Coated 3D electronically conductive network for use as an electrode

Abstract

A coated three-dimensional electronically conductive network (1) for acting as an electrode in a metal or metal-ion battery, wherein the metal is selected from the list consisting of Na, K, Li, Ca, Mg, and Al, (i) comprises a plurality of interconnected electronically conductive wires and has a porosity of at least 60% and a surface area of ​​at least 10 -3 m 2 / cm 3 ~100m 2 / cm 3 and (ii) an electronically insulating coating (11) conformally covering the entire surface of the network (10) and which is permeable and / or conductive to ions of the metal at at least one temperature in the range of -30°C to 150°C.

Description

[Technical Field]

[0001] The present invention relates to the field of batteries, and more specifically to a coated three-dimensional electronically conductive network, a method for forming the same, and a battery including a coated three-dimensional electronically conductive network acting as a negative electrode. [Background technology]

[0002] Currently, the negative electrodes of lithium-ion batteries often contain materials to which lithium can intercalate. However, negative electrodes containing lithium foil instead can offer a higher energy density. Therefore, batteries with negative electrodes made of lithium foil can achieve a much larger charge capacity. In the case of a lithium foil negative electrode, lithium is plated onto the lithium foil or negative electrode during battery charging, and the lithium is peeled off from the lithium foil or negative electrode during battery discharge.

[0003] Lithium foil presents several problems. Firstly, the high current density resulting from the planar shape of the lithium foil can cause lithium dendrites to grow on the foil or on the negative electrode. Lithium dendrites are rigid, branched structures containing lithium that, as they grow, can penetrate the battery separator and cause a short circuit. Secondly, metallic lithium can irreversibly react with electrolyte components and decomposition products to form a solid electrolyte interphase (SEI) on the surface of the lithium foil, leading to the consumption of lithium from the electrolyte. Furthermore, the SEI also acts as an interface that prevents lithium diffusion to the negative electrode. Consequently, the SEI reduces the charge-discharge rate of lithium batteries. Thirdly, lithium batteries containing lithium foil generally have poor cycle performance. Volume changes in the lithium foil during the plating (during charging) and delamination (during discharging) of lithium metal on the foil negatively affect the lifespan of the negative electrode. In particular, voids can form during delamination, generating mechanical stress and potentially causing the foil to crack. Also, especially when using a solid electrolyte as the battery electrolyte, volume changes can lead to loss of contact between the lithium foil and the solid electrolyte. Fourth, there are safety concerns regarding lithium-metal batteries that contain both metallic lithium and a liquid electrolyte containing a flammable solvent. Because lithium metal is highly reactive with air, especially H2O, there are safety issues in handling and manufacturing lithium foil, as well as in assembling battery cells using lithium anodes. Finally, lithium batteries containing lithium foil may have low charge and discharge rates, particularly due to the small surface area of ​​the lithium foil.

[0004] In cutting-edge technologies, electrodes containing porous structures to which lithium can be plated and stripped have been used to overcome at least some of the aforementioned problems. For example, Liang et al., in PNAS 113(2016)2862-2867, disclose a porous structure containing lithium-plated carbon fibers. By using a porous structure, the surface area to which lithium can be plated increases, potentially improving the rate of plating and stripping, and consequently the charge-discharge rate of the battery constituting the electrode. At the same time, the increased surface area reduces the current density on the electrode surface, which in principle suppresses lithium dendrite formation and simultaneously increases the achievable charge capacity. Finally, the volume change of electrodes containing porous structures due to lithium plating and stripping on the porous network is reduced, which reduces mechanical stress within the electrode and improves cycle performance.

[0005] However, the cycling performance of porous structures containing carbon fibers is still not very good. For example, because the lithium plated on the carbon fibers is not protected from the electrolyte, SEI (Stereolithography Inclusion) may form. Also, because carbon fibers form a random porous structure, the porosity and volumetric surface area of ​​carbon fibers containing porous structures are not controlled, which are important parameters for the charging rate of electrodes containing porous structures.

[0006] In this technical field, there is a need for inventions that address one or more of the above-mentioned problems. [Overview of the project]

[0007] The object of the present invention is to provide a coated three-dimensional electronically conductive network and a method for manufacturing a coated three-dimensional electronically conductive network. The above object is achieved by the method and apparatus according to the present invention.

[0008] An advantage of the embodiments of the present invention is that the coated three-dimensional electronically conductive network includes a three-dimensional electronically conductive network which can be incorporated into a battery for use as an electrode, such as an anode.

[0009] An advantage of embodiments of the present invention is that the coating on the entire surface of the network is permeable and / or conductive to metal ions commonly used in battery electrolytes. An advantage of embodiments of the present invention is that metal ions can permeate the coating and, by applying a potential to the three-dimensional electronically conductive network, the metal ions can plate the three-dimensional electronically conductive network, forming a plated metal on the three-dimensional electronically conductive network between the three-dimensional electronically conductive network and the coating. An advantage of embodiments of this method is that this plating may be reversible, so that the plated metal can be peeled off when a second potential is applied to the three-dimensional electronically conductive network, and thereafter the formed metal ions can permeate again through the coating.

[0010] An advantage of the embodiments of the present invention is that the plated metal is covered by a coating, thereby protecting it from the environment and preventing, for example, the formation of solid electrolyte interphase (SEI). An advantage of the embodiments of the present invention is that the formation of lithium dendrites on the surface of the coated three-dimensional electronically conductive network can be suppressed.

[0011] An advantage of embodiments of the present invention is that, since the coating uniformly covers the entire surface of the coated three-dimensional electronically conductive network, the metallic plating between the coating and the three-dimensional electronically conductive network can be uniform across the entire surface of the coated three-dimensional electronically conductive network. Uniform metallic plating can minimize the mechanical stress within the coating induced by the plated metal. An advantage of embodiments of the present invention is that the coating is non-conductive, and the surface of the coating facing the electrolyte may not be plated with metal, in which case the plated metal would be exposed to the environment.

[0012] It is an advantage of embodiments of the present invention that the porosity of the three-dimensional electronically conductive network is high so that the coated three-dimensional electronically conductive network can be impregnated by an electrolyte containing metal ions. An advantage of embodiments of the present invention is that, since the volume surface area of the three-dimensional electronically conductive network is large, for example, the contact area between an electrolyte composed of metal ions and the coated three-dimensional electronically conductive network impregnated by it is large. Further, in embodiments, since the volume surface area is large, when a current is applied to the electronically conductive region, the current density on the surface of the three-dimensional electronically conductive network is low.

[0013] According to a first aspect, the present invention is a coated three-dimensional electronically conductive network for use as an electrode of a metal or metal ion battery, wherein the metal is selected from the list consisting of Na + , K + , Li + , Ca 2+ , Mg 2+ , and Al 3+ , comprising: (i) a three-dimensional electronically conductive network comprising a plurality of interconnected electronically conductive wires, the three-dimensional electronically conductive network having a porosity of at least 60% and a volume surface area of 10 -3 m 2 / cm 3 ~ 100 m 2 / cm 3 , and (ii) an electronically insulating coating that conformally covers the entire surface of the network and is permeable and / or conductive to metal ions at at least one temperature in the range of -30 °C to 150 °C.

[0014] According to a second aspect, the present invention is a method for forming a coated three-dimensional electronically conductive network for use as an electrode of a metal or metal ion battery according to the first aspect of the present invention, comprising: (i) obtaining a three-dimensional electronically conductive network comprising a plurality of interconnected electronically conductive wires, the three-dimensional electronically conductive network having a porosity of at least 60% and 10-3 m 2 / cm 3 ~100m 2 / cm 3 The method comprises (ii) a step of having a volume surface area of ​​(i) a three-dimensional electronically conductive network (i.e., the entire surface of the wire), wherein the coating is permeable and / or conductive to metal ions at at least one temperature in the range of -30°C to 150°C.

[0015] According to a third aspect, the present invention relates to a coated and plated three-dimensional electronically conductive network according to a first aspect of the present invention, comprising a conformal layer of metal between an electronically insulating coating and a three-dimensional electronically conductive network.

[0016] According to a fourth aspect, the present invention relates to a coated and plated three-dimensional electronically conductive network for acting as an electrode for a metal or metal-ion battery, comprising: (i) a three-dimensional electronically conductive network; (ii) an electronically insulating coating on the three-dimensional electronically conductive network; and (iii) a conformal and uniform layer of metal plated between the three-dimensional electronically conductive network and the electronically insulating coating.

[0017] According to a fifth aspect of the present invention, the present invention relates to a method for plating a metal between a three-dimensional electronically conductive network and a coating of a coated three-dimensional electronically conductive network according to a first aspect of the present invention, the method comprising (i) obtaining a coated three-dimensional electronically conductive network impregnated with an electrolyte containing metal ions, and (ii) applying a first potential for plating a metal onto the three-dimensional electronically conductive network.

[0018] According to a sixth aspect, the present invention relates to a metal or metal-ion battery comprising a conductive substrate, a positive electrode provided on the conductive substrate, an electrolyte layer provided on the positive electrode, and a coated three-dimensional electronically conductive network according to a first aspect of the present invention. Here, the coated three-dimensional electronically conductive network is impregnated with an electrolyte, or is a coated and plated three-dimensional electronically conductive network according to a third or fourth aspect of the present invention, wherein the coated and plated three-dimensional electronically conductive network is impregnated with an electrolyte and acts as an anode on the electrolyte layer.

[0019] Particularly preferred embodiments of the present invention are described in the appended independent and dependent claims. Features of the dependent claims can be appropriately combined with features of the independent claims and other dependent claims, and are not merely explicitly described in the claims.

[0020] While devices in this field have undergone continuous improvement, change, and evolution, this concept is considered to represent substantially novel and innovative improvements, including deviations from previous implementations, resulting in more efficient, stable, and reliable devices of this nature.

