Electrically Connected Electrodes and Related Articles and Methods

Abstract

Methods for electrically connecting electrode portions in electrochemical devices, and related articles and systems, are broadly described. In some cases, a non-conductive layer is present between the electrode portions to be connected. In some cases, the methods comprise penetrating the article to establish an electrical connection between the electrode portions previously separated by the non-conductive layer.

Description

Related Applications

[0001] This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application No. 62 / 851,162, entitled "Electrically Connected Electrodes, and Related Articles and Methods," filed May 22, 2019. The provisional application is incorporated herein by reference in its entirety for all purposes. [Technical Field]

[0002] Methods for electrically connecting electrodes in electrochemical devices, and related articles and systems, are broadly described. [Background technology]

[0003] Electrochemical cells typically contain electrodes comprising electrode active materials that participate in electrochemical reactions to generate electrical current. A typical electrochemical device, such as a battery, includes terminals that can be used to electrically connect the electrodes of the electrochemical device to an external circuit. Certain embodiments of the present disclosure are directed to inventive methods, systems, and articles for connecting electrodes of an electrochemical cell. Summary of the Invention [Problem to be solved by the invention]

[0004] Summary Methods for electrically connecting electrode portions in electrochemical devices, as well as related articles and systems, have been broadly described. In some cases, a non-conductive layer is present between the electrode portions to be connected. In some cases, the method includes penetrating the article to establish an electrical connection between electrode portions previously separated by the non-conductive layer. The subject matter of the present invention, in some cases, includes interrelated products, alternative solutions to a particular problem, and / or multiple different uses of one or more systems and / or articles. [Means for solving the problem]

[0005] In one aspect, a method is described. In some embodiments, the method includes penetrating a portion of an article including a non-conductive layer having a first side and a second side, a first electrode portion adjacent to the first side of the non-conductive layer, and a second electrode portion adjacent to the second side of the non-conductive layer. In some embodiments, the method is performed such that an electrical connection is established between the first electrode portion and the second electrode portion.

[0006] In another aspect, an article is described. In some embodiments, the article includes a non-conductive layer including a first side and a second side. In some embodiments, the article includes a first electrode portion adjacent to the first side of the non-conductive layer, the first electrode portion having a polarity. In some embodiments, the article includes a second electrode portion adjacent to the second side of the non-conductive layer, the second electrode portion having the same polarity as the first electrode portion. In some embodiments, the first electrode portion is electrically connected to the second electrode portion by a conductive solid material region extending from the first electrode portion through the non-conductive layer to the second electrode portion.

[0007] Other advantages and novel features of the present invention will become apparent from the following detailed description of various non-limiting embodiments of the invention when considered in conjunction with the accompanying figures. In the event that the present specification and a document incorporated by reference include conflicting and / or inconsistent disclosure, the present specification shall control. [Brief explanation of the drawings]

[0008] BRIEF DESCRIPTION OF THE DRAWINGS Non-limiting embodiments of the present invention are described, by way of example, with reference to the accompanying drawings, which are schematic and not intended to be drawn to scale. In the drawings, each identical or nearly identical component shown is typically represented by a single numeral. For clarity, not every component is labeled in every drawing, and not every component of each embodiment of the present invention is shown unless illustration is necessary to enable those skilled in the art to understand the invention. [Figure 1A] FIG. 1A is an exemplary schematic diagram showing a cross-sectional view of an article comprising multiple electrode portions, according to certain embodiments. [Figure 1B] FIG. 1B is an exemplary schematic diagram illustrating a cross-sectional view of the article of FIG. 1A being penetrated, according to certain embodiments. [Figure 2] FIG. 2 is an exemplary schematic diagram showing a cross-sectional view of an article comprising multiple electrode portions, according to certain embodiments. [Figure 3] FIG. 3 is an exemplary schematic diagram showing a cross-sectional view of an article comprising multiple electrode portions containing cavities, according to certain embodiments. [Figure 4A] FIG. 4A is an exemplary schematic diagram showing a cross-sectional view of an article comprising a plurality of electrode portions and a conductive terminal, according to certain embodiments. [Figure 4B] FIG. 4B is an exemplary schematic diagram showing a cross-sectional view of an article comprising a plurality of electrode portions and a threaded conductive terminal, according to certain embodiments. [Figure 4C] FIG. 4C is an exemplary schematic diagram showing a cross-sectional view of an article comprising a plurality of electrode portions and a conductive terminal, according to certain embodiments. [Figure 4D] FIG. 4D is an exemplary schematic diagram showing a cross-sectional view of an article comprising a plurality of electrode portions and a conductive terminal, according to certain embodiments. [Figure 5A] FIG. 5A is an exemplary schematic diagram showing a cross-sectional view of an article comprising multiple double-sided electrode portions, according to certain embodiments. [Figure 5B] FIG. 5B is an exemplary schematic diagram showing a cross-sectional view of an article comprising multiple double-sided electrode portions, according to certain embodiments. [Figure 5C] FIG. 5C is an exemplary schematic diagram showing a cross-sectional view of an article comprising a plurality of double-sided electrode portions and a conductive terminal, according to certain embodiments. [Figure 6A] FIG. 6A is an exemplary schematic diagram showing a cross-sectional view of an article comprising multiple double-sided electrode portions, according to certain embodiments. [Figure 6B]FIG. 6B is an exemplary schematic diagram showing a cross-sectional view of an article comprising multiple double-sided electrode portions, according to certain embodiments. [Figure 7A] FIG. 7A is an exemplary schematic diagram showing a cross-sectional view of an article comprising multiple double-sided electrode portions, according to certain embodiments. [Figure 7B] FIG. 7B is an exemplary schematic diagram showing a cross-sectional view of an article comprising multiple double-sided electrode portions, according to certain embodiments. [Figure 8] FIG. 8 is an exemplary schematic diagram showing a cross-sectional view of an article comprising multiple electrode portions, according to certain embodiments. [Figure 9A] FIG. 9A is an exemplary schematic diagram showing a cross-sectional view of an article comprising multiple electrode portions, according to certain embodiments. [Figure 9B] FIG. 9B is an exemplary schematic diagram showing a cross-sectional view of an article comprising multiple double-sided electrode portions, according to certain embodiments. [Figure 10A] FIG. 10A is an exemplary schematic diagram showing a cross-sectional view of an electrode portion and a non-conductive layer, according to certain embodiments. [Figure 10B] FIG. 10B is an exemplary schematic diagram showing a cross-sectional view of an article comprising multiple electrode portions, according to certain embodiments. [Figure 11A] FIG. 11A is an exemplary schematic diagram showing a top view of an electrode and separator of an electrochemical device, according to certain embodiments. [Figure 11B] FIG. 11B is an exemplary schematic diagram illustrating an electrochemical device comprising an anode and an anode extension, and a cathode and a cathode current collector extension, according to certain embodiments. [Figure 11C] FIG. 11C is an illustrative schematic diagram of a cross-sectional view of the electrochemical device of FIG. 11B, according to certain embodiments. [Figure 11D] FIG. 11D is an illustrative schematic diagram of a cross-sectional view of the electrochemical device of FIG. 11B, according to certain embodiments. [Figure 11E] FIG. 11E is an illustrative schematic diagram of a cross-sectional view of the electrochemical device of FIG. 11B, according to certain embodiments. [Figure 11F]FIG. 11F is an illustrative schematic diagram of a cross-sectional view of the electrochemical device of FIG. 11B, according to certain embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0009] Methods for electrically connecting electrode portions within an electrochemical device, as well as related articles and systems, have been broadly described. Some methods comprise penetrating an article that is part of an electrochemical device (e.g., a battery) to electrically connect multiple electrode portions within the article separated by one or more non-conductive layers, thereby achieving electrical connection between the multiple electrode portions and a conductive terminal. As a non-limiting example, in some cases, an anode terminal of a battery stack is connected to an extension comprising an anode portion (e.g., a deposited lithium layer portion) from the battery stack, a non-conductive layer (e.g., a release layer) is inserted between the anode portions, and the anode portion within the anode extension at least partially penetrates at least a portion of the stack to have good electrical contact with the anode terminal. In some cases, the method comprises penetrating the article by piercing the article with a pin (e.g., crimping the article) to establish electrical contact between the electrode portions within the article. In some cases, conductive material regions (e.g., comprising an electrode active material such as lithium or a lithium alloy) and / or cavities extend from a particular electrode portion through a non-conductive layer (e.g., a release layer) to other electrode portions to establish electrical connection.

[0010] Ensuring efficient charge transport between electrodes and terminals of an electrochemical device can be important for the performance of that electrochemical device during cycling. However, some electrode configurations can make it difficult to transport charge from one portion of an electrode to a terminal. For example, in some cases, when a non-conductive layer separates electrode portions, charge transport from one electrode portion to another is difficult due to the lack of an easy conductive path, thereby creating high resistance between the electrochemical device and the electrode (e.g., anode) terminal. As one non-limiting example, some electrochemical devices may use a stack of double-sided electrodes of a "sandwich" type, such as an anode containing two vapor-deposited lithium layers separated by a release layer. The presence of the release layer can limit the ability of current to flow from one anode to another in the sandwich electrode and make it difficult to collect current from an anode that is not in direct contact with a terminal. While one can attempt to remove the non-conductive layer of the electrode, such a process can be difficult and expensive. A simple and inexpensive process for establishing electrical communication between electrodes separated by a non-conductive layer would be desirable. The methods described herein provide such a process in some cases. It has been unexpectedly discovered that penetrating an article comprising an electrode portion and a non-conductive layer (e.g., by piercing the article with a pin) can establish an electrical connection between the electrode portions, even when separated by a non-conductive layer. In some cases, penetrating the article forms a region of conductive solid material extending from a first electrode portion through the non-conductive layer to another electrode portion (e.g., having the same polarity as the first electrode portion), thereby establishing an electrical connection. In some cases, the object used to penetrate the article can be configured to provide an efficient electrical connection between the layers (e.g., through the use of pin geometries / shapes with a high perimeter-to-cross-sectional area ratio). The methods and articles described herein can, in some, but not necessarily all, cases, avoid the need to remove the non-conductive layer, thereby increasing manufacturing efficiency and reducing costs while maintaining adequate performance of the electrochemical device.

[0011] In one aspect, a method relating to establishing an electrical connection between two or more electrode portions within a particular article is broadly described.

[0012] In some embodiments, the method comprises piercing a portion of the article. FIG. 1A is a cross-sectional schematic diagram of an exemplary article 100. In some embodiments, upon piercing, an electrical connection can be established between two or more parts of the article. As noted above, in certain embodiments, the article being pierced is part of an electrochemical device (e.g., a battery). For example, in certain embodiments, article 100 is part of an electrochemical device (e.g., a terminal of the electrochemical device where current passing through the electrochemical device is directed to an external electrical component (e.g., during cycling of the battery)).

