Electrolyte with dual functional salt additive

Abstract

The present disclosure relates to an electrolyte product (1) formed as a solid or semi-solid layer, comprising a polymer-based matrix in which an amount of an electrolyte salt component (4) and an amount of an additive salt component (5) are dispersed. The present disclosure also relates to methods of manufacturing battery cell products comprising electrolyte products 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, which comprise a polymer-based matrix in which are dispersed: a quantity of an electrolyte salt component comprising an anodic metal cation; and a quantity of an additive metal salt component which is configured to form, upon participating in a redox reaction, a mixed metal alloy layer having the anodic metal and a solid electrolyte interface (SEI) layer. The present disclosure also relates to a method of manufacturing a battery cell product, a battery cell product comprising the electrolyte product, and a battery product comprising a plurality of battery cell products. Background Art

[0002] Lithium (Li) metal is considered an important anode material for next-generation rechargeable batteries due to its high theoretical specific capacity (3860 mAh·g -1 ) and low reduction voltage (-3.04 V vs. standard hydrogen electrode). However, the formation of Li dendrites, uncontrolled interfacial reactions, and large volume changes actually lead to performance problems such as low Coulombic efficiency and, thus, short cycle life.

[0003] Designing an artificial solid electrolyte interface (SEI) film on a Li metal electrode shows great potential for solving the aforementioned problems and enabling a Li metal battery (LMB) to have an extended life.

[0004] Some attempts are known from the prior art regarding providing a mixed metal layer to reduce Li metal reactivity or providing a protective solid electrolyte interface layer. Z. Zeng et al. disclosed in Journal of Power Sources, 451, 227730, 2020 the use of zinc bis(2-ethylhexanoate) as an additive for forming a solid-state lithium battery. It is reported that this additive enables the formation of a LiZn alloy layer and / or provides a plasticizing effect.

[0005] CN107665966A relates to a lithium-sulfur battery. The battery comprises a multi-layer composite separator and a liquid electrolyte component. It is reported that the electrolyte comprises one or more of various lithium-based salts containing lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as an additive, which is reported to help improve the reduction of the activity of the lithium anode, improve its stability, and reduce dendrite formation.

[0006] However, particularly for solid or semi-solid batteries, there is still a need to improve one or more of battery safety, stability, and life while at least maintaining, preferably improving, one or more aspects of battery performance such as total capacity and / or power density. Summary of the Invention

[0007] According to aspects of the present invention, an electrolyte product is provided. As will become clear from the description herein, the electrolyte product can be particularly advantageously used as a component of a battery cell product and a battery product including said cell product and / or for manufacturing a battery cell product and a battery product including said cell product.

[0008] The electrolyte product is generally formed as a solid or semi-solid (e.g., gel) layer comprising a polymer-based matrix. The electrolyte product also includes a quantity of an electrolyte salt component. The electrolyte salt is dispersed in the polymer matrix. The electrolyte salt includes a cation M of a suitable anodically active metal component I and a weakly coordinating counter anion X I . Due to its relatively large redox potential, preferred components include cations of one or more of the alkali metals and / or alkaline earth metals. The cation is preferably a cation of an element selected from the group consisting of Na, K, Li, Mg, and Cs.

[0009] At least initially prior to battery cycling, the electrolyte product also includes a quantity of an additive salt component. As will become clear from the description herein, a quantity of the additive salt can be advantageously consumed at least in part, for example, upon reaction with an anodic metal (e.g., a deposited or plated anodic metal, typically during an initial metal deposition or plating process). As will be understood from the description herein, the reaction of the additive salt advantageously produces a reaction product that significantly improves battery attributes, including but not limited to performance, safety, and / or operational life.

[0010] The additive salt component includes a cation of a further metal M II (the further metal being different from the first anodically active metal M I ) and one or more counter anions X II . While the counter ions can be the same as the weakly coordinating counter anion X I , it is highly preferred that the counter ions be different from X I .

[0011] The further metal ion is selected to have a higher reduction potential (lower negative potential) than M I , such that upon contact with the anodic metal, the further metal ion is reduced to the metallic state. It is then allowed to mix with the subsequently provided, e.g., deposited or plated, anodic metal to form a mixed metal layer. At the same time, the counter anion X II is selected to preferentially participate in the SEI-forming redox reaction upon contact with the previously provided anodic metal (M I ). Due to the dual function of the additive salt as provided herein, providing the additive salt component as described can advantageously improve the performance and life of a battery device, particularly a secondary anodic metal battery as a rechargeable Li-metal battery device.

[0012] The inventors have found that when a battery product is incorporated into a battery cell stack, the battery product advantageously causes in-situ and in-operando formation of a protective and battery-active hybrid layer at a location proximate to, i.e., close to, the anode (e.g., Li metal anode) of the battery stack. The active protective hybrid layer located and interfacing between the anode metal layer of the stack and the (remaining portion of the) electrolyte layer achieves one or more of the goals of battery performance, safety, and / or operable lifetime. As will become apparent from this specification, the in-situ generation of a protective layer comprising a hybrid metal layer and SEI components provides multiple benefits that synergistically contribute to the goal of providing improved battery performance. For example, in addition to the reduced apparent surface activity of the anode metal provided by the hybrid metal component and the ionic conductivity and stabilization properties of the SEI component, the inventors have also found that this combination provides a particularly advantageous combination of interlayer adhesion and cycle stability. The SEI / hybrid metal component can advantageously form in-situ, for example, during the initial battery charge cycle. This advantageously reduces or even eliminates the need for a dedicated deposition step (e.g., post-anode metal deposition), which can lead to adverse reactions due to the high sensitivity and reactivity of the anode metal (e.g., Li), such as as a result of contact with carbon dioxide, molecular nitrogen, or traces of humidity (forming lithium nitride and lithium carbonate) or other contaminants.

[0013] Without wishing to be bound by theory, it is believed that both the electrolyte salt (M I X I ) and the additive salt (M II X II ) can advantageously co-promote the formation of the protective hybrid layer. Corresponding portions of the electrolyte salt and additive salt components initially included in the electrolyte product can participate in the respective redox reactions with the anode metal (e.g., metal Li), such as as a result of an initial anode metal deposition step or during the initial battery cycling process.

[0014] The dual-functional additive salt can be consumed upon reaction with the anode metal to form a mixed metal alloy layer and an SEI layer. Both the alloy layer and the SEI layer improve the cycle life of the battery.