[0021] The above-mentioned and other features, characteristics and advantages of the present invention will become apparent from the following detailed description in conjunction with the accompanying drawings illustrating the principles of the present invention. This description is given for illustrative purposes only and without limiting the scope of the present invention. Reference figures referred to below refer to the accompanying drawings. [Brief explanation of the drawing]

[0022] [Figure 1A] This is a schematic example of a coated three-dimensional electronically conductive network according to an embodiment of the present invention. [Figure 1B] This is a schematic example of a coated three-dimensional electronically conductive network according to an embodiment of the present invention. [Figure 1C] This is a schematic example of a coated three-dimensional electronically conductive network according to an embodiment of the present invention. [Figure 2A] This is a schematic diagram of nickel foil coated with an electrolyte coating and plated with lithium underneath. [Figure 2B] This shows a cyclic voltammogram experimentally obtained by periodically plating lithium onto nickel foil covered with an electrolyte coating and then peeling off the lithium. [Figure 3] The results of a cyclic voltammetry experiment in which lithium was periodically plated and peeled off the surface of a nickel three-dimensional electronically conductive network according to an embodiment of the present invention are shown. [Figure 4A] This shows the change in Coulomb efficiency over three cycles obtained from cyclic voltammetry experiments, including lithium plating on titanium nitride coated with different thin film coatings and lithium stripping from titanium nitride. [Figure 4B] This shows the change in resistance over three cycles obtained from cyclic voltammetry experiments, including lithium plating on titanium nitride coated with different thin film coatings and lithium stripping from titanium nitride. [Figure 5A] This is a schematic diagram of a coated three-dimensional electronically conductive network according to an embodiment of the present invention, which is impregnated with a solid composite electrolyte. [Figure 5B] This is a schematic diagram of a coated three-dimensional electronically conductive network according to an embodiment of the present invention, which is impregnated with a solid composite electrolyte. [Figure 5C] This is a schematic diagram of a coated three-dimensional electronically conductive network according to an embodiment of the present invention, which is impregnated with a solid composite electrolyte. [Figure 6A] This is a schematic diagram of a battery according to an embodiment of the present invention. [Figure 6B] This is a schematic diagram of a battery according to an embodiment of the present invention. [Figure 6C] This is a schematic diagram of a battery according to an embodiment of the present invention. [Figure 6D] This is a schematic diagram of a battery according to an embodiment of the present invention. [Figure 7]This is a schematic diagram of a battery according to an embodiment of the present invention, which includes a coated three-dimensional electronically conductive network impregnated with a solid composite electrolyte, and the battery includes a separator. [Figure 8] This is a schematic diagram of a battery according to an embodiment of the present invention, which includes a coated three-dimensional electronically conductive network impregnated with a solid composite electrolyte and in contact with a conductive substrate, and the battery includes a separator. [Figure 9] This is a schematic diagram of a battery according to an embodiment of the present invention, which includes a coated three-dimensional electronically conductive network impregnated with a solid composite electrolyte. [Figure 10] This is a schematic diagram of a battery according to an embodiment of the present invention, which includes a coated three-dimensional electronically conductive network impregnated in a solid composite electrolyte and in contact with a conductive substrate. [Figure 11] This is a schematic diagram of a battery that includes a coated three-dimensional electronically conductive network as the negative electrode and a solid ceramic positive electrode.

[0023] In different figures, the same reference numeral indicates the same or similar elements. [Modes for carrying out the invention]

[0024] The present invention will be described with reference to specific embodiments with reference to specific drawings, but the present invention is not limited thereto and is limited only by the claims. The drawings provided are schematic and non-limiting. In the drawings, the size of some elements may be exaggerated for illustrative purposes and may not be drawn to scale. Dimensions and relative dimensions do not correspond to actual reductions in the implementation of the present invention.

[0025] Furthermore, terms such as first, second, third, etc., used herein and in the claims are used to distinguish similar elements and are not necessarily used to describe order in time, space, order, or otherwise. The terms used in this manner are interchangeable under appropriate circumstances, and it should be understood that embodiments of the invention described herein may operate in an order other than those described or illustrated herein.

[0026] Furthermore, terms such as "up," "down," and so on in this specification and claims are used for illustrative purposes only and not necessarily to describe relative positions. These terms are interchangeable under appropriate circumstances, and it should be understood that embodiments of the present invention described herein may also operate in orientations other than those described or illustrated herein.

[0027] It should be noted that the term “comprising” as used in the claims should not be interpreted as limiting the means listed thereafter, nor should it exclude other elements or steps. Therefore, the term should be interpreted as specifying the presence of the mentioned feature, integer, step, or component, but not as excluding the presence or addition of one or more other features, integers, steps, or components, or groups thereof. Accordingly, the term “comprising” includes the case where only the mentioned features exist (and thus can always be replaced with “consisting of” to limit the scope to the mentioned features) and the case where these features and one or more other features exist. Accordingly, the term “comprising” according to the present invention also includes, as one embodiment, the absence of further components. Accordingly, the scope of the expression “apparatus comprising means A and B” should not be interpreted as limiting the scope to an apparatus consisting only of components A and B.

[0028] Similarly, it should be noted that the term “coupled” as used in the claims should not be interpreted as being limited to direct connection only. The terms “coupled” and “connected” can be used together with their derivatives. It should be understood that these terms are not intended to be synonymous with each other. Therefore, the expression “device A coupled to device B” should not be limited to a device or system in which the output of device A is directly connected to the input of device B. “Coupled” may mean that two or more elements are in direct physical or electrical contact, or that two or more elements are not in direct contact with each other but still cooperate or interact with each other.

[0029] Throughout this specification, the terms "one embodiment" or "an embodiment" mean that certain features, structures, or characteristics described in relation to an embodiment are included in at least one embodiment of the present invention. Therefore, where the expressions "in one embodiment" or "in one embodiment" appear in various places throughout this specification, they do not necessarily all refer to the same embodiment, although this is possible. Furthermore, certain features, structures, or characteristics can be combined in any suitable manner in one or more embodiments, as will be apparent to those skilled in the art from this disclosure.

[0030] Similarly, in the description of exemplary embodiments of the present invention, it should be understood that various features of the invention may be grouped in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various aspects of the invention. However, this method of disclosure should not be interpreted as reflecting an intention that the claimed invention requires features beyond those explicitly stated in each claim. Rather, as reflected in the following claims, the aspects of the invention consist of fewer features than all of the features of a single, aforementioned disclosed embodiment. Accordingly, the claims following the detailed description are explicitly incorporated into this detailed description by each claim standing on its own as a distinct embodiment of the invention.

[0031] Furthermore, some embodiments described herein include some features included in other embodiments, and do not include other features, but combinations of features of different embodiments are within the scope of the invention and form different embodiments, as will be understood by those skilled in the art. For example, any combination of any of the claimed embodiments may be used in the following claims.

[0032] Furthermore, the elements described herein in the embodiments of the apparatus are examples of means for performing the functions performed by the elements for the purpose of carrying out the present invention.

[0033] Numerous specific details are provided in the description herein. However, it is understood that embodiments of the present invention may be carried out without these specific details. In other examples, well-known methods, structures, and techniques are not described in detail so as not to obscure the understanding of this specification.

[0034] In the context of this specification, when "cathode" or "anode" is referred to, it refers to the electrochemical function of the corresponding material during the discharge of a battery containing a cathode or anode. That is, during the charging of a battery, the "cathode" functions as a negative electrode, and the "anode" functions as a cathode. Similarly, when "anode" is referred to in this specification, it refers to the negative electrode. Similarly, when "cathode" is referred to in this specification, it refers to the positive electrode.

[0035] According to a first aspect, the present invention relates to a coated three-dimensional electronically conductive network for acting as an electrode for a metal or metal-ion cell, wherein the metal is selected from the list consisting of Na, K, Li, Ca, Mg, and Al, and: (i) a three-dimensional electronically conductive network consisting of a plurality of interconnected electronically conductive wires, wherein the three-dimensional electronically conductive network has a porosity of at least 60% and 10 -3 m 2 / cm 3 ~100m 2 / cm 3 Having a volume surface area of ​​preferably 2 m 2 / cm 3 ~90m 2 / cm 3 Comfortable 10m 2 / cm 3 ~50m 2 / cm 3 The present invention relates to a three-dimensional electronically conductive network having (i) a three-dimensional electronically conductive network having (ii) a coated three-dimensional electronically conductive network having a conformal coating over the entire surface of the network which is permeable and / or conductive to metal ions at at least one temperature in the range of -30°C to 150°C, for example, 20°C.

[0036] In an embodiment, the battery is a metal-air battery (e.g., Li-O 2The present invention may be selected from metal batteries such as lithium-ion batteries or metal-sulfur batteries (e.g., Li-S batteries), and metal-ion batteries such as Li-ion batteries. However, the present invention is not limited thereto. In embodiments, electronically conductive wires are electronically connected to one another. In embodiments, the wires may include a conductive material. The conductive material may include, for example, carbon or a metal, and the metal may include, for example, copper, aluminum, nickel, zinc, or sodium. In preferred embodiments, the conductive material is copper. Copper is preferred because it is a highly conductive material and does not intercalate lithium, i.e., does not alloy with lithium. Lithium batteries that instead include electrodes containing a conductive material that can alloy with lithium may exhibit significant capacity loss over time. Without being bound by theory, such capacity loss may be due to effects resulting from volume expansion of the conductive material, irreversible electrochemical reactions of the electrolyte, or diffusion-controlled capture of lithium in the conductive material. In embodiments, the material of the three-dimensional electronically conductive network is corrosion-resistant.

[0037] In embodiments, the three-dimensional electronically conductive network includes pores, which in embodiments include the volume of the three-dimensional electronically conductive network that does not constitute wires, i.e., all the space between wires. In embodiments, the pores form an interconnected network. In embodiments, the porosity of the three-dimensional electronically conductive network is the ratio of the volume of the three-dimensional electronically conductive network that constitutes pores, i.e., the volume of the three-dimensional electronically conductive network that does not constitute wires. In embodiments, a higher porosity allows for a greater amount of electrolyte to impregnate the network, potentially increasing the diffusivity of the electrolyte through the network and the metal ions in the electrolyte. In embodiments, the porosity of the three-dimensional electronically conductive network is at least 60%, preferably 65% ​​to 99%, more preferably 70% to 98%, and even more preferably 75% to 95%.

[0038] In embodiments, these pores can have an average width of 10 to 500 nm, for example, 30 to 120 nm, preferably 45 to 100 nm, more preferably 50 to 75 nm, and even more preferably 55 to 65 nm.

[0039] In a preferred embodiment, the coating on the surface of the three-dimensional electronically conductive network does not completely fill the pores of the three-dimensional electronically conductive network, so the coated three-dimensional electronically conductive network also has pores. In the embodiment, these pores may have an average width of 26 to 116 nm, preferably 41 to 96 nm, more preferably 46 to 71 nm, and even more preferably 51 to 61 nm.

[0040] Preferably, the pores of the coated three-dimensional electronically conductive network are interconnected. In embodiments, advantageously, the coated three-dimensional electronically conductive network may be impregnated with an electrolyte, thereby filling the pores of the coated three-dimensional electronically conductive network.

