion resistance of the subject matter materials, the bare current collector 14 may be made of copper, graphene, or carbon-coated copper foil. Alternatively, the bare current collector 14 may be made of nickel, stainless steel, or other conductive materials inert to reduction reactions, and specifically non-reactive to lithium in a Li-ion battery pack. The battery pack 10 also includes a cathode layer 16 having a matrix cathode material 18 (e.g., LiFePO4) which includes a transient anode element 18A, such as lithium ions. The bare current collector 14 is configured to receive transient anode elements (e.g., lithium ions in a Li-ion battery pack) contained on the cathode layer 16 during battery pack charging, thereby forming a transient anode.

[0065] The battery pack 10 also includes a high-temperature stable, i.e., thermally stable solid electrolyte layer 20. The solid electrolyte layer 20 includes solid electrolyte particles 20A, which may be, for example, oxide-based. Figure 1 As shown, the cathode layer 16 may further include solid electrolyte particles 20A. Furthermore, the solid electrolyte layer 20 defines voids 22. The cathode layer 16 is in direct contact with the solid electrolyte layer 20. To enhance the structural integrity of the solid electrolyte layer 20, the solid electrolyte layer 20 may include an adhesive material employing at least one of the following: polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), styrene rubber (SBR), nitrile rubber (NBR), and styrene-ethylene-butene-styrene copolymer (SEBS) solid electrolyte.

[0066] The battery pack 10 additionally includes a gel 24 located within each of the solid electrolyte layer 20 and the cathode layer 16. Specifically, in the fully assembled battery pack 10, the gel 24 may be located and dispersed between and therein the solid electrolyte particles 20A and the matrix cathode material 18 in the cathode layer 16, and similarly located in the solid electrolyte layer 20 to facilitate ion conduction between the cathode layer 16 and the solid electrolyte layer 20. The gel 24 may additionally be applied directly to the cathode layer 16 (e.g., ...). Figure 2A (as shown) to coat the matrix cathode material 18, and / or to be directly applied to the exposed current collector 14 (as shown) Figure 2B (As shown) to enhance the ion conduction of the anode element 18A. Gel 24 can be formed from a gel precursor solution having a polymer matrix or constituent material, a liquid electrolyte, and a solvent configured to dissolve the polymer matrix. The polymer matrix material, liquid electrolyte, and solvent may constitute 0.1-50% by weight, 5-90% by weight, and 10-80% by weight, respectively, of the gel precursor solution. Evaporation of the solvent is intended to form gel 24 in situ within the battery pack 10. The solvent can be efficiently evaporated from the gel precursor by drying the prefabricated battery pack structure at room temperature (25 degrees Celsius) or above for 30 minutes to 24 hours. The gel precursor can be loaded into the structure of the battery pack 10, for example, by coating the cathode layer 16 and / or the exposed current collector 14 by drop coating, spraying, or dip coating.

[0067] The gel 24 is selected to withstand the operating temperature of the battery pack 10 and is configured to permeate the voids 22 in the solid electrolyte layer 20, thereby forming a gelled solid electrolyte layer 26. The in-situ formed gel 24 is intended to wet the interface between the oxide electrolytes to establish good ion contact, thereby promoting ion conduction within the gelled solid electrolyte layer 26 and reducing the likelihood of shunt current in the battery pack. The proportion of gel 24 in the battery pack 10 can be up to 50% by weight. Various types of gel 24 can be used. Different gels 24 can be used to coat the cathode layer 16 and the exposed current collector 14 in the same battery pack 10.

[0068] like Figure 4 As shown, charging the battery pack 10 removes and extracts the anode element 18A (e.g., lithium) from the cathode layer 16. Furthermore, charging the battery pack 10 causes the anode element 18A to diffuse via a gelled solid electrolyte layer 26 to deposit and build the anode element onto the exposed current collector 14 via plating. Plating the anode element 18A onto the exposed current collector 14 in this way forms a temporary and transient, reversible in-situ battery pack anode. Therefore, after the battery pack is put into use, charging the battery pack 10 generates an anode. Discharging the battery pack 10 strips the in-situ formed anode element 18A from the current collector 14, and the anode element returns to the cathode layer 16 via the gelled solid electrolyte layer 26 (e.g., lithium). Figure 4 (as shown in the image).

