NL2029308B1

NL2029308B1 - Hybrid solid electrolyte and battery comprising hybrid solid electrolyte

Info

Publication number: NL2029308B1
Application number: NL2029308A
Authority: NL
Inventors: Jacob Visser Jelmer; Unnikrishnan Sandeep; Anothumakkool Bihag
Original assignee: Lionvolt B V
Priority date: 2021-10-01
Filing date: 2021-10-01
Publication date: 2023-04-12

Abstract

Aspects of the present disclosure relate to a metal ion battery (1), hybrid solid electrolyte (4) layer, and manufacturing methods The battery comprises an anode (2), a cathode (2) and a hybrid solid electrolyte (4). The hybrid solid electrolyte comprises: a polymer matrix (5), a metal salt (6) and at least first and second dispersed filler materials. The first filler material comprises inorganic high-k dielectric particles (8) . The second filler material comprises solid state electrolyte fibers (9). The second filler can consist of a metal ion conductive inorganic composition.

Description

Title: Hybrid solid electrolyte and battery comprising hybrid solid electrolyte

TECHNICAL FIELD AND BACKGROUND

The present disclosure relates to a battery, preferably a metal ion battery, comprising a hybrid solid electrolyte. In particular a hybrid solid electrolyte comprising at least first and second filler materials dispersed in the hybrid solid electrolyte. The disclosure further relates to methods of manufacturing the battery and to the hybrid solid electrolyte.

Metal-ion batteries, in particular lithium ion batteries, can potentially play a pivotal role in a global energy shift, for instance by the electrification of vehicles and storage of clean, renewable energy.

Improvement of battery safety, capacity, and power density of lithium battery cells remains an actively pursued topic. Moving towards batteries having lithium metal anodes with a high capacity lithium metal can improve capacity. However the cycle life of lithium metal anodes is poor as a consequence of porosity and dendrite formation of lithium during battery charging in liquid electrolytes.

CN107665966A discloses modifying a, commercial polymer separator with coating types including a coating of 15-75% inorganic solids (e.g. BTO) in a polymer matrix on one side and a PVDF layer on the inorganic coating and on the other side of the separator. A lithium-sulfur battery is formed using the modified separator after gellation with a lithium salt DOL/DME liquid electrolyte. The disclosed battery fails to offer improved power density.

CN108808077A discloses a lithium metal battery comprising a gradient polymer separator immersed with lithium salt liquid electrolyte.

The gradient polymer separator is formed by electrospinning multiple solutions with a PVDF-HFP copolymer and varying barium titanate concentrations to form a gradient polymer skeleton material. Similar as for

CN107665966A the disclosed battery can be improved in terms power density.

Z. Chen et al disclose (Adv. Energy Mater. 2021, 11, 2101339) a flexible hybrid film consisting of a PVDF-TrFE polymer matrix carrying

LATP particles and La+-conductive ionic liquid that is incorporated into a Li metal cell. The Li anode is coated with a protective polymer layer of the organically synthesized poly[2,3-bis(2,2,6,6-tetramethylpiperidine-N- oxycarbonyl)-norbornene] (PTNB). Chen fails to address battery safety and similar to CN108808077A there remains room to improve power density.

Y. Liang (Journal of Power Sources, 196, 2011, 436) discloses ionic-conducting lithium lanthanum titanate oxide/polyacrylonitrile submicron composite fiber-based lithium-ion battery separators. The LLTO particles are shown to improve ionic conductivity, however there remains room for further improvement, also in terms of battery safety.

SUMMARY

The present disclosure aims to address one or more of the above limitations by providing a metal ion battery, a hybrid solid electrolyte, and a method of manufacturing the electrolyte and battery.

As will be explained in more detail herein below the presently disclosed hybrid solid electrolyte and battery offer increased capacity, power delivery rate, in particular for lithium metal anodes in combination with enhancing intrinsic safety and/or mechanical stability of the battery.

The metal ion battery as disclosed herein comprises at least an anode, a cathode and a hybrid solid electrolyte. The hybrid solid electrolyte is formed as a layer between the anode and the cathode. The hybrid solid electrolyte separates the anode and cathode, preventing electrical shorts, while maintaining appropriate ion conductivity.

The hybrid solid electrolyte comprises: a polymer matrix, a metal salt dispersed in the hybrid solid electrolyte, typically throughout the polymer matrix. In addition the hybrid solid electrolyte comprises at least first and second dispersed filler materials. The first filler material comprises inorganic high-k dielectric particles. The second filler material comprises solid state electrolyte fibers.

Advantageously the fibrous solid state electrolyte fibers can provide an extended, elongate, pathway for ion transport. The second filler can essentially consist, of a metal ion conductive inorganic composition.

Alternatively, or in addition, the second filler can comprise a mixture of materials, e.g. a solid carrier having a coating comprising a metal ion conductive inorganic composition.

The first filler can comprise or essentially consist of an inorganic dielectric composition. The dielectric can be metal oxide or metalloid-oxide based, e.g. S102, TiO2, or combinations thereof. Preferably, the particles comprise, or essentially consist of a high-k dielectric, i.e. a material having a dielectric constant well in excess of about 4, at least over a temperature range of about 20°C to about 100°C. Preferably, the dielectric constant is > 20, more preferably > 40. Most preferably the dielectric constant is in excess of 100. Suitable materials include but are not limited to metal titanates (MTiOx), including but not limited to barium-, strontium-, calcium-, copper-, and yttrium-based titanites as well as combinations and/or derivatives thereof, e.g. doped metal titanates. Preferred examples include barium titanate, strontium titanate, and combinations thereof. Incorporation of dielectric particles was found to advantageously improve homogenization of an electric field across the hybrid solid electrolyte layer, WO2021034197A1 discloses high dielectric electrode additives. Inventors believe incorporation of dielectric fillers can homogenize metal ion transport across the layers and/or mitigate dendrite formation at an interface with an anode material as a result of repetitive charging and discharging cycles. Inventors found that the higher the dielectric constant the better the homogenization can be.

Preferably the particles are predominantly discrete particles with a homogeneous distribution within the hybrid solid electrolyte layer and/or in a sub-layer thereof. In addition to aligning the field the dielectric particles are found to advantageously reduce the softening and/or glass transition temperature of the polymer matrix, thus contributing to ion conductivity of the hybrid solid electrolyte. Inventors find that ion mobility increases with increased amounts of inorganic particles dispersed within the polymer matrix.