[0015] In particular, the electrolyte salt (M I X I ) and the additive salt (M II X II ) can form a mixed metal alloy layer, such as Li x (M II ) 1-xThis can transform the formed layer into an adjustable additional buffer / reservoir layer during charging / discharging of the battery. The reservoir advantageously allows for replenishment of, for example, the anodic metal portion that is lost due to adverse side reactions, i.e., no longer participates in the battery cycle. Additionally, this layer forms an ion-conductive matrix film with excellent ionic conductivity to and from the matrix, and also improves the metal smoothness and adhesion (fixation) to the anodic substrate, thereby resulting in a more uniform charge-discharge curve across the entire functional battery layer stack. It will be understood that the combination of metal salt additives disclosed in relation to the present invention is unique in that it combines and maximizes the functions of a single new class of additives dispersed in a hybrid polymer-inorganic host matrix in a layered manner.

[0016] Anions included in the electrolyte salt and / or additive salt (preferably and in particular, the counter anion X supplied by the additive salt component) II participate in the SEI (solid electrolyte interface) formation reaction.

[0017] Different from conventional electrolyte components where the counter ions of the electrolyte salt are mainly selected based on the performance of the electrolyte, the present invention allows for the addition / selection of reagents in the form of the counter ion X of a dual-functional additive based on its ability to participate in the formation of an SEI layer with relatively improved stability. II

[0018] These additives can be cations M of metals different from Li (such as In, Mg, Sn, Zn, Cs, etc.) II and anions X (such as bis(fluorosulfonyl)imide (FSI), TFSI, halides, nitrate...) that promote the diffusion of anodic metal ions (such as Li + ) through the electrolyte and also enhance the chemical and structural stability of the layer (protective hybrid layer). II

[0019] Another aspect of the present invention relates to an electrolyte product preferably as described above, wherein a solid or semi-solid layer is arranged in a multi-layer stack, whereby the additive salt component is restricted to or at least mainly contained in the outer layer of the stack (i.e., the side that can be contacted from the outside, such as the anodic side current collector or the metal anode). Thus, the outer layer containing the additive dual-functional salt can be assembled adjacent to the anode. Additionally, by arranging the solid or semi-solid layer in a multi-layer stack, the formation and mixing of a multi-layer polymer electrolyte (such as polyethylene oxide (PEO)) can be divided into multiple parts, where each of the multiple parts can include different dual-functional additive salts.

[0020] Because the electrolyte products as described herein can be advantageously used, for example, for the in-situ generation of a protective layer on the anode of a battery cell during an initial battery charging cycle, the electrolyte products are preferably suitable for manufacturing battery cell products.

[0021] For the same reason, when assembled into a battery product and used during charging and discharging cycles, the electrolyte product is preferably in its original state, which means that the electrolyte product has not undergone any battery cycling operations.

[0022] In a preferred embodiment, M I is Li, M II is an element of one or more metals selected from Group 2 or Groups 12 to 15 of the periodic table, preferably one or more of Zn, Cs, Mg, Al, Ga, In, Sn, Ca, Ge, Cs, and / or Bi, and wherein X II is or comprises a halide, preferably a fluoride, and / or comprises a polyatomic anion including a central nitrogen atom. The listed Group 2 or Groups 12 to 15 elements are found to be particularly advantageous for their affinity for alloys or at least for forming mixtures with metallic lithium. Suitable anions include PF6, BF4, preferably FSI (bis(fluorosulfonyl)imide), TFSI (bis(trifluoromethane)sulfonimide), DFOB (difluoro(oxalato)borate), and more preferably nitrate (NO3-). The counterion is selected based on its ability to participate in the SEI formation reaction so as to stabilize the underlying electrode metal. An SEI layer with a relatively high nitrogen content obtained from the nitrogen-containing counterion can form a particularly stable protective layer. Preferred examples of additive salts include Zn(FSI)2, MgF2, CaF2, In(NO3)3.

[0023] It will be understood that X I can be selected by the person skilled in the art from counterions known from electrolyte salts. In some embodiments, X I can be selected from the same list of compounds as X II , whereby X I and X II are preferably not equal for the reasons detailed herein.

[0024] The matrix can be selected from one or more components known in the art. Suitable materials include components selected from one or more of the following: polyethers, polyfluoropolymers, polyacrylates, polysiloxanes, and copolymers including one or more of them. Typical materials include PEO, polyvinylidene fluoride (PVDF), poly(vinylidene fluoride - hexafluoropropylene) (PVDF - HFP), poly(methyl methacrylate) (PMMA), and polydimethylsiloxane (PDMS).

[0025] In a preferred variant, based on the total weight of the polymer matrix and the electrolyte and other additives, the matrix comprises from 10 wt% to 50 wt% of an electrolyte salt component. Higher concentrations improve the electrochemical stability of the electrolyte layer and result in a longer cycle life. The upper limit is restricted by practical considerations (such as the capacity of the matrix) and can be determined by a person skilled in the art through routine experiments.

[0026] In another or additional preferred embodiment, the polymer matrix comprises from 1 wt% to 30 wt% of an additive salt component based on the total weight of the matrix and the electrolyte and other additives. In addition to the usual considerations regarding the electrolyte salt concentration within the electrolyte layer, providing an additive salt with a high salt concentration in the range of 1 wt% to 30 wt%, preferably higher (such as 2 wt% to 30 wt%,) more preferably 6 wt% to 10 wt% based on the total weight of the polymer matrix and the electrolyte and additive salt has the additional benefit of increasing the efficiency of alloy and SEI formation (such as during the initial charging routine). The reduced time for alloy / SEI layer formation, believed to be related to the relatively short diffusion paths during layer formation, mitigates the likelihood of adverse side reactions during, for example, the initial cycles. Advantageously, the higher the concentration of the electrolyte salt and the additive salt, the more effective the alloy and stable SEI formation. Generally, M I and M II are added in a relative ratio in the range of 0.1 to 0.9 (mole fraction). In absolute terms, the total concentration of the primary salt and the additive salt is in the range of 0.1 M to 8 M.

[0027] In a particularly preferred variant, the electrolyte salt component comprises more than or equal to 4 different weakly coordinating counter anions (X I ). The inventors have found that including multiple electrolyte salt components having different weakly coordinating counter anions can result in the formation of a particularly stable SEI layer, for example, during the initial stage of battery cycling. It will be understood that the number of different weakly coordinating counter anions (X I ) can be less than 4, such as 2 or 3, however the effect on SEI stability may be less beneficial.

