Electrolytes with dual function salt additives

Abstract

The present disclosure relates to an electrolyte product (1) formed as a solid or semi-solid layer comprising a polymer-based matrix having dispersed therein a predetermined amount of an electrolyte salt composition (4) and a predetermined amount of an additional salt composition (5). The disclosure further relates to methods of making battery cell products, battery cell products including the electrolyte product, and battery products comprising a plurality of battery cell products.

Description

[Technical Field]

[0001] The present disclosure relates to electrolyte products, particularly solid or at least semi-solid products, that include a polymer-based matrix dispersed therein, a quantity of an electrolyte salt composition including an anode metal cation, and a quantity of an additive metal salt composition configured to form a mixed metal alloy layer with the anode metal and a solid electrolyte interface (SEI) layer upon participating in a redox reaction. The disclosure also relates to methods of making battery cell products, battery cell products including the electrolyte products, and battery products comprising a plurality of battery cell products. [Background technology]

[0002] Lithium (Li) metal has a high theoretical specific capacity (3860 mAh g -1 Due to its high reactivity and low reduction potential (-3.04 V vs. the standard hydrogen electrode), it is considered an important anode material for next-generation rechargeable batteries. However, dendritic Li formation, uncontrolled interfacial reactions, and large volume changes may actually cause performance issues such as low coulombic efficiency and therefore short cycle life.

[0003] Engineering an artificial solid electrolyte interfacial (SEI) film on a Li metal electrode shows great potential to solve the above-mentioned problems and enable long-life Li metal batteries (LMBs).

[0004] Some attempts to provide a mixed metal layer to reduce Li metal reactivity or a protective solid electrolyte interfacial layer are known in the art. Z. Zeng et al. (Journal of Power Sources, 451, 227730, 2020) disclose the use of zinc bis(2-ethylhexanoate) as an additive to form solid-state lithium batteries. The additive is reported to enable the formation of a LiZn alloy layer and / or provide a plasticizing effect.

[0005] Chinese Patent No. 107665966 relates to a lithium-sulfur battery. The battery includes a multilayer composite separator and a liquid electrolyte composition. The electrolyte reportedly contains one or more of various lithium salts, including lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) as an additive, which reportedly contributes to improving the activity decline of the lithium anode, improving its stability, and reducing dendrite formation.

[0006] However, particularly for solid-state or semi-solid-state batteries, there remains a need to improve one or more of the battery's safety, stability, and lifetime, while at least maintaining and preferably improving battery performance in terms of one or more of overall capacity and / or power density. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Chinese Patent No. 107665966 [Non-patent literature]

[0008] [Non-Patent Document 1] Z. Zeng et al., Journal of Power Sources, 451, 227730, 2020 Summary of the Invention

[0009] According to one aspect of the present invention, an electrolyte product is provided, which, as will become apparent from the present specification, can be used to particular advantage as a component of and / or in the manufacture of battery cell products and battery products comprising said cell products.

[0010] The electrolyte product is typically formed as a solid or semi-solid (e.g., gel) layer containing a polymer matrix. The electrolyte product further includes a predetermined amount of an electrolyte salt composition. The electrolyte salt is dispersed in the polymer matrix. The electrolyte salt contains cations M of the appropriate anode active metal composition. I and weakly coordinating balance anion X I Due to their relatively high redox potentials, preferred compositions include one or more cations of alkali metals and / or alkaline earth metals, preferably selected from the group consisting of Na, K, Li, Mg, and Cs.

[0011] The electrolyte product further comprises, at least initially prior to cycling the battery, a predetermined amount of an additional salt composition. As will become apparent from this specification, the amount of additional salt may be advantageously consumed, at least in part, by, for example, reaction with the anode metal (e.g., deposited or plated anode metal), typically during the initial metal deposition or plating procedure. As will become apparent from this specification, reaction of the additional salt advantageously produces a reaction product that significantly improves battery characteristics, including, but not limited to, performance, safety, and / or operational life.

[0012] The additional salt composition may contain a further metal (the further metal being the first anode active metal M I (different from II and one or more balancing anions X II The balance ion is a weakly coordinating balance anion X I can be the same as X, but the balance ions are I It is highly preferred that it is different from

[0013] Further metal ions include M I The ions X are selected to have a higher (less negative) reduction potential so that, upon contact with the anode metal, the additional metal ions are reduced to the metallic state. This then intermixes with the subsequently provided, e.g., deposited or plated, anode metal to form a mixed metal layer. At the same time, the ions XII is the anode metal (M I The additional salt compositions are selected to preferentially participate in the SEI-forming redox reaction upon contact with the lithium ion battery (Li-ion battery), and ...

[0014] The inventors have found that the electrode product, when incorporated into a battery cell stack, advantageously provides for the in situ and in operando formation of a protective and battery-active hybrid layer adjacent, i.e., in close proximity, to the anode (e.g., Li metal anode) of the cell stack. The active protective hybrid layer, disposed between and interfacing the anode metal layer and the remainder of the electrolyte layer of the stack, achieves one or more of the following objectives: battery performance, safety, and / or operational life. As will become apparent from this specification, the in situ generation of a protective layer comprising a mixed metal layer and an SEI component provides multiple advantages that synergistically contribute to the objective of providing improved battery performance. For example, in addition to the reduced apparent surface reactivity of the anode metal provided by the mixed metal component and the ionic conductivity and stabilizing properties of the SEI component, the inventors have found that this combination provides a particularly favorable combination of interlayer adhesion and cycling stability. The SEI / mixed metal component can advantageously be formed in situ, e.g., during the first battery charging cycle. This advantageously reduces or even eliminates the need for dedicated deposition steps, such as a deposition step after anode metal deposition, which, due to the high sensitivity and reactivity of the anode metal (e.g., Li), may result in adverse reactions, such as contact with (trace amounts of) humidity, dinitrogen, or carbon dioxide (forming lithium nitride and lithium carbonate) or other contaminants.

[0015] Without wishing to be bound by theory, it is believed that the electrolyte salt (M I X I ) and added salt (M II XII It is believed that both the electrolyte salt and the additional salt composition may advantageously contribute to the formation of the protective hybrid layer. Portions of the electrolyte salt and the additional salt composition initially included in the electrolyte product may participate in respective redox reactions with the anode metal (e.g., metallic Li), for example, as a result of an initial anode metal deposition step or an initial battery cycling procedure.

[0016] The dual-functioning additive salt may be consumed upon reaction with the anode metal to form a mixed metal alloy layer and an SEI layer, both of which improve the cycle life of the battery.