Providing a hybrid solid electrolyte that includes fillers as disclosed herein was found to offer a number of benefits. Filler particles can also reduce the viscosity of a composite melt, e.g. if a melt-extrusion or melt- casting approach is adopted for fabrication. In addition for field homogenization by the dielectric particles, these benefits include improvement of ion conductivity within the hybrid solid electrolyte layer and improvement of mechanical stability of the electrolyte layer during its manufacturing, assembly, and/or during operation of a battery, e.g. during a condition wherein the matrix is in a gelled or semi-solid condition, e.g. as a result of a operation of the battery at or near a softening temperature of the matrix.

In particular inventors find that improved ion conductivity can be a result of one or more of: improved ion conduction along an external face of the filler (interfacial conduction or even conduction through the interphase); ion conduction along a pathway in the bulk of the ion conductive material comprised in the filler; and/or the contribution of the fillers to plasticization of the matrix, e.g. by reducing a softening or glass transition temperature of the matrix, thus indirectly improving ion conductivity of metal ions though portions of the matrix away from interfaces with the filler.

Improving ion conductance and mitigating field inhomogeneities advantageously enhances lithium deposition and/or plating uniformity during battery charging. Thus mitigating porosity and/or dendrite formation.

As will be explained in more detail herein below, the second filler, comprising solid state electrolyte fibers, can advantageously improve ion conductance over non-fibrous fillers, e.g. particles. Advantageously the fibers can, at least in part, be oriented in a direction between opposing faces of the electrolyte layer for respectively contacting electrodes, e.g. with an anode and a cathode of an energy storage device. This improves ion 5 conductance along a principal diffusion direction between anode and cathode. Further, orienting at least part of the second filler, fiber, in a direction between opposing electrodes, can provide the effects as to improved ion conductivity using a comparatively smaller volume fraction of the fillers within the electrolyte layer, as opposed to layers comprising randomly oriented fibers or fibers that are predominately oriented in a direction parallel between the anode/cathode. Minimizing the amount of fillers for a given conductance advantageously increases the volume per unit volume available for battery active ingredients such as metal ion species.

A further advantage can be increased Li* transference number.

Generally the polymer matrix may contain a liquid carrier for the metal salt, e.g. a solvent or solvent mixture having an appropriate affinity for the salt and polymer matrix. Alternatively the salt may, at least in part, be provided in a liquid form such as an ionic liquid, preferably having melting point below an operating temperature of the battery, such as below 80 or 60 °C. Inclusion of liquid carriers and/or liquid salts was found to advantageously improve ion mobility across the hybrid solid electrolyte layer. For similar reasons the hybrid solid electrolyte can optionally

Increase one or more plasticizers.

Inventors found that the above features may be particularly beneficial for batteries comprising a metal lithium anode, also referred to as

Lithium metal batteries. Accordingly, in preferred embodiments the battery 1s a lithium metal battery, whereby the metal salt comprises or essentially consists of an appropriate lithium salt. Examples include but are not limited to: LiITFSI (lithium bis(trifluoromethanesulfonyl)imide), LiFSI (lithium bis(fluorosulfonyl)imide), LiPF6 (lithium hexafluorophosphate), LiODFB

(lithium difluoro(oxalate)borate), LiBOB (lithium bis(oxalato)borate), LiBF4 (lithium tetrafluoroborate), LiFOB (lithium difluoro(oxalato)borate), and mixtures thereof. In other or further preferred embodiments the battery comprises a metal anode, e.g. a lithium anode, such as a lithium metal film or strip. Lithium metal barriers advantageously offer a higher capacity of about 3800 mAh/g, well above a conventual, more limited, capacity of graphite anodes, which is typically below 370 mAh/g.

In a preferred embodiment, the metal ion conductive inorganic composition comprises or essentially consists of a ceramic composition.

Preferred compositions include Lithium Aluminum Titanium Phosphate (LATP), Lithium Aluminum Germanium Phosphate (LAGP), Lithium

Lanthanum Zirconium Oxide (LLZO), Halide electrolytes (e.g., Liz.«Mi- «Zr:Clg M = Y, Er), Sulphide electrolytes (e.g. LiioGeP2Si2 , LigPS:;:X (X = Cl,

Br or I), 67(75Li12S-25P2S5)-33LiBH 4 , 30Li2S-26B2S3-44Lil) or derivatives and/or mixtures thereof. The fibers can be dispersed throughout the matrix as discrete elements. Advantageously, the fibers can be added in an amount above a percolation threshold, forming a percolation pathway for ion conduction between opposing faces of the polymer matrix, enhancing overall ion conductance. The pathway can be a direct pathway along a single elongate filler, such as a fiber. Alternatively, or in addition, the pathway may be a formed as a network comprising or plurality of adjacent or adjoining fillers, or a composite pathway wherein part of the percolation trajectory 1s formed by gaps between fillers across a volume of the matrix, e.g. matrix between adjacent fillers separated by a separation distance.

Advantageously, in some embodiments the fibers can be physically inter-twined. This enhances inter-fiber conductivity. Optionally the fibers may be linked, e.g. fused, together forming a network of interlinked fibers, which removes inter-fiber diffusion barriers and further enhances inter-fiber diffusivity.

The second fillers can be fibers comprising the metal ion conductive composition, such as LATP, LAGP, LLZO, halide electrolyte materials, sulphide electrolyte materials or mixtures thereof. The fibers may be essentially formed of the metal ion conductive composition or comprise a coating of such composition. Preferably, the elongate fillers have an aspect ratio (length along an axial direction over width) at least 5, preferably at least 10. The higher the aspect ratio of the elongate fillers the smaller an amount requires to provide a path between opposing faces of the hybrid solid electrolyte layer can be. Advantageously the fibers can have an aspect ratio > 50, preferably larger, e.g. >100, allowing to further minimize the amount required for forming a percolation pathway for ion conduction between opposing faces of the polymer matrix.

Generally the fibers have a length of at least 100 nm, e.g. in a range > 500 nm. Longer fibers are possible, e.g. in excess of 5, 10 or even 100 pm. Fibers can even have a length up to several centimeters, e.g. up to 1 cm or more such as up to 10 cm. Fibers of specified length can be provided as disclosed herein, e.g. using methods such as electrospinning and extrusion.

Typically the fibers do not extend beyond the polymer matrix.

Short fibers, fibers having a length less than a thickness of the polymer matrix, can be processed, intermixed, e.g. in melt, with the polymer matrix or precursor thereto. Longer fibers are typically incorporated in a preformed dry fiber structure, e.g. a mat, as will be explained herein. In some embodiments, elongate fillers are predominately (>50% by mass) oriented along a direction between the anode and the cathode. Preferably the fillers are predominately oriented along a principal direction between opposing faces of the polymer matrix. Preferably the deviation is between -20 and +20 degrees, most preferably between -10 and +10 degrees.