[0041] In embodiments, volumetric surface area is the ratio of the surface area to the volume of a three-dimensional electronically conductive network, where the surface area consists of the total surface area of ​​the wires in the three-dimensional electronically conductive network, and the volume consists of the volume of the three-dimensional electronically conductive network, i.e., including the volume of the pores in the three-dimensional electronically conductive network. Advantageously, because the volumetric surface area is large, the three-dimensional electronically conductive network can have a much larger surface area compared to, for example, a metal foil. For example, the surface area of ​​a three-dimensional electronically conductive network with a thickness of the order of 10 micrometers and a specific lateral dimension may be several orders of magnitude larger than the surface area of ​​a metal foil with the same specific lateral dimension. In embodiments, when a current or potential is applied to the three-dimensional electronically conductive network, a larger volumetric surface area can correspond to a lower current density on the surface of the three-dimensional electronically conductive network. Furthermore, in embodiments, a larger surface area may result in a greater overall rate of metal plating and delamination on the surface of the three-dimensional electronically conductive network between the coating and the three-dimensional electronically conductive network. In embodiments, the wires may be nanowires. In embodiments, the nanowire may have an average thickness of 20 nm to 500 nm, preferably 25 nm to 300 nm, and more preferably 30 nm to 200 nm.

[0042] In embodiments, the three-dimensional electronically conductive network is an ordered network, i.e., the interconnected electronically conductive wires are not randomly oriented relative to one another. In embodiments, the pore widths of the three-dimensional electronically conductive network are uniform. For example, 95% of the pores may have a width of no more than 10% of each other. A narrow pore size distribution is advantageous because it optimizes performance for a given volume. Pores can have similar sizes and coating thicknesses, and therefore the amount of electrolyte will also be the same. It also facilitates the deposition of a uniform metal (e.g., Li). Therefore, in embodiments, for a network with a constant porosity and a constant volume surface area, uniform pore size may result in the maximum diffusion rate that can be achieved.

[0043] In embodiments, interconnected electronically conductive wires include: spaced electronically conductive first wires, each making an angle of up to 20°, for example, up to 10°, preferably up to 1°, most preferably 0°, with respect to a first direction; and electronically conductive nanoconnectors interconnecting adjacent first wires and being integral therewith. In embodiments, the electronically conductive nanoconnectors make an angle of at most 20°, for example, at most 10°, preferably at most 1°, most preferably 0°, with respect to a plane transverse to the first direction. In embodiments, the first spacing between two adjacent first wires is 20 nm to 200 nm. In embodiments, the second spacing between two adjacent electronically conductive nanoconnectors is 20 nm to 200 nm. In embodiments, the diffusion rate of electrolytes or ions through the coated three-dimensional electronically conductive network is limited by the minimum first or second spacing. Accordingly, in embodiments, for a network having a certain porosity and a certain volumetric surface area, uniform first and second spacings can result in the maximum diffusion rate that can be achieved. In embodiments, the three-dimensional electronically conductive network is monolithic. In embodiments, interconnected electronically conductive wires form a mesh as described in EP2018 / 068671 and / or EP2980014A1, which are included herein by reference.

[0044] In the embodiment, the coating of the coated three-dimensional electronically conductive network is Na + , K + Li + Ca 2+ Mg 2+ , and Al 3+ At least one of the following, preferably Na + Li + Mg 2+ , and Al 3+ Preferably Li +In contrast, at at least one temperature in the range of -30°C to 150°C, for example at 20°C, it is permeable and / or conductive. In embodiments, the metal is Li, and the electronic insulating coating is Li at at least one temperature in the range of -30°C to 150°C. + It is permeable and / or conductive to Li. + Batteries containing Li may have better performance compared to batteries containing other metal ions, for example, in terms of cycle life and capacity per unit mass. + It is preferably included in the electrolyte of the battery to provide ion conduction. In embodiments, the permeability of the coating is advantageous, allowing metal ions to diffuse through the coating. As a result, for example, advantageously in embodiments, the metal can be plated between the coating and the three-dimensional electronically conductive network by applying a potential to the three-dimensional electronically conductive network.

[0045] In the embodiment, the coating is insulating, i.e., nonconductive to electrons. As a result, no electron current flows from the three-dimensional electron-conducting network to the coating. Consequently, plating of metal ions onto the coating surface facing the pores does not occur. Metals plated onto the coating surface facing the electrolyte come into direct contact with the environment, such as the electrolyte, and a reaction between the metal and the electrolyte is possible, which is highly undesirable.

[0046] The coating preferably conformally covers the entire surface of the network. That is, the coating is preferably continuous, i.e., pinhole-free, so that no part of the three-dimensional electronically conductive network, or any metal plated on the three-dimensional electronically conductive network, comes into direct contact with the electrolyte impregnating the network. In embodiments, the coating's conformity further ensures that the diffusion time of metal ions through the coating is uniform throughout the coated three-dimensional electronically conductive network. In embodiments, for example, if metal ions contained in the electrolyte impregnating the coated three-dimensional electronically conductive network diffuse through a uniform coating when a potential is applied to the three-dimensional electronically conductive network, this can result in a uniform layer of plated metal formed from reduced metal ions between the coating and the three-dimensional electronically conductive network. A uniform layer of plated metal can advantageously minimize mechanical stress within the coating induced by the plated metal. In embodiments, the electronically insulating coating has a thickness of 2 to 500 nm, preferably 2 to 100 nm, more preferably 2 to 50 nm, even more preferably 2 to 25 nm, and even more preferably 2 to 5 nm. The coating is preferably as thin as possible so that the diffusion of metal ions through the coating is still rapid. The coating is preferably thick enough to have sufficient structural strength to withstand periodic plating and delamination of the metal between the coating and the three-dimensional electronically conductive network.

[0047] In a defined form, the electrochemical stability window of the coating is defined by the metal ion (e.g., Li + The reduction potential of the metal ion (e.g., Li) covers a range of at least 0 to 4.5 V, for example, 0 to 5.5 V. In these embodiments, it is advantageous to apply the first potential to the three-dimensional electronically conductive network to the metal ion (e.g., Li). + ) is reduced to form a metal (e.g., lithium) between the three-dimensional electronically conductive network and the coating for plating, and then a second potential is applied to oxidize the plated lithium. +A coating may be formed, and neither the first nor the second potential will induce an electrochemical reaction involving the coating.

[0048] In one embodiment, an electrolyte containing metal ions is impregnated with a coated three-dimensional electronically conductive network, and the conductivity of the electronically insulating coating to the metal ions is 0.1σ. i,11 Larger, preferably 1σ i,11 Larger, and more preferably 10σ i,11 Larger, and in some cases up to 1000σ i,11 For example, 100σ i,11 The following is σ i,11 The following formula: It is given by TIFF0007847593000001.tif1553. Here, d 11 is the thickness of the electronically insulating coating (μm), P is the porosity (%) of the coated 3D electronically conductive network, l1 is the thickness of the coated 3D electronically conductive network (μm), and Av is the volumetric surface area (m²) of the coated 3D electronically conductive network. 2 / cm 3 ) and σ 12is the ionic conductivity of the electrolyte. In embodiments, an electrolyte containing metal ions, the coating of which is permeable and / or conductive, impregnates a coated three-dimensional electronically conductive network, and the conductivity of the coating to metal ions is lower than the thickness of the coating divided by the sheet resistance of the electrolyte over the thickness of the coated three-dimensional electronically conductive network, preferably at least 10 times lower. In embodiments, the conductivity of the coating to metal ions is not zero. In embodiments, the sheet resistance of the electrolyte over the thickness of the coated three-dimensional electronically conductive network can be calculated by dividing the thickness of the coated three-dimensional electronically conductive network by the conductivity of the electrolyte to metal ions. In embodiments, the ionic conductivity is preferably high enough that the conduction of metal ions through the coating is not negligible. In embodiments, the conductivity of the coating to metal ions is, however, preferably low enough so that the coated three-dimensional electronically conductive network is uniformly plated. In embodiments, uniform plating can be achieved when the sheet conductivity of the electrolyte to metal ions over the thickness of the coated three-dimensional electronically conductive network, i.e., the reciprocal of the sheet resistance, is higher than the sheet conductivity of the coating to metal ions, preferably at least 10 times higher. In this way, metal ions can permeate the coating and, when a potential is applied, penetrate far enough into the coated three-dimensional electronically conductive network before plating between the coating and the three-dimensional electronically conductive network. In embodiments, the longer the distance that metal ions can penetrate into the coated three-dimensional electronically conductive network before permeating the coating, the more uniform the metal plating between the coating and the three-dimensional electronically conductive network may be.

[0049] In the embodiments, the coated three-dimensional electronically conductive network has a thickness of up to 50 μm, for example, from 0.1 μm to 35 μm. Thicker networks may require a coating with very slow metallic ion conductivity to achieve uniform plating: the metallic plating rate between the coating and the three-dimensional electronically conductive network may therefore be very small. In the embodiments, it is preferable to seek a trade-off between a large volume area of ​​the coated three-dimensional electronically conductive network and a high plating rate. Another problem with thicker coated three-dimensional electronically conductive networks is that the uniformity of the metallic plating thickness may be poor. For example, a difference of more than 20% may be observed between the metallic plating thickness on the top of the coated three-dimensional electronically conductive network and the metallic plating thickness on the bottom of the coated three-dimensional electronically conductive network, which is not optimal.

[0050] In embodiments, the electrolyte impregnating the network may be any electrolyte suitable for battery applications. In embodiments, the electrolyte may be the following metal ions: Na + Li + Mg 2+ , and Al 3+ It includes one of the following, preferably Li +In embodiments, the electrolyte may be a liquid electrolyte, a gel electrolyte, a solid electrolyte, an ionic liquid electrolyte, or a composite electrolyte. The composite electrolyte may be such as those described in EP3043406 and Science Advances 6(2020)eaav3400 by Chen et al. For example, the composite electrolyte may be a material comprising an electronic insulating material having multiple pores, e.g., a continuous layer of electronic insulating material; and a solid electrolyte material covering the inner surfaces of the multiple pores. In embodiments, the composite electrolyte is preferred due to its potentially very high ion mobility and high flexibility. In embodiments, the electrolyte is non-flammable, for example, up to a temperature of 300°C, e.g., up to 250°C, e.g., up to 150°C. Furthermore, the electrolyte preferably has a decomposition temperature of at least 300°C, e.g., at least 250°C, e.g., at least 150°C.