[0028] It will be understood that the electrolyte product can include one or more additives known in the art, such as plasticizers (to increase ion mobility). For example, plasticizers such as succinonitrile are also incorporated into the (quasi)-solid electrolyte layer to counteract any brittleness and stiffness of the new inorganic interlayer components throughout the battery layer stack. Alternatively or additionally, the matrix can include high-k dielectric particles (relative dielectric constant ∈ Rone or more of inorganic particles such as ≥4, preferably ≥100), and / or a Li-ion conductive material including nanoparticles and / or fibers. Alternatively or additionally, the matrix may be provided with hollow compressible beads (such as hollow polymer beads) so that the product can adapt to the stress caused by the swelling / shrinking process during battery operation.

[0029] In a particularly preferred embodiment, the electrolyte product is arranged as a multi-layer stack, whereby the additive salt component is confined to or at least mainly 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 the additive salt component to or at least mainly providing it to the outer layer of the electrolyte product advantageously allows the layer with the additive 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 arranged along the face of the first current collector, whereby the outer layer of the stack faces the first current collector, such that the dual-functional salt is close to the current collector. This is advantageous for in-situ formation of a protective layer on the anode of the battery cell product.

[0030] It will be understood that the electrolyte salt may but need not be mainly contained in the remaining layers. An additional benefit of arranging the electrolyte product as a multi-layer stack is that the polymer materials forming the matrix in the respective layers can be different. That is, one or more optimal additives, at least mainly a portion of the total amount, and / or the polymer matrix in the layer retaining the additive salt component can be selected independently of one or more of the remaining layers. Incorporating different polymers can be particularly advantageous for manufacturing. For example, when forming the electrolyte product in a process comprising multiple solution-based processes, the polymers in the respective layers can be selected such that the formed layers do not degrade or redissolve significantly during subsequent solution processing steps. Alternatively or additionally, the polymer in the layer comprising the additive salt can be selected so as to, for example, promote in combination with one or more balancing anions X II participate partially in the SEI formation reaction.

[0031] Arranging the solid or semi-solid layer as a multi-layer stack as described above, whereby the additive salt component is confined to or at least mainly contained in the outer layer of the stack, preferably also applies to the electrolyte product in its original state, i.e., before any initial battery cycles to which the electrolyte product may be exposed, since such a multi-layer stack arrangement has an advantage in in-situ formation of a protective layer on the anode of the battery cell. In the case where such a multi-layer stack arrangement will only be formed during or after the electrolyte product is exposed to battery cycles, these advantages of the multi-layer stack arrangement will not exist or will be at least less obvious.

[0032] An optional anodic metal receiving layer may be disposed between the electrolyte product and the first current collector. The receiving layer comprises a receptor material that is prone to adsorb an alkali metal (such as lithium) and / or an alkaline earth metal (such as magnesium). The anodic metal receiving layer may be suitably applied to one or more of the face of the current collector and / or the outward face of the electrolyte product (such as extending along the outer layer of the multi-layer stack including the dual-functional salt as described above). Anodic receiving materials are known in the art and may be applied using known methods. Suitable lithium metal receiving materials include layers comprising one or more of Si, Sn, and graphite.

[0033] In some embodiments, the first current collector includes a plurality of aligned and conductive pillar structures extending from a support face of the first current collector, and the plurality of aligned and conductive pillar structures are at least spaced apart by the electrolyte product.

[0034] According to a further aspect of the present invention, there is provided a method of manufacturing a battery cell product. In a preferred embodiment, the product is a secondary (also known as rechargeable) anodic metal battery product, such as a secondary Li metal battery cell. The method comprises at least: providing an electrolyte product; providing a first current collector and a second current collector and a cathode component; and forming a layered assembly, wherein the second current collector extends along a face of the electrolyte product opposite to the first current collector, and wherein the cathode component extends between the electrolyte product and the second current collector.

[0035] The method may further comprise depositing an amount of an alkali metal and / or an 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, an amount of an alkali metal and / or an alkaline earth metal (such as lithium) may be provided by electroplating by means of the electrolyte product that has been pre-assembled onto the first current collector.

[0036] In one embodiment, electroplating is performed in situ (in a complete unit cell or unit stack) using the formed layered assembly, whereby the inventory for electroplating is provided by the cathode component.

[0037] Alternatively or additionally, electroplating can be performed in a separate step before providing (including in a partial stack d) the cathode component and the second current collector in a plating bath, whereby the inventory for electroplating is provided by the bath. Performing the plating in external inventory before completing the unit stack can advantageously result in the formation of a cell unit stack with an anode metal buffer layer as the plating layer. In addition to the inventory supplied by the cathode component, the electroplated anode metal can also provide an additional anode metal inventory. This anode metal layer provides several benefits. In addition to the benefits regarding the formation of the mixed metal layer and SEI formation, providing the anode metal layer can also serve as a buffer capable of replenishing the lost anode metal during the ongoing battery cycles. Additionally, the provided anode metal layer advantageously serves as a planarizing, wetting layer for the anode metal (e.g., lithium plated during the initial battery charge) to be subsequently plated.

[0038] According to yet another aspect of the present invention, a cell unit product is provided. The cell unit product includes an electrolyte product as disclosed herein. In a preferred embodiment, the electrolyte product is formed as a layered assembly as described herein. The unit product further includes a first current collector, a second current collector, and a cathode component, wherein the second current collector extends along a face of the electrolyte product opposite to the first current collector, and wherein the cathode component extends between the electrolyte product and the second current collector.

[0039] In one embodiment, the cell unit product further includes an anode metal receiving layer disposed between the electrolyte product and the first current collector, the receiving layer comprising a receptor material that is prone to adsorb alkali metals and / or alkaline earth metals, wherein the receptor material includes one or more of Si, Sn, and graphite.

[0040] The first current collector may include a plurality of aligned and conductive column structures extending from a support face of the first current collector, the plurality of aligned and conductive column structures being at least spaced apart by the electrolyte product.

[0041] In other or additional embodiments, the second current collector includes a plurality of aligned and conductive column structures extending from a support face of the second current collector, the plurality of aligned and conductive column structures being at least spaced apart by the cathode component.