[0017] In particular, electrolyte salts (M I X I ) and added salt (M II X II ) is an anode, e.g., a Li-containing anode, on which a mixed metal alloy layer, e.g., Li x (M II ) 1-x This allows the formation of a tunable additional buffer / reservoir layer during battery charge / discharge. The reservoir advantageously allows for the replenishment of anode metal fractions that are lost, e.g., due to deleterious side reactions, i.e., no longer participating in battery cycling. Furthermore, this layer forms an ion-conducting matrix membrane with excellent ionic conductivity with the matrix, and also improves metal smoothing and adhesion to the anode substrate, resulting in a more uniform charge / discharge profile throughout the functional battery layer stack. It will be appreciated that the metal salt additive combinations disclosed in connection with the present invention are unique in combining and maximizing the functionality of a single new type of additive dispersed in layers within a hybrid polymer-inorganic host matrix.

[0018] The anions contained in the electrolyte salt and / or the additional salt, preferably the balance anions X provided by the additional salt composition, II is involved in the SEI (solid electrolyte interface) formation reaction.

[0019] Unlike conventional electrolyte compositions in which the counter ion of the electrolyte salt is selected primarily based on its performance as an electrolyte, the present invention allows for the addition / selection of a reagent in the form of a dual-function additive, balance ion XII, based on its ability to participate in the formation of an SEI layer with relatively improved stability.

[0020] These additives are cations M, which are metals different from Li, such as In, Mg, Sn, Zn, and Cs. II , and anode metal ions (e.g., Li) through the electrolyte. + ) anion X that promotes diffusion and strengthens the chemical and structural stability of the layer (protective hybrid layer) II It may also be a salt with (for example, bis(fluorosulfonyl)imide (FSI), TFSI, a halide, a nitrate, ...).

[0021] A further aspect of the present invention relates to an electrolyte product, preferably as described above, in which the solid or semi-solid layers are arranged as a multilayer stack, whereby the additional salt composition is confined to, or at least predominantly contained in, the outer layer of the stack (i.e., the side that can contact the outside, such as the anode-side current collector or metal anode). Thus, an outer layer containing the additional dual-function salt can be assembled adjacent to the anode. Furthermore, by arranging the solid or semi-solid layers as a multilayer stack, the formation and hybridization of a multilayer polymer electrolyte, such as polyethylene oxide (PEO), can be divided into multiple portions, each of which may contain a distinct dual-function additional salt.

[0022] The electrolyte products described herein are preferably suitable for the manufacture of battery cell products, as they can be advantageously used for the in-situ generation of a protective layer on the anode of a battery cell, for example, during the first battery charging cycle.

[0023] For the same reason, the electrolyte product is preferably in a virgin state, meaning that it has not been subjected to any battery cycling when assembled into a battery product and used in a charging and depleting cycle.

[0024] In a preferred embodiment, M I is Li and M II is one or more metals of group 2 or group 12-15 elements, preferably an element selected from one or more of Zn, Cs, Mg, Al, Ga, In, Sn, Ca, Ge, Cs and / or Bi, and X II is or comprises a halide, preferably fluoride, and / or a polyatomic anion containing a central nitrogen atom. The listed Group 2 or Groups 12-15 elements have been found to be particularly advantageous for their affinity to alloy with metallic lithium, or at least form mixtures with it. Suitable anions include PF6, BF4, preferably FSI (bis(fluorosulfonyl)imide), TFSI (bis(trifluoromethane)sulfonimide), DFOB (difluoro(oxalato)borate), and more preferably nitrate (NO3 - Counterions are selected based on their ability to participate in the SEI formation reaction and stabilize the underlying electrode metal. SEI layers with relatively high nitrogen content, such as those obtained from nitrogen-containing counterions, can form particularly stable protective layers. Preferred examples of additional salts include Zn(FSI)2, MgF2, CaF2, and In(NO3)3.

[0025] X I It will be appreciated that X may be selected by one of skill in the art from known counterions from electrolyte salts. I is X II and X may be selected from the same list of compounds as I and X II are preferably not equal for reasons detailed herein.

[0026] The matrix can be selected from one or more compositions known in the art. Suitable materials include compositions selected from one or more of polyethers, polyfluorinated polymers, polyacrylates, polysiloxanes, and copolymers comprising one or more thereof. Exemplary materials include PEO, polyvinylidene fluoride (PVDF), poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP), poly(methyl methacrylate) (PMMA), and polydimethylsiloxane (PDMS).

[0027] In a preferred variation, the matrix contains 10 to 50 wt. % of the electrolyte salt composition, based on the total weight of the polymer matrix, electrolyte, and other additives. Higher concentrations improve the electrochemical stability of the electrolyte layer and result in longer cycle life. The upper limit is limited by practical considerations, such as the capacity of the matrix, and can be determined by those skilled in the art through routine experimentation.

[0028] In another or even more preferred embodiment, the matrix comprises 1 to 30 wt. % of the additional salt composition, based on the total weight of the polymer matrix, electrolyte, and additional salt. In addition to the usual considerations of electrolyte salt concentration in the electrolyte layer, providing a high salt concentration of the additional salt, in the range of 1 to 30 wt. %, preferably higher, e.g., 2 to 30 wt. %, more preferably 6 to 10 wt. %, based on the total weight of the polymer matrix, electrolyte, and additional salt, has the additional advantage of increasing the efficiency of alloy and SEI formation (e.g., during the initial charging routine). The reduced time to form the alloy / SEI layer, believed to be related to the relatively short diffusion path during layer formation, reduces the possibility of adverse side reactions, for example, during initial cycles. Advantageously, the higher the concentration of the electrolyte salt and additional salt, the more effective the alloy and stable SEI formation. In general, M I and M II are added in relative ratios ranging from 0.1 to 0.9 (molar fraction). In absolute terms, the total concentration of the main salt and additional salts is in the range of 0.1 to 8M.

[0029] In a particularly preferred variant, the electrolyte salt composition comprises four or more mutually different weakly coordinating balance anions (X I The present inventors have found that the inclusion of multiple electrolyte salt compositions having mutually different weakly coordinating balance anions can result in the formation of a particularly stable SEI layer, for example, in the early stages of battery cycling. I ) may be less than 4, for example 2 or 3, although it will be appreciated that the effect on SEI stability may be less beneficial.

[0030] It will be appreciated that the electrolyte product may include one or more additives known in the art, such as plasticizers (to improve ion mobility). For example, plasticizers such as succinonitrile may also be mixed into the (quasi-)solid electrolyte layer to counteract the brittleness and rigidity of the new inorganic interlayer components in the overall battery layer stack. Alternatively or additionally, the matrix may contain high-k dielectric particles (dielectric constant ε R ≧4, preferably ≧100) and / or inorganic particles such as Li-ion conducting materials including nanoparticles and / or fibers. Alternatively or additionally, the matrix may be provided with hollow compressible beads, e.g. hollow polymeric beads, to allow the product to adapt to stresses resulting from expansion / contraction processes during battery operation.

[0031] In a particularly preferred embodiment, the electrolyte product is arranged as a multi-layer stack, whereby the additional salt composition is confined to, or at least predominantly contained in, the outer layer of the stack. It will be understood that each layer is formed as a solid or semi-solid layer comprising the polymer-based matrix disclosed herein. Confining, or providing at least predominantly, the additional salt composition in the outer layer of the electrolyte product advantageously allows the layer, along with the added salt, to be positioned adjacent to the anode-side current collector of the battery stack. In other words, the multi-layer configuration allows the electrolyte product to be positioned along the face of the first current collector, whereby the outer layer of the stack faces the first current collector so that the dual-function salt is close to the current collector. This is advantageous for in situ generation of a protective layer on the anode of a battery cell product.