[0013] In some embodiments, the article to be pierced comprises a first electrode portion and a second electrode portion separated by a non-conductive layer. For example, FIG. 1A shows an article 100 comprising a non-conductive layer 130 between a first electrode portion 110 and a second electrode portion 120. The non-conductive layer 130 comprises a first side 131 and a second side 132. According to certain embodiments, the first electrode portion 110 is adjacent to the first side 131, and the second electrode portion 120 is adjacent to the second side 132. In some cases, each of the two or more electrode portions of the article (e.g., the first electrode portion 110 and the second electrode portion 120) has the same polarity (e.g., both the first and second electrode portions are anodic portions, or both the first and second electrode portions are cathodic portions). If the article is part of an electrochemical device, it may be desirable to collect current from two or more electrode portions (e.g., first electrode portion 110 and second electrode portion 120) from a common electrical component (e.g., the terminals of a battery). In certain such cases, the two or more electrode portions are electrically connected such that current can flow between the common electrical component and the two or more electrode portions with lower resistance than if the two or more electrode portions were not connected.

[0014] In certain embodiments, piercing a portion of the article is performed such that an electrical connection is established between the first electrode portion and the second electrode portion. Establishing an electrical connection between the first electrode portion and the second electrode portion by piercing the article may, in certain cases, provide a simple and inexpensive process for electrically connecting electrode portions (e.g., in battery terminals) that are electrically separated by a non-conductive layer without using complex and expensive manufacturing processes. Non-limiting examples of how an electrical connection can be established between the first electrode portion and the second electrode portion by piercing the article are described in more detail below.

[0015] In some embodiments, penetrating the article comprises piercing the article with a solid object. The solid object may be selected from any of a variety of suitable objects capable of penetrating the article. Exemplary solid objects that can be used to penetrate the article include, but are not limited to, pins, punches, rivets, fasteners (e.g., threaded fasteners), blades, teeth, needles, and combinations thereof. As a non-limiting example, FIG. 1B illustrates a cross-sectional schematic diagram of an article 100 penetrated by a pin 160, according to certain embodiments. In FIG. 1B, the pin 160 penetrates the article 100 by piercing the first surface 101 of the article 100 and traveling through at least a portion of the first electrode portion 110, the first surface 131 of the non-conductive layer 130, the second surface 132 of the non-conductive layer 130, and the second electrode portion 120, according to certain embodiments.

[0016] In some embodiments, penetrating the article (e.g., with a solid object such as a pin) comprises driving the solid object partially through the article. While FIG. 1B illustrates pin 160 penetrating first side 101 of article 100 and completely through to second side 102, it should be understood that in some cases, pin 160 may penetrate article 100 by piercing first side 101, first electrode portion 110, non-conductive layer 130, and second electrode portion 120, but not completely through to second side 102. Penetrating the article so that the solid object does not pass completely through the article may be beneficial in certain, but not necessarily all, cases, as it may avoid the formation of certain undesirable features on the second side of the article. For example, in some cases, penetrating the entire article may result in the formation of a burr, which may be undesirable in certain applications, such as certain types of batteries.

[0017] The solid object used to penetrate (e.g., by piercing) the article may have any of a variety of suitable configurations for performing the penetrating steps described herein. For example, the solid object (e.g., pin 160) may comprise a solid material and have dimensions (e.g., aspect ratio) suitable for piercing the article without damaging the article (e.g., without rendering the article no longer suitable for its intended purpose, such as being part of an electrochemical device). In certain embodiments, penetrating the article includes orienting the solid object (e.g., pin) relative to the article and applying a directional force to the solid object, thereby driving the solid object toward the article. Referring again to FIG. 1B , penetrating the article 100 may include applying a force to the pin 160 in the direction indicated by arrow 161 such that the pin 160 pierces the article 100. In some cases, penetrating the article may also include using other forces in addition to the directional force to penetrate the solid object. For example, in some cases, a rotational force may be generated in conjunction with the directional force. As another example, in some cases, when a solid article penetrates an article, vibrations are created with directional forces.

[0018] In some embodiments, the methods described herein include removing the solid object. For example, if a pin 160 penetrates the exemplary article 100 (e.g., to establish an electrical connection between the first electrode portion 110 and the second electrode portion 120), the pin 160 can then be removed from the article 100, according to certain embodiments. In some embodiments, a solid object (e.g., a pin) is used to penetrate the article using a spring-loaded mechanism, and then a spring-loaded mechanism is used to retract the solid object from the article following the penetration step. In some cases, a scraper is used during removal of the solid object. The use of such a scraper can aid in removing the solid object from the article (and optionally from a conductive terminal coupled to the article), especially in certain cases where the solid object becomes attached to parts of the article and / or the conductive terminal. Even after the solid object (e.g., a pin) used to penetrate the article is removed from the article, the electrical connection between the first electrode portion and the second electrode portion established during the penetration step can remain. In this manner, the electrochemical device can be cycled following removal of the solid object, according to certain embodiments.

[0019] In some embodiments, penetrating the article forms a conductive solid material region within the article. For example, with reference to Figure 2, penetrating article 100 may form conductive solid material region 140 within article 100. In certain cases, the conductive solid material region extends from the first electrode portion, through the non-conductive layer, to the second electrode portion.

[0020] It should be understood that when a region (e.g., a conductive solid material region) extends to a component of an article (e.g., a second electrode portion), the region may extend beyond the component (e.g., extend through the component, extend to another region of the article distal to the component), or the region may terminate at the component to which it extends. For example, referring again to FIG. 2 , conductive solid material region 140 extends from first electrode portion 110, through non-conductive layer 130, to second electrode portion 120. In certain embodiments, conductive solid material region 140 stops as shown in FIG. 2 , while in certain other embodiments, conductive solid material region 140 extends beyond second electrode portion 120 to another region of article 100 not shown.

[0021] In some embodiments, the conductive solid material region electrically connects the first electrode portion and the second electrode portion. For example, referring again to FIG. 2 , the conductive solid material region 140 electrically connects the first electrode portion 110 and the second electrode portion 120. In other words, current can flow from the first electrode portion through the conductive solid material region to the second electrode portion. In certain cases, the presence of the conductive solid material region enables current flow from one electrode portion (e.g., the first electrode portion) to another electrode portion (e.g., the second electrode portion) that would otherwise be impossible due to, for example, the placement of a non-conductive layer between the two electrode portions. In certain cases, the presence of the conductive solid material region enables current flow from one electrode portion to another electrode portion with lower resistance than would be present in the absence of the conductive solid material region. Establishing an electrical connection between the first electrode portion and the second electrode portion (e.g., via the solid conductive material region) in such a manner can improve the performance of an electrochemical device comprising the article. For example, if the article is part of a battery terminal, reducing the resistance between the first electrode portion and the second electrode portion may allow current to be more efficiently collected from or injected into the battery (e.g., during cycling of the battery).

[0022] The conductive solid material can include any suitable conductive material. In some cases, the conductive solid material is or comprises a metal, a metal alloy, and / or a conductive composite. As described in more detail below, in some cases, the conductive solid material of the conductive solid material region comprises a material that also comprises a first electrode portion and a second electrode portion, such as an electrode active material.

[0023] In some embodiments, piercing the article forms a cavity in the article. For example, if a solid object (e.g., a pin) is pierced through the article so that the solid object penetrates the article, and then the solid object is removed, a cavity in the article may exist in the space where the solid object advanced. In some embodiments, the cavity extends from the first electrode portion through the non-conductive layer to the second electrode portion. Referring to FIG. 3 , the article 100 comprises a cavity 150 extending from the first electrode portion 110 through the non-conductive layer 130 to the second electrode portion 120. Certain methods described herein comprise piercing the article 100 by piercing the article 100 with a pin 160 to establish an electrical connection between the first electrode portion 110 and the second electrode portion 120, and removing the pin 160, thereby resulting in the article 100 comprising the cavity 150. One non-limiting embodiment comprises crimping the article, where the crimping provides an electrical connection between the first and second electrode portions of the article (e.g., so that the article can be used to connect to a terminal of an electrochemical device with improved performance).

[0024] In some embodiments, the first electrode portion comprises an active electrode material, and the second electrode portion comprises the same active electrode material. For example, in some embodiments, the first electrode portion 110 and the second electrode portion 120 each comprise the same active electrode material. As used herein, the term "active electrode material" refers to any electrochemically active species associated with an electrode. For example, "cathode active material" refers to any electrochemically active species associated with a cathode, and "anode active material" refers to any electrochemically active species associated with an anode. In some embodiments, the first electrode portion and the second electrode portion comprise lithium and / or a lithium metal alloy as the active electrode material. The first electrode portion and the second electrode portion, according to certain embodiments, can comprise lithium metal and / or a lithium metal alloy as the active electrode material during at least some or all of the charge and / or discharge process of the electrochemical cell. Lithium and / or a lithium metal alloy can, for example, be the active anode material. Suitable active cathode and anode materials are described more fully below.

[0025] In some embodiments, the conductive solid material region also comprises an active electrode material present in the first electrode portion and the second electrode portion. For example, referring again to FIG. 2 , in some cases, the first electrode portion 110 comprises an active anode material (e.g., lithium or a lithium alloy), the second electrode portion 120 comprises the same active anode material, and the conductive solid material region 140 extending from the first electrode portion 110 through the non-conductive layer 130 to the second electrode portion 120 comprises the same active anode material as the first electrode portion 110 and the second electrode portion 120. It has been observed that penetrating the article can displace a portion of the active electrode material of the first electrode portion and / or the second electrode portion such that the portion of the active electrode material forms at least a portion of the conductive solid material region extending from the first electrode portion through the non-conductive layer to the second electrode portion, thereby electrically connecting the first electrode portion and the second electrode portion. As one non-limiting example, the first electrode portion 110 and the second electrode portion 120 can each comprise lithium and / or a lithium alloy as an electrode active material, and piercing the article 100 (e.g., with a pin 160) causes a portion of the lithium and / or lithium alloy of the first electrode portion 110 and / or the second electrode portion 120 to migrate across the pierced portion of the non-conductive layer 130 such that a conductive solid material region comprising lithium and / or a lithium alloy electrically connects the first electrode portion 110 and the second electrode portion 120.

[0026] In some embodiments, at least a portion of the conductive solid material is disposed along a wall of the cavity. The wall of the cavity occupies the interface between the cavity and a solid portion of the article surrounding the cavity. Referring again to FIG. 3 , according to certain embodiments, the cavity 150 of the article 100 (e.g., formed by penetrating the article 100) comprises a wall 151. According to certain embodiments, the wall 151 is formed along the interface between the cavity 150 and the first electrode portion 110, the interface between the cavity 150 and the non-conductive layer 130, and the interface between the cavity 150 and the second electrode portion 120. As shown in FIG. 3 , optional conductive solid material regions 140 are disposed along the wall 151 according to certain embodiments. In some cases, a portion of the conductive solid material region disposed along the cavity wall is created when the article is pierced (e.g., by being pierced with a solid object such as a pin), and a portion of the electrode active material (e.g., lithium or a lithium alloy) from the first electrode portion and / or the second electrode portion moves along the direction of travel of the piercing solid object (e.g., the pin), and when the piercing object is subsequently removed from the article, a portion of the electrode active material remains disposed along the wall of the resulting cavity. In some cases, a portion of the conductive solid material along the cavity wall extends from the first electrode portion through a non-conductive layer to the second electrode portion, thereby electrically connecting the first electrode portion and the second electrode portion. In some cases, penetrating the article to form a conductive solid material disposed along the cavity wall provides a facile and relatively inexpensive technique for electrically connecting the electrode portions (which can be connected to the terminals of an electrochemical device).