[0042] Both the first current collector and the second current collector can be advantageously provided in the form of a flexible film. The flexible film can include a flexible substrate (e.g., plastic foil) provided along one or more sides with a conductive coating (e.g., metal coating). Alternatively or additionally, the first current collector and / or the second current collector can be provided as a metal foil. The anode-side current collector (first current collector) preferably includes copper (e.g., as a coating or Cu foil). A flexible substrate with a copper foil / copper coating is particularly suitable for Li-metal battery applications and / or allows for large-scale manufacturing processes, such as roll-to-roll manufacturing. Additionally, a copper-containing or copper-coated surface is known to be particularly suitable as a substrate for forming multiple aligned and conductive pillar structures, which can be extended, for example, by processes known in the art involving the controlled growth of carbon nanotubes.

[0043] Regarding one aspect of the present invention, the battery cell product further includes: an anode layer including 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 the 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 can be provided as an additional layer before an initial battery cycling stage (e.g., in the case of Si or Sn, by electroplating from a separate plating bath or by other coating techniques). Alternatively or additionally, the anode layer can be provided as a reduction product from an initial charging cycle.

[0044] It will be understood that when providing the anode metal layer, the dual-salt additive in the electrolyte product can be mostly or completely consumed. Thus, in one embodiment, the mixed metal alloy layer includes a mixture of an alkali metal and / or alkaline earth metal and an additional metal, the additional metal being reduced from at least a portion, optionally all, of the M II cations initially included in the electrolyte product. Similarly, the SEI layer includes at least a portion, optionally all, of the X II anions or reaction products thereof initially included in the electrolyte product, the electrolyte product including M II and / or X II and the optional remaining portion thereof.

[0045] Note that since even when the cell is in its original state, i.e., before any battery cycling operation, the battery cell product can be distinguished from known cells, for example, due to the presence of the electrolyte product in the multi-layer stacked arrangement of layers.

[0046] According to yet another aspect, a battery product is provided. The battery product includes one or more of battery cell products. According to the battery product, a cathode side contact portion, an anode side contact portion, and a battery housing can be provided. In some embodiments, one or more battery cell products are arranged as a pouch.

[0047] In some embodiments, one or more battery cells are arranged in series and / or in parallel corresponding to a desired potential output of the battery product. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] These and other features, aspects, and advantages of the devices, systems, and methods of the present disclosure will become better understood from the following specification, the appended claims, and the accompanying drawings in which:

[0049] Figure 1 A cross-sectional side view of an electrolyte product is provided;

[0050] Figure 2 A cross-sectional side view of an electrolyte product is provided;

[0051] Figure 3 A cross-sectional side view of an electrolyte product is provided;

[0052] Figure 4 A cross-sectional side view of an electrolyte product is provided;

[0053] Figure 5 A cross-sectional side view of an electrolyte product is provided;

[0054] Figure 6 A method of manufacturing a battery cell product is shown;

[0055] Figure 7A 、 Figure 7B 、 Figure 7C and Figure 7D Cross-sectional side views of the battery cell product during different manufacturing steps are provided;

[0056] Figure 8 A cross-sectional side view of the battery cell product is provided;

[0057] Figure 9A and Figure 9B A cross-sectional side view of a protective layer including a mixed metal alloy layer and an SEI layer is provided; and

[0058] Figure 10 A cross-sectional side view of a battery product including a plurality of battery cell products is provided. DETAILED DESCRIPTION

[0059] The terms used to describe particular embodiments are not intended to limit the present invention. As used herein, unless the context clearly dictates otherwise, the singular forms "a", "an", and "the" are intended to include the plural forms as well. 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 "comprises" and / or "comprising" specify the presence of the stated features, but do not preclude the presence or addition of one or more other features. It will be further understood that when a particular step of a method is referred to as being after another step, that step can be directly after the other step or one or more intermediate steps can be performed before the particular step, unless otherwise stated. Similarly, it will be understood that when describing a connection between structures or components, that connection can be established directly or through intermediate structures or components, unless otherwise stated.

[0060] The term "non-coordinating or weakly coordinating anion" means that the anion does not form a coordination bond with a metal in aqueous solution. Examples of non-coordinating or weakly coordinating anions include trifluoromethanesulfonate ([CF3SO3] - )、hexafluorophosphate ([PF6] - )、tetrafluoroborate ([BF4] - )、perchlorate ([ClO4] - )、pentafluorotellurate (teflate) ([OTeF5] - )、BArF ([B(ArH x F y )4] - )(where Ar is an aryl group and x + y = 5, for example [B(C6F5)4] - )、p-toluenesulfonate ([CH3C6H4SO3] - )、FSI ([(FSO2)2N] - )、and TFSI ([CF3(SO2)2N] - ).

[0061] The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which embodiments of the invention are shown. In the drawings, for the sake of clarity, the absolute and relative dimensions of systems, components, layers, and regions may be exaggerated. Embodiments may be described with reference to schematic illustrations and / or cross-sectional illustrations of possible idealized embodiments and intermediate structures of the present invention. In the specification and drawings, like reference numerals always refer to like elements. Related terms and their derivatives should be construed to refer to the orientation shown in the subsequent description or the drawings discussed. Unless otherwise stated, these relative terms are for convenience of description and do not require the system to be constructed or operated in a particular orientation.

[0062] Now will refer to Figures 1 to 5Further elaborate on the battery product 1 in detail.

[0063] Generally speaking, for example, as Figure 1 , Figure 2 , Figure 3 , Figure 4 and Figure 5 shown, the battery product 1 is formed to include a solid or semi - solid layer 2 based on a polymer matrix 3, in which a certain amount of electrolyte salt component 4 and a certain amount of additive salt component 5 are dispersed.

[0064] Solid or semi - solid is understood to be different from liquid electrolytes. On the contrary, solid or semi - solid includes materials and components in a solid or quasi - solid aggregated state (at room temperature). Solid or semi - solid also explicitly includes materials such as polymer electrolytes, so - called dry polymer electrolytes for example, which differ from liquid electrolytes in that the salt additives are directly dissolved in the solid medium. Solid or semi - solid also explicitly includes so - called gel electrolytes, which can be understood as liquids contained in a flexible lattice framework (polymer matrix). The polymer matrix forms a continuous phase that accommodates or supports one or more potential liquid additives (such as ionic liquids and / or one or more solvents). Although in some aspects similar to solids, such as having the ability to support its own weight and maintain its shape, quasi - solids also share

[0065] some properties of liquids, such as having a shape that conforms to the object applying pressure to it. Additionally, solid or semi - solid electrolytes can include one or more solid (such as ceramic) particles.