[0069] Typically, the effectiveness of the anode active material in embedding energy particles directly affects the performance of the battery pack. For example, in a typical Li-ion battery pack, the ability of the active material to hold lithium directly affects the energy density and cycle capacity of the battery pack. The in-situ formation of the anode material on the current collector 14 is specifically intended to provide the battery pack 10 with higher performance, namely, increased energy density. The use of the solid electrolyte layer 20 is further intended to improve the battery pack's tolerance to harsh conditions such as overheating, foreign object penetration, and internal and external short circuits. In addition, assembling the battery pack 10 without a pre-fabricated anode can reduce the complexity and cost of the battery pack.

[0070] like Figure 3-5 As shown, the battery pack 10 can be configured as a battery pack module having multiple bipolar stacked battery cells 10-1, 10-2, and 10-3, i.e., the negative electrode is connected to the positive electrode, thereby allowing the cells to be connected in series. Although three cells 10-1, 10-2, and 10-3 are specifically shown assembled in the battery pack module 10, this does not preclude the use of fewer or more cells in the module. Therefore, by using a solid electrolyte layer 26 in the battery pack module 10, the output voltage and power of the module can be constructed simply and efficiently via the bipolar stacking of individual cells. Thus, such a battery pack module 10 can employ an appropriate number of individual cells stacked together to produce a 48-volt output, as required in some automotive applications. The battery pack module 10 can be encapsulated in a housing or enclosure 28, which is configured to maintain a unidirectional pressure P, for example, a pressure along the X-axis via panel 28A, of 10-5,000 kPa (e.g., Figure 3 (As shown in the diagram). The uniaxial pressure P of this topic is intended to enhance the consistent cycle performance of battery pack cells, such as cells 10⁻¹, 10⁻², and 10⁻³.

[0071] like Figure 4 As shown, individual battery cells 10-1, 10-2, and 10-3 include corresponding current collectors 14-1, 14-2, and 14-3, and cathode layers 16-1, 16-2, and 16-3. Figure 3In the battery module 10 shown, the current collector 14-1 is an outer or edge current collector disposed on the outer battery cell 10-1. The outer current collector 14-1 can then be configured as a single layer of copper foil. Furthermore, as shown, the inner or intermediate cathode layers 16-1 and 16-2, i.e., the cathode layers located inside the battery module 10, can be disposed directly adjacent to the corresponding inner current collectors 14-2 and 14-3. Each of the intermediate cathode layers 16-1 and 16-2 can be specifically configured as a cladding foil having a copper layer 30 (operating as an exposed current collector or electrode) and an aluminum layer 32 (operating as a cathode electrode or substrate), such that the aluminum layer is disposed between the copper layer and the corresponding cathode layers 16-1, 16-2, 16-3. In the cladding foil embodiment of the cathode layers 16-1, 16-2, 16-3, the copper layer 30 is intended to shield and protect the corresponding aluminum layer 32 from interference from the corresponding solid electrolyte layer 26.

[0072] like Figure 5 As further shown, the battery module 10 may further include individual blocking elements 34 configured to hermetically seal the respective batteries 10-1, 10-2, and 10-3, thereby reducing the possibility of ion short circuits between them. The blocking elements 34 are arranged along the sides of the respective batteries 10-1, 10-2, and 10-3. Furthermore, the blocking elements 34 may be configured to adhere to the respective cladding foil to encapsulate and seal the gel 24 and the solid electrolyte layer 20 within their respective individual batteries 10-1, 10-2, and 10-3. The blocking elements 34 may have a thickness of 2-200 micrometers. The blocking elements 34 may be made of a suitable chemically stable and liquid-impermeable material, such as a polymer. The materials of the blocking elements 34 may specifically include hot melt adhesives, polyethylene resins or polypropylene resins, silicones (polyamides or epoxy resins), acrylic resins or acrylic rubbers, isocyanate adhesives, and / or acrylic adhesives or cyanoacrylate adhesives.