[0027] Certain methods described herein further include filling at least a portion of the cavity with a conductive material. Filling at least a portion of the cavity with a conductive material (e.g., following formation of the cavity by piercing the article) can form a relatively large conductive solid material region extending from the first electrode portion through the non-conductive layer to the second electrode portion. Filling at least a portion of the cavity with a conductive material can also improve (e.g., increase) the contact area between the first electrode portion, the second electrode portion, and the conductive solid material region, thereby improving the electrical connection between the first electrode portion and the second electrode portion. The presence of such a relatively large conductive solid material can provide a relatively low-resistance medium through which current can flow from the first electrode portion to the second electrode portion and vice versa. For example, the piercing article 100 can first form a cavity 150, as shown in FIG. 3, and at least a portion of the cavity 150 can then be filled (e.g., via coating, deposition, etc.) with a conductive solid material. In some embodiments, filling at least a portion of the cavity includes filling all or substantially all of the cavity, as shown in FIG.

[0028] In some embodiments, a relatively large percentage of the cavity's volume is filled with the conductive material. In some embodiments, at least 10 percent by volume (10 vol%), at least 25 vol%, at least 50 vol%, at least 75 vol%, at least 90 vol%, at least 95 vol%, at least 99 vol%, or up to 100 vol% of the cavity is filled with the conductive material. Combinations of these ranges are possible. For example, in some embodiments, the methods described herein comprise filling the cavity such that at least 10 vol% and up to 100 vol% of the cavity is filled with the conductive material.

[0029] In some cases, the cavity is filled with a conductive solid material. In some, but not all, cases, the conductive solid material is a material different from the electrode active material of the first electrode portion and / or the second electrode portion. The material used to fill the cavity may, according to certain embodiments, include a metal, a metal alloy, a conductive composite material, a conductive polymer, and / or a combination thereof. Exemplary materials that can be used to fill the cavity may include, but are not limited to, copper, aluminum, and lithium.

[0030] In some embodiments, piercing the article is performed after the article has been otherwise manufactured and incorporated into an electrochemical cell. For example, in some cases, the article is electrically connected to a conductive terminal of an electrochemical device, and the piercing step is performed after the article is connected to the conductive terminal. Referring to FIG. 4A , according to certain embodiments, article 100 is electrically connected to conductive terminal 170. In some cases, after article 100 is connected to conductive terminal 170, according to certain embodiments, the combined article including both article 100 and conductive terminal 170 is pierced according to methods described herein (e.g., pin 160). In some such cases, as shown in FIG. 4B , piercing article 100 may also include piercing conductive terminal 170. Some embodiments may include removing the object used to pierce the combined article including the article and conductive terminal, thereby leaving a cavity extending from a portion of the conductive terminal through the first electrode portion, through the non-conductive layer, and to the second electrode portion. For example, Figure 4C shows a cavity 150 extending from the conductive terminal 170 through the first electrode portion 110, through the non-conductive layer 130, and to the second electrode portion 120, according to certain embodiments. In some cases, the cavity extending from the conductive terminal through the first electrode portion, through the non-conductive layer, and to the second electrode portion is filled with a conductive material (e.g., to improve electrical connection between the first electrode portion, the second electrode portion, and the conductive terminal). For example, referring to Figure 4D, a conductive solid material region 140 extends from the conductive terminal 170 through the first electrode portion 110, through the non-conductive layer 130, and to the second electrode portion 120.

[0031] In another aspect, the article is broadly described. In some cases, as described above, the article is part of an electrochemical cell. In certain cases, the article may be useful for forming an electrical connection between a conductive terminal (e.g., a battery terminal) of an electrochemical cell and an electrode portion therein. As described above, FIG. 1A shows a cross-sectional schematic view of an exemplary article 100.

[0032] The articles described herein may include multiple electrode portions. As described above, the articles may include a first electrode portion and a second electrode portion. In some cases, a non-conductive layer may be disposed between the first electrode portion and the second electrode portion.

[0033] In some embodiments, the non-conductive layer has a first surface (or first side or first side or first portion) and a second surface (or second side or second side or second portion). In some embodiments, the article comprises a first electrode portion adjacent to the first surface of the non-conductive layer. In certain cases, the article comprises a second electrode portion adjacent to the second surface of the non-conductive layer. For example, referring again to FIG. 1A , according to certain embodiments, the non-conductive layer 130 comprises a first surface 131, and the article 100 comprises a first electrode portion 110 adjacent to the first surface 131. Similarly, in some cases, the article 100 comprises a second electrode portion 120 adjacent to the second surface 132 of the non-conductive layer 130.

[0034] The first electrode portion and the second electrode portion can be disposed directly on the non-conductive layer (e.g., one or both can be formed via a deposition or coating process). For example, in FIG. 1A , the first electrode portion 110 is directly on the non-conductive layer 130, and the second electrode portion 120 is directly on the non-conductive layer 130. Direct contact between the electrode portion and the non-conductive layer is not required, but in some embodiments, one or more intervening layers (e.g., solid layers) exist between the non-conductive layer and an adjacent electrode portion. For example, in FIG. 1A , an intervening layer can be between the first electrode portion 110 and the non-conductive layer 130 and / or between the second electrode portion 120 and the non-conductive layer 130. The first electrode portion adjacent to the first surface of the non-conductive layer can be within a relatively short distance from the first surface of the non-conductive layer. For example, the first electrode portion can be within 5.0 mm, 1.0 mm, 500 micrometers, 100 micrometers, 50 micrometers, 10 micrometers, or less of the non-conductive layer (e.g., the first surface of the non-conductive layer). In some embodiments, the first electrode portion is directly adjacent to the first surface of the non-conductive layer. Similarly, the second electrode portion, adjacent to the second surface of the non-conductive layer, can be within a relatively short distance from the second surface of the non-conductive layer. For example, the second electrode portion can be within 5.0 mm, 1.0 mm, 500 micrometers, 100 micrometers, 50 micrometers, 10 micrometers, or less of the second surface of the non-conductive layer. In some embodiments, the second electrode portion is directly adjacent to the second surface of the non-conductive layer.

[0035] As noted above, in some cases, the non-conductive layer is or comprises a release layer. Exemplary materials and properties of release layers are described in more detail below. The release layer can comprise a polymeric material, and the release layer can be used as part of the manufacturing process for one or more components of the articles and / or electrochemical devices described herein. For example, in some cases, it is convenient to form an electrode portion for use in an electrochemical device by depositing or coating an electrode material onto a release layer on a substrate (e.g., a substrate used as a solid surface on which a particular article and / or component of an electrochemical device is formed during manufacturing, but which is not necessarily included in the finished article or electrochemical device), and then use the release layer to separate the deposited or coated electrode portion from the substrate (e.g., which can be incorporated into an electrochemical device such as a battery). As one non-limiting example, an anode comprising lithium and / or a lithium alloy as the anode active material can be formed by depositing lithium onto a release layer on a substrate, followed by separating the release layer (the resulting layer of deposited lithium or lithium alloy) from the substrate. One example of such an anode is described in U.S. Patent Publication No. 2008 / 0014501, published January 17, 2008, filed July 23, 2007 as application Ser. No. 11 / 781,915, patented June 17, 2014 as U.S. Patent No. 8,753,771, and entitled "Lithium Anode for Electrochemical Cells," which is incorporated herein by reference in its entirety and for all purposes.

[0036] FIG. 10A is an exemplary diagram of a multilayer structure comprising a non-conductive layer 130 (e.g., comprising a release layer) having an adjacent electrode portion 110 (e.g., comprising lithium and / or a lithium alloy). In some cases, an electrode for use in an electrochemical device may comprise two combined multilayer structures as shown in FIG. 10B. Such a double-sided electrode portion—comprising a non-conductive layer (which itself may comprise two release layers) having a first side and a second side, a first electrode portion adjacent to the first side, and a second electrode portion adjacent to the second side—can provide a high-energy-density electrode for an electrochemical device such as a battery. Because of the presence of the non-conductive layer (e.g., a release layer) between the first and second electrode portions, methods described herein can be useful for establishing an electrical connection between the first and second electrode portions, which can reduce resistance when collecting or injecting current from or into an electrochemical device comprising such an article (e.g., during discharging and / or charging of the electrochemical device). As noted above, the methods described herein (e.g., including penetrating the article) may result in an article in which a first electrode portion is electrically connected to a second electrode portion by a region of conductive solid material extending from the first electrode portion through the non-conductive layer to the second electrode portion.

[0037] The methods of establishing electrical connections between electrode portions described herein may allow for relatively efficient charge transport (e.g., electrical current) to and from the electrodes of an electrochemical cell when the electrode portions are incorporated into an electrochemical cell, while a non-conductive layer, such as a release layer, remains attached to the electrode portions.

[0038] In some embodiments, the non-conductive layer has a relatively low conductivity. For example, in some embodiments, the non-conductive layer has a conductivity of 10 -2 S / cm or less, 10 -3 S / cm or less, 10 -4 For example, in some cases, the release layer has a conductivity of 2.5×10 S / cm or less. -3 S / cm or more and 3×10 -3 It has a conductivity of less than S / cm.

[0039] As described above, in some embodiments, the first electrode portion has a polarity. For example, in some cases, the first electrode portion is part of an anode. In some embodiments, the second electrode portion has the same polarity as the first electrode portion. For example, in some cases, the second electrode portion is also an anode portion. According to certain embodiments, referring to FIG. 1A, the first electrode portion 110 has a polarity, and the second electrode portion 120 has the same polarity as the first electrode portion 110. In some cases, the first electrode portion and the second electrode portion have the same polarity and comprise the same electrode active material (e.g., the first electrode portion 110 is an anode portion comprising lithium and / or a lithium alloy as the anode active material, and the second electrode portion 120 is an anode portion also comprising lithium and / or a lithium alloy as the anode active material). In some embodiments, the first electrode portion and the second electrode portion are each a cathode portion.

[0040] As used herein, "cathode" refers to an electrode in which the electrode active material is oxidized during charging and reduced during discharging, and "anode" refers to an electrode in which the electrode active material is reduced during charging and oxidized during discharging.

[0041] As described above, in some embodiments, the non-conductive layer, the first electrode portion, and the second electrode portion form a double-sided electrode portion. For example, according to certain embodiments, the article 100 shown in FIG. 1A may be a double-sided electrode portion. A double-sided electrode portion, or "sandwich electrode" portion, may be part of an electrochemical device (e.g., a battery) having any of a variety of suitable configurations, including, but not limited to, a stacked configuration, a folded configuration, or a wound configuration. In some embodiments, the double-sided electrode portion comprises a conductive solid material region extending through at least a portion of the double-sided electrode portion. According to certain embodiments, for example, with reference to FIG. 2, as described above, the article 100 comprises a double-sided electrode portion, wherein the conductive solid material region 140 extends from the first electrode portion 110 through the non-conductive layer 130 to the second electrode portion 120, thereby electrically connecting the first electrode portion 110 to the second electrode portion 120. According to certain embodiments, electrically connecting the electrode portions of a double-sided electrode portion can reduce the electrical resistance between the two surfaces of the double-sided electrode portion, thereby improving the performance of an electrochemical device comprising the double-sided electrode portion during cycling of the electrochemical device. The portion of the double-sided electrode portion through which the conductive solid material region extends can, in certain embodiments, be the portion of the double-sided electrode used to form an electrical connection with a conductive terminal of an electrochemical device, while another portion of the double-sided electrode portion can be used to participate in an electrochemical reaction (e.g., during cycling of the electrochemical device).