[0066] The electrolyte salt component 4 includes: cations of alkali metals and / or alkaline earth metal elements M I selected from the group consisting of Na, K, Li, Mg, and Cs; and weakly coordinating counter anions X I . The additive salt component 5 includes: cations of additional metals M I having a higher reduction potential than M II ; and one or more counter anions X I different from X I and selected to participate in a redox reaction for SEI formation with M II . Counter ions generally have a valence of negative one. The additive salt component 5 serves a dual function, where the additive salt participates in a redox reaction with the anodic element in the metallic state (such as Li 0) redox reaction. The additive salt is at least partially consumed when forming a protective layer including a mixed metal alloy phase and an SEI phase. The layers of the mixed metal alloy phase and the SEI phase can advantageously form a structure (e.g., a bilayer structure) that alleviates the adverse reactions of the underlying additional anode metal (e.g., Li) especially during the manufacturing / assembly of a closed battery cell assembly. Additionally, the protective layer, for example, acts as a homogenizing layer and a wetting layer for the subsequently deposited anode metal during battery cycling, alleviating non-uniform anode metal plating / stripping, especially during the initial battery cycling process. Figure 9A and Figure 9B A cross-sectional side view of a protective layer including a mixed metal alloy layer 1021 and an SEI layer 1022 is provided. Depending on the directionality of the anode metal (e.g., Li(0)) exposure to the film, process conditions, and / or relative reactivity, the protective layer 1020 can be characterized by a mixture of multilayer structures. Generally, the protective layer is formed by side A and side B, where side A includes a major portion of the alloy or mixed metal component facing the anode current collector 1025, and side B includes a major portion of the SEI component facing away from the anode side current collector.

[0067] The thickness of the protective layer varies with the initial amount of the additive salt added to the electrolyte product. The thickness is generally at least 0.5 μm and can extend to several micrometers, usually ≤10 μm.

[0068] During the initial charging cycle, the anode metal ions supplied migrate through the protective layer towards the current-collecting anode side for plating, forming a battery-active anode metal layer covered / protected by the protective layer. Thus, both the mixed metal alloy layer and the SEI layer are used to improve the cycle life of the battery.

[0069] In Figure 2 , a solid or semi-solid layer 2 including a polymer-based matrix 3 is depicted as arranged along the face 9f of the conductive first current collector 9. As described above, the first current collector can be a metal foil (e.g., a copper foil) or a metal coating, such as a copper film, deposited on a carrier (preferably, a flexible carrier, such as a polymer foil).

[0070] The solid or semi-solid layer 2 can include a mixture of different polymers PEO and / or block copolymers. Generally, the polymer matrix includes one or more materials selected from the group consisting of polyvinylidene fluoride, polydimethylsiloxane, polyethylene oxide, polymethyl methacrylate, polyethylene diacrylate, polyacrylonitrile, hexafluoropropylene, and their copolymers. The average molar mass (M W ) of the polymer material is generally between 10000 g / mol and 1000000 g / mol. The polymer matrix provides a network that restricts the filler while allowing the metal salt to diffuse as its ions between the opposite faces of the solid or semi-solid layer 2.

[0071] By dispersing a metal salt (e.g., Li salt [Li + -X I ) into a polymer-based matrix, an ion-conductive matrix film can be formed that has far better ion conductivity for improved metal smoothness of the substrate and adhesion to the substrate, such as a Cu(Li) substrate.

[0072] In a further embodiment, the solid or semi-solid layer 2 is arranged as a multi-layer stack 6, such as Figure 3 shown. In such a multi-layer stack 6 configuration, the additive salt component 5 is confined to or at least mainly contained in the outer layer 7 of the stack 6. By confining the additive salt 5 to the outer layer 7 of the stack, the stack 6 can be arranged on a first current collector such that the dual-functional additive salt component is adjacent to the first current collector, where the first current collector can be, for example, an anode. Having the additive salt close to the first current collector or anode can advantageously increase the rate of formation of the alloy layer and the SEI layer.

[0073] It will be understood that one or more plasticizers (e.g., succinonitrile) can be mixed into the solid or semi-solid layer 2 in any or all of the layers included in the multi-layer stack 6. These plasticizers are used to counteract any brittleness and stiffness in the overall electrolyte product 1 and the components of the battery cell product formed therefrom. It will also be understood that the solid or semi-solid layer 2 can further include additional additives that include a certain amount of a liquid carrier (e.g., an ionic liquid and / or an organic solvent) or inorganic nanoparticles (including fibers, hollow compressible beads, etc.). It is contemplated that the electrolyte product 1 further includes an inorganic solid electrolyte (e.g., LLZO (LiLaZrO)), and / or other crystalline, glass, and / or glass-ceramic electrolytes, see, e.g., 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.

[0074] In a preferred embodiment, the metal ion-conductive inorganic component comprises or substantially consists of a ceramic component. Preferred components include lithium aluminum titanium phosphate (LATP), lithium aluminum germanium phosphate (LAGP), lithium lanthanum zirconium oxide (LLZO), halide electrolytes (e.g., Li 3–x M 1–x Zr x Cl6 M = Y, Er), sulfide electrolytes (e.g., Li 10 GeP2S 12, Li6PS5X (X = Cl, Br or I), 67(75Li2S - 25P2S5)-33LiBH4, 30Li2S - 26B2S3 - 44LiI) or derivatives and / or mixtures thereof, lithium borohydrides including but not limited to closo-borates, closo-carbaborates and derivatives and / or mixtures thereof.

[0075] The layers of the multi-layer stack 6 can be separated by an optional interfacial layer.

[0076] Such as Figure 1 , Figure 2 , Figure 3 and Figure 4 As depicted, the electrolyte salt 4 includes M I and X I , and the additive salt 5 includes M II and X II . In one embodiment, M I is Li, and M II is an element of one or more metals selected from Group 2 or Groups 12 to 15, preferably one or more of Zn, Cs, Mg, Al, Ga, In, Sn, Ca, Ge, Cs and / or Bi. The counter ion and X II are halides, preferably fluorides, or polyatomic anions including a central nitrogen atom, such as PF6, BF4, preferably FSI, TFSI, DFOB, more preferably nitrate. The listed M II cations are selected based on their suitability to form alloys with Li. All of these elements have a higher reduction potential than lithium and will be reduced to their metallic state when undergoing a redox reaction with Li(0). The listed X II anions are specifically selected based on their ability to participate in stable SEI formation reactions.