[0032] It will be understood that the electrolyte salt may be, but need not be, predominantly contained in the remaining layers. A further advantage of arranging the electrolyte product as a multilayer stack is that the polymeric material forming the matrix in each layer may be different. That is, the polymeric matrix in a layer carrying the additional salt composition, or at least a majority of the total amount, and / or one or more optional additives, may be selected independently from one or more of the remaining layers. Incorporating different polymers may be particularly advantageous in manufacturing. For example, if the electrolyte product is formed using a process involving multiple solution-based processes, the polymer in each layer may be selected so that the formed layer does not appreciably decompose or redissolve during subsequent solution processing steps. Alternatively or additionally, the polymer in the layer containing the additional salt may be selected to contain, for example, one or more balance anions X. II may be selected to contribute to and partially participate in the SEI formation reaction in combination with

[0033] The arrangement of the solid or semi-solid layers as a multilayer stack, in which the additional salt composition is confined to or at least predominantly contained in the outer layers of the stack, as described above, preferably also applies to the electrolyte product in its unused state, i.e., before any initial battery cycles to which the electrolyte product may be subjected, due to the advantages of such a multilayer stack arrangement in the in situ generation of a protective layer on the anode of a battery cell. If such a multilayer stack configuration is formed only during or after the electrolyte product has been subjected to battery cycles, these advantages of the multilayer stack configuration are absent, or at least less pronounced.

[0034] An optional anode metal receiving layer may be disposed between the electrolyte product and the first current collector. The receiving layer comprises a receiving material that sorbs and receives an alkali metal (e.g., lithium) and / or an alkaline earth metal (e.g., magnesium). The anode metal receiving layer may be suitably applied to one or more of the surfaces of the current collector and / or the outer surfaces of the electrolyte product (e.g., extending along the outer layers of the multilayer stack containing the dual function salt as described above). Anode receiving materials are known in the art and can be applied using known methods. Suitable lithium metal receiving materials include layers containing one or more of Si, Sn, and graphite.

[0035] In some embodiments, the first current collector comprises a plurality of aligned conductive pillar structures extending from a support surface of the first current collector and spaced apart by at least the electrolyte product.

[0036] According to a further aspect of the present invention, a method for manufacturing a battery cell product is provided. In a preferred embodiment, the product is a secondary (also called rechargeable) anode metal battery product, such as a secondary Li metal battery cell. The method includes at least the steps of providing an electrolyte product, providing first and second current collectors and a cathode composition, and forming a laminated assembly whereby the second current collector extends along a surface of the electrolyte product opposite the first current collector, and whereby the cathode composition extends between the electrolyte product and the second current collector.

[0037] The method may further include depositing a predetermined amount of alkali and / or alkaline earth metal between the first current collector and the electrolyte product. The metal is selected from the group consisting of Na, K, Li, Mg, and Cs. Advantageously, the predetermined amount of alkali and / or alkaline earth metal (e.g., lithium) can be provided by electroplating through an electrolyte product pre-assembled on the first current collector.

[0038] In one embodiment, electroplating is performed in situ (within the complete cell battery or cell stack) with the stacked assembly formed, whereby the inventory for electroplating is provided by the cathode composition.

[0039] Alternatively or additionally, electroplating can be performed in a separate step in a plating bath prior to providing the cathode composition (located in the partial stack with the second current collector), thereby providing inventory for electroplating via the bath. Performing plating as an external inventory prior to completing the cell stack can advantageously form a battery cell stack with an anode metal buffer as a plating layer. The plated anode metal can provide additional anode metal inventory in addition to the inventory provided by the cathode composition. This anode metal layer provides several advantages. In addition to the benefits associated with mixed metal layer formation and SEI formation, providing an anode metal layer acts as a buffer that can replenish lost anode metal during progressive battery cycling. Furthermore, the provided anode metal layer advantageously acts as a planarizing wetting layer for subsequently plated anode metal (e.g., lithium plated during initial battery charging).

[0040] According to a further aspect of the present invention, a battery cell product is provided. The battery cell product includes the electrolyte product disclosed herein. In a preferred embodiment, the electrolyte product is formed as a laminated assembly described herein. The cell product further includes a first current collector, a second current collector, and a cathode composition, whereby the second current collector extends along a surface of the electrolyte product opposite the first current collector, and whereby the cathode composition extends between the electrolyte product and the second current collector.

[0041] In one embodiment, the battery cell product further includes an anode metal receiving layer disposed between the electrolyte product and the first current collector, the receiving layer including a receptor material that sorbs and receives an alkali metal and / or an alkaline earth metal, the receptor material including one or more of Si, Sn, and graphite.

[0042] The first current collector may include a plurality of aligned conductive pillar structures extending from a support surface of the first current collector and spaced apart by at least the electrolyte product.

[0043] In other or further embodiments, the second current collector comprises a plurality of aligned conductive pillar structures extending from the support surface of the second current collector and spaced apart by at least the cathode composition.

[0044] Both the first and second current collectors can be advantageously provided in the form of flexible films. The flexible film may comprise a flexible substrate (e.g., a plastic foil) provided with a conductive coating, e.g., a metal coating, along one or more sides. Alternatively, or additionally, the first and / or second current collectors can be provided as metal foils. The anode-side current collector (first current collector) preferably comprises copper (e.g., as a coating or Cu foil). Copper foil / coated flexible substrates are particularly suitable for Li-metal battery applications and / or can enable large-scale manufacturing processes, e.g., roll-to-roll manufacturing. Furthermore, copper-containing or copper-coated surfaces are known to be particularly suitable substrates for the formation of extended, aligned conductive pillar structures, e.g., by processes known in the art for the controlled growth of carbon nanotubes.

[0045] In accordance with one embodiment of the present invention, a battery cell product includes an anode layer comprising an alkali metal and / or alkaline earth metal selected from the group consisting of Na, K, Li, Mg, and Cs, the anode layer extending between a first current collector and a polymer-based matrix; a mixed-metal alloy layer extending between the anode layer and the electrolyte product; and an SEI layer extending between the mixed-metal alloy layer and the polymer-based matrix. The anode layer may be provided as an additional layer prior to an initial battery cycle stage (e.g., by electroplating from a separate plating bath or, in the case of Si or Sn, by other coating techniques). Alternatively, or additionally, the anode layer may be provided as a result of reduction products from an initial charge cycle.