[0042] In some embodiments, the non-conductive layer, the first electrode portion, and the second electrode portion form a first double-sided electrode portion, and the article further comprises a second double-sided electrode portion adjacent to the first double-sided electrode portion. For example, referring to FIG. 5A , according to certain embodiments, article 100 comprises first double-sided electrode portion 105 comprising first electrode portion 110, non-conductive layer 130, and second electrode portion 120, and second double-sided electrode portion 205 comprising first electrode portion 210, non-conductive layer 230, and second electrode portion 220. In some embodiments, the first double-sided electrode portion and the second double-sided electrode portion are substantially parallel. However, in some cases, the first double-sided electrode portion and the second double-sided electrode portion adjacent to the first double-sided electrode portion are concentric (e.g., when the article is part of an electrochemical cell having a wound configuration). An article may include such a combination of first and second double-sided electrode portions, for example, when it is part of an electrochemical cell comprising multiple double-sided electrode portions (e.g., in a stacked configuration).

[0043] In some cases, the electrode portions of the first double-sided electrode portion and the second double-sided electrode portion each have the same polarity. For example, in certain cases, the first double-sided electrode portion includes a first anode portion and a second anode portion (e.g., disposed on either side of a non-conductive layer), and the second double-sided electrode portion also includes a first anode portion and a second anode portion (e.g., disposed on either side of a different non-conductive layer). In some embodiments, the electrode portion of the first double-sided electrode portion may be directly adjacent to the electrode portion of the second double-sided electrode portion. In other words, in some cases, there is no intervening layer between at least a portion of the electrode portion of the first double-sided electrode portion and at least a portion of the electrode portion of the second double-sided electrode portion. Referring again to FIG. 5A, in some embodiments, the second electrode portion 120 of the first double-sided electrode portion 105 is directly adjacent to the first electrode portion 210 of the second double-sided electrode portion 205.

[0044] In some embodiments, the first double-sided electrode portion is electrically connected to the second double-sided electrode portion by a conductive solid material region. For example, referring to FIG. 5A , according to certain embodiments, the first double-sided electrode portion 105 is electrically connected to the second double-sided electrode portion 205 by the conductive solid material region 140. In other words, in some cases, current can flow from a component of the first double-sided electrode portion through at least a portion of the conductive solid material region to the second double-sided electrode portion. According to certain embodiments, as an example, current generated at the first electrode portion 110 of the first double-sided electrode portion 105 (e.g., during discharge of an electrochemical device comprising the article 100) flows from the first electrode portion 110 to the conductive solid material region 140 and then from the conductive solid material region 140 to the second electrode portion 220 of the second double-sided electrode portion 205. In this manner, current can be transported from different double-sided electrode portions (e.g., double-sided anode portions) within the article, which can be useful when the article is used, at least in part, to connect electrodes of an electrochemical device to conductive terminals.

[0045] In some embodiments, the conductive solid material regions extend through the first and second double-sided electrode portions in a direction perpendicular to the first and second sides of each non-conductive layer. Perfect perpendicularity is not required for an object to extend in a direction perpendicular to another object (e.g., a side or surface); in some cases, the angle between an object extending in a direction perpendicular to another object (e.g., a side or surface) and the other object (e.g., a side or surface) can deviate from 90 degrees by up to 1 degree, up to 2 degrees, up to 5 degrees, or up to 10 degrees. Referring again to FIG. 5A , the conductive solid material regions 140 extend through the first and second double-sided electrode portions 105 and 205 in a direction perpendicular to the first and second sides 131 and 132 of the non-conductive layer 130 and the first and second sides 231 and 232 of the non-conductive layer 230. In some cases, the conductive solid material regions extending through the first and second double-sided electrode portions in the methods described herein may be formed by penetrating an article comprising the first and second double-sided electrode portions in accordance with the methods described herein (e.g., by piercing the first and second double-sided electrode portions with a solid object, such as a pin).

[0046] In some embodiments, the cavity extends through the first and second double-sided electrode portions in a direction perpendicular to the first and second surfaces of each non-conductive layer. In some cases, the cavity extending through the first and second double-sided electrode portions in the above manner is formed according to the methods described herein. For example, in some cases, an article including the first and second double-sided electrode portions is pierced (e.g., with a solid object such as a pin), and a cavity is formed after the article is pierced (e.g., after a step of removing the solid object). FIG. 5B shows an exemplary cavity extending through the first and second double-sided electrode portions 105 and 205 in a direction perpendicular to the first and second surfaces 131 and 132 of the non-conductive layer 130 and the first and second surfaces 231 and 232 of the non-conductive layer 230. As noted above, in some cases, at least a portion of the conductive solid material is disposed along the walls of the cavity. For example, referring again to FIG. 5B , according to certain embodiments, at least a portion of wall 151 of cavity 150 comprises conductive solid material region 140. In some such cases, the portion of the conductive solid material region disposed along the cavity wall extends from a first double-sided electrode portion to a second double-sided electrode portion. In some such cases, that conductive solid material region along the cavity wall electrically connects a component of the first double-sided electrode portion (e.g., an electrode portion) with a component of the second double-sided electrode portion (e.g., another electrode portion). While conductive solid material region 140 in FIG. 5B is shown as a continuous region extending from first electrode portion 110 to second electrode portion 220, in some cases, multiple distinct conductive solid material regions may be disposed along wall 151 of cavity 150. According to certain embodiments, for example, a first conductive solid material region disposed along wall 151 of cavity 150 may extend from first electrode portion 110 to second electrode portion 120 of first double-sided electrode portion 105, while a second conductive solid material region disposed along wall 151 of cavity 150 may extend from first electrode portion 210 to second electrode portion 220 of second double-sided electrode portion 205, with the first conductive solid material region and second conductive solid material region being separate.

[0047] In some embodiments, the methods and articles described herein may be useful for transporting charge (e.g., passing electrical current) to and from certain electrode portions of the articles described herein, where efficient transport of charge would otherwise be difficult. Some such cases include when the article is electrically connected to a conductive terminal. For example, referring to FIG. 5C , according to certain embodiments, article 100 is electrically connected to conductive terminal 170. In some cases, the conductive terminal is useful for transporting charge between an electrode (e.g., an anode comprising lithium or a lithium alloy) of an electrochemical device (e.g., a battery) and the external circuitry of the electrochemical device. In some cases, such as certain cases where a double-sided electrode is used in an electrochemical device, certain electrode portions (e.g., internal electrode portions) of the double-sided electrode may be separated from the conductive solid in contact with the conductive terminal by the conductive terminal and / or a non-conductive layer (e.g., a release layer) of the double-sided electrode, thereby making efficient transport of charge from those certain electrode portions to the conductive terminal difficult. 5C , according to certain embodiments, for example, while first electrode portion 110 and second electrode portion 220 are in direct contact with conductive terminal 170, thereby allowing efficient charge transport to and from conductive terminal 170 (e.g., during cycling of electrochemical device 100 comprising the article), second electrode portion 120 and first electrode portion 210 are not in direct contact with conductive terminal 170 and are separated from conductive terminal 170 by non-conductive layer 130 and non-conductive layer 230, respectively. Without certain features described herein (e.g., conductive solid material regions formed during the piercing step), efficient charge transport between the conductive terminal (e.g., conductive terminal 170) and internal electrode portions such as second electrode portion 120 and first electrode portion 210 may detrimentally affect the performance of an electrochemical device (e.g., battery) comprising the article (e.g., due to high electrical resistance).

[0048] However, when features of the articles and methods described herein are employed, inefficient charge transport between the internal electrode portion and the conductive terminal is avoided. For example, the presence of a conductive solid material region extending through the first and second double-sided electrode portions in the manner described above can establish an efficient electrical connection between the internal electrode portion and the conductive terminal. Referring again to FIG. 5C , according to certain embodiments, the conductive solid material region 140 extends from the conductive terminal 170, through the first electrode portion 110, through the non-conductive layer 130, through the second electrode portion 120, through the first electrode portion 210, through the non-conductive layer 230, and to the second electrode portion 220. In some such embodiments, current can flow from the second electrode portion 120 to the conductive solid material region 140, and the current can flow from the conductive solid material region 140 to the conductive terminal 170, thereby electrically connecting the second electrode portion 120 to the conductive terminal 170 even in the presence of the non-conductive layer 130. In some cases, but not necessarily all, articles described herein comprising conductive solid material regions may enable efficient electrical connection from a terminal to an electrochemical device, even when the electrochemical device has a configuration including a stack of double-sided electrodes with an embedded non-conductive layer (e.g., a release layer).

[0049] While the above embodiments refer to an article comprising a first double-sided electrode portion and a second double-sided electrode portion, in some cases, the article can include more than two double-sided electrodes (e.g., substantially parallel and adjacent, or concentric and adjacent to one another). Figures 6A-6B show an exemplary article 100 comprising a first double-sided electrode portion 105, a second double-sided electrode portion 205, and a third double-sided electrode portion 305 according to certain embodiments. In some embodiments, the article comprises at least one double-sided electrode portion, at least two double-sided electrode portions, at least three double-sided electrode portions, at least four double-sided electrode portions, at least five double-sided electrode portions, at least six double-sided electrode portions, at least 10 double-sided electrode portions, and / or up to 15 double-sided electrode portions, up to 20 double-sided electrode portions, up to 50 double-sided electrode portions, up to 100 double-sided electrode portions, or more double-sided electrode portions. Other combinations of these ranges are also possible. For example, in some embodiments, the article comprises between 1 and 100 double-sided electrode portions.

[0050] The extent to which the conductive solid material regions and / or cavities described herein extend through some of the double-sided electrode portions of the articles described herein can depend on many factors, including the desired complexity of the manufacturing process. In some embodiments, the conductive solid material regions extend through each double-sided electrode portion of the article. According to certain embodiments, for example, with reference to FIG. 6A , exemplary article 100 comprises three double-sided electrode portions (first double-sided electrode portion 105, second double-sided electrode portion 205, and third double-sided electrode portion 305), and conductive solid material region 140 comprises three double-sided electrode portions. Extending a conductive solid material region through each double-sided electrode portion of the article can be useful in certain cases where a single conductive solid material region is desired to electrically connect each electrode portion of the double-sided electrode portions of the article. Similarly, in some embodiments, the cavities described herein extend through each double-sided electrode portion of the article (e.g., in a pierced article such that an object penetrating the article passes through the entire article).