[0073] The cathode layer 16, solid electrolyte layer 20, and gel 24 can be enhanced in effectiveness by using specially selected materials. For example, in an embodiment where the anode-free solid-state battery pack 10 is a Li-ion battery pack, the matrix cathode material 18 of the cathode layer 16 may include one or more of olivine, multi-anion cathodes, and lithium transition metal oxide (e.g., rock salt layered oxide, spinel) active materials. Furthermore, the cathode layer 16 may have a cathode material surface-coated thereon and / or doped with lithium transition metal oxides and / or low-voltage cathode materials (e.g., lithium metal oxide / sulfide or lithium sulfide). The material of the cathode layer 16 may additionally include additives, such as mixing with at least one of carbon black, graphite, graphene, graphene oxide, acetylene black, and carbon nanofibers / nanotubes, to enhance the conductivity of the cathode.

[0074] For example, the cathode layer 16 may include solid electrolyte particles 20A, the materials of which are, for example: Li7La3Zr2O 12 , Li 6.2 Ga 0.3 La 2.95 Rb 0.05 Zr2O 12 , Li 6.85 La 2.9 Ca 0.1 Zr 1.75 Nb 0.25 O 12 , Li 6.25 Al 0.25 La3Zr2O 12 , Li 6.75 La3Zr 1.75 Nb 0.25 O 12 , Li 6.75 La3Zr 1.75 Nb 0.25 O 12 , Li 2+2x Zn 1-x GeO4 (where 0 < x < 1), Li 14 Zn(GeO4)4, Li 3+x (P 1−x Si x )O4 (where 0 < x < 1), Li 3+x Ge x V 1-x O4 (where 0 < x < 1), LiMMʹ(PO4)3 (where M and Mʹ are independently selected from Al, Ge, Ti, Sn, Hf, Zr, and La), Li 3.3 La 0.53 TiO3, LiSr 1.65 Zr 1.3 Ta 1.7 , Li 2x-y Sr 1- x Ta y Zr 1-y O3 (where x = 0.75y and 0.60 < y < 0.75), Li 3 / 8 Sr 7 / 16 Nb 3 / 4 Zr 1 / 4 , Li 3x La (2 / 3-x) TiO3 (where 0 < x < 0.25), aluminum (Al) or niobium (Nb) doped Li7La3Zr2O 12 , antimony (Sb) doped Li7La3Zr2O 12, Gallium (Ga)-doped Li7La3Zr2O 12 , Chromium (Cr) and / or vanadium (V)-substituted LiSn2P3O 12 , Aluminum (Al)-substituted Li 1+x+y Al x Ti 2-x Si Y P 3-y O 12 (where 0 < x < 2 and 0 < y < 3), Li2S-P2S5 system, Li2S-P2S5-MO x system (where 1 < x < 7), Li2S-P2S5-MS x system (where 1 < x < 7), Li 10 GeP2S 12 (LGPS), Li6PS5X (where X is Cl, Br or I) (lithium thiogermanate), Li7P2S8I, Li 10.35 Ge 1.35 P 1.65 S 12 , Li 3.25 Ge 0.25 P 0.75 S4 (thio-LISICON), Li 10 SnP2S 12 , Li 10 SiP2S 12 , Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 , (1 - x)P2S5 - xLi2S (where 0.5 ≤ x ≤ 0.7), Li 3.4 Si 0.4 P 0.6 S4, PLi 10 GeP2S 11.7 O 0.3 , Li 9.6 P3S 12 , Li7P3S 11 , Li9P3S9O3, Li 10.35 Ge 1.35 P 1.63 S 12 , Li 9.81 Sn 0.81 P 2.19 S 12 , Li 10 (Si 0.5 Ge 0.5 )P2S 12 , Li 10 (Ge0.5 Sn 0.5 P2S 12 Li 10 (Si 0.5 Sn 0.5 P2S 12 Li 3.833 Sn 0.833 As 0.16 S4, LiI-Li4SnS4, Li4SnS4, Li3N, Li7PN4, LiSi2N3, LiBH4, LiBH4-LiX (where x=Cl, Br or I), LiNH2, Li2NH, LiBH4-LiNH2, Li3AlH6, LiI, Li3InCl6, Li2CdC l4 Li2MgCl4, LiCdI4, Li2ZnI4, Li3OCl, Li2B4O7, Li2O-B2O3-P2O5 and their combinations.