[0046] It will be appreciated that the dual salt additive in the electrolyte product may be largely or completely consumed in providing the anode metal layer. Thus, in one embodiment, the mixed metal alloy layer comprises an alkali metal and / or alkaline earth metal and the M initially contained in the electrolyte product. II The SEI layer may also comprise a mixture of at least some, and optionally all, of the cations reduced with additional metals. Similarly, the SEI layer may comprise at least some of the X originally contained in the electrolyte product. II and the electrolyte product comprises at least a portion, optionally all, of the anion or its reaction products, II and / or X II and optionally the remainder of

[0047] It should be noted that a battery cell product can be distinguished from known cells, for example, by the presence of an electrolyte product within the multi-layer stacked arrangement layers, even when the cell is still in a virgin state, i.e., before any battery cycling.

[0048] According to yet a further aspect, a battery product is provided. The battery product includes one or more battery cell products. The battery product may include a cathode contact, an anode contact, and a battery housing. In some embodiments, the one or more battery cell products are disposed within a pouch.

[0049] In some embodiments, one or more battery cells are arranged in series and / or parallel depending on the desired potential output of the battery product.

[0050] These and other features, aspects, and advantages of the devices, systems, and methods of the present disclosure will become better understood from the following description, appended claims, and accompanying drawings. [Brief explanation of the drawings]

[0051] [Figure 1] FIG. 1 is a cross-sectional side view of an electrolyte product. [Figure 2] FIG. 1 is a cross-sectional side view of an electrolyte product. [Figure 3]FIG. 1 is a cross-sectional side view of an electrolyte product. [Figure 4] FIG. 1 is a cross-sectional side view of an electrolyte product. [Figure 5] FIG. 1 is a cross-sectional side view of an electrolyte product. [Figure 6] 1A-1C illustrate a method for manufacturing a battery cell product. [Figure 7A] 1A-1D are cross-sectional side views of a battery cell product during different manufacturing steps. [Figure 7B] 1A-1D are cross-sectional side views of a battery cell product during different manufacturing steps. [Figure 7C] 1A-1D are cross-sectional side views of a battery cell product during different manufacturing steps. [Figure 7D] 1A-1D are cross-sectional side views of a battery cell product during different manufacturing steps. [Figure 8] FIG. 2 is a cross-sectional side view of a battery cell product. [Figure 9A] FIG. 1 is a cross-sectional side view of a protective layer comprising a mixed metal alloy layer and an SEI layer. [Figure 9B] FIG. 1 is a cross-sectional side view of a protective layer comprising a mixed metal alloy layer and an SEI layer. [Figure 10] FIG. 1 is a cross-sectional side view of a battery assembly including a plurality of battery cell assemblies. DETAILED DESCRIPTION OF THE INVENTION

[0052] The terms used to describe particular embodiments are not intended to limit the invention. As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms unless the context clearly dictates otherwise. The term "and / or" includes any and all combinations of one or more of the associated listed items. It will be understood that the terms "comprising" and / or "comprising" specify the presence of the stated features but do not exclude the presence or addition of one or more other features. When a particular step of a method is recited after another step, it will be further understood that, unless otherwise specified, it may follow the other step directly, or that one or more intermediate steps may be performed before performing the particular step. Similarly, when a connection between structures or components is described, it will be understood that this connection may be established directly or through an intermediate structure or component, unless otherwise specified.

[0053] The term "non- or weakly coordinating anion" means that the anion does not form coordinate bonds with the metal in aqueous solution. An example of a non- or weakly coordinating anion is trifluoromethanesulfonate ([CF3SO3] - ), hexafluorophosphate ([PF6] - ), tetrafluoroborate ([BF4] - ), perchlorate ([ClO4] - ), tetrafluoroethylene ([OTeF5] - ), BArF([B(ArH x F y )4] - , where Ar is aryl and x+y=5, e.g., [B(C6F5)4] - ), tosylate ([CH3C6H4SO3] - ), FSI([(FSO2)2N] - ), and TFSI([CF3SO2)2N] - ) is included.

[0054] The present invention is described more fully hereinafter with reference to the accompanying drawings, in which embodiments of the invention are shown. In the drawings, absolute and relative sizes of systems, components, layers, and regions may be exaggerated for clarity. Embodiments may be described with reference to schematic and / or cross-sectional illustrations of potentially idealized embodiments and intermediate structures of the invention. In the specification and drawings, like numbers refer to like elements throughout. Relative terms and their derivatives should be construed to refer to the orientation as described or shown in the drawings under discussion. These relative terms are for convenience of description and do not require that the system be constructed or operated in a particular orientation, unless specifically specified.

[0055] Next, the electrode product 1 will be described in more detail with reference to FIGS.

[0056] The electrode product 1 is generally formed as a solid or semi-solid layer 2 comprising a polymeric matrix 3 having dispersed therein a predetermined amount of an electrolyte salt composition 4 and a predetermined amount of an additional salt composition 5, as shown, for example, in FIGS. 1, 2, 3, 4, and 5.

[0057] Solid or semi-solid should be interpreted as distinct from liquid electrolytes. Instead, solid or semi-solid includes materials and compositions that are in a solid or quasi-solid aggregate state (at room temperature). Solid or semi-solid also explicitly includes materials known as polymer electrolytes, such as dry polymer electrolytes, which differ from liquid electrolytes in that the salt additive is dissolved directly in the solid medium. Solid or semi-solid also explicitly includes so-called gel electrolytes, which can be understood as a liquid contained in a flexible lattice structure (polymer matrix). The polymer matrix forms a continuous phase that holds or supports more potentially liquid additives, such as an ionic liquid and / or one or more solvents. While similar to solids in some respects, such as the ability to support their own weight and retain their shape, quasi-solids also share some properties of liquids, such as the ability to conform to pressure. Additionally, solid or semi-solid electrolytes may contain one or more solids, such as ceramic particles.

[0058] The electrolyte salt composition 4 contains a cation M of an alkali metal and / or alkaline earth metal element selected from the group consisting of Na, K, Li, Mg, and Cs. I and a weakly coordinating balance anion X I The additional salt composition 5 comprises M I a cation M of a further metal having a higher reduction potential than II and X I Unlike M I One or more balancing anions X are selected to participate in the SEI-forming redox reaction with II The balance ion typically has a valence of minus one. The additional salt composition 5 is a salt composition in which the additional salt is in a metallic state (e.g., Li 0The protective layer 1020 serves the dual function of participating in a redox reaction with the anode element (e.g., Li(0)). The additional salt is at least partially consumed to form a protective layer including a mixed metal alloy phase and an SEI phase. The mixed metal alloy phase and SEI phase layers can advantageously form a structure, e.g., a two-layer structure, that mitigates adverse reactions with additional anode metal (e.g., Li), particularly during the fabrication / assembly of a closed battery cell assembly. Additionally, the protective layer functions as a homogenizing and wetting layer for subsequently deposited anode metal, e.g., during battery cycling, mitigating uneven anode metal plating / deplating, particularly during the initial battery cycling process. Figures 9A and 9B provide side cross-sectional views of a protective layer comprising a mixed metal alloy layer 1021 and an SEI layer 1022. Depending on the relative reactivity, process conditions, and / or directionality of anode metal (e.g., Li(0)) exposure onto the film, the protective layer 1020 can be characterized by a multi-layered structure. Typically, the protective layer is formed with a side A that faces the anode current collector 1025 and contains the majority of the alloy or mixed metal composition, and a side B that faces away from the anode current collector and comprises the majority of the SEI composition.