[0051] In embodiments, the coating comprises any of the following materials: a solid electrolyte, an oxide such as a porous oxide, a polymer, a hybrid inorganic-organic material, an organometallic skeleton, or a covalent organic skeleton. In embodiments, the electronically insulating coating is nonreactive to metals, preferably Li, at least -30°C to 180°C, for example -30°C to 150°C. In embodiments, the coating is nonreactive to metals, preferably Li, at least -30°C to 180°C, for example -30°C to 150°C. + It is nonreactive to ions. In embodiments where the metal is Li, the electronically insulating coating is at least one temperature in the range of -30°C to 150°C, for example 60°C, Li + It may be permeable and / or conductive to the electrolyte. In embodiments, the coating is stable to electrolytes commonly used in batteries. In embodiments, the coating is flexible, and advantageously, metal plating and delamination between the coating and the three-dimensional electronically conductive network does not create mechanical stress on the coating.

[0052] In embodiments, the solid electrolyte comprises one of the following materials: Li3PO4, N-doped Li3PO4 (LiPON), Li-doped poly(phenylene oxide), Li-doped poly(ethylene oxide), and a Li salt selected from LiTFSI, LiFSI or LiBOB or LiDFOB, LiSO3CF3, LiClO4, LiBF4, LiPF6, LiAsF6, Li2O, doped-Li2O, LiI, LiCl, LiBr, Li2CO3, and Li2SO4. In embodiments, the oxide may also include La2O3, TiO2, MgO, InZnO, and ZrO2. In embodiments, the hybrid inorganic-organic material may also include a metal alkoxide, which may be a reaction product of a metal precursor and an organic alcohol, and the metal precursor may include lanthanum, aluminum, titanium, zinc, zirconium, indium, or tin.

[0053] In embodiments, the porous oxide may include oxides or phosphates of silicon, aluminum, zirconium, titanium, or combinations thereof. In embodiments, the porous oxide may include pores with an average diameter of 100 nanometers or less, preferably with an average diameter of 2 to 50 nanometers. In embodiments, the pores form an interconnection network.

[0054] In embodiments, an advantage of the coated three-dimensional electronically conductive network is that it does not need to contain a metal, such as lithium, before being incorporated into a battery, such as a solid-state battery. In embodiments, the absence of lithium, which is highly reactive to CO2 and H2O, for example, facilitates the handling and storage of the coated three-dimensional electronically conductive network. In embodiments, the absence of lithium makes it easier to incorporate the coated three-dimensional electronically conductive network into a battery cell. In embodiments, the absence of lithium facilitates the transportation of batteries consisting of coated three-dimensional electronically conductive networks compared to batteries consisting of lithium foil, for example.

[0055] In other embodiments, preferably, the metal is included in the coated three-dimensional electronically conductive network, for example, as a conformal metal layer, i.e., as a conformal layer of metal on a wire. Thus, in embodiments, the coated three-dimensional electronically conductive network includes a conformal metal layer between the coating and the three-dimensional electronically conductive network, the metal layer consisting of one of the following metals: aluminum, lithium, magnesium, and sodium, preferably lithium. In embodiments, the metal layer contains one of at least one metal ions, i.e., a metal in which the coating is permeable and / or conductive. Advantageously, in embodiments in which the coated three-dimensional electronically conductive network includes a conformal metal layer, peeling the conformal metal layer by applying a potential may generate an electric current, which can be used, for example, to power an external device. In embodiments, the conformability of the metal layer minimizes the mechanical stress in the coating induced by the metal layer.

[0056] In the embodiment, there is a difference of less than 20%, preferably less than 15%, more preferably less than 10%, and most preferably less than 5% between the thickness of the conformal metal layer at the top of the coated three-dimensional electronically conductive network and the thickness of the conformal metal layer at the bottom of the coated three-dimensional electronically conductive network, and the top and bottom are separated by the thickness of the coated three-dimensional electronically conductive network.

[0057] In embodiments, the coated three-dimensional electronically conductive network includes a seed layer between the coating and the three-dimensional electronically conductive network, the seed layer being such that it promotes the growth of a layer of metal, a metal compound, or a metal alloy, and the seed layer conformally covers the entire surface of the network. In embodiments where the coated electronically conductive network includes a conformal metal layer, the conformal metal layer is included between the coating and the seed layer. In embodiments, the plating rate of the metal on the seed layer is higher than the plating rate of the metal on the three-dimensional electronically conductive network. In embodiments, the seed layer is conductive to electric current. In embodiments, the seed layer is in electrical contact with the three-dimensional electronically conductive network. Advantageously, in these embodiments, a potential can be applied to the seed layer via the three-dimensional electronically conductive network to plate metal onto the surface of the seed layer between the coating and the seed layer, for example.

[0058] The presence of a seed layer is advantageous because, in its absence, islands of plated metal may form on the three-dimensional electronically conductive network. When islands of plated metal are present, they may function as seed islands, causing the plating rate on the islands to be faster than the plating rate on the three-dimensional electronically conductive network. As a result, the plating of the metal between the coating and the three-dimensional electronically conductive network may become uneven, potentially inducing mechanical stress within the coating by the plated metal and leading to coating failure. In embodiments, the seed layer can prevent the formation of metal islands. Preferably, the plating rate on the seed layer is faster than the plating rate on the metal islands. Therefore, in embodiments, the seed layer can induce the formation of a conformal metal layer.

[0059] In the embodiment, the seed layer is made of the following materials: carbon, silicon, germanium, tin, and indium; oxides or nitrides of carbon, silicon, germanium, tin, and indium; materials that can be alloyed with metal compounds, such as Au, Al, Sn, Si, Ge, ITO, AuSn, LixSi where 0≦x≦4.4, LixSn where 2 / 5≦x≦22 / 5, for example Li2Sn5, LiSn, Li7Sn3, Li5Sn2, Li13Sn5, Li7Sn2, or Li 22 The materials include Sn5, LixIny with 0 ≤ x ≤ 1.5, such as LiIn, Li5In4, or Li3In2, or LixAuSn with 0 ≤ x ≤ 2.2; and composites of polymers and carbon, such as polytetrafluoroethylene (PTFE) / carbon, polyvinylidene fluoride (PvDF) / carbon, and silver / carbon. In embodiments, the seed layer has a thickness of 2 to 100 nm, preferably 2 to 25 nm. In embodiments, the sum of the seed layer thickness and the coating thickness may be less than 40% of the wire-to-wire distance between adjacent wires, for example less than 30%, preferably less than 25%.

[0060] Any feature of any embodiment of the first aspect may be described independently in correspondence with any embodiment of other aspects of the present invention.

[0061] According to a second aspect, the present invention relates to a method for forming a coated three-dimensional electronically conductive network according to a first aspect of the present invention, comprising the steps of: (i) obtaining a three-dimensional electronically conductive network comprising a plurality of interconnected electronically conductive wires, wherein the three-dimensional electronically conductive network has a porosity of at least 60% and 10 -3 m 2 / cm 3 ~100m 2 / cm 3 For example, 2m 2 / cm 3 ~90m 2 / cm 3 (ii) a step of conformally coating the entire surface of a three-dimensional electronically conductive network with an electronically insulating coating, wherein the coating is permeable and / or conductive to metal ions at at least one temperature in the range of -30°C to 150°C, for example, 20°C.

[0062] Any feature of any embodiment of the second aspect may be described independently so as to correspond to any embodiment of other aspects of the invention.

[0063] In embodiments, the coating in step (ii) may be carried out using at least one of the following techniques: atomic layer deposition, molecular layer deposition, electrochemical deposition, chemical solution deposition, sol-gel deposition, dip coating, spray coating, chemical vapor deposition, electrolytic polymerization, electrolytic deposition, electrochemically assisted self-assembly, and electrolytic deposition. In embodiments, advantageously, these techniques are very suitable for forming conformal coatings. In particular, in embodiments, atomic layer deposition and molecular layer deposition may constitute surface-limited reactions and thus result in highly conformal coatings. Conformal deposition of coatings using these techniques is described, for example, in the literature: B. Put et al. J. Electrochem. Soc. 166 (2019) A1239-A1242; S. Deheryan et al. Carbon 88 (2015) 42-50; and M. Timmermans et al. J. of Appl. Polym. Sci. 134 (2016) 44533-44539.

[0064] In embodiments, a three-dimensional electronically conductive network may be obtained by any method suitable for yielding a three-dimensional electronically conductive network. In embodiments, the three-dimensional electronically conductive network may be formed by, for example, anodizing a material such as alumina, thereby forming a template containing pores; plating a precursor of the material for the three-dimensional electronically conductive network into the pores of the template; and removing the template material, i.e., by etching the template material. In embodiments, methods such as those described in EP2018 / 068671 and / or EP2980014A1 may be used to form a three-dimensional electronically conductive network.

[0065] In an embodiment, obtaining a three-dimensional electronically conductive network is a step of forming a porous solid material comprising a plurality of interconnected wires, as described in claim 1 of the published EP2018 / 068671, wherein the plurality of interconnected wires form an ordered network comprising a plurality of first wires having a first longitudinal direction and a plurality of second wires having a second longitudinal direction different from the first longitudinal direction, the plurality of first wires and the plurality of second wires are arranged according to a regular pattern having a predetermined average wire-to-wire distance between adjacent wires, the plurality of first wires and the plurality of second wires have a predetermined average wire diameter, and this method is The process of creating a template that includes multiple interconnected channels; Subsequently, a step of depositing solid material into multiple interconnected channels of the template; and, The process then includes the step of removing the template to obtain a porous solid material, The process of creating a template is: A step of performing a protective treatment for porous channels, comprising: a first anodizing step of anodizing a doped valve metal layer at a predetermined anodizing voltage, thereby anodizing at least a portion of the valve metal layer in the thickness direction, thereby forming a porous layer of lubricating metal oxide containing a plurality of interconnected channels, wherein the plurality of interconnected channels form a regular network containing a plurality of first channels having a first longitudinal direction and a plurality of second channels having a second longitudinal direction, wherein the plurality of first channels and the plurality of second channels are arranged according to a regular pattern having a predetermined average wiring distance between adjacent channels, the plurality of first channels and the plurality of second channels have an average channel width, each channel has a channel wall, the plurality of first channels have a channel bottom, and the channel bottom is coated with a first insulating metal oxide barrier layer as a result of the first anodizing step; A process of inducing hydrophobic surfaces on the channel walls and channel bottom by protective treatment of a porous layer of valve metal oxide; A step of performing a second anodizing step at a predetermined anodizing voltage after protective treatment, thereby substantially removing the first insulating metal oxide barrier layer from the bottom of the channel, inducing anodizing only at the bottom of the multiple first channels, and forming a second insulating metal oxide barrier layer at the bottom of the channel; and, The method includes performing an etching step in an etching solution, thereby removing a second insulating metal oxide barrier layer from the bottom of the channel without substantially increasing the average channel width.