[0075] Figure 6 The text describes the fabrication of anode-free solid-state battery packs, as shown in the reference. Figure 1-5 Method 100 of the battery pack 10 is described below and is disclosed in detail. Method 100 begins at block 102, where electrodes of the battery pack 10 are provided. Thus, in block 102, the method includes providing a composite cathode layer 16 by applying a matrix cathode material 18, such as LiFePO4 (which contains a transient anodic element 18A (e.g., lithium ions)), to a substrate (e.g., cladding foils 30, 32). After block 102, the method proceeds to block 104.

[0076] In block 104, the method includes arranging a solid electrolyte 20A and a gel precursor adjacent to the composite cathode layer 16. Specifically, in block 104, the method may include applying, for example, spreading or coating, a mixture of the solid electrolyte 20A and the gel precursor onto the composite cathode layer 16. Thus, the gel precursor impregnates the cathode layer 16 by filling voids 22 in the matrix cathode material 18 (and voids 22 in the solid electrolyte layer 20). The mixture of the solid electrolyte 20A and the gel precursor can be achieved by combining or blending these two components to achieve a generally homogeneous consistency. The solid electrolyte 20A may be provided as a granular material or a powder. The gel precursor may comprise a polymeric component material and a gel precursor solution having a liquid electrolyte, a polymeric matrix, and a solvent, each distributed in weight percent of the gel. The solvent is specifically included in the gel precursor to subsequently dissolve the polymeric matrix.

[0077] Following box 104, the method proceeds to box 106. In box 106, the method includes forming a gel 24 within the solid electrolyte layer 20 and within each of the cathode layers 16. Forming the gel 24 may include evaporating a solvent from the gel precursor by drying the prefabricated structure of the battery pack 10 at room temperature (25 degrees Celsius) or higher for 30 minutes to 24 hours. By evaporating the solvent in this way, the gel 24 will form in the voids 22 of the cathode layer 16 and in the voids 22 of the solid electrolyte layer 20, thereby forming a gelled solid electrolyte layer 26. In box 106, solvent evaporation may be permitted, allowing the gel 24 to form in situ within the battery pack 10.

[0078] The method proceeds from block 106 to block 108, wherein the method includes arranging an exposed current collector 14 against the gelled solid electrolyte layer 26. (See reference...) Figure 1-5 As described, the in-situ formed gel 24 is configured to facilitate ion conduction of the anode element 18A through the gelled solid electrolyte layer 26 between the cathode layer, the solid electrolyte layer 20, and the exposed current collector 14. Specifically, charging of the battery pack 10 extracts the anode element 18A from the cathode layer 16, diffuses the anode element via the gelled solid electrolyte layer 26, and deposits the anode element onto the exposed current collector 14. Furthermore, discharging of the battery pack 10 returns the anode element 18A from the current collector 14 to the cathode layer 16 via the gelled solid electrolyte layer 26. Charging and discharging of the battery pack 10 are achieved through ion transfer of the anode material via the gel 24 and reversible in-situ formation of the anode material on the current collector 14. This method of generating a temporary anode on the current collector 14 is intended to provide a battery pack 10 with high energy density and cycle capacity.

[0079] Following block 108, the method may continue to block 110. In block 110, the method may include arranging the polymer barrier element 34 within the battery pack 10. (See reference...) Figure 1-5 As described above, the polymer barrier element 34 is configured to adhere to each of the cathode layer 16 and the exposed current collector 14 to encapsulate and seal the gel 24 and the solid electrolyte layer 20 within the respective battery pack cells. The material of the polymer barrier element 34 may specifically include one or more adhesives for efficiently sealing individual cells, such as cells 10-1, 10-2, and 10-3 in the battery pack module embodiment of battery pack 10.