Generally the dielectric particles have a maximum dimension (diameter) below 1 pm (sub-micron), preferably smaller, e.g. below 0.5 pm.

Typically, the particles have a maximum dimension in a range between 10 nm and 800 nm or in a range between 20 and about 500 nm. The smaller the particles the smaller the total amount required (volume per unit volume) for field homogenization and/or plasticizing the matrix. Sub-micron particles can e.g. be obtained by spark ablation and/or by on wet-chemical synthesis methods.

In some embodiments, the nanoparticles are dispersed in polymer matrix among the other constituents. This reduces a number of process steps required during manufacturing.

Alternatively or in addition at least part of the particles can be comprised in a separate layer. Accordingly, the hybrid solid electrolyte layer is configured as a stack of layers including a first layer confining the solid state electrolyte fibers and a second layer, comprising at least part of the dielectric particles. The second layer, i.e. the layer without fibers preferably faces the anode. Providing the nanoparticles in a separate layer may advantageously decouple dispersing of the elongate fillers and the nanoparticles. Arranging the layer with particles closest to the anode can have the dual advantage of: aligning the electrical field directly where disturbances have the strangest effect, i.e. near the position where anode metal, e.g. Li, 1s plated, during battery operation plating; mitigating potential chemical degradation by avoiding direct mechanical contact between the anode material and the ion conductive fibers.

According to another or further aspect the present disclosure relates to the hybrid solid electrolyte layer as disclosed herein, e.g. comprising one or more of the features as described in relation to the battery. In some embodiments, the hybrid solid electrolyte comprises: a polymer matrix; a metal salt dispersed in the polymer matrix, and elongate fillers, fibers, of a metal ion conductive inorganic composition orientated along a direction between the opposing faces of the polymer matrix of the hybrid solid electrolyte.

According to other or yet further aspects the present disclosure relates to an electrochemical device comprising the hybrid solid electrolyte as disclosed herein.

Yet further aspects related to a method of manufacturing a metal ion battery and/or a hybrid solid electrolyte layer, preferably the metal ion battery and/or hybrid solid electrolyte as disclosed herein. In a broad sense the manufacturing the electrolyte comprises forming a layer comprising: a polymer matrix, a metal salt dispersed in the hybrid solid electrolyte, and at least first and second filler materials dispersed in the hybrid solid electrolyte, wherein the first filler material comprises inorganic high-k dielectric particles and the second filler material comprises solid state electrolyte fibers. Manufacturing the battery typically further comprises at least providing an anode and a cathode, whereby the hybrid solid electrolyte formed as a layer between the anode and the cathode. Advantageously, the hybrid solid electrolyte can be manufactured as an individual self-standing layer, e.g. by removing the hybrid solid electrolyte from a suitable carrier substrate. Alternatively the hybrid solid electrolyte can be manufactured onto an electrode layer. It will be appreciated that further layers such a catholyte and/or anolyte layer can be added as appropriate, either directly to the hybrid solid electrolyte, or as part of battery manufacturing.

In a preferred embodiment, providing the hybrid solid electrolyte comprises dispensing a pre-formed dispersion comprising the fibers and the polymer matrix and/or a precursor in an appropriate liquid carrier.

Accordingly, providing the hybrid solid electrolyte comprises: dispensing, forming a dispensed layer comprising the solid state electrolyte fibers in a carrier further comprising the polymer matrix and/or a precursor thereto.

Following dispensing, e.g. by printing, the polymer matrix is solidified. For example, by evaporating excess carrier and/or by curing/crosslinking the polymer matrix and/or the precursor thereto.

Dispensing may be performed by any known suitable method including but not limited to melt casting, solution casting, and/or melt extrusion. Advantageously extrusion may be solvent free extrusion. Forcing the composition through an aperture can advantageously result in an at least a partial alignment of the fillers. C. Aitken-Nichol et al (Pharmaceutical Res., 13 804-808 (1996) provides an overview of hot melt extrusion methods.

Alternatively, or in addition, the method may comprise a step of aligning the fibers, e.g. during or after dispensing the composition but before solidification. Inventors found that alignment can be suitably obtained by applying an external field along a direction of alignment, for example an electric field or magnetic field. Desired alignment can be attained by selecting appropriate field strength, duration, and/or direction, e.g. perpendicularly to the dispensed layer.

In a strongly preferred embodiment wherein providing the hybrid solid electrolyte comprises impregnating a preformed structure of the elongate fillers. Accordingly, the step of wherein providing the hybrid solid electrolyte can be understood to comprise: generating a dry porous structure comprising solid state electrolyte fibers, and impregnating the dry porous structure with a composition comprising the polymer matrix and/or a precursor thereto, followed by solidifying polymer matrix and/or the precursor thereto. In this case of pre-forming a porous substrate, providing the hybrid solid electrolyte can comprise melt casting; melt-extrusion will be less preferred because of potentially damaging the fiber structure.

The solid state electrolyte fibers can be suitably formed as desired to a desired specification. Methods include extrusion, e.g. melt extrusion, electrospinning, e.g. co-axial electrospinning, and coating of suitable carrier, e.g. fibers, etched structures, grown pillars. If desired formed structures, e.g. coated fibers, can be cut, chopped up to shorter wires. Electrospinning is preferred for forming structures comprising bulk continuous fibers.

Preformed dry porous structure comprising solid state electrolyte fibers can be suitably provided using method comprising extrusion and/or electrospinning, e.g. of a metal ion conductive inorganic composition or mixture thereof onto a carrier substrate. A preferred predominant alignment can be obtained by electrospinning a solid state electrolyte composition from a deposition nozzle onto a carrier, whereby, during deposition, a lateral displacement rate of the nozzle relative to the carrier is smaller than a deposition rate of the fiber from the nozzle.

BRIEF DESCRIPTION OF DRAWINGS

These and other features, aspects, and advantages of the apparatus, systems and methods of the present disclosure will become better understood from the following description, appended claims, and accompanying drawing wherein:

FIG 1A provides a schematic cross-section side view of an embodiment of metal ion battery comprising a hybrid solid electrolyte,

FIG 1B provides a schematic cross section side view of a hybrid solid electrolyte;

FIG 2A depicts a schematic cross section side view of a hybrid solid electrolyte;

FIG 2B and 3A provide schematic exploded cross-section side views a metal ion batteries;

FIG 3B provides a schematic cross-section side view of a metal ion battery;

FIG 4A schematically illustrates a method manufacturing a metal ion battery; and

FIG 4B, 5A and 5B schematically illustrate certain aspects of methods of manufacturing a hybrid solid electrolyte layer.