[0066] In some embodiments, any term of the embodiments described above may be described independently to correspond to the description in EP2018 / 068671.

[0067] In an embodiment, the step of preparing a template may include the step of anodizing an assembly of two consecutive layers, as described in claim 11 of EP2980014A1, wherein the first layer is made of a material that forms a network of interconnected channels upon anodizing, and the second layer is made of a material that forms a cluster of aligned, isolated channels upon anodizing, and the template is for forming a cluster of aligned wires, and the template includes an assembly of two consecutive layers, the first layer includes a cluster of aligned, isolated channels, and the second layer includes a network of aligned, interconnected channels. In an embodiment, any term of the embodiment described above may be described independently to correspond to the description in EP2980014A1.

[0068] In embodiments in which the coated three-dimensional electronically conductive network includes a seed layer between the coating and the three-dimensional electronically conductive network, the method for forming the coated three-dimensional electronically conductive network may further include step a', after step a and before step b, conformally coating the entire surface of the three-dimensional electronically conductive network with the seed layer. In embodiments, if step b is applied after step a', the coating conformally covers the seed layer. In embodiments, the seed layer can be deposited using any of the techniques for depositing the coating.

[0069] In embodiments in which a coated three-dimensional electronically conductive network is impregnated with an electrolyte, the method may further include a step c after step b, in which the coated three-dimensional electronically conductive network is impregnated with the electrolyte. In embodiments, the electrolyte comprises metal ions, preferably metal ions for which the coating is permeable and / or conductive. In embodiments in which the electrolyte is a liquid electrolyte, the liquid electrolyte can be advantageously poured onto the coated three-dimensional electronically conductive network, and the liquid electrolyte then flows through the pores of the coated three-dimensional electronically conductive network, thereby impregnating the coated three-dimensional electronically conductive network. In embodiments in which the electrolyte is a solid electrolyte, for example, a liquid precursor for a solid electrolyte, which forms a solid electrolyte upon application of a potential across the liquid precursor, is first impregnated into the coated three-dimensional electronically conductive network, and then, for example, a solid electrolyte is formed from the liquid precursor via an electrochemical reaction upon application of a potential across the liquid precursor. In embodiments in which the electrolyte is a solid electrolyte, the coated three-dimensional electronically conductive network may be pressed into the solid electrolyte, or the solid electrolyte may be pressed into the coated three-dimensional electronically conductive network. In such embodiments, the solid electrolyte is preferably soft or flexible. In embodiments, the solid electrolyte may be a polymer electrolyte, and thermoplastic molding of the polymer electrolyte may be used.

[0070] According to a third aspect, the present invention relates to a coated and plated three-dimensional electronically conductive network according to a first aspect of the present invention, comprising a conformal layer of metal between an electronically insulating coating and a three-dimensional electronically conductive network.

[0071] Any feature of any embodiment of the third aspect may be described independently in correspondence with any embodiment of other aspects of the present invention.

[0072] In embodiments, the thickness of the conformal layer of the metal may be 5 to 500 nm, preferably 10 to 100 nm. In embodiments, the sum of the thickness of the conformal layer of the metal, the thickness of the coating, and optionally the thickness of the seed layer may be less than 40% of the wire-to-wire distance between adjacent wires, for example less than 30%, preferably less than 25%.

[0073] According to a fourth aspect, the present invention relates to a coated and plated three-dimensional electronically conductive network for acting as an electrode for a metal or metal-ion battery, comprising: (i) a three-dimensional electronically conductive network; (ii) an electronically insulating coating on the three-dimensional electronically conductive network; and (iii) a conformal and uniform layer of metal plating between the three-dimensional electronically conductive network and the electronically insulating coating.

[0074] Any feature of any embodiment of the fourth aspect may be described independently so as to correspond to any embodiment of other aspects of the present invention.

[0075] In embodiments, a coated and plated three-dimensional electronically conductive network can be considered an active electrode.

[0076] In the embodiment, uniformity includes the three-dimensional electronically conductive network having a thickness extending from a first surface to a second surface of the network, and the average thickness of the metal layer on the first surface being within 50%, preferably within 20%, of the thickness of the metal layer on the second surface.

[0077] According to a fifth aspect of the present invention, the present invention relates to a method for plating a metal between a three-dimensional electronically conductive network according to a first aspect of the present invention and a coating of a coated three-dimensional electronically conductive network, the method comprising (i) obtaining a coated three-dimensional electronically conductive network impregnated with an electrolyte containing metal ions, and (ii) applying a first potential for plating a metal onto the three-dimensional electronically conductive network.

[0078] A three-dimensional electronically conductive network can act as a first electrode and function as an electrode.

[0079] The second electrode is coated with metal ions (e.g., Li) that are permeable and / or ionic conductive. + ) is selected so that it can be supplied to the electrolyte.

[0080] In embodiments, the three-dimensional electronically conductive network may be part of the electrochemical cell within the battery, and step (ii) may be performed after the formation of the electrochemical cell and battery by using the positive electrode of the electrochemical cell as a second electrode.

[0081] In some embodiments, the three-dimensional electronically conductive network may be plated before the formation of the battery and electrochemical cell.

[0082] Any feature of any embodiment of the fifth aspect may be described independently in correspondence with any embodiment of other aspects of the present invention.

[0083] In one embodiment, the step (i) of obtaining an electrolyte-impregnated coated three-dimensional electronically conductive network may include a method of the second embodiment, which includes a step c of the second embodiment, which includes a step of impregnating the coated three-dimensional electronically conductive network.

[0084] In the embodiment, the metal ions contained in the electrolyte include metal ions that make the coating permeable and / or conductive. Thus, in the embodiment, the metal ions can permeate the coating and, in some cases, electronically contact a three-dimensional electronically conductive network.

[0085] In embodiments, the first potential is negative. In these embodiments, applying the first potential to the three-dimensional electronically conductive network induces the reduction of metal ions on the surface of the three-dimensional electronically conductive network, thereby plating the metal between the three-dimensional electronically conductive network and the coating. In embodiments where the coated three-dimensional electronically conductive network includes a seed layer between the three-dimensional electronically conductive network and the coating, applying a potential to the three-dimensional electronically conductive network applies a potential to the seed layer. Thus, in these embodiments, for example, the reduction of ions occurs on the surface of the seed layer, thereby plating the metal between the seed layer and the coating. Alternatively, in embodiments where the seed layer alloys with the metal, the reduction of ions may cause the seed layer to alloy with the metal. In embodiments, the first potential is sufficient to reduce the ions. In embodiments, the first potential is not sufficient to damage the coating. In embodiments, the first potential is not sufficient to induce an electrochemical reaction between the coating and the electrolyte.

[0086] In embodiments, the method includes a further step (iii) of periodically applying a second potential to strip the metal between the three-dimensional electronically conductive network and the coating, and applying a first potential to plate the metal between the three-dimensional electronically conductive network and the coating. In embodiments, the first and second potentials are applied to the three-dimensional electronically conductive network. In embodiments, the second potential is sufficient to oxidize the metal, thereby forming metal ions. Subsequently, in embodiments, the metal ions may permeate the coating and then move into the electrolyte. In embodiments, the second potential is positive. In embodiments, the second potential is sufficient not to damage the coating. In embodiments, the second potential is sufficient not to induce an electrochemical reaction between the coating and the electrolyte.

[0087] In embodiments, the electrolyte used for plating the three-dimensional electronically conductive network may be the same electrolyte used to impregnate the coated three-dimensional electronically conductive network in a metal or metal-ion battery. However, this is not essential. In embodiments, for example, the coated three-dimensional electronically conductive network may be initially impregnated with a first electrolyte containing metal ions for metal plating according to an embodiment of the fifth aspect, and the first electrolyte may then be removed by a process including rinsing, for example, and the coated three-dimensional electronically conductive network may then be impregnated with a second electrolyte.

[0088] According to a sixth aspect, the present invention relates to a metal or metal-ion battery comprising a conductive substrate, a positive electrode provided on the conductive substrate, an electrolyte layer provided on the positive electrode, and a coated three-dimensional electronically conductive network according to a first aspect of the present invention, wherein the coated three-dimensional electronically conductive network is impregnated with an electrolyte or coated and plated according to a third or fourth aspect of the present invention, and the coated and plated three-dimensional electronically conductive network is impregnated with an electrolyte and acts as an anode on the electrolyte layer.

[0089] Any feature of any embodiment of the sixth aspect may be described independently so as to correspond to any embodiment of other aspects of the present invention.

[0090] In one embodiment, the battery rests on a coated three-dimensional electronically conductive network and further includes a current collector in electrical contact with it. In another embodiment, the current collector includes a metal foil containing a metal suitable for use as an anode in a solid-state battery, such as copper, nickel, or stainless steel.

[0091] In embodiments, the positive electrode may be a composite positive electrode, i.e., a positive electrode formed from multiple materials. In embodiments, in the context of the sixth embodiment of the battery, “positive electrode” and “negative electrode” indicate the corresponding electrochemical functions of the materials during the discharge of the battery. In embodiments, during the charging of the battery, the “positive electrode” functions as the negative electrode, while the “negative electrode” functions as the positive electrode.

[0092] In embodiments, the positive electrode is in electrical contact with a conductive substrate. In embodiments, the composite positive electrode may include electrode particles containing an electrode material, the electrode particles being in electrical contact with one another. In embodiments, the electrode material may include at least one material selected from lithium manganese nickelate (LMNO), lithium manganese oxide (LMO), lithium iron phosphate (LFP), lithium iron manganese phosphate (LMFP), lithium manganese phosphate (LMP), lithium cobalt oxide (LCO), lithium nickel manganese cobalt oxide (NMC), and lithium nickel cobalt aluminate (NCA). In these embodiments, the electrode particles can be bound together with a polymer binder or binder to physically stabilize the porous active material electrode material. Furthermore, in embodiments in which the porous active material electrode material includes electrode particles, the electrical contact between the electrode particles can be improved by including conductive additives such as carbon black, graphite, carbon fibers and beads, or stainless steel fibers in the pores and bringing them into electrical contact with the porous active material electrode material. For example, the conductive additive contained within the pores may be 0 to 10 wt%, preferably 0.1 to 10 wt%, relative to the weight of the porous active material electrode.