[0077] In one embodiment, based on the total weight of the polymer matrix 3 and the electrolyte salt 4 and the additive salt 5, the matrix 3 includes 0.1 wt% to 10 wt%, preferably 1 wt% to 10 wt% of the additive salt component 5. Providing a higher concentration of the additive salt component 5, and thus providing more, possibly excessive, M II and X IIIons can advantageously lead to more efficient alloy and stable SEI layer formation. The thickness / amount of the mixed metal layer (alloy) can be appropriately adjusted by the amount of additive salt initially included in the electrolyte product (e.g., in layer 7 closest to the first current collector). Preferably, the mixed metal layer is a conformal layer with a thickness of not less than 20 nm (preferably thicker, e.g., ≥50 nm) to reduce the number of potential point defects. The upper limit can be defined 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 total energy density of the resulting cell. Generally, the thickness of the mixed metal layer ≤1 μm, preferably ≤500 nm, e.g., in the range of 100 nm to 400 nm. The concentration of additive salt in the electrolyte for a given layer thickness can be determined by routine experiments.

[0078] Another aspect of the present invention relates to an electrolyte product, wherein the electrolyte salt component 4 comprises ≥4, preferably ≥5, more preferably ≥6, and most preferably ≥7 different weakly coordinating counter anions X I . Surprisingly, it has been found that adding more types of weakly coordinating counter anions further improves the life cycle of the battery cell product.

[0079] In one embodiment, based on the total weight of the polymer matrix 3 and the electrolyte salt 4 and additive salt 5, the matrix 3 comprises 5 wt% to 50 wt%, preferably 10 wt% to 50 wt% of the electrolyte salt component 4. A higher concentration of the electrolyte salt component improves the electrochemical stability of the electrolyte layer and results in a battery cell product with a longer cycle life. The upper limit is limited by practical considerations.

[0080] As Figure 3 depicted, in some embodiments, the electrolyte product 1 is arranged along the surface 9f of the first current collector 9, whereby if the solid or semi-solid layer 2 is arranged as a multi-layer stack 6, the outer layer 7 of the stack 6 faces the first current collector 9. The additional layer 7f of the stack 6 faces away from the first current collector 9. As previously discussed, this arrangement ensures that the additive salt component 5 is close to the first current collector 9, which increases the rate of alloy layer and SEI layer formation. As discussed, the polymers forming the matrix 3-1, 3-2 in the respective layers of the stack 6 can be the same, but can be different from each other (independently selected). Generally, the outer layer 7 of the stack (closest to, e.g., directly contacting the anode-side current collector) comprises both the additive salt (M II X II ) and the electrolyte salt (M I X I ). The additional layer 7f comprises at least the electrolyte salt (M I X I)。Of course, one or more of the additional layers may include a certain amount of the same additive salt component or another additive salt component. For the multilayer electrolyte product 1 that is clearly suitable and configured to fabricate Li metal battery products, the electrolyte salt includes or substantially includes Li cations combined with a suitable weakly coordinating anion X I (such as FSI, TFSI, halides, nitrate, etc.) as the metal salt M Id . The additive salt includes or substantially includes metal cations M other than Li and having a high reduction potential (less negative potential) as disclosed herein II and a stabilizing anion different from X I as disclosed herein and selected to participate in the SEI formation reaction.

[0081] As Figure 4 shown, an optional anode metal receiving layer 10 containing a receptor material 11 may be disposed between the electrolyte product 1 and the first current collector 9. The receptor material 11 is prone to adsorb alkali metals and / or alkaline earth metals. For Li metal batteries, the anode metal receiving layer may include one or more of Si, Sn, and graphite, each of which is well-known in the art for its ability to act as a Li accepting component. The receiving layer 10 can advantageously facilitate the diffusion of ions through the electrolyte product and / or the battery cell product. The receiving layer 10 can adsorb the anode metal (such as Li) and distribute the anode metal therein, thereby alleviating or preventing the formation of "dead" zones of insulating non-activated anode metal. Of course, the receiving layer can be applied to other embodiments disclosed herein with corresponding effects, including but not limited to those Figure 1 , Figure 5 and Figure 8 described.

[0082] In yet another embodiment, as Figure 5 shown, the first current collector 9 includes a plurality of aligned and conductive column structures 12 extending from the support surface 9f of the first current collector 9, and the plurality of aligned and conductive column structures 12 are at least spaced apart by the electrolyte product 1. The plurality of aligned and conductive column structures 12 produce a current collector with a 3D structure. The 3D structure results in an increased contact area between the first current collector 9 and at least the electrolyte product 1, which in turn produces an increased current flowing between the components. The conductive column structures 12-1, 12-2 can be implemented as metals or metal-coated columns. Alternatively or additionally, the conductive column structures 12-1, 12-2 can be implemented as carbon nanotubes or carbon nanotube structures.

[0083] It will be understood that the electrolyte product can be disposed between the cathode and the anode to provide ion transport from the cathode side towards the anode side during the charging cycle of the battery and from the anode side towards the cathode side during discharge.

[0084] According to a further aspect of the present invention, as Figure 6 shown in the flow chart of, a method of manufacturing a battery cell product is provided. 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. These include but are not limited to wet deposition of a solution including a polymer matrix or a precursor thereof (e.g., a curable monomer component), followed by drying of the component. Suitable wet deposition methods include but are not limited to spraying, spin coating, and / or dip coating. Solid additives (e.g., high-k dielectric particles) can be suitably added (e.g., suspended) to the liquid. Salts including electrolyte salt and additive salt components can be added (e.g., dissolved) to the liquid. Alternatively or additionally, salts can be added after the initial polymer layer deposition, e.g., injected from a separate solution or as an ionic liquid. For a multi-layer stack 6 (e.g., as Figure 3 shown), the stack of each layer can be formed, for example, by depositing the corresponding layer on a previously deposited layer.

[0085] In a preferred embodiment, the electrolyte product can be provided directly onto a current collector substrate (e.g., a first carrier substrate, such as a Cu foil). Alternatively, the electrolyte product can be formed on a carrier substrate (e.g., a temporary carrier for later use). Thus, in one embodiment, the 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, and providing a cathode component 115 in step 304; and forming a layered assembly 116 (e.g., as Figure 7A shown), wherein the second current collector 114 extends along a face of the electrolyte product 101 opposite to the first current collector 109, and wherein the cathode component 115 extends between the electrolyte product 101 and the second current collector 114. In one embodiment, forming the layered assembly 116 includes adhering the electrolyte product 101 to the first current collector 109, e.g., by coating or laminating the electrolyte product 101 onto the first current collector 109, wherein the first current collector is, for example, a metal current collector. In some embodiments, the current collector is an elongated metal foil or a metal-coated polymer foil, such as a copper foil.