DESCRIPTION OF EMBODIMENTS

Terminology used for describing particular embodiments is not intended to be limiting of the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates 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 "comprises" and/or "comprising" specify the presence of 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 subsequent to another step, it can directly follow said other step or one or more intermediate steps may be carried out before carrying out the particular step, unless specified otherwise. Likewise it will be understood that when a connection between structures or components is described, this connection may be established directly or through intermediate structures or components unless specified otherwise.

The invention is described more fully hereinafter with reference to the accompanying drawings, in which embodiments of the invention are shown. In the drawings, the 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- section illustrations of possibly idealized embodiments and intermediate structures of the invention. In the description and drawings, like numbers refer to like elements throughout. Relative terms as well as derivatives thereof should be construed to refer to the orientation as then described or as shown in the drawing 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 stated otherwise.

FIG 1A provides a schematic cross-section side view of an embodiment of metal ion battery 1 comprising a hybrid solid electrolyte 4.

The hybrid solid electrolyte 4 is positioned between an anode 2 and a cathode 3. The hybrid solid electrolyte 4 separates the anode 2 and the cathode 3, preventing direct electrical contact. At the same time the hybrid solid electrolyte 4 provides ion transport, from cathode towards anode during a charging cycle of the battery and vice versa during discharging.

As illustrated in FIG 1B the hybrid solid electrolyte 4 comprises a metal salt 6, dielectric particles 8, and solid state electrolyte fibers 9. These constituents are distributed, dispersed through the hybrid solid electrolyte 4 in a polymer matrix. The polymer matrix provides a network, schematically illustrated by cross-hatched pattern, which confines particles and fibers while allowing the metal salt, ions, to diffuse between opposing faces 4a,4c of the hybrid solid electrolyte 4. In the embodiment as shown the face marked 4c faces a cathode 3, whereas face 4a faces an anode of 1 battery device.

It will be appreciated that the hybrid solid electrolyte 4 can comprise further additives (not shown for clarity) including, but not limited to an amount of liquid carriers such as ionic liquid and/or organic solvents, and plasticizer in the polymer matrix. In some embodiments, small amounts, e.g. up to 30 vol% each, of ionic liquid or organic solvents or other additives, such as a plasticizer like succinonitrile, may be added into the

Polymer Matrix.

Likewise it will be understood that the battery and/or hybrid solid electrolyte 4 can comprise one or more further constituents such as anolyte, catholyte, a shielding layer, and a passivation layer, as will be explained in more detail in relation to FIGs 2B, 3A, and 3B.

In some embodiments, any of the filler particles, e.g. the dielectric particles 8 filler and/or the solid state electrolyte fibers 9 can be provided with a coating comprising a metal ion conductive composition, e.g. an organic coating, such as an organic monolayer, providing functional end groups capable of reversible associating to metal cations, e.g. capable forming an electric double layer. For example, end groups such as -carboxyl groups, hydroxyls, phosphates and the like.

Advantageously, a layer, coating, like this can serve the function of enhancing interfacial contact between the polymer matrix and the fillers (thus avoiding voids).

Alternatively, or in addition, such a coating could also have a different function e.g. adsorbing/arresting polysulphide molecules which can migrate (during battery cycling) from a Sulphur cathode to a Lithium anode of a Lithium-Sulphur battery.

As will be explained in more detail below the dielectric particles 8 and solid state electrolyte fibers 9 serve to increase 1on mobility thought the polymer matrix 5, whereby the solid and elongate nature if the electrolyte fibers 9 additionally improves mechanical integrity of the hybrid solid electrolyte 4, in particular when the matrix is in a semi-solid, e.g. gel-like, condition during battery operation. For example, example as a result of an elevated temperature of the electrolyte during operation (e.g. about 40- 80°C), and/or due reduction of a plasticization temperature or glass transition temperature due to addition of the dielectric particles 8 and solid state electrolyte fibers 9 and/or the other constituents.

In a preferred embodiment, e.g. as shown, the solid state electrolyte fibers 9 are predominantly orientated along a principal direction

D between the anode 2 and the cathode 3. As such the fibers provide mechanical support along a direction between the anode 2 and cathode 3, while also improving ion transport in the principal direction D between opposing faces 44,4c of the hybrid solid electrolyte 4.

Preferably, the solid state electrolyte fibers are provided in an amount above a percolation threshold. This allows forming a network for ion transport throughout the polymer matrix 5. As shown by the dashed arrow ion 6 transport is believed to takes place along and outer surface of the solid state electrolyte fiberf(s) 9. Alternatively, or in addition, ion transport can take place along the dielectric particles 8, within the bulk of the solid state electrolyte fibers 9, or via a combination thereof.

In some embodiments, at least part of the solid state electrolyte fibers 9 are chemically interconnected, e.g. fused as indicated by the crossing fibers marked X1. Fusing can be obtained for example by annealing of a preformed fiber structure or by hot processing of the wires, e.g. during electrospinning as will be explained in relation to FIG 5B. In other or further embodiments, the, fat least part of the fibers are intertwined, e.g. as shown in the crossing marked X2.

The dielectric particles 8 homogenize an electric field along a direction between the anode 2 and the cathode 3 during battery operation (marked direction D). In some embodiments, e.g. as shown, the dielectric particles 8 are distributed, dispersed, throughout the polymer matrix 5. In other or further embodiments, e.g. as shown in FIG 2A, the particles can be distributed along a layer along one of the terminal faces of the hybrid solid electrolyte 4.

In some embodiments, e.g. as shown in FIG 1B, the dielectric particles 8 and the solid state electrolyte fibers 9 are intermixed in a single layer L1. Intermixing the dielectric particles 8 and the solid state electrolyte fibers 9 in a single layer can reduce a number of process steps for manufacturing the hybrid solid electrolyte 4 as opposed to a multilayer configuration.

In other or further embodiments, e.g. as shown in FIG 2A, 3A and 3B, the dielectric particles 8 and the solid state electrolyte fibers 9 are provided in separate layers L1.1, L1.2, whereby the particles and fibers are each dispersed throughout a polymer matrix 5.1,5.2 along with a metal salt 6. The salt and matrix material are typically similar or even of the same composition. Using the same, or at least of the same class, mitigates a diffusion barrier between the interfaced between the layers L1.1, L1.2.

When the hybrid solid electrolyte 4 is configured as a stack the layer comprising the dielectric particles 8, e.g. layer 1.2, is preferably oriented towards the anode 2, e.g. as shown in FIG 3A.