[0059] The thickness of the protective layer varies depending on the initial amount of additional salt added to the electrolyte product. The thickness is generally at least 0.5 μm and can extend up to several micrometers, typically up to 10 μm or less.

[0060] The anode metal ions supplied during the initial charging cycle migrate through the protective layer toward the collected anode current for plating to form the battery's active anode metal layer covered / protected by the protective layer. This allows both the mixed metal alloy layer and the SEI layer to help improve the cycle life of the battery.

[0061] In Figure 2, a solid or semi-solid layer 2 comprising a polymeric matrix 3 is shown disposed along a face 9f of an electrically conductive first current collector 9. As noted above, the first current collector may be a metal foil (e.g., copper foil) or a metal coating, such as a copper film, deposited on a carrier, preferably a flexible carrier, such as a polymer foil.

[0062] The solid or semi-solid layer 2 may comprise a block copolymer and / or a mixture of different polymers. Typically, the polymer matrix comprises one or more materials selected from the group consisting of polyvinylidene fluoride, polydimethylsiloxane, polyethylene oxide, polymethyl methacrylate, polyethylene diacrylate, polyacrylonitrile, hexafluoropropylene, and copolymers thereof. The average molecular weight (M W ) is typically between 10,000 and 1,000,000 g / mol. The polymer matrix provides a network that traps the filler while allowing the metal salts to diffuse as their ions between opposing faces of the solid or semi-solid layer 2.

[0063] Metal salts, such as Li salts [Li + -X I By dispersing [Chemical Formula 1] in a polymer matrix, an ion-conducting matrix membrane can be formed, with much better ion conductivity, as well as improved metal smoothing and adhesion to the substrate, e.g., Cu(Li) substrate.

[0064] In a further embodiment, the solid or semi-solid layer 2 is arranged as a multi-layer stack 6, for example, as shown in FIG. 3 . In such a multi-layer stack 6 configuration, the additional salt composition 5 is confined to, or at least predominantly contained in, an outer layer 7 of the stack 6. By confining the additional salt 5 to the outer layer 7 of the stack, the stack 6 may be disposed on a first current collector, which may be, for example, the anode, such that the dual-function additional salt composition is in proximity to the first current collector. The proximity of the additional salt to the first current collector or anode can advantageously improve the rate at which the alloy layer and SEI layer are formed.

[0065] It will be appreciated that in any or all of the layers included in the multilayer stack 6, one or more plasticizers, such as succinonitrile, may be incorporated into the solid or semi-solid layer 2. These plasticizers act to offset the brittleness and rigidity of components in the overall electrolyte product 1 and the battery cell product formed therefrom. It will also be appreciated that the solid or semi-solid layer 2 may include additional additives, including a predetermined amount of a liquid carrier, such as an ionic liquid and / or an organic solvent, or inorganic nanoparticles, including fibers, hollow compressible beads, and the like. The electrolyte product 1 may further include an inorganic solid electrolyte, such as LLZO (LiLaZrO), and / or other crystalline, glassy, ​​and / or glass-ceramic electrolytes, such as those reviewed in A.K. Mishra et al., Review—Inorganic Solid State Electrolytes: Insights on Current and Future Scope, J. Electrochem. Soc. 168, 080536 (2021), which is incorporated herein by reference.

[0066] In a preferred embodiment, the metal ion conducting inorganic composition comprises or consists essentially of a ceramic composition. Preferred compositions include lithium aluminum phosphate (LATP), lithium aluminum germanium phosphate (LAGP), lithium lanthanum zirconium oxide (LLZO), halogenated electrolytes (e.g., Li 3-x M 1-x Zr x Cl6M=Y, Er), sulfide electrolytes (e.g., Li10GeP2S12, Li6PS5X (X=Cl, Br or I), 67(75Li2S-25P2S5)-33LiBH4, 30Li2S-26B2S3-44LiI) or derivatives and / or mixtures thereof, lithium hydroborates including, but not limited to, closo-borate, closo-carborate and derivatives and / or mixtures thereof.

[0067] The layers of the multilayer stack 6 may be spaced apart with optional interfacial layers.

[0068] As shown in FIGS. 1, 2, 3 and 4, the electrolyte salt 4 is M I and X I Contains additional salt 5M II and X II In one embodiment, M I is Li and M II is one or more metals of Group 2 or Groups 12-15 elements, preferably an element selected from one or more of Zn, Cs, Mg, Al, Ga, In, Sn, Ca, Ge, Cs, and / or Bi. The balance ions and X II is a halide, preferably fluoride, or a polyatomic anion containing a central nitrogen atom, such as PF6, BF4, preferably FSI, TFSI, DFOB, more preferably nitrate. II The cations were chosen based on their suitability for forming alloys with Li. All of these elements have higher reduction potentials than lithium and are reduced to their metallic state upon redox reactions with Li(0). II The anions were specifically chosen based on their ability to participate in stable SEI-forming reactions.

[0069] In one embodiment, the matrix 3 comprises 0.1 to 10 wt. %, preferably 1 to 10 wt. %, of the additional salt composition 5, based on the total weight of the polymer matrix 3 and the electrolyte 4 and additional salt 5. By providing a higher concentration of the additional salt composition 5, more, possibly excess, M II and X IIThe provision of ions can advantageously result in more effective alloying and stable SEI layer formation. The thickness / amount of the mixed metal layer (alloy) can be appropriately adjusted by adjusting the amount of additional salt initially included in the electrolyte product, e.g., the layer 7 closest to the first current collector. Preferably, the mixed metal layer is a conformal layer having a thickness of 20 nm or more, preferably thicker, e.g., 50 nm or more, to reduce the number of potential point defects. The upper limit can be determined by the desired energy density range (Wh / unit volume) of the target battery cell. The higher the amount of additive metal (other than lithium), the lower the overall energy density of the resulting cell. Typically, the thickness of the mixed metal layer is 1 μm or less, preferably 500 nm or less, e.g., in the range of 100 to 400 nm. The concentration of additional salt in the electrolyte for a given layer thickness can be determined by routine experimentation.

[0070] In yet another embodiment of the present invention, the electrolyte salt composition 4 comprises four or more, preferably five or more, more preferably six or more, and most preferably seven or more weakly coordinating balance anions X that are different from one another. I Surprisingly, it has been found that the addition of a greater variety of weakly coordinating equilibrium anions further improves the life cycle of the battery cell product.

[0071] In one embodiment, matrix 3 comprises 5-50 wt %, preferably 10-50 wt %, of electrolyte salt composition 4, based on the total weight of polymer matrix 3, electrolyte 4, and additional salt 5. Higher concentrations of electrolyte salt composition improve the electrochemical stability of the electrolyte layer and extend the cycle life of the battery cell product. The upper limit is limited by practical considerations.