[0051] However, in some embodiments, the conductive solid material region extends through some, but not all, of the article's double-sided electrode portions. For example, in some cases, an article may include three double-sided electrode portions, with the conductive solid material region extending from the first double-sided electrode portion to the second double-sided electrode portion but not extending to the third double-sided electrode portion. According to certain embodiments, FIG. 6B illustrates one such embodiment in which the conductive solid material region 140 extends from the first double-sided electrode portion 105 to the second double-sided electrode portion 205 but does not reach the third double-sided electrode portion 305. Similarly, in some embodiments, the cavities described herein extend through some, but not all, of the article's double-sided electrode portions. Such cavities may be formed, for example, by penetrating some, but not all, of the article (e.g., with a solid object such as a pin). Extending the conductive solid material region through some, but not all, of the article's double-sided electrode portions may be useful in various situations. For example, in some cases, penetrating the entire article may result in the formation of features on the article's surface that may be detrimental to the article's performance as part of a terminal for an electrochemical device. For example, in some cases, penetrating the entire article (e.g., to form cavities and / or conductive solid material regions extending through each of the double-sided electrode portions) may result in the formation of burrs. Removing such burrs may, in certain cases, complicate and costly the manufacture of the article or electrochemical device. In some cases, such complexity and cost may be undesirable. However, in other certain cases, removal of such burrs or other features that are detrimental to the performance of the article may be performed.

[0052] In some embodiments, an article comprises multiple conductive solid material regions and / or cavities. For example, in some embodiments, the conductive solid material region is a first conductive solid material region, and the article comprises a second conductive solid material region. Similarly, in some cases, the cavity described herein is a first cavity, and the article comprises a second cavity. Such multiple conductive solid material regions and / or cavities may be formed as a result of multiple penetration steps (e.g., penetrating the article multiple times with one or more solid objects (e.g., pins) either sequentially or simultaneously). Having multiple conductive solid material regions and / or cavities extending through a portion of the article as described above, in some cases, improves electrical connections between components within the article (e.g., an electrochemical cell comprising the article). FIG. 7A shows an exemplary article 100 comprising a first conductive solid material region 140 and a second conductive solid material region 141, according to certain embodiments. Similarly, FIG. 7B shows an exemplary article 100 comprising a first cavity 150 and a second cavity 152 .

[0053] In some embodiments, an article comprises a first side and a second side opposite the first side. For example, referring to FIG. 1B , exemplary article 100 comprises a first side 101 and a second side 102 opposite the first side 101. In some cases, the first side of the article is substantially parallel to the second side of the article. In some cases, the first and second sides are substantially parallel to the non-conductive layer. For example, referring again to FIG. 1B , first side 101 and second side 102 of article 100 are substantially parallel to first side 131 and second side 132 of non-conductive layer 130. In some embodiments, two objects (e.g., surfaces, layers, sides, etc.) that are substantially parallel have a region that is at most 1 degree, at most 2 degrees, at most 5 degrees, or at most 10 degrees from parallel.

[0054] In some embodiments, an article comprises a first side and a second side opposite the first side, and the conductive solid material region extends from the first side to the second side. With reference to FIG. 2, for example, article 100 comprises conductive solid material region 140 extending from first side 101 of article 100 to second side 102 of article 100, with first side 101 being opposite second side 102. As another example, with reference to FIG. 6A, conductive solid material region 140 extends from first side 101 of exemplary article 100 to second side 102 of article 100. Similarly, in some cases, cavities (e.g., cavity 150) described herein extend from the first side to the second side. The cavity and / or conductive solid material region may extend from the first side of the article to the second side of the article if the entire article is penetrated. For example, in some cases, an article is penetrated with a solid object (e.g., a pin) such that the solid object penetrates a first side of the article, travels throughout the interior of the article, and exits a second side of the article. As noted above, penetrating the article in such a manner to result in the formation of conductive solid material regions and / or cavities extending from the first side of the article to the second side of the article is desirable so that all of the electrode portions and / or double-sided electrode portions of the article are electrically connected in a single penetration step.

[0055] However, in some embodiments, the conductive solid material regions and / or cavities described herein extend from the first surface to a point within the interior of the article, but do not extend completely to the second surface of the article.

[0056] In some embodiments in which an article comprises multiple conductive solid material regions and / or cavities, the conductive solid material regions and / or cavities may extend through different regions of the article. In some such cases, the conductive solid material regions and / or cavities are positioned to provide efficient charge transport from an electrode portion within the article (e.g., an internal electrode portion of a double-sided electrode portion). In some embodiments, at least one conductive solid material region extends from the first side of the article but does not reach the second side, and at least one conductive solid material region extends from the second side of the article but does not reach the first side. Similarly, in some embodiments, at least one cavity extends from the first side of the article but does not reach the second side, and at least one cavity extends from the second side of the article but does not reach the first side. For example, referring again to FIG. 7A , article 100, according to certain embodiments, comprises first conductive solid material region 140 and second conductive solid material region 141. In some cases, according to particular embodiments, conductive solid material region 140 extends from first side 101 of article 100 but does not reach second side 102 of article 100, while second conductive solid material region 141 extends from second side 102 but does not reach first side 101. Similarly, for example, referring again to Figure 7B, article 100, according to particular embodiments, comprises first cavity 150 and second cavity 152. In some cases, according to particular embodiments, first cavity 150 extends from first side 101 of article 100 but does not reach second side 102 of article 100, while second cavity 152 extends from second side 102 but does not reach first side 101. A configuration in which at least one cavity and / or conductive solid material region extends from the first side but not to the second side, and at least one cavity and / or conductive solid material region extends from the second side but not to the first side, can allow for electrical connection of all electrode portions of the article while avoiding disadvantages (e.g., burring as described above) that may arise when the cavities and / or conductive solid material extend completely through the article.Some such configurations can be achieved, for example, by penetrating the article from multiple different sides of the article (eg, penetrating the article from a first side and a second side).

[0057] In some cases, the article comprises cavities and / or conductive solid material regions that alternate with extensions through the article (e.g., from a first side to a second side, or from a second side to a first side). According to certain embodiments, for example, FIG. 8 shows a top view of an exemplary article 100. In FIG. 8, each of the eight circles depicted represents a cavity and / or a conductive solid material region extending through the article 100 in a direction perpendicular to the plane of FIG. 8. The solid circles in FIG. 8 represent cavities and / or conductive solid material regions that extend from the top of the article toward the bottom of the article (not shown) into the page of FIG. 8 (but not to the bottom of the article), while the dashed circles represent cavities and / or conductive solid material regions that extend from the bottom of the article (not shown) toward the top of the article (shown) out of the page of FIG. 8 (but not to the top of the article). In some cases, such an alternating pattern of cavities and / or conductive solid material regions extending through the article may provide efficient transport of electrical current to and from electrode portions within the article (e.g., when the article is part of a terminal of an electrochemical cell). Such a configuration may, in certain cases, be achieved by alternately penetrating the article (e.g., by piercing a solid object such as a pin) as shown in FIG.

[0058] As noted above, in some embodiments, the articles described herein are part of an electrochemical device. The electrochemical device may, in some cases, be or include an electrochemical cell. In certain cases, the electrochemical device comprises multiple electrochemical cells. For example, in certain cases, the electrochemical device is a multi-cell battery, such as a multi-cell lithium or lithium-ion battery. In some cases, the electrode portion and / or double-sided electrode portion are part of an electrode of an electrochemical device. In certain cases, the electrode portion and / or double-sided electrode portion in the articles described herein may be part of an electrode extension of an electrochemical device used to connect to a terminal (e.g., a battery terminal) of the electrochemical device. As described in more detail below, the electrochemical device may include certain other components other than the above-described article components. For example, the electrochemical device may include an electrode having an opposite polarity to the polarity of the electrode portion included in the article, as well as a separator, electrolyte, and / or current collector. In some embodiments, the article is electrically connected to a conductive terminal of an electrochemical device. For example, referring back to FIG. 4A , conductive terminal 170 may be a conductive terminal of an electrochemical device comprising article 100. In some cases, the conductive terminal is a battery terminal. In some embodiments, the conductive terminal electrically connected to the article is an anode terminal. For example, in some cases, the electrode portion (e.g., first electrode portion, second electrode portion) of the article is an anode portion, and the article is electrically connected to the anode terminal. Features of the methods and articles described herein may, in some, but not necessarily all, cases, enable relatively efficient transport of charge (e.g., current) from an electrode of an electrochemical cell to the conductive terminal, for example, by providing a conductive pathway from an electrode portion (e.g., an internal electrode portion) to the conductive terminal, even when the electrode of the electrochemical device comprises a non-conductive layer. Those skilled in the art, guided by this disclosure, will recognize suitable materials and methods for electrically connecting the articles described herein to the conductive terminal of an electrochemical device.For example, in some cases, the conductive terminals are tabs made of a conductive solid (e.g., a metal, a metal alloy, a composite material, a conductive polymer, and / or a combination thereof). Suitable conductive solids may include, for example, metal foils (e.g., aluminum foil), polymer films, metallized polymer films (e.g., aluminized plastic films such as aluminized polyester films), conductive polymer films, polymer films with a conductive coating, conductive polymer films with a conductive metal coating, and polymer films with conductive particles dispersed therein.

[0059] In some embodiments, the conductive terminals include one or more conductive metals, such as aluminum, copper, chromium, stainless steel, and nickel. For example, the conductive terminals may include a copper metal layer. Optionally, another conductive metal layer, such as titanium, may be disposed on the copper layer. Titanium may promote adhesion of the copper layer to another material, such as an electroactive material layer (e.g., the first electrode portion). Other conductive terminals may include, for example, expanded metal, metal mesh, metal grid, expanded metal grid, metal wool, woven carbon fiber, woven carbon mesh, nonwoven carbon mesh, and carbon felt. Additionally, the conductive terminals may be electrochemically inert. However, in other embodiments, the conductive terminals may include an electroactive material. For example, the conductive terminals may include a material used as an electroactive material layer (e.g., as an anode or cathode as described herein).

[0060] In some embodiments, the article further comprises a liquid electrolyte in electrochemical communication with the first electrode portion and / or the second electrode portion. For example, if the article is part of an electrochemical device (e.g., a battery stack), the liquid electrolyte in electrochemical communication with the first electrode portion (e.g., first electrode portion 110) and / or the second electrode portion (e.g., second electrode portion 120) can be present to facilitate electrochemical reactions in the electrochemical cells during charging and / or discharging processes of the electrochemical device. Suitable electrolytes comprising the liquid electrolyte are described in more detail below.

[0061] Some embodiments described herein include cycling an electrochemical device including an article described herein. For example, in some cases, an electrochemical device comprising an article described herein is charged (e.g., by a power source or charger that applies a voltage to an electrochemical cell within the electrochemical device), and during the charging process, current flows from the power source to a particular electrode of the electrochemical device via the conductive terminals and electrode portions (e.g., a portion of a double-sided electrode portion) of the article described herein. In some such cases, current flows relatively efficiently (e.g., with relatively low resistance) from the electrode to the power source / charger (e.g., via conductive solid material regions extending through an electrically non-conductive layer), at least in part due to the presence of electrical connections in the electrode portions of the article. Similarly, in some embodiments, an electrochemical device comprising an article described herein is discharged (e.g., by generating electricity via an electrochemical reaction between the electrodes of the electrochemical device), and current is transferred from the electrode of the electrochemical device to the conductive terminal (e.g., the anode terminal), at least in part due to the presence of the conductive solid material regions and / or cavities (e.g., formed by penetrating the article).