In a preferred embodiment, e.g. as shown in FIG 1B, the solid state electrolyte fibers 9 do not extend to or beyond the opposing faces 4a,4c of the hybrid solid electrolyte 4. This mitigates potential (electro)chemical interaction between the fiber and the electrode materials, in particular

Lithium. Such configuration can for example be obtained by provision of one or more interlayers without fibers such as a shielding layer LO and a passivation layer L2.

It will be appreciated that the benefits as to improved ion conduction are not to be understood to the presence of solid state electrolyte fibers. Inventors found that similar benefits can be obtained with fibers of a high-k dielectric composition. In general, advantageous aspects as to electric field homogenization, improved mechanical stability and ion conductance along an interface between fibers and the dielectric matrix can be obtained with inorganic dielectric fibers, even when the solid state electrolyte in a particulate, e.g. non-fibrous, form such as nanoparticles. Accordingly, is some aspects the present invention relates to the hybrid solid electrolytes as disclosed herein whereby at least one of the dielectric filler, preferably high- k dielectric filler, and the solid state electrolyte is in fibrous form. In view of the contribution of the solid state electrolyte to ion conduction, fibrous solid state electrolytes as disclosed herein are preferred.

In one embodiment, the hybrid solid electrolyte can be understood to comprise: a polymer matrix, a metal salt dispersed in the hybrid solid electrolyte, typically throughout the polymer matrix. In addition the hybrid solid electrolyte comprises at least first and second dispersed filler materials, wherein the first filler material comprises an inorganic high-k dielectric, the second filler material comprises a solid state electrolyte, and wherein at least one of the first and second filler is at least in part in a fibrous form.

In some embodiments, at least part of the other of the first and second filler is also in a fibrous form. The different fibers can be intermixed, e.g. homogenously distributed, e.g. in a preformed dry fiber structure.

Alternatively the fibers can be intermixed, e.g. during melt or solution processing. Dry structures of intermixed fibers with different composition can be suitably made by co-spinning or co-extruding of corresponding materials. In another or further embodiment, the fibrous solid-electrolyte and the fibrous high-k filler can be spatially separated in two different layers, e.g. as explained in relation to layers L1.1 and L1.2.

In other or further preferred embodiments, the hybrid solid electrolyte comprises one or more of a shielding layer and a capping layer.

The shielding and capping layer can each advantageously shield the fillers from direct contact with one or more of the anode, the cathode, anolyte, and a catholyte, mitigating degradation of the fillers, e.g. by chemical interaction with the metal ion conductive inorganic composition.

In one embodiment, e.g. as shown in FIG 2B, the hybrid solid electrolyte comprises a passivation layer L2 at an anode side of the hybrid solid electrolyte. The passivation layer L2 is provided along an anode side 4a of the hybrid solid electrolyte 4. The layer shields the hybrid solid the solid state electrolyte fibers from a direct contact with the anode 2 and/or an anolyte composition.

Advantageously, the passivation layer can be formed of a composition which facilitates the formation of a solid electrolyte interphase (SEI) and/or that acts as a wetting or adhesion layer for the anode.

The passivation layer L2 can be suitable comprised of a composition including a polymer matrix. The matrix can be the same or similar as the matrix comprising the fibers and/or particles. Typically the polymer matrix comprises one or more materials selected from the group of polyvinylidene fluoride, polydimethylsiloxane, polyethylene oxide, polymethyl methacrylate, polyethylene diacrylate, polyacrylonitrile,

hexafluoropropylene, and copolymers thereof. The average molecular weight (Mw) of the polymer materials is generally between 10000 and 1000000 g/mol. The thickness of the shielding layer is typically between 0.1 and 50 pm. Additives can include one or more of : a solid electrolyte interphase (SEI) forming composition and a plasticizer. SEI forming materials include but are not limited to: ionic liquids, e.g. N-Propyl-N-methylpyrrolidinium.

Optionally lithium salts can be included such as: lithium bis(trifluoromethanesulfonyDimide, lithium bis(fluorosulfonyl)imide,

Lithium tetrafluoroborate, Lithium dioxalate borate, lithium imide, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium nitrate or a combination thereof.

The passivation layer L2 can further advantageously mitigate progressive surface roughening and/or depositon of porous anode material, due to repetitive metal-ion deposition (plating) and desorption (de-plating) during consecutive (dis)charging cycles of the battery

In other or further embodiments, e.g. as shown in FIG 3A, the hybrid solid electrolyte comprises both a passivation layer L2 and one or more shielding layer LO at a cathode side 4c of the hybrid solid electrolyte 4.

In the embodiment as shown in FIG3A the metal ion battery 1 comprises a hybrid solid electrolyte 4 that is configured as a stack of layers

L1. The stack includes a first layer L1.1 comprising the fibers and a second layer L1.2 that comprises the dielectric particles 8, as shown in FIG 2A.

Similar to the embodiment shown in FIG 2B a passivation layer L2 is provided that faces the anode 2. In addition a shielding layer LO is provided along at an cathode side of the hybrid solid electrolyte. The passivation layer can comprise similar or even the same constituents as the shielding layer and can have a thickness in the same range, e.g. about 500 nm, about 2 pm, or about 10 pm. The combination of the shielding and passivation layers was found to optimally protect the ion conductance improving fillers and/or the polymer matrix from degradation.

FIG 3B provides a schematic cross-section side view of a metal ion battery 1. In comparison to the embodiments shown in FIG3A the first layer

L1.1 and the second layer L1.2 are arranged in preferred orientation whereby the layer comprising the particles, i.e. layer L1.2, faces the anode 2.

In addition the battery includes an anolyte 12 and catholyte 13.

The catholyte and the anolyte are positioned at interfaces between the hybrid solid electrolyte 4 and respectively the cathode 3 and the anode 2.

The catholyte and anolyte improve contact between the hybrid solid electrolyte 4 and the electrode materials, in particular when the anode/cathode are formed of solid materials, e.g. metal films or foils, have surface undulations or roughness R that does not match a surface profile of the opposing face of the hybrid solid electrolyte 4. If the cathode and/or the anode is a porous layer, then the catholyte and/or the anolyte will also penetrate into the porosity, e.g. be present inside the bulk of the electrodes.

Their function is not only to improve the interfacial contact with the hybrid solid electrolyte membrane, but also to enable an ion-conduction path within the bulk of the electrode layers. As an exemplary embodiment it is foreseen that at least one of the electrodes, e.g. the anode, can be a 3D structured electrode, e.g. upstanding pillars comprising electrode material and/or pillars coated with electrode material.

Aspects concerning manufacturing the hybrid solid electrolyte 4 and metal ion battery 1 will now be explained in more detail with reference to FIGs 4A-B and 5A-B, wherein FIG 4A schematically illustrates a method manufacturing a metal ion battery; and FIGs 4B, 5A and 5B schematically illustrate certain aspects of methods of manufacturing a hybrid solid electrolyte layer.