[0072] As shown in FIG. 3 , in some embodiments, the electrolyte product 1 is disposed along a face 9f of a first current collector 9, such that when the solid or semi-solid layers 2 are arranged as a multilayer stack 6, an outer layer 7 of said stack 6 faces the first current collector 9. A further layer 7f of the stack 6 faces outward from the first current collector 9. As previously mentioned, this arrangement ensures the proximity of the additional salt composition 5 to the first current collector 9, improving the rate at which the alloy and SEI layers are formed. As explained, the polymers forming the matrices 3-1, 3-2 of each layer of the stack 6 may be the same or may be different (selected independently). Generally speaking, the outer layer 7 of the stack (located closest, e.g., in direct contact with the anode-side current collector) contains the additional salt (M II X II ) and electrolyte salt (M I X I The additional layer 7f contains at least an electrolyte salt (M I X I Of course, one or more additional layers may contain a predetermined amount of the same or a further additional salt composition. In the case of a multilayer electrolyte product 1 that is clearly suitable for and configured to manufacture a Li-metal battery product, the electrolyte salt is a metal salt M I and a Li cation as a suitable weakly coordinating anion X as disclosed herein. I The additional salts may comprise or consist essentially of Li cations in combination with metal cations M other than Li that have high (less negative) reduction potentials as disclosed herein (e.g., FSI, TFSI, halides, nitrates, etc.). II and X I and a stabilizing anion selected to participate in the SEI-forming reactions disclosed herein.

[0073] As shown in FIG. 4 , an optional anode metal receiving layer 10 may be disposed between the electrolyte product 1 and the first current collector 9, and the receiving layer 10 includes a receptor material 11. The receptor material 11 is receptive to sorbing alkali metals and / or alkaline earth metals. In the case of a Li metal battery, the anode metal receiving layer may include one or more of Si, Sn, and graphite, each of which is known in the art for its ability as a Li-receptor composition. The receiving layer 10 can advantageously promote ion diffusion through the electrolyte product and / or battery cell product. The receiving layer 10 can sorb and distribute the anode metal, e.g., Li, therein, thereby reducing or preventing the formation of a "dead" zone of isolated, inert anode metal. Naturally, the receiving layer can be applied with corresponding effects to other embodiments disclosed herein, including, but not limited to, those described in connection with FIGS. 1 , 5 , and 8 .

[0074] In yet another embodiment, as shown in FIG. 5 , the first current collector 9 includes a plurality of aligned conductive pillar structures 12 extending from the support surface 9f of the first current collector 9 and spaced apart by at least the electrolyte product 1. The aligned conductive pillar structures 12 provide a three-dimensional structure for the current collector. The 3D structure increases the contact area between the first current collector 9 and at least the electrolyte product 1, thereby increasing the current flow between the components. The conductive pillar structures 12-1, 12-2 can be embodied as metal or metal-coated pillars. Alternatively or additionally, the conductive pillar structures 12-1, 12-2 can be embodied as carbon nanotubes or carbon nanotube structures.

[0075] It will be appreciated that an electrolyte product can be disposed between the cathode and anode to provide ion transport from the cathode side toward the anode side during the charge cycle of the battery, and vice versa during discharge.

[0076] According to a further aspect of the present invention, a method for manufacturing a battery cell product is provided, as shown in the flow diagram of FIG. 6. The method generally includes providing or manufacturing 301 an electrolyte product as disclosed herein. The electrolyte product can be suitably provided using one or more dry and / or wet processing methods, including, but not limited to, wet deposition of a solution (e.g., a curable monomer composition) containing a polymer matrix or its precursor, followed by drying of the composition. Suitable wet deposition methods include, but are not limited to, spray casting, spin coating, and / or dip coating. Solid additives, such as high-k dielectric particles, may be suitably added to the liquid, e.g., suspended. Salts, including electrolyte salts and additional salt compositions, may be added, e.g., dissolved, in the liquid. Alternatively or additionally, salts may be added, e.g., from a separate solution after deposition of an initial polymer layer, or injected as an ionic liquid. In the case of a multilayer stack 6 (e.g., as shown in FIG. 3), each stack of layers can be formed, for example, by depositing each layer on a previously deposited layer.

[0077] In a preferred embodiment, the electrolyte product can be provided directly on a current collector substrate (e.g., a first carrier substrate such as a Cu foil). Alternatively, the electrolyte product may be formed on a carrier substrate, e.g., a temporary carrier for later use. Thus, in one embodiment, a method includes providing an electrolyte product 101 in step 301, providing a first current collector 109 in step 302, providing a second current collector 114 in step 303, providing a cathode composition 115 in step 304, and forming a stacked assembly 116 (e.g., as shown in FIG. 7A ), whereby the second current collector 114 extends along a side of the electrolyte product 101 opposite the first current collector 109, and whereby the cathode composition 115 extends between the electrolyte product 101 and the second current collector 114. In one embodiment, forming the laminate assembly 116 includes adhering the electrolyte product 101 to a first current collector 109, for example, a metal current collector, for example, by coating or laminating the electrolyte product 101 onto the first current collector 109. In some embodiments, the current collector is an elongated metal foil or metal-coated polymer foil, for example, a copper foil.

[0078] Cathode compositions are known in the art. For lithium metal batteries, suitable compositions include, but are not limited to, "layered lithiated transition metal oxides" such as LiCoO2, preferably high-energy density cathode materials such as LMNC (LiNiCoMnzO2), LFP (LiFePO4), and oxides containing vanadium pentoxide, as well as polyanion-type materials. For exemplary positive electrode materials for lithium ion batteries, see the review by A.O. Soge et al., J. of New Materials for Electrochemical Systems, 24, 229 (2021), which is incorporated herein by reference.

[0079] In one embodiment, the laminate assembly 116 further comprises an optional anode metal receiving layer 110 provided in step 305 disposed between the electrolyte product 101 and the first current collector 109, the receiving layer 110 including a receiving material 111 that sorbs and receives an alkali metal and / or alkaline earth metal, the receiving material 111 including one or more of Si, Sn, and graphite. If the receiving layer 110 is used, forming the laminate assembly 116 includes adhering the electrolyte product 101 to the receiving layer 110, for example, by coating or laminating the electrolyte product 101 onto the receiving layer 110.

[0080] It will be understood that the steps do not necessarily have to be performed in the order shown, and components may be assembled or constructed together in any suitable order.

[0081] 7A-7C show a further embodiment, in which the method includes depositing a predetermined amount of an alkali metal and / or alkaline earth metal selected from the group consisting of Na, K, Li, Mg, and Cs between a first current collector 109 and an electrolyte product 101. The predetermined amount of alkali metal and / or alkaline earth metal is provided by electroplating 307a / 307b through an electrolyte product pre-assembled on the first current collector.