[0062] Some embodiments may include piercing the article so that an electrical connection is established between the first electrode portion and the second electrode portion, and then cycling an electrochemical device comprising the article.

[0063] The electrochemical cell can have any of a variety of suitable configurations. For example, in some cases, the electrochemical device has a stacked configuration. In some such stacked configurations, components of the electrochemical device (e.g., electrodes, current collectors, separators, etc.) can be coated or deposited on each other as layers, or the components can be formed separately and then attached to each other (e.g., via lamination). In some cases, the electrochemical device has a wound configuration in which the components of the electrochemical device are wound around a central axis to form a cylindrical electrochemical device. In some embodiments, the electrochemical device has a folded configuration, such as a "Z-fold" or "W-fold" configuration. In some cases, the electrochemical device has a "jelly roll" prismatic configuration.

[0064] In some embodiments, a portion of the first electrode portion or the second electrode portion is covered by a third electrode portion. For example, in some cases, the article is part of an electrochemical device (e.g., comprising an electrochemical cell), and the electrochemical device comprises a third electrode portion covering a portion of either the first electrode portion (e.g., an anode portion) or the second electrode portion (e.g., an anode portion) such that the electrochemical reaction comprises an electrode active material of the first electrode portion (e.g., an anode portion) or the second electrode portion (e.g., an anode portion) and an electroactive material of the third electrode portion (e.g., a cathode portion). Referring to FIG. 9A , according to certain embodiments, the third electrode portion 190 covers a portion of the first electrode portion 110. In some embodiments, the third electrode portion has a polarity opposite to that of the first electrode portion and the second electrode portion. For example, in some cases, the first electrode portion and the second electrode portion are anode portions (e.g., comprising lithium and / or a lithium alloy), and the third electrode portion covering a portion of the first electrode portion and / or the second electrode portion is a cathode portion. In some cases, the separator portion is between the third electrode portion and the first or second electrode portion. FIG. 9A shows an optional separator portion 195 according to certain embodiments. In some embodiments, the third electrode portion covers some, but not all, of the first or second electrode portion. In some cases, it is undesirable for the conductive solid material region and / or cavity extending through a portion of the article to extend through any of the third electrode portions because establishing an electrical connection between the third electrode portion and the first or second electrode portion could cause a short circuit in an electrochemical device comprising the article. Thus, in some embodiments, the conductive solid material region or cavity extending through the first electrode portion, the non-conductive layer, and the second electrode portion does not extend through any of the third electrode portions. For example, referring again to FIG. 9A , the conductive solid material region 140 extends through the first electrode portion 110, the non-conductive layer 130, and the second electrode portion 120, but the conductive solid material region 140 does not extend to or even cross the third electrode portion 190.

[0065] In some embodiments, the article comprises a third electrode portion disposed between a portion of the first double-sided electrode portion and a portion of the second double-sided electrode portion. For example, in some cases, the article is part of an electrochemical device (e.g., comprising an electrochemical cell), and the electrochemical device comprises a third electrode portion disposed between the first double-sided electrode portion and the second double-sided electrode portion such that an electrochemical reaction can occur (e.g., during charging or discharging of the electrochemical device) involving an electrode active material of the third electrode portion and an electrode active material of the first double-sided electrode portion and / or the second double-sided electrode portion. Referring to Figure 9B, exemplary article 100 comprises first double-sided electrode portion 105 and second double-sided electrode portion 205, and the article further comprises a third electrode portion 190 disposed between first double-sided electrode portion 105 and second double-sided electrode portion 205.

[0066] In some embodiments, the third electrode portion has a polarity different from the polarity of the electrode portion of the first double-sided electrode portion and the electrode portion of the second double-sided electrode portion. For example, in some cases, the first double-sided electrode portion comprises an anode portion, the second double-sided electrode portion comprises an anode portion (e.g., comprising lithium and / or a lithium alloy), and the third electrode portion disposed between the first and second double-sided electrode portions is a cathode portion. In some cases, the third electrode portion is disposed some, but not all, of the space between the first and second double-sided electrode portions. As noted above, to avoid short circuits, it may be undesirable for the conductive solid material region and / or cavity extending through a portion of the article to extend through any of the third electrode portions. Thus, in some cases, the conductive solid material region extending through the first and second double-sided electrode portions does not extend through the third double-sided electrode portion disposed between the first and second double-sided electrode portions. For example, referring again to Figure 9B, according to certain embodiments, conductive solid material region 140 extends through first double-sided electrode portion 105 and second double-sided electrode portion 205, but conductive solid material region 140 does not extend through or intersect third electrode portion 190. In some cases, the article further comprises a separator portion between the third electrode portion and the first double-sided electrode portion, and the article further comprises a separator portion between the third electrode portion and the second double-sided electrode portion. Figure 9B shows exemplary optional separator portions 195 and 196, according to certain embodiments.

[0067] 11A-11F show schematic diagrams of exemplary electrochemical devices and components, according to certain embodiments. FIG. 11A shows top (top) and cross-sectional (bottom) views of exemplary electrochemical device components, including an anode 430, a separator 450, and a cathode 440, according to certain embodiments. While the following description refers to an anode 430 (e.g., a double-sided deposited lithium metal anode) and a cathode 440 (e.g., a double-sided cathode comprising cathode active material deposited on a current collector 193 (e.g., a metal layer)), it should be understood that other configurations, such as embodiments comprising a cathode 430 and an anode 440, are possible. According to certain embodiments, the anode 430 comprises a double-sided anode portion 105, which is an extension of the anode 430 (e.g., as in the articles described herein). Additionally, in some embodiments, the cathode 440 comprises a current collector extension 275.

[0068] FIG. 11B shows a top view of an exemplary electrochemical device 400 according to certain embodiments, comprising an anode 430 (including a double-sided anode portion 105), a separator 450 (hidden behind the cathode 430), and a cathode 440 (hidden behind the anode 430 and separator 450, but including a cathode current collecting extension 275 (which is not hidden)). As noted above, in certain embodiments, electrical connection between electrode portions of the double-sided anode portion 105 of the electrochemical device 400 can be established by penetrating the double-sided anode portion 105 (e.g., with a solid object such as a pin), thereby forming a region of conductive solid material. In some embodiments, the conductive terminal 170 in FIG. 11B is electrically connected to the extension of the anode 430 comprising the double-sided electrode portion 105 by contacting the conductive terminal 170 with the double-sided anode portion 105 and penetrating both the double-sided anode portion 105 and the conductive terminal 170. In some embodiments, the conductive terminal 270 is electrically connected to the current collector extension 275 of the current collector 193 such that a complete electrical circuit is established that includes the electrochemical device 400 .

[0069] FIG. 11C shows a schematic cross-sectional view of an electrochemical device 400 from view A shown in FIG. 11B according to certain embodiments. As shown in FIG. 11C, according to certain embodiments, the electrochemical device 400 has a stacked configuration and includes the following components arranged in order: an anode 430, a separator 450, and a cathode 440 comprising a current collector 193. In some cases, as shown in FIG. 11C, this arrangement of components is repeated in the electrochemical device 400. In FIG. 11C, current collector extension 275a extends beyond other components of the electrochemical device 400 and, in some cases, may be used to form an electrical connection with a terminal (e.g., the cathode terminal 270 shown in FIG. 11B). Similarly, according to certain embodiments, other current collector extensions, such as current collector extension 275b and current collector extension 275c, may also extend beyond other components of the electrochemical device 400 and may be used to form an electrical connection with a terminal.

[0070] FIG. 11D shows a schematic cross-sectional view of an electrochemical device 400 from view B shown in FIG. 11B, according to certain embodiments. As shown in FIG. 11D, the double-sided anode portion 105a extends beyond other components of the electrochemical device 400, according to certain embodiments. It should be understood that each of the double-sided anode portions 105 (e.g., double-sided anode portions 105a, 105b, 105c, and 105d in FIG. 11D) appears similar to the double-sided electrode portions 105 shown in FIGS. 5A-7B and is shown as a single layer in FIGS. 11A-11E for clarity of illustration. For example, in some embodiments, the double-sided anode 105a in FIG. 11D comprises a first electrode portion, a second electrode portion, and a non-conductive layer between the first and second electrode portions. In some embodiments, electrical connection between double-sided anode portions 105a, 105b, 105c, and 105d can be established by penetrating double-sided anode portions 105a, 105b, 105c, and 105d and, in some cases, conductive terminal 170 (if present). For example, as shown in Figure 11E, in some cases, double-sided anode portions 105a, 105b, 105c, and 105d form part of an article described herein, and conductive solid material region 140 is penetrated extending from double-sided anode portion 105a to double-sided anode portion 105d. This can be useful for establishing good electrical connection to the anodes (including anode 430) of electrochemical device 400. 11F, penetrating double-sided anode portions 105a, 105b, 105c, and 105d forms a cavity 150 that extends from double-sided anode portion 105a to double-sided anode portion 105d. In certain cases, at least a portion of the walls of cavity 150 comprise conductive solid material regions 140.

[0071] As noted above, some methods described herein may include piercing an article described herein with a solid object (e.g., a pin) configured to establish a relatively efficient electrical connection between a first electrode portion and a second electrode portion. In some cases, the object is configured so that the cavity and / or conductive solid material region formed during the methods described herein have specific shapes or geometries. For example, in some cases, the methods described herein include piercing the article with a specific cross-sectional shape. In some embodiments, the article comprises a cavity or conductive solid material region having a cross-section perpendicular to its length. The length of the cavity or conductive solid material region refers to the dimension of the cavity or conductive region that spans the electrode portions. For example, in FIG. 2, the length of the conductive solid material region 140 spans the first electrode portion 110 and the second electrode portion 120. In some embodiments, the cross-section of the cavity and / or conductive solid material region is substantially parallel to the first and second surfaces of the non-conductive layer. It has been unexpectedly discovered that in some, but not all, cases, penetrating an article with a solid object (e.g., a pin) having a particular shape establishes a more effective electrical connection within the article than other shapes, when taking into account the cross-sectional area or maximum cross-sectional dimension of the resulting cavity and / or conductive solid material region. As described above, the article may include a cavity extending from a first electrode portion through a non-conductive layer to a second electrode portion, with at least a portion of the conductive solid material disposed along the walls of the cavity. It has been unexpectedly observed that penetrating an article with a solid object (e.g., a pin) having a relatively high cross-sectional perimeter-to-cross-sectional area (perimeter-to-area) ratio results in the deposition of a relatively large amount of conductive material on the walls of the cavity, thereby enhancing the effectiveness of the electrical connection between the electrode portions.