As illustrated in FIG 4A, the method of manufacturing a metal ion battery comprises: providing an anode 101, providing a cathode 102 and providing a hybrid solid electrolyte 103. Optionally the method can include the steps of providing and anolyte 110 and/or providing a catholyte 111,

whereby the provided constituents are suitably arranged in a battery configuration as disclosed herein. It will be appreciated that the steps need not necessarily be performed in the depicted order. The constitutes may be assembled or even build upon each other in any suitable order. In particular the step of providing the electrolyte may be performed independently resulting in preformed hybrid solid electrolyte 4 layers of films which can be stored, used, or sold independently, e.g. as part of another electrochemical device.

The step of providing 103 the hybrid solid electrolyte 4 generally comprises forming 104 a layer comprising: a polymer matrix 5, a metal salt 6 dispersed in the hybrid solid electrolyte 4, and at least first and second filler materials dispersed in the hybrid solid electrolyte 4. As discussed herein the first filler material comprises inorganic high-k dielectric particles 8 and the second filler material comprises solid state electrolyte fibers 9.

FIG 4B depicts exemplary aspects of forming the hybrid solid electrolyte 4. The top-left illustrates a nozzle 201 during depositing 104 a layer 4’. The layer comprises solid state electrolyte fibers 9 and a polymer matrix or precursor thereto 5p. The layer is deposited onto a carrier substrate 202 from which the hybrid solid electrolyte 4 can be delaminated as a membrane after forming. Alternatively the hybrid solid electrolyte 4 can be assembled directly onto a functional battery layer, e.g. an anode or cathode. During deposition the composition is in a liquid, e.g. molten of solubilized state.

In another or further preferred embodiment, the composition is a slurry be mixed into the slurry comprising the polymer and/or precursor thereto along with the solid state electrolyte fibers 9 and dielectric particles, e.g. BTO particles.

Following deposition layer is hardened 106 to form the polymer matrix 5, e.g. by evaporating excess solvent and or curing of the polymer and precursor thereto. The bottom left drawing depicts the process during

UV curing (wavy arrows) of the layer.

In some embodiments, e.g. as shown in the bottom right drawing, the hardening step is preceded by aligning 106 the solid state electrolyte fibers. In the embodiment as shown alignment is performed by applying an electromagnetic field in a perpendicular direction across the layer. This field aligns the fibers in the still liquid, uncured, layer 4’. The length of the fibers can be adapted to a target thickness of the hybrid solid electrolyte layer, e.g. by shortening, e.g. cutting or chopping, longer preformed fibers.

After hardening the procedure may include delaminating 109 the hardened layer from the carrier 202 to yield a free standing hybrid solid electrolyte 4.

The metal salt 6 (not depicted in the drawings) and/or other constituents can be included in the mixture or slurry as deposited.

Alternatively the metal salt 6 and any one or more of the other constituents, e.g. plasticizer, can be added at a later stage, e.g. after hardening, by exposing the polymer matrix to a solution with salt/additives in a solvent with affinity to the polymer, e.g. swelling the polymer matrix.

In some embodiments, providing 103 the hybrid solid electrolyte 4 comprises: generating, pre-forming, a dry porous structure comprising solid state electrolyte fibers 9. The preformed structure of fibers can subsequently be impregnated with a composition comprising the polymer matrix and/or a precursor thereto, followed by solidifying polymer matrix and/or the precursor thereto. As discussed above the salt and/or or additives can be added along with the precursor compositor or introduced afterwards, e.g. in a swelling step.

In some embodiments, the structure of the fibers can comprise intrinsically porous fibers. Intrinsic porosity can be made, for example, within the electrospun fibers by e.g. trapping small gas bubbles or mixing solvents in the precursor that after spinning & annealing of the fibers result in voids. Provision of pores/voids advantageously increases surface area of the fibers while reducing a net weight of the fiber. In other or further embodiments, the structure of the fibers can be a co-axially layered structure of the fibers.

Advantageously, the fibers may be post-treated for surface modifications or coatings, before mixing in with the polymer matrix. (e.g. for better interaction/wetting with the matrix).

FIG 5A (top left) depicts procedure following a step 108 of preforming a dry porous structure 9’comprising solid state electrolyte fibers 9. As shown the structure can be formed on a carrier substrate 202.

Subsequently the formed structure, either on the carrier or on a battery active layer, is impregnated 107 with a composition with a composition comprising the polymer matrix and/or a precursor thereto 5p. After impregnation the polymer matrix and/or the precursor thereto is hardened, e.g. by curing and/or evaporation of excess solvent yielding a polymer matrix 5 with embedded solid state electrolyte fibers 9 (5A, bottom right). Following the hardening the formed hybrid solid electrolyte 4 can be delaminated 109 from carrier.

FIG 5B schematically illustrates how electrospinning can be used to yield a preformed structure 9’ of solid state electrolyte fibers 9 on face of a substrate, e.g. a carrier 202. Alternatively the spun fibers can be cut to smaller pieces, collected, and used in a melt or solution process as described in relation to FIG 5A. Thus a structure 9’ or mat can be formed which can be collected separately or which can be used directly in an impregnation process as described in relation to FIG 5A or 5B. For dry mats structural integrity can be improved by interconnecting deposited fibers and/or portions of deposited fibers, e.g. by intertwining or chemical interconnections such as fused portions.

In a preferred embodiment, the dry porous structure 9’ is formed in a process comprising electrospinning a precursor to the solid state electrolyte fibers from a deposition nozzle 201 onto a carrier 202, whereby a lateral displacement rate of the nozzle s201 relative to the carrier 202 is smaller than an ejection rate of spun fiber s9 from the nozzle. By deposition the spun fiber at a higher rate than a lateral displacement rate of the nozzle, preferably at least 10 times higher, the deposited fiber forms vertical loops away from the substrate whereby the height of the loops increases with increasing difference between spin and translation rates.

Additionally, the electrospinning can have the benefit of forming chemically interconnected crossings between fibers and/or fiber portions, for example, when during deposition deposited spun fiber is kept close over slightly above a softening or fusing temperature.

For the purpose of clarity and a concise description, features are described herein as part of the same or separate embodiments, however, it will be appreciated that the scope of the invention may include embodiments having combinations of all or some of the features described.

For example, while embodiments were shown for hybrid solid electrolyte with intermixed dielectric particles and solid state electrolyte fibers , also alternative ways may be envisaged by those skilled in the art having the benefit of the present disclosure for achieving a similar function and result.