[0082] 7A illustrates an embodiment in which electroplating 307a is performed in situ using the formed stacked assembly 116, whereby inventory 124 for electroplating 307a is provided by cathode composition 115. In the illustrated embodiment, the anode metal (Li(s)) is sorbed by the optional silicon layer (Li-receiving layer 110).

[0083] FIG. 7B shows an alternative embodiment in which electroplating 307b is performed in a separate step prior to providing the cathode composition 115 and second current collector 114 in the plating bath 117, thereby providing inventory 124 for electroplating 307b with the bath 117.

[0084] 7C shows the battery cell product 100' in a virgin state. Such a battery cell product is considered to be in a virgin state immediately after completion of manufacturing steps including electroplating 307b of an anode metal from a cathode composition, but prior to initial or further plating.

[0085] Depending on the charge level, the amount of anode metal ions included in the cathode composition decreases from the initial inventory 124'. Figure 7D shows schematically the assembly of Figure 7C in a relatively more charged state, with the respective amounts of anode metal ions and anode metal included in the cathode / anode side of the stack represented by the change in thickness of the respective layers.

[0086] In a preferred embodiment, as shown by the process diagram of FIG. 6 , electroplating 307b is first performed in a separate step in plating bath 117 before providing cathode composition 115 and second current collector 114, whereby inventory 124 for electroplating 307b is provided by bath 117, and after providing cathode composition 115 and second current collector 114, a further electroplating step 307a is performed in situ using the formed stacked assembly 116, whereby further inventory 124′ for electroplating 307a is provided by cathode composition 115.

[0087] 8 , there is provided a battery cell product 1000 including an electrolyte product 1001 formed into a stacked assembly 1016 further including a first current collector 1009, a second current collector 1014, and a cathode composition 1015, whereby the second current collector 1014 extends along a side of the electrolyte product 1001 opposite the first current collector 1009, and whereby the cathode composition 1015 extends between the electrolyte product 1001 and the second current collector 1014. It will be understood that the first current collector 1009 can be provided on a support substrate 1025.

[0088] In one embodiment not shown, the battery cell product 1000 further comprises an anode metal receiving layer disposed between the electrolyte product 1001 and the first current collector 1009, the receiving layer 1010 comprising a receiving material that sorbs and receives alkali metals and / or alkaline earth metals, the receiving material comprising one or more of Si, Sn and graphite.

[0089] The first current collector 1009 may comprise a plurality of aligned conductive pillar structures extending from a support surface of the first current collector 1009 and spaced apart by at least the electrolyte product 1001 .

[0090] In another embodiment, the second current collector 1014 comprises a plurality of aligned conductive pillar structures extending from a support surface of the second current collector 1014 and spaced apart by at least the cathode composition 1015.

[0091] In yet another embodiment, both the first and second current collectors comprise a plurality of aligned conductive pillar structures extending from the support surface of the first / second current collector.

[0092] It will be appreciated that the second current collector 1014 may be provided along a carrier substrate. For example, like the first current collector, the second (cathode-side) current collector may be provided as a conductive coating (e.g., of a suitable metallic composition known in the art) provided along a flexible substrate such as a plastic foil.

[0093] 8 shows the battery cell product in a charged state after reaction of the additional salt composition, i.e., after formation of alloy layer 1021 and / or SEI layer 1022. In such an embodiment, battery cell product 1000 further includes an anode layer 1020 comprising an alkali metal and / or alkaline earth metal selected from the group consisting of Na, K, Li, Mg, and Cs. Note that the illustrated embodiment does not include an anode metal-receiving layer 1010, and thus the anode metal is formed as a mixed metal alloy layer 1021 with anode metal layer 1020 extending between first current collector 1009 and electrolyte product polymer-based matrix 1003.

[0094] In accordance with another aspect of the present invention, a battery product 2000 (FIG. 10) is provided. The illustrated embodiment includes a plurality of battery cell products 1000. The illustrated embodiment includes a total of five battery cell products 1000-1 through 1000-5 arranged in series. Of course, battery products may be provided in different numbers that can be arranged in various configurations, including parallel and series configurations and combinations thereof.

[0095] The multiple battery cell products may be arranged in any suitable form known in the art, including, but not limited to, a pouch type, a prismatic type, a button cell type, etc. The battery product may be arranged, for example, in a cylindrical cell format, and the battery product may be provided with a cathode side contact 2031 and an anode side contact 2032 that function as conductive surfaces between corresponding anode and cathode sides of the multiple battery cell products and the ambient environment. The battery product may further be provided with an insulating housing 2030 to protect the multiple battery cell products from the ambient environment.

[0096] Although for clarity and conciseness of description, features are described herein as part of the same or separate embodiments, it will be understood that the scope of the present invention may include embodiments having all or any combination of the described features.

[0097] When interpreting the appended claims, it should be understood that the word "comprising" does not exclude the presence of other elements or acts than those recited in a given claim; the words "a" or "an" preceding an element do not exclude the presence of a plurality of such elements; any reference signs in the claims do not limit their scope; several "means" may be represented by the same or different items or implemented structures or functions; any of the disclosed apparatuses or parts thereof may be combined together or separated into further parts unless otherwise specified. When a claim refers to another claim, this may indicate synergistic advantages achieved by the combination of their respective features. However, the mere fact that certain measures are recited in mutually different claims does not indicate that a combination of these measures cannot also be advantageously used. Thus, the present embodiments may include all actual combinations of claims, where each claim may in principle refer to any preceding claim, unless clearly excluded by the context. [Explanation of symbols]

[0098] 1 Electrode products, multilayer electrolyte products 2. Solid or semi-solid layer 3 Polymer matrix, polymer matrix 4. Electrolyte salt composition 5 Additional Salt Composition 6 Multi-layer stack 7 Outer layer 7f Further layers, additional layers 9 First current collector 9f Support surface of first current collector 9 10 Anode metal receiving layer 11 Receptor material 12 Conductive pillar structure 100% unused battery cell product 101 Electrolyte products 109 First current collector 110 Li-receptor layer, anode metal-receptor layer 111 Receptor Materials 114 Second current collector 115 Cathode Composition 116 Laminated Assembly 117 Plating bath 124 Inventory 124' Initial Inventory 307a Electroplating, Electroplating Step 307b Electroplating 1000 Battery Cell Products 1001 Electrolyte products 1003 Electrolyte Products Polymer Matrix 1009 First current collector 1010 Anode metal receiving layer 1014 Second current collector 1015 Cathode composition 1016 Stacked Assembly 1020 Protective layer, anode metal layer, anode layer 1021 mixed metal alloy layer 1022 SEI layer 1025 Anode current collector, supporting substrate 2000 battery products 2030 Insulation Housing 2031 Cathode contact 2032 Anode side contact

Claims

1. An electrolyte product (1) suitable for manufacturing a battery cell product, formed as a solid or semi-solid layer (2), comprising a polymer-based matrix (3) dispersed therein: Cations of alkali metals and / or alkaline earth metals selected from the group consisting of Na, K, Li, Mg and Cs (M I ) and a weakly coordinating balance anion (X I a predetermined amount of an electrolyte salt composition (4) having A predetermined amount of additional salt composition (5), said additional salt composition (5) comprising (M I cations of further metals (M II ) and (X I ), and one or more balancing anions (X) selected to participate in an SEI-forming redox reaction with said alkali metal and / or alkaline earth metal. II ), wherein the solid or semi-solid layers (2) are arranged as a multi-layer stack (6) such that the additional salt composition (5) is confined to, or at least predominantly contained in, an outer layer (7) of the stack (6); Electrolyte products, including (1).