[0086] Cathode components are known in the art. For lithium metal batteries, suitable components include but are not limited to "layered lithiated transition metal oxides" such as, for example, LiCoO2, but preferably like LMNC (LiNi x Co y Mn zO2), LFP (LiFePO4), and cathode materials with higher energy density such as oxides containing vanadium pentoxide, as well as polyanionic materials. For exemplary cathode materials for lithium-ion batteries, reference is made to the review by A.O. Soge et al. in J. of New Materials for Electrochemical Systems, 24, 229 (2021), which is incorporated herein by reference.

[0087] In one embodiment, the layered assembly 116 further includes an optional anode metal receiving layer 110 provided in step 305 and disposed between the electrolyte product 101 and the first current collector 109. The receiving layer 110 includes a receptor material 111 that is prone to adsorb alkali metals and / or alkaline earth metals, where the receptor material 111 includes one or more of Si, Sn, and graphite. If the receiving layer 110 is used, forming the layered assembly 116 includes adhering the electrolyte product 101 to the receiving layer 110, such as by coating or laminating the electrolyte product 101 onto the receiving layer 110.

[0088] It should be understood that the steps do not necessarily have to be performed in the depicted order. The components can be assembled in any suitable order or even built on top of each other.

[0089] Figures 7A to 7C Another embodiment is depicted, where the method includes depositing a quantity of alkali metals and / or alkaline earth metals selected from the group consisting of Na, K, Li, Mg, and Cs between the first current collector 109 and the electrolyte product 101. The quantity of alkali metals and / or alkaline earth metals is provided by electroplating 307a / 307b through the electrolyte product that has been pre-assembled onto the first current collector.

[0090] Figure 7A One embodiment is shown, where electroplating 307a is performed in-situ using the formed layered assembly 116, and thus the stock 124 for electroplating 307a is provided by the cathode component 115. In the shown embodiment, the anode metal (Li) is adsorbed by the optional silicon layer (Li receiving layer 110).

[0091] Figure 7B An alternative embodiment is shown, where electroplating 307b is performed in a separate step in the plating bath 117 before providing the cathode component 115 and the second current collector 114, and thus the stock 124 for electroplating 307b is provided by the bath 117.

[0092] Figure 7CThe battery cell product 100’ in its pristine state is shown. The battery cell product is considered to be in its pristine state directly after the manufacturing step including electroplating 307b is completed but before initial or additional plating of the anode metal from the cathode component.

[0093] Depending on the charge level, the amount of anode metal ions included in the cathode component decreases from the initial inventory 124’. Figure 7D The components of 7C in a relatively more charged state are schematically depicted, where the respective amounts of anode metal ions and anode metal at the stacked cathode / anode sides are represented by the thickness variations of the corresponding layers.

[0094] In a preferred embodiment, as Figure 6 depicted in the process diagram in, electroplating 307b is first performed in a separate step before providing the cathode component 115 and the second current collector 114 in the plating bath 117, whereby the inventory 124 for electroplating 307b is provided by the bath 117; wherein, after providing the cathode component 115 and the second current collector 114, an additional electroplating step 307a is performed in situ using the formed layered assembly 116, whereby an additional inventory 124’ for electroplating 307a is provided by the cathode component 115.

[0095] According to yet another aspect of the present invention, as Figure 8 depicted, a battery cell product 1000 is provided, which includes an electrolyte product 1001 formed in a layered assembly 1016, which further includes a first current collector 1009, a second current collector 1014, and a cathode component 1015, wherein the second current collector 1014 extends along the face of the electrolyte product 1001 opposite to the first current collector 1009, and wherein the cathode component 1015 extends between the electrolyte product 1001 and the second current collector 1014. It will be understood that the first current collector 1009 may be disposed on a support substrate 1025.

[0096] In an embodiment not shown, the battery cell product 1000 further includes an anode metal receiving layer disposed between the electrolyte product 1001 and the first current collector 1009, and the receiving layer 1010 contains a receptor material that is prone to adsorbing alkali metals and / or alkaline earth metals, wherein the receptor material includes one or more of Si, Sn, and graphite.

[0097] The first current collector 1009 may include a plurality of aligned and conductive column structures extending from the support surface of the first current collector 1009, and the plurality of aligned and conductive column structures are at least spaced apart by the electrolyte product 1001.

[0098] In another embodiment, the second current collector 1014 includes a plurality of aligned and conductive pillar structures extending from a support surface of the second current collector 1014, and the plurality of aligned and conductive pillar structures are at least spaced apart by the cathode component 1015.

[0099] In yet another embodiment, both the first current collector and the second current collector include a plurality of aligned and conductive pillar structures extending from a support surface of the first / second current collector.

[0100] It will be appreciated that the second current collector 1014 may be disposed along the carrier substrate. For example, similar to the first current collector, the second (cathode side) current collector may be provided as a conductive coating (e.g., of a suitable metal component known in the art) disposed along a flexible substrate (e.g., plastic foil).

[0101] Figure 8 A battery cell product in a charged state after the reaction of the additive salt component, i.e., after the formation of the alloy layer 1021 and / or the SEI layer 1022, is depicted. In such embodiments, the battery cell product 1000 further includes an anode layer 1020, and the anode layer 1020 includes an alkali metal and / or alkaline earth metal selected from the group consisting of Na, K, Li, Mg, and Cs. Note that the depicted embodiment does not include the anode metal receiving layer 1010, so the anode metal is formed as: an anode metal layer 1020 extending between the first current collector 1009 and the polymer-based matrix 1003 of the electrolyte product; a mixed metal alloy layer 1021.

[0102] According to another aspect of the present invention, there is provided a battery product 2000 ( Figure 10 ). The illustrated embodiment includes a plurality of battery cell products 1000. The illustrated embodiment includes a total of five battery cell products 1000-1 to 1000-5 arranged in series. Of course, different numbers of battery products may be provided, and the battery products may be arranged in various configurations, including parallel configurations, series configurations, and combinations thereof.

[0103] The plurality of battery cell products may be arranged in any suitable form known in the art, including but not limited to pouch, prismatic, or button cell formats, etc. The battery product may be arranged, for example, in a cylindrical battery format, and may be provided with a cathode side contact portion 2031 and an anode side contact portion 2032 to serve as conductive surfaces between the corresponding anode side and cathode side of the plurality of battery cell products and the surrounding environment. The battery product may also be provided with an insulating housing 2030 to protect the plurality of battery cell products from the surrounding environment.