[0093] In one embodiment, the battery includes an electrolyte, which impregnates a three-dimensional electronically conductive network, a (e.g., composite) cathode, and an electrolyte layer.

[0094] In embodiments, the electrolyte layer is nonconductive to electric current. Advantageously, the electrolyte layer can function as a separator between the negative and positive electrodes of the battery. In embodiments, the electrolyte layer prevents short circuits between the positive and negative electrodes. In embodiments, the electrolyte layer has a thickness of at most 30 μm, preferably at most 15 μm, to minimize space usage. In embodiments, the electrolyte layer is permeable to metal ions. Preferably, the electrolyte layer allows metal ions to pass through without obstruction. In embodiments, the electrolyte layer is porous. In these embodiments, metal ions may diffuse between the negative and positive electrodes, for example, during charging and discharging of the battery. In embodiments, the metal ions are the same metal ions to which the coating of a three-dimensional electronically conductive network coated is permeable and / or conductive. For example, lithium. In embodiments, the electrolyte layer is resistant to penetration by burrs or dendrites, for example, dendrites growing on the negative and / or positive electrodes. In embodiments, the electrolyte layer is resistant to contamination of the electrode coatings to prevent potential short circuits between the electrodes. In embodiments, the electrolyte layer may be a mechanical spacer, a glass fiber cloth, or a flexible plastic film made from nylon, polyethylene, or polypropylene. Preferably, mechanical properties such as burr penetration, dendrite growth, or permeability to metal ions are maintained even at temperatures above room temperature, i.e., the temperature at which the battery normally operates. In embodiments, the electrolyte layer contains ions of the same metal as the electrolyte impregnating the electronically conductive network. In embodiments, the electrolyte layer is made of the same material as the electrolyte impregnating the electronically conductive network, for example.

[0095] In the embodiment, the electrolyte is a solid electrolyte (e.g., a gel electrolyte), and the battery is a solid-state battery. Advantageously, solid-state batteries, i.e., batteries made of a solid electrolyte, are safer than batteries made of a liquid electrolyte. Preferably, the electrolyte is a gel electrolyte such as a polymer gel electrolyte. More preferably, the electrolyte is a solid composite electrolyte (SCE), and most preferably a solid nanocomposite electrolyte (nanoSCE).

[0096] In one embodiment, charging the battery corresponds to applying a first potential to the negative electrode, thereby plating a metal such as lithium between the coating and the three-dimensional electronically conductive network. In another embodiment, discharging the battery corresponds to applying a second potential to the negative electrode, thereby stripping the metal. In yet another embodiment, the stripping of the metal generates a current that can be used to power an external device.

[0097] Accordingly, in embodiments, advantageously, periodic charging and discharging of the battery may include periodic plating and stripping of the metal. In embodiments, periodic plating and stripping of the metal may include a method according to an embodiment of a fifth aspect of the present invention. In embodiments, advantageously, the battery may be periodically charged and discharged, i.e., the battery may be a rechargeable battery. An advantage of embodiments of the present invention is that the volume change during plating and stripping of the metal between the coating and the coated three-dimensional electronically conductive network is such that the volume change of the coated three-dimensional electronically conductive network becomes negligible, and the pressure exerted on the cell by the coated three-dimensional electronically conductive network is limited.

[0098] In the embodiment, the conductive substrate includes a metal foil containing a metal suitable for use as the positive electrode of a battery, such as aluminum, nickel, or stainless steel. Preferably, the conductive substrate may also be corrosion-resistant, which may be a characteristic of the conductive substrate material. The conductive substrate can also be made corrosion-resistant by coating it with a protective layer.

[0099] In some embodiments, a metal or metal-ion battery according to an embodiment of the sixth aspect may be used in devices such as computers; telephones; vehicles such as automobiles, scooters, boats, or airplanes; drones; satellites; or robots.

[0100] Next, the present invention will be described by a detailed description of some embodiments of the present invention. It will be apparent that other embodiments of the present invention can be constructed according to the knowledge of those skilled in the art without departing from the technical teachings of the present invention, and the present invention is limited only by the language of the appended claims.

[0101] Example 1: Metal plating between a three-dimensional electronically conductive network and a coating covering the three-dimensional electronically conductive network Please refer to Figure 1A. Figure 1A schematically shows a coated three-dimensional electronically conductive network 1 according to an embodiment of the first aspect of the present invention. The coated three-dimensional electronically conductive network 1 includes a three-dimensional electronically conductive network 10 and a coating 11 conformally covering the entire surface of the three-dimensional electronically conductive network 10. Furthermore, in this embodiment, an electrolyte 12 is impregnated into the coated three-dimensional electronically conductive network 1. In this embodiment, the three-dimensional electronically conductive network 10 is in electronic contact with a current collector 2. However, in an alternative embodiment, the coated three-dimensional electronically conductive network 1 may be self-supporting and may not require a current collector 2. The current collector 2 can be obtained during the formation of the three-dimensional electronically conductive network 1 by growing the current collector 2 on an electronically conductive substrate 1.

[0102] Referring to Figure 1B, a magnified view of the portion of Figure 1A indicated by the dashed frame is shown, illustrating in more detail the three-dimensional electronically conductive network 10 fitted with coating 11, and the electrolyte 12 impregnating the coated three-dimensional electronically conductive network 1. The electrolyte 12 is, for example, the following metal ion: Na + Li + Mg 2+ and Al 3+ The electrolyte may be a liquid or solid electrolyte containing at least one of the following. The electrolyte 12 is preferably a gel (e.g., nano-SCE). The coating 11 is permeable and / or conductive to the metal ions contained in the electrolyte 12.

[0103] As an example of plating according to a fifth aspect of the present invention, the electrolyte 12 may be in contact with a second electrode (not shown), which may be a negative electrode, and the three-dimensional electronically conductive network 10 may be a first electrode, for example, a positive electrode. The potential may be applied across the electrolyte 12 through the first and second electrodes. In this embodiment, metal ions that have permeated the coating 11 are plated between the coating 11 and the three-dimensional electronically conductive network 10. The coating 11 is electronically insulating. In this example, the coating 11 is electrochemically resistant, and the applied potential does not induce an electrochemical reaction between the coating 11 and, for example, the electrolyte 12 or the metal being plated.

[0104] Next, referring to Figure 1C, the coated three-dimensional electronically conductive network 1 of Figure 1B is shown, where the metal 14, i.e., the metal ions of the electrolyte that penetrated the coating 11 after reduction by the three-dimensional electronically conductive network 10, are plated between the coating 11 and the three-dimensional electronically conductive network 10. Because the coating 11 in this example is flexible, it does not break during the plating of the metal 14.

[0105] An advantage of the embodiments of the present invention is that the coating 11 allows for the uniform plating of a metal, such as lithium metal, on an optional seed layer between the coating 11 and the electronically conductive wires 10 contained within the three-dimensional electronically conductive network 1. In the absence of the coating, the metal would preferentially plate out to the top of the three-dimensional electronically conductive network rather than the bottom due to the potential drop on the three-dimensional electronically conductive network. For example, if a 35 μm thick three-dimensional electronically conductive network, such as a nanomesh with an effective open porosity of 58% (i.e., considering a 10 nm coating), is filled with an electrolyte having, for example, a lithium ion conductivity of 1 mS / cm, the surface resistance on the three-dimensional electronically conductive network would be (35 μm) / (1 mS / cm × 0.58) = 6 Ω·cm 2 The plating current density is 10 mA / cm². 2 In this case, the potential difference on the 3D network is 6 Ω·cm. 2×10mA / cm 2 =60mV. The presence of coating 11 enables uniform plating. Without being constrained by theory, it is assumed that this is achieved by the potential difference on coating 11 being equal to, or preferably greater than, the potential difference on the three-dimensional electronic conductivity network. Minimum ionic conductivity of coating 11 σ i,11 The formula is as follows: This is inferred from TIFF0007847593000002.tif1452. Here, d 11 is the thickness (μm) of the electronic insulating coating 11, P is the porosity (%) of the coated three-dimensional electronic conductive network 1, l1 is the thickness (μm) of the coated three-dimensional electronic conductive network 1, and Av is the volumetric surface area (m²) of the coated three-dimensional electronic conductive network 1. 2 / cm 3 ) and σ 12 This is the ionic conductivity of electrolyte 12.

[0106] Here, in an embodiment, we estimate the conductivity of a coating 11 that is considered preferable for achieving conformal plating of metal 14. In this example, the coated three-dimensional electronically conductive network 1 is a nanomesh with an average pore size of 64 nm and a thickness of 35 μm. The electrolyte 12 has, for example, an ionic conductivity of 1 mS / cm for lithium ions. In this example, the coating 11 may have a thickness of 10 nm. After such coating, the porosity of the three-dimensional electronically conductive network may be 58%. In an embodiment, preferably, to achieve conformal plating of metal 14, the conductivity of the coating 11 for lithium ions is 2 × 10 for an area increase of 1000. -10is equal to or less than S / cm. For example, poly(p-phenylene oxide) (PPO), Li3PO4, Li2O, and Li2CO3 may have such low conductivity, and thus would be particularly suitable materials for use in the coating 11 of the present example. The coating 11 made of PPO can advantageously be manufactured by electropolymerization, which is a scalable and cost-effective technique. A further advantage of PPO is that the electropolymerization may be a self-limiting process, so the coating may be conformal. Furthermore, the coating 11 made of PPO has viscoelastic properties and can withstand volume changes.

[0107] In other examples, the coated three-dimensional electronic conductive network 1 may be a copper foam with an average pore size of 200 μm and a thickness of 100 μm. The electrolyte 12 may have, for example, an ionic conductivity of 1 mS / cm with respect to lithium ions. In this example, the coating 11 may have a thickness of up to 100 nm. After such a coating, the porosity of the three-dimensional electronic conductive network may be 70%. In an embodiment, preferably, in order to achieve conformal plating of the thin film metal 14, and thus the conductivity of the coating 11 with respect to lithium ions is 0.7×10 for a 1 effective area increase -6 is equal to or less than S / cm. For example, LiPON may have such low conductivity, and thus would be a particularly suitable material for use in the coating 11 in this example.