2. The electrolyte product (1) according to claim 1, wherein the electrolyte product is in a virgin state.

3. M I is Li and M II is one or more metals of group 2 or group 12-15 elements, preferably an element selected from one or more of Zn, Cs, Mg, Al, Ga, In, Sn, Ca, Ge, Cs and / or Bi, and X II is a halide, preferably fluoride, or a polyatomic anion containing a central nitrogen atom, e.g., PF 6 , B.F. 4 Electrolyte product (1) according to claim 1 or 2, preferably FSI, TFSI, DFOB, more preferably nitrate.

4. 4. The electrolyte product (1) according to claim 1, wherein the matrix (3) comprises 1 to 30 wt. % of the additional salt composition (5), based on the total weight of the polymer matrix (3), the electrolyte (4) and the additional salt (5).

5. The electrolyte salt composition (4) contains four or more of the weakly coordinating balance anions (X I Electrolyte product (1) according to any one of claims 1 to 4, comprising:

6. 6. The electrolyte product (1) according to any one of claims 1 to 5, wherein the matrix (3) comprises 10 to 50 wt. % of the electrolyte salt composition (4), based on the total weight of the polymer matrix (3), the electrolyte (4), the additional salt (5) and further additives, if any.

7. 7. The electrolyte product (1) according to any one of claims 1 to 6, wherein the electrolyte product (1) is arranged along a face (9f) of a first current collector (9) so that the outer layer (7) of the multilayer stack (6) faces the first current collector (9).

8. 8. The electrolyte product (1) of claim 7, further comprising an anode metal receiving layer (10) disposed between the electrolyte product (1) and the first current collector (9), the receiving layer (10) including a receiving material (11) that sorbs and receives an alkali metal and / or an alkaline earth metal, the receiving material (11) including one or more of Si, Sn, Li, Mg, and graphite.

9. 9. The electrolyte product (1) of claim 7 or 8, wherein the first current collector (9) comprises a plurality of aligned conductive pillar structures (12) extending from a support surface (9f) of the first current collector (9) and spaced apart by at least the electrolyte product (1).

10. Electrolyte product (1) according to any one of claims 1 to 9, wherein the polymer-based matrices (3-1, 3-2) in each layer of the multilayer stack (6) comprise different polymers.

11. A method of manufacturing a battery cell product (100), the method comprising: Providing an electrolyte product (101) according to any one of claims 1 to 10; Providing a first current collector (109), a second current collector (114), and a cathode composition (115); forming a laminated assembly (116) whereby the second current collector (114) extends along a surface of the electrolyte product (101) opposite the first current collector (109), and whereby the cathode composition (115) extends between the electrolyte product (101) and the second current collector (114); A method comprising:

12. 12. The method of claim 11, wherein the stacked assembly (116) further comprises an anode metal receiving layer (110) disposed between the electrolyte product (101) and the first current collector (109), the receiving layer (110) comprising a receptor material (111) that sorbs and receives an alkali metal and / or an alkaline earth metal, the receptor material (111) comprising one or more of Si, Sn, Li, Mg, and graphite.

13. 13. The method of claim 11 or 12, further comprising the step of depositing a quantity of an alkali metal and / or alkaline earth metal selected from the group consisting of Na, K, Li, Mg and Cs between the first current collector (109) and the electrolyte product (101).

14. 14. The method of claim 13, wherein the predetermined amount of alkali metal and / or alkaline earth metal is provided by electroplating (307) through the electrolyte product (101) pre-assembled on the first current collector (109).

15. 15. The method of claim 14, wherein the electroplating (307a) is performed in situ using a formed stacked assembly, whereby inventory (124) for the electroplating is provided by the cathode composition (115).

16. 15. The method of claim 14, wherein the electroplating (307b) is performed in a separate electroplating step prior to providing the cathode composition (115) and the second current collector (114).

17. 11. A battery cell product (1000) comprising the electrolyte product (1001) of any one of claims 1 to 10 formed into a stacked assembly, further comprising a first current collector (1009), a second current collector (1014), and a cathode composition (1015), whereby the second current collector (1014) extends along a surface of the electrolyte product (1001) opposite the first current collector (1009), and whereby the cathode composition (1015) extends between the electrolyte product (1001) and the second current collector (1014).

18. 18. The battery cell product of claim 17, further comprising an anode metal receiving layer (1010) disposed between the electrolyte product (1001) and the first current collector (1009), the receiving layer comprising a receptor material that sorbs and receives an alkali metal and / or an alkaline earth metal, the receptor material (1011) comprising one or more of Si, Sn, Li, Mg, and graphite.

19. 19. The battery cell product of claim 17 or 18, wherein the first current collector (1009) comprises a plurality of aligned conductive pillar structures extending from a support surface of the first current collector (1009) and spaced apart by at least the electrolyte product (1001).

20. 20. The battery cell product of claim 17, wherein the second current collector (1014) comprises a plurality of aligned conductive pillar structures (1018) extending from a support surface of the second current collector (1014) and spaced apart by at least the cathode composition (1015).

21. A battery cell product (1000) preferably obtainable by the manufacturing method according to any one of claims 11 to 16, an anode layer (1020) comprising an alkali metal and / or alkaline earth metal selected from the group consisting of Na, K, Li, Mg and Cs, said anode layer (1020) extending between said first current collector (1009) and said polymer-based matrix (1003); a mixed metal alloy layer (1021), said mixed metal alloy layer extending between said anode layer (1020) and said electrolyte product (1001); an SEI layer (1022) extending between the mixed metal alloy layer (1021) and the polymer matrix (1003); further comprising The mixed metal alloy layer (1021) is formed by mixing the alkali metal and / or alkaline earth metal with the M initially contained in the electrolyte product (1001). II a mixture with a further metal (A) reduced from at least a portion, optionally all, of its cation, The SEI layer (1022) is formed by removing the X originally contained in the electrolyte product (1001). II and the electrolyte product (1001) comprises at least a portion, optionally all, of the anion or reaction product thereof (B), II and / or X II 21. The battery cell product (1000) of any one of claims 17 to 20, including an optional remainder.

22. 22. The battery cell product (1000) of any one of claims 17 to 21, wherein the battery is in a virgin state.

23. A battery product (2000) comprising a plurality of electrolyte products (1) according to any one of claims 1 to 10 and / or a battery cell product (1000) according to any one of claims 17 to 22.

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