[0104] For purposes of clarity and concise description, features are described herein as being part of separate or identical embodiments, however it will be understood that the scope of the invention may include embodiments having a combination of all or some of the described features.

[0105] In interpreting the appended claims, it should be understood that the word "comprising" does not exclude the presence of other elements or actions than those listed in a given claim; the word "a" or "an" preceding an element does not exclude the presence of a plurality of such elements; any reference numerals in a claim do not limit its scope; several "devices" may be represented by identical or different items or implemented structures or functions; unless otherwise specifically stated, any disclosed device or part thereof may be combined together or separated into further parts. Where one claim refers to another claim, this may indicate the cooperative advantages achieved by combining 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 used advantageously. Therefore, the present embodiment may include all working combinations of the claims, each of which may in principle refer to any preceding claim unless the context clearly excludes it.

Claims

1. An electrolyte product (1) suitable for manufacturing battery cell products, the electrolyte product (1) being formed as a solid or semi-solid layer (2), the solid or semi-solid layer (2) comprising a polymer-based matrix (3), in which are dispersed: A quantity of an electrolyte salt component (4), the electrolyte salt component (4) having: a cation of an alkali metal and / or an alkaline earth metal (M I ) selected from the group consisting of Na, K, Li, Mg, and Cs; and a weakly coordinating counter anion (X I ); and a quantity of an additive salt component (5), Among them, The additive salt component (5) comprises: cations of a further metal (M I ) having a higher reduction potential than (M II ); and one or more counter anions (X I ) different from (X II ) and selected to participate in the SEI-forming redox reaction with the alkali metal and / or alkaline earth metal, and wherein the solid or semi-solid layer (2) is arranged as a multi-layer stack (6), whereby the additive salt component (5) is confined to or at least mainly contained in the outer layer (7) of the stack (6).

2. The electrolyte product (1) according to claim 1, wherein, The electrolyte product is in its original state.

3. The electrolyte product (1) according to claim 1 or 2, wherein: M I is Li, M II is an element of one or more metals selected from Group 2 or Groups 12 to 15, preferably one or more of Zn, Cs, Mg, Al, Ga, In, Sn, Ca, Ge, Cs and / or Bi, and wherein X II is a halide, preferably a fluoride, or a polyatomic anion including a central nitrogen atom, such as PF6, BF4, preferably FSI, TFSI, DFOB, more preferably nitrate.

4. The electrolyte product (1) according to any one of the preceding claims, wherein, The matrix (3) comprises from 1 wt% to 30 wt% of the additive salt component (5) based on the total weight of the electrolyte (4), the additive salt (5) and the polymer matrix (3).

5. The electrolyte product (1) according to any one of the preceding claims, wherein, The electrolyte salt component (4) includes at least 4 different weakly coordinating counter anions X I .

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

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

8. The electrolyte product (1) according to claim 7 further comprises an anodic metal receiving layer (10) disposed between the electrolyte product (1) and the first current collector (9), the receiving layer (10) comprising a receptor material (11) which is prone to adsorb alkali metals and / or alkaline earth metals, wherein, The receptor material (11) comprises one or more of Si, Sn, Li, Mg and graphite.

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

10. The electrolyte product (1) according to any one of the preceding claims, wherein, The polymer-based matrices (3-1, 3-2) in the respective layers of the multi-layer 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 the preceding claims 1 to 10, providing a first current collector (109), a second current collector (114) and a cathode component (115); and forming a layered assembly (116), wherein the second current collector (114) extends along a face of the electrolyte product (101) opposite to the first current collector (109), and wherein the cathode component (115) extends between the electrolyte product (101) and the second current collector (114).

12. The method according to claim 11, wherein, The layered 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) containing a receptor material (111) capable of adsorbing alkali metals and / or alkaline earth metals, wherein the receptor material (111) comprises one or more of Si, Sn, Li, Mg and graphite.

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

14. The method according to claim 13, wherein, The quantity of alkali metals and / or alkaline earth metals is provided by electroplating (307) through the electrolyte product (101) already pre-assembled onto the first current collector (109).

15. The method according to claim 14, wherein The electroplating (307a) is performed in situ using the formed layered component, whereby the inventory (124) for the electroplating is provided by the cathode component (115).

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

17. A battery cell product (1000) includes an electrolyte product (1001) according to any one of the preceding claims 1 to 10, the electrolyte product (1001) being formed in a layered assembly that further includes a first current collector (1009), a second current collector (1014), and a cathode component (1015), wherein, The second current collector (1014) extends along a face of the electrolyte product (1001) opposite to the first current collector (1009), and wherein the cathode component (1015) extends between the electrolyte product (1001) and the second current collector (1014).

18. The battery cell product according to claim 17 further includes 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 capable of adsorbing alkali metals and / or alkaline earth metals, wherein, The receptor material (1011) includes one or more of Si, Sn, Li, Mg, and graphite.

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

20. The battery cell product according to any one of claims 17 to 19, wherein, The second current collector (1014) includes a plurality of aligned and conductive column structures (1018) extending from a support face of the second current collector (1014) and spaced apart at least by the cathode component (1015).

21. The battery cell product (1000) according to any one of claims 17 to 20, preferably obtainable by a method according to any one of claims 11 to 16, wherein, The battery cell product (1000) further includes: An anode layer (1020), the anode layer (1020) including an alkali metal and / or alkaline earth metal selected from the group consisting of Na, K, Li, Mg, and Cs, the anode (1020) extending between the first current collector (1009) and the polymer-based matrix (1003); A mixed metal alloy layer (1021), the mixed metal alloy layer extending between the anode layer (1020) and the electrolyte product (1001); and An SEI layer (1022), the SEI layer (1022) extending between the mixed metal alloy layer (1021) and the polymer-based matrix (1003), Wherein, the mixed metal alloy layer (1021) comprises a mixture of the alkali metal and / or alkaline earth metal and an additional metal (A), and the additional metal (A) is optionally fully reduced from at least a part of the M II cations initially included in the electrolyte product (1001). Wherein, the SEI layer (1022) includes at least a portion, optionally all, of the X initially included in the electrolyte product (1001), and the electrolyte product (1001) includes M II and / or an optional remaining portion of X II and / or X II in the anion or a reaction product (B) thereof 22. The battery cell product (1000) according to any one of claims 17 to 21, wherein, The battery cell product is in an original 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.

Images