[0108] In these embodiments, the metal 14 conformally and uniformly covers the three-dimensional electronically conductive network 10. In this way, the mechanical stress induced in the coating 11 by the plated metal 14 is minimized. Here, uniformity, or thickness uniformity, means that the three-dimensional electronically conductive network has a thickness extending from a first surface to a second surface of the network, and the average thickness of the metal layer on the first surface is within 50%, preferably within 20%, of the thickness of the metal layer on the second surface. Thickness uniformity is determined by the resistance of the coating 11. The resistance of the coating is the resistivity, σ 11 It is determined by the thickness. Lower conductivity improves uniformity, but the plating overvoltage also increases. Therefore, the trade-off between uniformity and overvoltage is σ 11 It might be possible to find the value by setting it to a range between 10 times lower and 10 times higher than the value determined by the above formula.

[0109] Furthermore, the uniformity of the coating thickness 11 can be intentionally made non-uniform, with a slightly higher thickness (e.g., +20% thicker than the nominal value) at the top of the three-dimensional electronically conductive network 1 (i.e., at the interface with the electrolyte) and a slightly lower thickness (e.g., -20% thinner) at the bottom (near the current collector in the case of a closed network, or in the central part in the case of an open network as a negative electrode relative to the positive electrodes on both sides; see schematic diagram of a battery). By gradually changing the thickness, the resistance value changes gradually (higher at the top, lower at the bottom), resulting in a uniform thickness of the metal thin film.

[0110] Example 2: Lithium plating between nickel foil and LiPON Refer to Figure 2A. Nickel foil 3 is conformally covered with a coating 11 made of LiPON, which has a thickness of 5 nm. Nickel foil 3 is used as the first electrode. An electrolyte 12 made of 1 M LiClO4, i.e., lithium ions, covers the coating 11. The coating 11 is permeable and / or conductive to lithium ions, with low but not zero conductivity to lithium ions. The electrolyte 12 is in contact with a second electrode (not shown). When a first potential is applied, a conformal layer 14 of lithium is plated between the coating 11 and the nickel foil 3. The thickness of the lithium layer thus formed is 100 nm.

[0111] Referring to Figure 2B, an example of a cyclic voltammogram measured with the structure shown in Figure 2A is presented, showing the current density j (unit: mA·cm). -2 ) but, Li + The reduction potential is plotted as a function of the applied potential V. The applied potential is adjusted at a scan rate of 25 mV / s.

[0112] First, the applied potential is lowered. At applied potentials below 0V, a negative current density is observed in the voltammogram, which corresponds to the reduction of lithium ions and plating between the coating and the nickel foil. Next, when the potential is increased, the lithium layer peels off, i.e., the lithium is oxidized, which can form lithium ions that may permeate the coating and move into the electrolyte. Oxidation is indicated by an increase in current density. In this example, the current density is 3.5 mA·cm at 0.75V. -2 The current density drops to zero above a potential of approximately 0.75V, indicating that all lithium has been stripped off at that point. Therefore, even when the applied potential is further increased to approximately 3V, the current remains zero. Figure 2B shows that the current density remains similar in subsequent cycles, indicating high reproducibility of plating and stripping, and high stability of the coating.

[0113] In this example, a nickel foil was used where the current density reaches 3.5 mA·cm -2 , i.e., 0.75 V. In a further example, the nickel foil can be replaced with a coated three-dimensional electronic conductive network having the same lateral dimensions, a thickness of 35 μm, and a volume surface area of 28 m 2 / cm 3 , i.e., in accordance with an embodiment of the present invention. The effective area of the coated three-dimensional electronic conductive network, which consists of the entire surface of the coated three-dimensional electronic conductive network, is 1000 times the surface area of the copper foil (i.e., 35 μm × 28 m 2 / cm 3 ). Thus, in an embodiment of the present invention, by using a coated three-dimensional electronic conductive network instead of a copper foil, the effective current density can reach approximately 3.5 Acm -2 .

[0114] Next, refer to FIG. 3 showing an example of cyclic voltammetry performed on a three-dimensional electronic conductive network made of nickel and not including a coating. The scan rate is 10 mV / second, and the electrolyte impregnating the three-dimensional electronic conductive network consists of 1 M LiClO4 in propylene carbonate (PC). In contrast to the cyclic voltammogram of FIG. 2B, in FIG. 3, the current density in subsequent scan cycles lacks reproducibility, which is particularly evident at positive potentials where the lithium plating layer peels off, i.e., is oxidized. From FIG. 3, when the potential is increased, in subsequent cycles, as indicated by the arrow, it is observed that the charge density decreases to zero at a lower potential in each cycle. Thus, it seems that the amount of lithium peeled off in subsequent scan cycles is decreasing. This may indicate that the thickness of the lithium plating layer is decreasing in each cycle. For example, a solid electrolyte interphase (SEI) may be formed, and since the SEI consumes lithium ions from the electrolyte, the lithium ion concentration in the electrolyte decreases, and the thickness of the layer of lithium plated in each scan cycle may be decreasing. In the example of FIG. 2B, such an SEI is not observed, indicating the importance of the coating that prevents the formation of SEI.

[0115] Example 3: Evaluation of the advantages of different coatings Electrochemical experiments such as cyclic voltammetry can be used to evaluate the advantages of different coatings. Cyclic voltammetry experiments on titanium nitride substrates coated with different thin-film oxides were replicated to determine the advantages of the different coatings. See Figure 4A. To compare the different coatings, the Coulomb efficiency is determined from the cyclic voltammetry plots. This is the ratio of the integrated charge density during stripping (potential > 0V) to the integrated charge during plating (potential < 0V). The Coulomb efficiency η against subsequent cycles, i.e., the number of cycles, is shown in Figure 4A for subsequent cycles. Ideally, the Coulomb efficiency is approximately 100% in each cycle, and the amount of lithium stripped is equal to the amount of lithium plated.

[0116] Refer to Figure 4B. Furthermore, the resistance R can be determined for each cycle number by corresponding to the reciprocal of the slope of the cyclic voltammogram for each coating from -0.5V to 0.5V. Preferably, the resistance value is low, for example 200Ω in this example, and remains constant for subsequent cycles.

[0117] These results are illustrative and illustrate what experiments are possible to evaluate appropriate coatings. Since different experimental setups may yield different results regarding coatings, the results in Figures 4A and 4B cannot be extrapolated to different experiments and / or setups.

[0118] Example 4: Coated 3D electronically conductive network impregnated with a solid composite electrolyte Refer to Figures 5A, 5B, and 5C. In these examples, the coated three-dimensional electronically conductive network 1 is impregnated with an electrolyte 12, which is a solid composite electrolyte. The solid composite electrolyte 12 fills the pores of the coated three-dimensional electronically conductive network 1. Furthermore, the solid composite electrolyte 12 includes an overfill region 121 that extends outside the coated three-dimensional electronically conductive network 1. Otherwise, the overfill region 121 of the solid composite electrolyte 12 is on top of the coated three-dimensional electronically conductive network 1. Advantageously, the overfill region 121 can function as a separator. For example, in a battery including the coated three-dimensional electronically conductive network 1 acting as the positive electrode according to these embodiments, the negative electrode may be in contact with the overfill region 121. In that case, the coated three-dimensional electronically conductive network 1 is not in contact with the negative electrode. However, ions may flow from the negative electrode through the overfill region 121 to the coated three-dimensional electronically conductive network 1. The overfill region 121 may be present on one side of the coated three-dimensional electronically conductive network 1, as shown in Figure 5A. In Figure 5A, the coated three-dimensional electronically conductive network 1 is in contact with the current collector 2 on the side opposite to the side in contact with the overfill region 121. Figure 5B shows an example of a current collector 2 in electrical contact with the coated three-dimensional electronically conductive network 1 on both sides. In this example, both coated three-dimensional electronically conductive networks 1 are impregnated with a solid composite electrolyte 12. The solid electrolyte further includes an overfill region 121 that covers both coated three-dimensional electronically conductive networks 1. Figure 5C shows an example of a self-supporting coated three-dimensional electronically conductive network 1. The coated three-dimensional electronically conductive network 1 is impregnated with a solid composite electrolyte 12. The solid composite electrolyte 12 includes two overfill regions 121 on opposing sides of the coated three-dimensional electronically conductive network 1.

[0119] Example 5: Battery containing a coated three-dimensional electronically conductive network Referring to Figure 6A, a metal-ion battery comprising a coated three-dimensional electronically conductive network 1 according to an embodiment of the present invention is shown. The battery cell of this battery comprises a conductive substrate 5 and a composite positive electrode 6 on the conductive substrate. The composite positive electrode 6 in this example comprises electrode particles 61 bound together by a binder 62, such as a polymer, wound around the electrode particles 61. A conductive additive 63 is used to bring the electrode particles 61 into electronic contact with each other. In this example, the composite positive electrode 6 and the coated three-dimensional electronically conductive network 1, which is the negative electrode of the battery, are separated from each other by an electrolyte layer separator 4, such as a mechanical spacer, glass fiber cloth, flexible plastic film, or solid electrolyte, thereby preventing short circuits between the positive and negative electrodes. The coated three-dimensional electronically conductive network 1 is impregnated with an electrolyte 12 containing metal ions such as aluminum, magnesium, sodium, or lithium. In embodiments where the electrolyte separator 4 is a solid electrolyte, the separator comprises a second electrolyte which may be the same as or different from the electrolyte 12. The electrolyte separator 4 contains metal ions. The electrolyte separator 4 is permeable to at least metal ions. The composite positive electrode 6 is impregnated with a third electrolyte 64 containing metal ions. The third electrolyte 64 may be the same as or different from the second electrolyte. Also, the third electrolyte 64 may be the same as or different from electrolyte 12.

[0120] The battery in this embodiment includes multiple battery cells. Each battery cell shares a conductive substrate 5 with an adjacent first battery cell. Furthermore, this battery shares a coated three-dimensional electronically conductive network 1 with an adjacent second battery cell. In this configuration, multiple battery cells can be stacked on top of each other, thereby sharing the coated three-dimensional electronically conductive network 1 and the conductive substrate 5 between adjacent battery cells. This reduces the amount of material required compared to a configuration in which the coated three-dimensional electronically conductive network 1 and the conductive substrate 5 are not shared between adjacent battery cells, and allows for the creation of a battery with very high capacity and power.