[0080] Following block 110, the method can proceed to block 112. In block 112, the method may include assembling battery packs 10 (e.g., battery pack cells 10-1, 10-2, 10-3 having bipolar stacks) as battery pack modules within housing 28. Furthermore, in block 112, battery packs 10 may be assembled to enhance the cycle life of the respective battery pack cells by maintaining uniaxial pressure thereon, for example, via panel 28A. Assembling the battery pack 10 modules may include arranging exposed current collectors 14-1 on the outer battery pack cells. The outer current collectors 14-1 may be configured as a single layer of copper foil. Furthermore, such copper foil may be part of each intermediate current collector 14-2, 14-3. Specifically, as referenced... Figure 4 The construction of the battery pack 10 module may include arranging intermediate current collectors 14-2, 14-3, each configured as a cladding foil having a copper layer 30 and an aluminum layer 32, such that the aluminum layer 32 is disposed between the copper layer 30 and the solid electrolyte layer 20 of the corresponding battery pack cells 10-1, 10-2, 10-3. In block 114, the method may end with the completion of the battery pack 10, which, for example, has a temporary and reversible battery pack anode generated on the exposed current collectors 14, for example by welding the battery pack module tabs into the housing 28.

[0081] Detailed descriptions and drawings are provided to support and illustrate this disclosure, but the scope of this disclosure is defined only by the claims. While some best modes and other embodiments for carrying out the claimed disclosure have been described in detail, various alternative designs and embodiments exist for practicing the disclosure as defined in the appended claims. Furthermore, features of the embodiments shown in the drawings or the various embodiments mentioned in this specification are not necessarily to be construed as independent embodiments. Rather, each feature described in one embodiment can be combined with one or more other desired features from other embodiments, thereby producing other embodiments not described in words or with reference to the drawings. Therefore, such other embodiments still fall within the scope of the appended claims.

Claims

1. An anode-free solid-state battery pack, comprising: The cathode layer has a matrix cathode material containing transient anodic elements; An exposed current collector, characterized in that it does not contain non-transient anode material and is configured to receive the transient anode element thereon during battery pack charging; A solid electrolyte layer, defining a void and disposed between the current collector and the cathode layer; and A gel, located within each of the solid electrolyte and the cathode layer, is configured to permeate the voids in the solid electrolyte layer to form a gelled solid electrolyte layer, coat the matrix cathode material, and promote ion conduction of the anodic element between the cathode layer, the solid electrolyte layer, and the exposed current collector. in: The charging of the battery pack involves extracting the anode element from the cathode layer, diffusing the anode element through the gelled solid electrolyte layer, and reversibly depositing the anode element onto the exposed current collector to form a transient anode material; and The discharge of the battery pack returns the anode element from the current collector to the cathode layer via the gelled solid electrolyte layer.

2. The anode-free solid-state battery pack according to claim 1, wherein the anode-free solid-state battery pack comprises a plurality of bipolar stacked battery cells.

3. The anode-free solid-state battery pack according to claim 2, wherein the exposed current collector is an outer current collector disposed on the outer battery pack cells and configured as a single layer of copper foil.

4. The anode-free solid-state battery pack of claim 2, wherein the exposed current collector is part of an intermediate current collector arranged between individual battery cells and configured as a cladding foil having a copper layer and an aluminum layer, such that the aluminum layer is arranged between the copper layer and the cathode layer.

5. The anode-free solid-state battery pack of claim 1, further comprising a polymer barrier element configured to encapsulate and seal the gel and the solid electrolyte within the battery pack.

6. The anode-free solid-state battery pack according to claim 5, wherein the polymer blocking element is made of at least one of hot melt adhesive, polyethylene resin or polypropylene resin, silicone, and acrylic resin or acrylic rubber, isocyanate adhesive, acrylic adhesive or cyanoacrylate adhesive.

7. The anode-free solid-state battery pack according to claim 1, wherein the anode-free solid-state battery pack is a lithium-ion battery pack, wherein the matrix cathode material includes at least one of olivine, multi-anion cathode, lithium transition metal oxide, cathode material with surface coated and / or doped with lithium transition metal oxide, and low-pressure lithiated metal oxide / sulfide or lithium sulfide.