[0072] Thus, in some, but not necessarily all, cases, it may be beneficial to form cavities and / or regions of conductive solid material in articles having cross sections with relatively high ratios of cross-sectional perimeter to cross-sectional area. Such perimeter-to-area ratios may be adjusted by selecting the particular cross-sectional shape of the object used to penetrate the article. For example, a 0.95 mm 2 The perimeter of the circle is 3.45 mm, and the ratio of perimeter to area is 3.63 mm. -1 However, the area of ​​a six-sided star (e.g., corresponding to the shape of TORX®) is 0.62 mm 2 In this case, the perimeter is 3.61 and the ratio of perimeter to area is 5.8 mm. -1 Having a relatively high ratio of cross-sectional perimeter to cross-sectional area can provide a relatively efficient electrical connection (e.g., low electrical resistance) between portions connected by the cavity and / or conductive solid material region, while maintaining a relatively small overall penetration area, which can reduce structural perturbations to the article during the penetration step and / or reduce the force required to penetrate the article. In some embodiments, the ratio of cross-sectional perimeter to cross-sectional area (e.g., of the cavity, conductive solid material region, and / or object used to penetrate the article) is less than 1 mm -1 More than 2mm -1 or more, 3mm -1 More than 5mm -1 More than 10mm -1 In some embodiments, the ratio of cross-sectional perimeter to cross-sectional area is 30 mm or greater. -1 Below, 25mm -1 Below, 20mm -1 Below, 15mm -1 Combinations of these ranges are possible. For example, in some embodiments, the ratio of the cross-sectional perimeter to the cross-sectional area is 1 mm -1 More than 30mm -1 The following is the result.

[0073] In some embodiments, a solid object (e.g., a pin) used to penetrate the article has a cross-sectional shape selected from a square, a rectangle, a circle, an ellipsoid, a triangle, a four-sided star, a five-sided star, and a six-sided star. In some embodiments, the article comprises a cavity and / or a region of conductive solid material having a cross-sectional shape selected from a square, a rectangle, a circle, an ellipsoid, a triangle, a four-sided star, a five-sided star, and a six-sided star. When a solid object (e.g., a pin) having a cross-sectional shape corresponding to the above shapes is penetrated through the article, in some cases, a cavity and / or a region of conductive solid material having a cross-sectional shape selected from the above list can be formed.

[0074] In some embodiments, the solid object (e.g., pin) used to penetrate the article has a relatively small cross-sectional area. In some embodiments, the cavity and / or conductive solid material region has a relatively small cross-sectional area. As noted above, having a relatively small cross-sectional area can be beneficial in some, but not necessarily all, cases by reducing structural perturbation of the article and / or reducing the force required to penetrate the article. In some embodiments, the solid object (e.g., pin) used to penetrate the article has a cross-sectional area of ​​25 mm or less. 2 Below, 5mm 2 Below, 1.0mm 2 Less than or equal to 0.5 mm 2 In some embodiments, the solid object (e.g., pin) used to penetrate the article has a cross-sectional area of ​​0.005 mm 2 More than 0.01mm 2 More than 0.1mm 2 Over 0.5mm 2 In some embodiments, the cavity and / or the conductive solid material region has a cross-sectional area of ​​25 mm or greater. 2 Below, 5mm 2 Below, 1.0mm 2 Below, 0.5mm 2 In some embodiments, the cavity and / or the conductive solid material region has a cross-sectional area of ​​0.005 mm 2 More than 0.01mm 2 More than 0.1mm2 Over 0.5mm 2 Combinations of these ranges are possible. For example, in some embodiments, the solid object (e.g., pin) used to penetrate the article has a cross-sectional area of ​​0.005 mm or greater. 2 More than 25mm 2 In some embodiments, the cavity and / or the conductive solid material region has a cross-sectional area of ​​0.005 mm 2 More than 25mm 2 It has the following cross-sectional area:

[0075] In some embodiments, the solid object (e.g., pin) used to penetrate the article has a relatively small maximum cross-sectional dimension. In some embodiments, the cavity and / or conductive solid material region may have a relatively small maximum cross-sectional dimension. In some embodiments, the solid object (e.g., pin) used to penetrate the article has a maximum cross-sectional dimension of 5 mm or less, 2 mm or less, or 1 mm or less. In some embodiments, the solid object used to penetrate the article has a maximum cross-sectional dimension of 0.1 mm or more, 0.5 mm or more, 0.8 mm or more, or more. In some embodiments, the cavity and / or conductive solid material region has a maximum cross-sectional dimension of 5 mm or less, 2 mm or less, 1 mm or less, or less. In some embodiments, the cavity and / or conductive solid material region has a maximum cross-sectional dimension of 0.1 mm or more, 0.5 mm or more, 0.8 mm or more, or more. Combinations of these ranges are possible. For example, in some embodiments, the solid object (e.g., pin) used to penetrate the article has a maximum cross-sectional dimension of 0.1 mm or more and 5 mm or less. In some embodiments, the cavity and / or the region of conductive solid material has a maximum cross-sectional dimension of at least 0.1 mm and at most 5 mm.

[0076] According to certain embodiments, various anode active materials are suitable for use with the articles and electrode portions of the electrochemical cells described herein. In some embodiments, the anode active material comprises lithium (e.g., lithium metal), such as lithium foil, lithium deposited on a conductive or non-conductive substrate (e.g., a release layer), and lithium alloys (e.g., lithium-aluminum alloys and lithium-tin alloys). The lithium can be included as a film or as multiple films, optionally separated. Lithium alloys suitable for use in the embodiments described herein can include alloys of lithium with aluminum, magnesium, silicon, indium, and / or tin. In some embodiments, the anode active material comprises lithium metal (e.g., lithium metal and / or lithium metal alloys) during at least some or all of the charge and / or discharge process of the electrochemical cell.

[0077] In some embodiments, the anode active material comprises at least 50 wt% lithium. In some cases, the anode active material comprises at least 75 wt%, at least 90 wt%, at least 95 wt%, or at least 99 wt% lithium.

[0078] In some embodiments, the anode is an electrode into which lithium ions are released during discharge and incorporated (e.g., inserted) during charge. In some embodiments, the anode active material is a lithium intercalation compound (e.g., a compound capable of reversibly inserting lithium ions into lattice and / or interstitial sites). In some embodiments, the anode active material comprises carbon. In certain cases, the anode active material is or comprises a graphitic material (e.g., graphite). Graphitic materials generally refer to materials comprising multiple layers of graphene (i.e., layers comprising carbon atoms covalently bonded in a hexagonal lattice). Adjacent graphene layers are typically attracted to each other via van der Waals forces, although in some cases, covalent bonds may exist between one or more sheets. In some cases, the carbon-containing anode active material is or comprises coke (e.g., petroleum coke). In certain embodiments, the anode active material comprises silicon, lithium, and / or any alloy or combination thereof. In certain embodiments, the anode active material is lithium titanate (LiTiO 12 (also referred to as "LTO"), tin-cobalt oxide, or any combination thereof.

[0079] According to some embodiments, the article and / or electrode (e.g., lithium anode) of the electrochemical cell may include one or more coatings or layers formed from polymers, ceramics, and / or glasses. The coatings act as protective layers and perform a variety of functions. These functions may include preventing the formation of dendrites during recharge, which could cause short circuits, preventing reactions between the electrode active material and the electrolyte, and improving cycle life. Examples of such protective layers include those described in U.S. Pat. No. 8,338,034 to Affinito et al. and U.S. Patent Publication No. 2015 / 0236322 to Laramie et al., each of which is incorporated by reference in its entirety for all purposes. Additional details regarding specific protective layers that may be used are discussed in more detail below.

[0080] According to certain embodiments, various cathode active materials are suitable for use with the cathodes of the electrochemical cells described herein. In some embodiments, the cathode active material comprises a lithium intercalation compound (e.g., a compound capable of reversibly inserting lithium ions into lattice and / or interstitial sites). In some cases, the cathode active material comprises a layered oxide. Layered oxide generally refers to an oxide having a lamellar structure (e.g., multiple sheets or layers stacked on top of each other). Non-limiting examples of suitable layered oxides include lithium cobalt oxide (LiCoO), lithium nickel oxide (LiNiO), and lithium manganese oxide (LiMnO). In some embodiments, the layered oxide is lithium nickel manganese cobalt oxide (LiNi x Mn y Co z O2, also referred to as "NMC" or "NCM"). In some such embodiments, the sum of x, y, and z is 1. For example, a non-limiting example of a suitable NMC compound is LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 In some embodiments, the layered oxide has the formula (LiMnO) x(LiMO2) (1-x) where M is one or more of Ni, Mn, and Co. For example, the layered oxide may have the structure (Li2MnO3) 0.25 (LiNi 0.3 Co 0.15 Mn 0.55 O2) 0.75 In some embodiments, the layered oxide may be lithium nickel cobalt aluminum oxide (LiNi x Co y Al z O2, also referred to as "NCA"). In some such embodiments, the sum of x, y, and z is 1. For example, a non-limiting example of a suitable NCA compound is LiNi 0.8 Co 0.15 Al 0.05 In certain embodiments, the cathode active material is a transition metal polyanion oxide (e.g., a compound comprising a transition metal, oxygen, and / or an anion having an absolute charge greater than one). A non-limiting example of a suitable transition metal polyanion oxide is lithium iron phosphate (LiFePO4, also referred to as "LFP"). Another non-limiting example of a suitable transition metal polyanion oxide is lithium manganese iron phosphate (LiMn x Fe 1-x PO4, also referred to as "LMFP"). Non-limiting examples of suitable LMFP compounds include LiMn 0.8 Fe 0.2 PO4. In some embodiments, the cathode active material is a spinel (e.g., a compound having the structure AB2O4, where A can be Li, Mg, Fe, Mn, Zn, Cu, Ni, Ti, or Si, and B can be Al, Fe, Cr, Mn, or V). Non-limiting examples of suitable spinels include those having the formula LiM x Mn 2-x Lithium manganese oxide having 0, where M is one or more of Co, Mg, Cr, Ni, Fe, Ti, and Zn. In some embodiments, x is equal to 0, and the spinel can be lithium manganese oxide (LiMnO, also referred to as "LMO"). Another non-limiting example is lithium manganese nickel oxide (LiNi x Mn2-x O4, also referred to as "LMNO"). A non-limiting example of a suitable LMNO compound is LiNi 0.5 Mn 1.5 In some cases, the electroactive material of the second electrode is Li 1.14 Mn 0.42 Ni 0.25 Co 0.29 O2 ("HC-MNC"), lithium carbonate (Li2CO3), lithium carbides (e.g., Li2C2, Li4C, Li6C2, Li8C3, Li6C3, Li4C3, Li4C5), vanadium oxides (e.g., V2O5, V2O3, V6O 13 ), and / or vanadium phosphate (e.g., lithium vanadium phosphate such as Li3V2(PO4)3), or any combination thereof.

[0081] In some embodiments, the cathode active material comprises a conversion compound. For example, the cathode can be a lithium conversion cathode. It is recognized that cathodes comprising a conversion compound can have relatively high specific capacities. Without wishing to be bound by theory, relatively high specific capacities can be achieved by utilizing all possible oxidation states of the compound through conversion reactions in which multiple electron transfers occur per transition metal (e.g., 0.1 to 1 electron transfer in intercalation compounds). Suitable conversion compounds include, but are not limited to, transition metal oxides (e.g., Co3O4), transition metal hydrides, transition metal sulfides, transition metal nitrides, and transition metal fluorides (e.g., CuF2, FeF2, FeF3). Transition metals generally refer to elements whose atoms have a partially filled d subshell (e.g., Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Rf, Db, Sg, Bh, Hs).