[0121] Please refer to Figure 6B. A battery according to an embodiment of the present invention, similar to that shown in Figure 6A, is shown, in this example comprising two battery cells, with a coated three-dimensional electronically conductive network 1 shared by the two battery cells. The battery in this example includes a conductive substrate 5, on which a composite positive electrode 6 is located. An electrolyte separator 4 is located on the composite positive electrode 6, and on which the coated three-dimensional electronically conductive network 1 is located. Furthermore, another electrolyte separator 4 is located on the coated three-dimensional electronically conductive network 1, and on which another composite positive electrode 6 is located. The other composite positive electrode 6 is further in contact with and covered by the conductive substrate 5.

[0122] Refer to Figure 6C. As another example, instead of using a coated three-dimensional electronically conductive network that is freestanding and open on both sides (i.e., without current collectors) as in Figure 6A, current collectors may be made in contact with the coated three-dimensional electronically conductive network 1 as in Figure 6C. Freestanding means that the coated three-dimensional electronically conductive network 1 is not supported by a conductive substrate. Alternatively, current collectors 2 may be used to prevent the coated three-dimensional electronically conductive network 1 from being freestanding. In embodiments, the use of current collectors 2 improves the stability of the coated three-dimensional electronically conductive network, but comes at the cost of requiring more material and becoming heavier and thicker. In this configuration, current collectors 2 can be shared between adjacent battery cells instead of the coated three-dimensional electronically conductive network 1, as in the example in Figure 6A.

[0123] Please refer to Figure 6D. As another example, a battery consisting of two battery cells, as described in Figure 6B, may also include a current collector 2 used to prevent the coated three-dimensional electronically conductive network 1 from standing on its own. However, the present invention is not limited to these embodiments, and different battery configurations can be envisioned.

[0124] Example 6: Battery containing a coated 3D electronically conductive network impregnated with a solid composite electrolyte. Referring to Figure 7, a metal-ion battery is shown that includes a coated three-dimensional electronically conductive network 1 as the negative electrode according to an embodiment of the present invention. An electrolyte 12, which is a solid composite electrolyte, impregnates the coated three-dimensional electronically conductive network 1. The solid composite electrolyte 12 further includes two overfill regions 121 on opposite sides of the coated three-dimensional electronically conductive network 1. A second electrolyte 7, also a solid composite electrolyte, impregnates the composite positive electrode 6 of the battery. Electrolytes 12 and the second electrolyte 7 may or may not contain different types of solid composite electrolytes. The second electrolyte 7 also includes an overfill region 71. In this example, the batteries are stacked such that the composite positive electrode 7 is located on both sides of the coated three-dimensional electronically conductive network 1, i.e., the negative electrode. An electrolyte separator 4, which is a solid composite electrolyte separator, is located between the overfill regions 71 of the solid composite electrolyte 7 that impregnate each composite positive electrode 6 and the overfill regions 121 of the solid composite electrolyte 12 that impregnate the coated three-dimensional electronically conductive network 1. In this example, the coated three-dimensional electronically conductive network 1 is self-supporting. However, as shown in Figure 8, a similar configuration is possible for the negative electrode, which consists of a conductive substrate 2 to which the three-dimensional electronically conductive network 1 coated on both sides is in contact.

[0125] Refer to Figure 9. Since the overfill regions 71 and 121 are electrolyte layers that act as separators, no separate separator element is required. In this example, the overfill region 71 of the solid composite electrolyte 7 impregnating each of the composite positive electrodes 6 and the overfill region 121 of the solid composite electrolyte 12 impregnating the coated three-dimensional electronically conductive network 1 are in physical contact with each other. This allows the battery to be assembled without including a separate separator element. This simplifies manufacturing and reduces the material cost of the battery. Referring to Figure 10, a similar configuration to Figure 9 is shown. In Figure 9, the coated three-dimensional electronically conductive network 1 is freestanding, whereas in Figure 10, the coated three-dimensional electronically conductive network is in contact with the conductive substrate 2.

[0126] Example 7: Battery including a coated three-dimensional electronically conductive network and a solid ceramic cathode Refer to Figure 11, which shows a solid metal battery. In this example, the negative electrode includes a coated three-dimensional electronically conductive network 1. In this embodiment, the coated three-dimensional electronically conductive network 1 is in contact with a conductive substrate 2, but this is not mandatory, and the coated three-dimensional electronically conductive network 1 may instead be freestanding. The coated three-dimensional electronically conductive network 1 is impregnated with a solid composite electrolyte 12. In this example, the solid composite electrolyte 12 includes an overfill region 121. In this example, the positive electrode is a solid ceramic positive electrode including a positive electrode active material 61, optionally a binding polymer 62, and a conductive additive 63, which are in electrical contact with a current collector 5. The positive electrode further includes an inorganic solid electrolyte 8, which includes an oxide or sulfide. In this example, the overfill region 121 and the inorganic solid electrolyte 8 are separated by an electrolyte separator 4. However, this is not mandatory, and the overfill region 121 may instead function as the separator.

[0127] The above provides numerous examples of specific battery types including coated three-dimensional electronically conductive networks according to embodiments of the present invention. Those skilled in the art will understand that coated three-dimensional electronically conductive networks may also be included in different types of batteries without departing from the scope of the present invention. For example, similarly, in a metal-sulfur battery or a metal-air battery, the negative electrode may include a coated three-dimensional electronically conductive network. Furthermore, in a metal-sulfur battery or a metal-air battery, the coated three-dimensional electronically conductive network may be impregnated with a liquid electrolyte or a solid composite electrolyte, but the present invention is not limited thereto. Moreover, in a metal-sulfur battery or a metal-air battery, the solid composite electrolyte may include, for example, an overfill region that functions as a separator layer.

[0128] While specific configurations for batteries are shown in these embodiments, many other configurations are possible, including coated three-dimensional electronically conductive networks, and the present invention is not limited to these embodiments.

[0129] While this specification has described preferred embodiments, specific structures, and configurations of the devices according to the present invention, as well as materials, it should be understood that various changes or modifications can be made in form and detail without departing from the scope and spirit of the invention. For example, any formula given above is merely representative of the procedures that may be used. Steps may be added or deleted from the methods described within the scope of the invention.

Claims

1. A coated three-dimensional electronically conductive network (1) for acting as an electrode in a metal or metal-ion battery, wherein the metal is selected from a list consisting of Na, K, Li, Ca, Mg, and Al, (i) A three-dimensional electronically conductive network (10) comprising a plurality of interconnected electronically conductive wires, wherein the porosity is at least 60% and 10 －３ I understand ２ / cm ３ ~100m ２ / cm ３ A three-dimensional electronically conductive network (10) having a volume surface area, and (ii) Electronic insulating coating (11): i. The entire surface of the network (10) is conformally coated, and ii. Permeable and / or conductive to metal ions at at least one temperature in the range of -30°C to 150°C, A coated three-dimensional electronically conductive network (1) including [a specific component].

2. The coated three-dimensional electronically conductive network (1) according to claim 1, wherein the electronically insulating coating (11) has an average thickness of 2 to 500 nm.

3. The metal is Li, and the electronically insulating coating (11) is Li at at least one temperature in the range of -30°C to 150°C. ＋ A coated three-dimensional electronically conductive network (1) according to claim 1 or 2, which is transparent and / or conductive to the

4. The coated three-dimensional electronically conductive network (1) according to any one of claims 1 to 3, wherein the electronically insulating coating (11) is nonreactive to the metal at a temperature of at least -30°C to 180°C.

5. An electrolyte (12) containing metal ions is impregnated into a three-dimensional electronically conductive network (1) coated with an electronically insulating coating (11) with respect to the metal ions, and the conductivity of the electronically insulating coating (11) to the metal ions is 0.1σ. ｉ，１１ Larger, here, σ ｉ，１１ The following formula: Given, Here, d １１ is the thickness (μm) of the electronic insulating coating (11), P is the porosity (%) of the coated three-dimensional electronic conductive network (1), and l １ is the thickness (μm) of the coated three-dimensional electronic conductive network (1), Av is the volume surface area (m ２ / cm ３ ) of the coated three-dimensional electronic conductive network (1), and σ １２ is the ionic conductivity of the electrolyte (12), the coated three-dimensional electronic conductive network (1) according to any one of claims 1 to 4.

6. The coated three-dimensional electronically conductive network (1) according to any one of claims 1 to 5, wherein the coating (11) comprises one of the following materials: a solid electrolyte, an oxide, a polymer, a hybrid inorganic-organic material, an organometallic framework (MOF), or a covalent organic framework (COF).

7. A coated three-dimensional electronically conductive network (1) according to any one of claims 1 to 6, comprising a seed layer between the coating (11) and the three-dimensional electronically conductive network (10), wherein the seed layer promotes the growth of a layer of metal, a metal compound, or a metal alloy, and the seed layer conformally covers the entire surface of the network (10).

8. The seed layer has a thickness of 2 to 100 nm, and the coated three-dimensional electronically conductive network (1) is as described in claim 7.

9. The three-dimensional electronically conductive network (10) is 10 m ２ / cm ３ ~50m ２ / cm ３ A coated three-dimensional electronically conductive network (1) according to any one of claims 1 to 8, having a volume surface area.

10. A method for fabricating a coated three-dimensional electronically conductive network (1) to act as an electrode for a metal or metal-ion battery according to any one of claims 1 to 9, (i) A step of obtaining a three-dimensional electronically conductive network (10) comprising a plurality of interconnected electronically conductive wires, wherein the three-dimensional electronically conductive network (10) has a porosity of at least 60% and 10 －３ I understand ２ / cm ３ ~100m ２ / cm ３ A process having a volume surface area, and (ii) A method comprising the step of conformally coating the entire surface of a three-dimensional electronically conductive network (1) with an electronically insulating coating (11), wherein the coating (11) is permeable to and / or conductive to metal ions at at least one temperature in the range of -30°C to 150°C.

11. A coated and plated three-dimensional electronically conductive network (1) according to any one of claims 1 to 9, comprising a conformal layer of metal (14) between an electronically insulating coating (11) and a three-dimensional electronically conductive network (10).

12. (iii) A step of impregnating an electrolyte (12) containing ions of a metal (14) with a coated three-dimensional electronically conductive network, and (iv) The method according to claim 10, further comprising the step of applying a first potential for plating a metal onto a three-dimensional electronically conductive network (1).

13. The method according to claim 12, further comprising the step of periodically applying a second potential and a first potential for stripping a metal.

14. A metal-ion battery comprising a conductive substrate (5), a positive electrode (6) provided on the conductive substrate (5), an electrolyte layer (4) provided on the positive electrode (6), and a coated three-dimensional electronically conductive network (1) impregnated with an electrolyte (12) as described in any of claims 1 to 9, which acts as a negative electrode on the electrolyte layer (4).

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