E.g. the fibers and particles may be combined or split up into one or more layers. The various elements of the embodiments as discussed and shown offer certain advantages, such as improved ion conductance, mechanical integrity, and electrolyte stability. Of course, it is to be appreciated that any one of the above embodiments or processes may be combined with one or more other embodiments or processes to provide even further improvements in finding and matching designs and advantages. It is appreciated that this disclosure offers particular advantages to rechargeable lithium batteries and in particular lithium metal batteries, and in general can be applied for any application, e.g. electrode with electrolyte, benefitting from improved ion conductance.

In interpreting the appended claims, it should be understood that the word "comprising" does not exclude the presence of other elements or acts 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 signs in the claims do not limit their scope; several "means" may be represented by the same or different item(s) or implemented structure or function; any of the disclosed devices or portions thereof may be combined together or separated into further portions unless specifically stated otherwise.

Where one claim refers to another claim, this may indicate synergetic advantage achieved by the combination of their respective features.

But 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 to advantage.

The present embodiments may thus include all working combinations of the claims wherein each claim can in principle refer to any preceding claim unless clearly excluded by context.

Claims

CONCLUSIESCONCLUSIONS

1. Een metaalionbatterij (1) omvattende een anode (2), een kathode (3) en een hybride vaste elektrolyt (4), gevormd als een laag (L1) tussen de anode (2) en de kathode (3), de hybride polymeer elektrolyt (4) omvattende: een polymeer matrix (5), een metaal zout (6) gedispergeerd in de hybride vaste elektrolyt (4), en ten minste eerste en tweede vulmiddelen gedispergeerd in de hybride vaste elektrolyt (4), waarbij het eerste vulmiddel anorganische hoge-k diëlektrische deeltjes (8) omvat en het tweede vulmiddel elektrolytvezels in vaste toestand (9) omvat.A metal ion battery (1) comprising an anode (2), a cathode (3) and a hybrid solid electrolyte (4), formed as a layer (L1) between the anode (2) and the cathode (3), the hybrid polymer electrolyte (4) comprising: a polymer matrix (5), a metal salt (6) dispersed in the hybrid solid electrolyte (4), and at least first and second fillers dispersed in the hybrid solid electrolyte (4), the first filler comprises inorganic high-k dielectric particles (8) and the second filler comprises solid state electrolyte fibers (9).

2. De metaalionbatterij (1) volgens conclusie 1, waarin de elektrolytvezels in vaste toestand (9) hoofdzakelijk zijn georiënteerd langs een hoofdrichting tussen de anode (2) en de kathode (3).The metal ion battery (1) according to claim 1, wherein the solid state electrolyte fibers (9) are oriented substantially along a principal direction between the anode (2) and the cathode (3).

3. De metaalionbatterij (1) volgens conclusie 1 of 2, waarin de diëlektrische deeltjes (8) en de elektrolytvezels in vaste toestand (9) zijn vermengd.The metal ion battery (1) according to claim 1 or 2, wherein the dielectric particles (8) and the solid state electrolyte fibers (9) are mixed.

4. De metaalionbatterij (1) volgens conclusie 1 of 2, waarin de laag is gericht als een stapel met een eerste laag (L1.1) die de elektrolytvezels in vaste toestand (9) opsluit en een tweede laag (L1.2), die tenminste een deel van de diëlektrische deeltjes (8) omvat, en waarin de tweede laag (L1.2) naar de anode (2) is gericht.The metal ion battery (1) according to claim 1 or 2, wherein the layer is arranged as a stack having a first layer (L1.1) confining the solid state electrolyte fibers (9) and a second layer (L1.2), comprising at least part of the dielectric particles (8), and in which the second layer (L1.2) faces the anode (2).

5. De metaalionbatterij (1) volgens een de voorgaande conclusies, waarin de elektrolytvezels in vaste toestand (9) een lithium ion geleidende samenstelling of combinatie daarvan omvat.The metal ion battery (1) according to any one of the preceding claims, wherein the solid state electrolyte fibers (9) comprise a lithium ion conductive compound or combination thereof.

6. De metaalionbatterij (1) volgens een vaneen van de voorgaande conclusies, waarin de diëlektrische deeltjes (8) een diëlektrische constante hebben > 100.The metal ion battery (1) according to any one of the preceding claims, wherein the dielectric particles (8) have a dielectric constant > 100.

7. De metaalionbatterij (1) volgens een van de voorgaande conclusies, waarin de elektrolytvezels in vaste toestand (9) onderling zijn verbonden en een geconnecteerd netwerk vormen voor iongeleiding tussen tegenover gelegen vlakken (4a,4c) van de polymeer matrix (5).The metal ion battery (1) according to any one of the preceding claims, wherein the solid state electrolyte fibers (9) are interconnected and form a connected network for ion conduction between opposing faces (4a,4c) of the polymer matrix (5).

8. De metaalionbatterij (1) volgens een van de voorgaande conclusies, waarin de hybride vaste elektrolyt (4) een afschermende laag (LO) omvat, aan een kathodezijde van de hybride vaste elektrolyt (4), welke de hybride vaste elektrolyt (4) en de elektrolytvezels in vaste toestand (9) daarin omvat afschermt van de kathode en/of een katholiet samenstelling (12).The metal ion battery (1) according to any one of the preceding claims, wherein the hybrid solid electrolyte (4) comprises a shielding layer (LO), on a cathode side of the hybrid solid electrolyte (4), which protects the hybrid solid electrolyte (4). and the solid state electrolyte fibers (9) comprising shielding of the cathode and/or a catholyte composition (12) therein.

9. De metaalionbatterij (1) volgens een van de voorgaande conclusies, waarin de metaalionbatterij (1) een passiveringslaag (L2) omvat, aan een anodezijde van de hybride vaste elektrolyt (4) welke de hybride vaste elektrolyt (4) en de eerste en/of tweede vulmiddelen daarin omvat beschermt van een direct contact met de anode en/of een anoliet samenstelling.The metal ion battery (1) according to any one of the preceding claims, wherein the metal ion battery (1) comprises a passivation layer (L2) on an anode side of the hybrid solid electrolyte (4) which contains the hybrid solid electrolyte (4) and the first and and/or second fillers contained therein protects from direct contact with the anode and/or an anolyte composition.