8. The anode-free solid-state battery pack of claim 7, wherein the material of the cathode layer further comprises a conductive additive having at least one of carbon black, graphite, graphene, graphene oxide, acetylene black, and carbon nanofibers / nanotubes.

9. The anode-free solid-state battery pack of claim 1, wherein at least one of the matrix cathode material and the solid electrolyte layer further comprises an adhesive material having at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), styrene rubber (SBR), nitrile rubber (NBR), and styrene-ethylene-butene-styrene copolymer (SEBS).

10. The anode-free solid-state battery pack of claim 1, wherein the gel comprises a polymeric material and a liquid electrolyte.

11. A method for manufacturing an anode-free solid-state battery pack, the method comprising: Arrange the following layers adjacent to each other: A solid electrolyte layer that defines voids and is combined with a gel precursor containing a solvent, such that the gel precursor permeates the voids; and The cathode layer has a matrix cathode material containing transient anodic elements; A gel is formed within the solid electrolyte layer and the cathode layer to form a gelled solid electrolyte layer and coat the matrix cathode material. as well as An exposed current collector is disposed against the gelled solid electrolyte layer, the exposed current collector being characterized by being free of non-transient anode material and being configured to receive the transient anode element thereon during battery charging, wherein the gel thus formed promotes ion conduction of the anode element between the cathode layer, the solid electrolyte layer and the exposed current collector; Make: The charging of the battery pack involves extracting the anode element from the cathode layer, diffusing the anode element through the gelled solid electrolyte layer, and reversibly depositing the anode element onto the exposed current collector to form a transient anode material; and The discharge of the battery pack returns the anode element from the current collector to the cathode layer via the gelled solid electrolyte layer.

12. The method of claim 11, wherein stacking the exposed current collector, the cathode layer and the solid electrolyte relative to each other comprises constructing a battery pack of multiple bipolar stacks.

13. The method of claim 12, further comprising arranging the exposed current collector on an outer battery pack cell, wherein the exposed current collector is an outer current collector configured as a single layer of copper foil.

14. The method of claim 12, further comprising arranging the exposed current collector between individual battery cells, wherein the exposed current collector is part of an intermediate current collector configured to have a cladding foil having a copper layer and an aluminum layer, further comprising arranging the intermediate current collector such that the aluminum layer is disposed between the copper layer and the cathode layer.

15. The method of claim 11, further comprising arranging polymer barrier elements to encapsulate and seal the gel and the solid electrolyte within the battery pack.

16. The method of claim 15, wherein the material of the polymer blocking element comprises at least one of hot melt adhesive, polyethylene resin or polypropylene resin, silicone, and acrylic resin or acrylic rubber, isocyanate adhesive, acrylic adhesive or cyanoacrylate adhesive.

17. The method of claim 11, wherein the anode-free solid-state battery pack is a lithium-ion battery pack, wherein the matrix cathode material comprises at least one of olivine, multi-anion cathode, lithium transition metal oxide, cathode material coated and / or doped with lithium transition metal oxide, and low-pressure lithiated metal oxide / sulfide or lithium sulfide.

18. The method of claim 17, wherein the material of the cathode layer further comprises a conductive additive having at least one of carbon black, graphite, graphene, graphene oxide, acetylene black, and carbon nanofibers / nanotubes.

19. The method of claim 11, wherein at least one of the matrix cathode material and the solid electrolyte layer further comprises an adhesive material having at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), styrene rubber (SBR), nitrile rubber (NBR), and styrene-ethylene-butene-styrene copolymer (SEBS).

20. The method of claim 11, wherein the formed gel comprises a polymeric constituent material and a liquid electrolyte, the method further comprising loading a gel precursor having the polymeric constituent material, the liquid electrolyte, and a solvent onto the solid electrolyte prior to arranging the solid electrolyte and the cathode layer adjacent to each other, and wherein forming the gel comprises evaporating the solvent from the gel precursor after the solid electrolyte and the cathode layer have been arranged adjacent to each other.

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