10. Een hybride vaste elektrolyt (4), gevormd als een laag, omvattende: een polymeer matrix (5), een metaal zout (6) gedispergeerd 1n de hybride vaste elektrolyt (4), en ten minste eerste en tweede vulmiddelen gedispergeerd in de hybride vaste elektrolyt (4), waarbij het eerste vulmiddel anorganische hoge-k diëlektrische deeltjes (8) omvat en het tweede vulmiddel elektrolytvezels in vaste toestandA hybrid solid electrolyte (4) formed as a layer comprising: a polymer matrix (5), a metal salt (6) dispersed in the hybrid solid electrolyte (4), and at least first and second fillers dispersed in the hybrid solid electrolyte (4), the first filler comprising inorganic high-k dielectric particles (8) and the second filler solid-state electrolyte fibers

(9) omvat.(9) includes.

11. Een werkwijze voor het vervaardigen van een metaalionbatterij omvattende: het verschaffen van een anode, een kathode en een hybride vaste elektrolyt tussen de anode en de kathode, waarin het verschaffen (103) van de hybride vaste elektrolyt (4) omvat: het vormen een laag omvattende: een polymeer matrix (5), een metaal zout (6) gedispergeerd in de hybride vaste elektrolyt (4), en ten minste eerste en tweede vulmiddelen gedispergeerd in de hybride vaste elektrolyt (4), waarbij het eerste vulmiddel anorganische hoge-k diëlektrische deeltjes (8) omvat en het tweede vulmiddel elektrolytvezels in vaste toestand (9) omvat.A method of manufacturing a metal ion battery comprising: providing an anode, a cathode and a hybrid solid electrolyte between the anode and the cathode, wherein providing (103) the hybrid solid electrolyte (4) comprises: forming a layer comprising: a polymer matrix (5), a metal salt (6) dispersed in the hybrid solid electrolyte (4), and at least first and second fillers dispersed in the hybrid solid electrolyte (4), the first filler having inorganic high -k comprises dielectric particles (8) and the second filler comprises solid state electrolyte fibers (9).

12. De werkwijze volgens conclusie 11 omvattende het impregneren van de hybride vaste elektrolyt (4) met een vloeibare samenstelling die een metaal zout (6) omvat.The method of claim 11 comprising impregnating the hybrid solid electrolyte (4) with a liquid composition comprising a metal salt (6).

13. De werkwijze volgens een van de conclusies 11-12, waarin de elektrolytvezels in vaste toestand (9) zijn voorzien in een hoeveelheid boven een percolatiedrempel.The method of any one of claims 11-12, wherein the solid state electrolyte fibers (9) are provided in an amount above a percolation threshold.

14. De werkwijze volgens een van conclusies 11-13, waarin de elektrolytvezels in vaste toestand (9) worden gevormd door elektrospinnen van een overeenkomstige voorlopersamenstelling daarvan.The method according to any one of claims 11-13, wherein the solid state electrolyte fibers (9) are formed by electrospinning a corresponding precursor composition thereof.

15. De werkwijze volgens een van de conclusies 11-14, waarm het verschaffen (103) van de hybride vaste elektrolyt (4) omvat:The method of any one of claims 11-14, wherein providing (103) the hybrid solid electrolyte (4) comprises:

het afgeven (104), vormen van een afgegeven laag die de elektrolytvezels in vaste toestand (9) omvat in een drager die verder de polymeer matrix (5) en/of een voorloper (5p) daarvan omvat, gevolgd door het witharden (105) van de polymeer matrix (5) en/of de voorloper daarvan.releasing (104), forming a released layer comprising the solid state electrolyte fibers (9) in a carrier further comprising the polymer matrix (5) and/or a precursor (5p) thereof, followed by whitehardening (105) of the polymer matrix (5) and/or its precursor.

16. De werkwijze volgens conclusie 15, waarin de werkwijze omvat het uitlijnen (106) van de elektrolytvezels in vaste toestand (9) in een elektromagnetisch veld, waarbij genoemd veld loodrecht of de afgegeven laag is georiënteerd.The method of claim 15, wherein the method comprises aligning (106) the solid state electrolyte fibers (9) in an electromagnetic field, said field being oriented perpendicular to the released layer.

17. De werkwijze volgens een van de conclusies 15-16, waarin de afgegeven lag verder de diëlektrische deeltjes (8) omvat.The method of any one of claims 15-16, wherein the delivered layer further comprises the dielectric particles (8).

18. De werkwijze volgens een van de conclusies 11-17, waarin het afgeven smeltgieten en/of smeltextrusie omvat.The method of any one of claims 11-17, wherein the dispensing comprises melt molding and/or melt extrusion.

19. De werkwijze volgens een van conclusies 11-14, waarin het verschaffen (103) van de hybride vaste elektrolyt (4) omvat: het genereren van een droge poreuze structuur omvattende de elektrolytvezels in vaste toestand (9), en het impregneren van de droge poreuze structuur met een samenstelling omvattende de polymeer matrix en/of een voorloper daarvan, gevolgd door het uitharden van de polymeer matrix en/of de voorloper daarvan.The method of any one of claims 11-14, wherein providing (103) the hybrid solid electrolyte (4) comprises: generating a dry porous structure comprising the solid state electrolyte fibers (9), and impregnating the dry porous structure with a composition comprising the polymer matrix and/or a precursor thereof, followed by curing of the polymer matrix and/or its precursor.

20. De werkwijze volgens conclusie 19, waarin het genereren van de droge poreuze structuur is gevormd in een proces omvattende elektrospinnen van een voorloper van de elektrolytvezels in vaste toestand vanuit een afzettingsmondstuk op een drager, waarbij een laterale verplaatsingssnelheid van het mondstuk ten opzichte van de drager kleiner is dan een afzettingssnelheid van de vezel uit het mondstuk.The method of claim 19, wherein the generation of the dry porous structure is formed in a process comprising electrospinning a precursor of the electrolyte fibers in a solid state from a deposition nozzle onto a support, wherein a lateral displacement velocity of the nozzle relative to the carrier is less than a deposition rate of the fiber from the nozzle.

21. De werkwijze volgens een van conclusies 19-20, waarin het verschaffen (103) van de hybride vaste elektrolyt (4) smeltgieten omvat.The method of any one of claims 19-20, wherein providing (103) the hybrid solid electrolyte (4) comprises melt molding.

22. De werkwijze volgens een van conclusies 11-19, verder omvattende het deponeren van een afschermlaag (L0), aan kathodezijde van de hybride vaste elektrolyt (4).The method of any one of claims 11-19, further comprising depositing a shielding layer (L0) on the cathode side of the hybrid solid electrolyte (4).

23. De werkwijze volgens een van conclusies 11-20, verder omvattende het verschaffen van een passiveringslaag (L2), aan een anodezijde van de hybride vaste elektrolyt (4).The method according to any one of claims 11-20, further comprising providing a passivation layer (L2), on an anode side of the hybrid solid electrolyte (4).