[0082] In some cases, the cathode active material can be doped with one or more dopants to alter the electrical properties (e.g., conductivity) of the cathode active material. Non-limiting examples of suitable dopants include aluminum, niobium, silver, and zirconium.

[0083] In some embodiments, the cathode active material may be modified with a surface coating comprising an oxide. Non-limiting examples of surface oxide coating materials include MgO, Al2O3, SiO2, TiO2, ZnO2, SnO2, and ZrO2. In some embodiments, such a coating may prevent direct contact between the cathode active material and the electrolyte, thereby inhibiting side reactions.

[0084] In certain embodiments, the cathode active material comprises sulfur. In some embodiments, the cathode active material comprises an electroactive sulfur-containing material. As used herein, "electroactive sulfur-containing material" refers to an electrode active material comprising elemental sulfur in any form, where electrochemical activity includes oxidation or reduction of sulfur atoms or moieties. As an example, the electroactive sulfur-containing material can comprise elemental sulfur (e.g., S). In some embodiments, the electroactive sulfur-containing material comprises a mixture of elemental sulfur and a sulfur-containing polymer. Thus, suitable electroactive sulfur-containing materials can include, but are not limited to, elemental sulfur, which can be organic or inorganic, sulfides or polysulfides (e.g., of alkali metals), and organic materials comprising sulfur atoms and carbon atoms, which may or may not be polymeric. Suitable organic materials include organic materials further comprising heteroatoms, conductive polymer segments, composite materials, and conductive polymers. In some embodiments, the electroactive sulfur-containing material in an electrode (e.g., cathode) comprises at least 40 wt% sulfur. In some cases, the electroactive sulfur-containing material comprises at least 50 wt%, at least 75 wt%, or at least 90 wt% sulfur.

[0085] Examples of sulfur-containing polymers include those described in U.S. Pat. Nos. 5,601,947 and 5,690,702 to Skoteim et al., U.S. Pat. Nos. 5,529,860 and 6,117,590 to Skoteim et al., U.S. Pat. No. 6,201,100 to Gorkovenko et al., issued March 13, 2001, and PCT Publication No. WO 99 / 33130, each of which is incorporated herein by reference in its entirety for all purposes. Other suitable electroactive sulfur-containing materials containing polysulfide bonds are described in U.S. Pat. No. 5,441,831 to Skoteim et al., U.S. Pat. No. 4,664,991 to Perichaud et al., and U.S. Pat. Nos. 5,723,230, 5,783,330, 5,792,575, and 5,882,819 to Naoi et al., each of which is incorporated by reference in its entirety for all purposes. Further examples of electroactive sulfur-containing materials include those comprising disulfide groups, as described, for example, in U.S. Pat. No. 4,739,018 to Armand et al., U.S. Pat. Nos. 4,833,048 and 4,917,974 to De Jonghe et al., U.S. Pat. Nos. 5,162,175 and 5,516,598 to Visco et al., and U.S. Pat. No. 5,324,599 to Oyama et al., each of which is incorporated by reference in its entirety for all purposes.

[0086] The one or more electrodes may further include additional additives such as conductive additives, binders, as described in U.S. Pat. No. 9,034,421 to Mikhaylik et al. and U.S. Patent Application Publication No. 2013 / 0316072, each of which is incorporated by reference in its entirety for all purposes.

[0087] In some embodiments, an electrode or electrochemical cell includes one or more release layers. For example, in some cases, the non-conductive layer described above (e.g., between the first electrode portion and the second electrode portion) can be or include a release layer. The release layers described herein can be configured to have one or more of the following characteristics: relatively good adhesion to a first layer (e.g., an electrode active material, a current collector, or a substrate or other layer), but relatively moderate or poor adhesion to a second layer (e.g., a substrate, or in other embodiments, a current collector or other layer), high mechanical stability that facilitates delamination without mechanical collapse, high thermal stability, and compatibility with processing conditions (e.g., compatibility with the deposition of layers on the release layer and the techniques used to form the release layer). When the release layer is incorporated into an electrochemical device (e.g., comprising an electrochemical cell), the release layer can be thin (e.g., less than 10 microns) to reduce overall weight (e.g., the weight of the battery). Release layers also generally must be smooth and uniform in thickness to facilitate the formation of a uniform layer thereon. Furthermore, release layers generally must be stable in the electrolyte and generally must not interfere with the structural integrity of the electrodes in order for the electrochemical device to have high electrochemical "capacity" or energy storage capability (i.e., reduced capacity fade). The use of release layers to remove substrates from one or more components of an electrochemical cell is described in detail in U.S. patent application Ser. No. 12 / 862,513, filed Aug. 24, 2010, entitled "Release System for Electrochemical Cells."

[0088] The release layer can be formed, for example, of a ceramic, a polymer, or a combination thereof. In some embodiments, the substrate and / or the release layer comprises a polymeric material. In some cases, at least a portion of the polymeric material of the release layer is crosslinked, and in other cases, the polymeric material is substantially uncrosslinked. Examples of polymeric materials include hydroxyl-containing polymers such as polyvinyl alcohol (PVOH), polyvinyl butyral, polyvinyl formal, vinyl acetate-vinyl alcohol copolymer, ethylene-vinyl alcohol copolymer, and vinyl alcohol-methyl methacrylate copolymer.

[0089] The thickness of the release layer can vary over a range from 0.1 microns to 50 microns. For example, the thickness of the release layer can be 0.1-1 micron thick, 0.1-2 microns thick, 0.1-3 microns thick, 1-5 microns thick, 5-10 microns thick, 5-20 microns thick, or 10-50 microns thick. In certain embodiments, the thickness of the release layer is, for example, 10 microns or less, 7 microns or less, 5 microns or less, 3 microns or less, 2.5 microns or less, 2 microns or less, 1.5 microns or less, 1 micron or less, or 0.5 microns or less. Relatively thick release layers can be suitable for applications where the release layer is not incorporated into an electrochemical cell (e.g., released with a carrier substrate), whereas relatively thin release layers can be desirable when the release layer is incorporated into an electrochemical cell.

[0090] Electrolytes used in electrochemical devices (e.g., electrochemical or battery cells) can function as a medium for the storage and transport of ions; in the special cases of solid and gel electrolytes, these materials can also function as a separator between the anode and cathode. Any liquid, solid, or gel material capable of storing and transporting ions can be used as long as the material facilitates the transport of ions (e.g., lithium ions) between the anode and cathode. The electrolyte is non-conductive to prevent short circuits between the anode and cathode. In some embodiments, the electrolyte can include a non-solid electrolyte.

[0091] In some embodiments, the electrolyte comprises a fluid that can be added at any point in the manufacturing process. In some cases, an electrochemical cell can be manufactured by providing a cathode and an anode, applying an anisotropic force component normal to the active surface of the anode, and then adding a fluid electrolyte such that the electrolyte is in electrochemical communication with the cathode. In other cases, a fluid electrolyte can be added to the electrochemical cell before or simultaneously with the application of the anisotropic force component, after which the electrolyte is in electrochemical communication with the cathode and anode.

[0092] The electrolyte may include one or more ionic electrolyte salts to provide ionic conductivity and one or more liquid electrolyte solvents, gel polymer materials, or polymer materials. Suitable non-aqueous electrolytes may include organic electrolytes comprising one or more materials selected from the group consisting of liquid electrolytes, gel polymer electrolytes, and solid polymer electrolytes. Examples of non-aqueous electrolytes for lithium batteries are described in Dorniney, New Materials, Developments, and Prospects for Lithium Batteries, Chapter 4, pp. 137-165, Elsevier, Amsterdam (1994). Heterogeneous electrolyte compositions that can be used in the batteries described herein are described in U.S. Patent Application Serial No. 12 / 312,764, filed May 26, 2009, by Mikhaylik et al., entitled "Segregated Electrolytes," which is incorporated herein by reference in its entirety.

[0093] Examples of useful non-aqueous liquid electrolyte solvents include, but are not limited to, non-aqueous organic solvents such as N-methylacetamide, acetonitrile, acetals, ketals, esters, carbonates, sulfones, sulfites, sulfolane, aliphatic ethers, cyclic ethers, glymes, polyethers, phosphate esters, siloxanes, dioxolanes, N-alkylpyrrolidones, substituted forms of the foregoing, and blends thereof. Fluorinated derivatives of the foregoing are also useful as liquid electrolyte solvents.

[0094] In some cases, an aqueous solvent can be used as an electrolyte, for example, in a lithium battery. The aqueous solvent can include water, which can include other components, such as ionic salts. As noted above, in some embodiments, the electrolyte can include species such as lithium hydroxide to reduce the concentration of hydrogen ions in the electrolyte, or other species that make the electrolyte basic.

[0095] Liquid electrolyte solvents can also be useful as plasticizers for gel polymer electrolytes, i.e., electrolytes comprising one or more polymers that form a semi-solid network. Examples of useful gel polymer electrolytes include, but are not limited to, one or more polymers selected from the group consisting of polyethylene oxide, polypropylene oxide, polyacrylonitrile, polysiloxane, polyimide, polyphosphazene, polyether, sulfonated polyimide, perfluorinated membranes (NAFION resin), polydivinyl polyethylene glycol, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polysulfone, polyethersulfone, derivatives of the foregoing, copolymers of the foregoing, crosslinked and network structures of the foregoing, and blends of the foregoing, and, optionally, one or more plasticizers. In some embodiments, the gel polymer electrolyte comprises 10-20%, 20-40%, 60-70%, 70-80%, 80-90%, or 90-95% by volume of a heterogeneous electrolyte.

[0096] In some embodiments, one or more solid polymers can be used to form the electrolyte. Examples of useful solid polymer electrolytes include polyethers, polyethylene oxides, polypropylene oxides, polyimides, polyphosphazenes, polyacrylonitriles, polysiloxanes, derivatives of the foregoing, copolymers of the foregoing, crosslinked and network structures of the foregoing, and blends of the foregoing.

[0097] In addition to the electrolyte solvents, gelling agents, and polymers known in the art to form the electrolyte, the electrolyte may further include one or more ionic electrolyte salts, also known in the art, to enhance ionic conductivity.

[0098] Examples of ionic electrolyte salts for use in the electrolyte of the present invention include, but are not limited to, LiSCN, LiBr, LiI, LiClO, LiAsF, LiSOCF, LiSOCH, LiBF, LiB(Ph), LiPF, LiC(SOCF), LiN(SOCF), and lithium bis(fluorosulfonyl)imide (LiFSI). Other useful electrolyte salts include lithium polysulfide (LiS). x ), and lithium salts of organic polysulfides (LiS x R) n where x is an integer from 1 to 20, n is an integer from 1 to 3, and R is an organic group, as well as those disclosed in U.S. Pat. No. 5,538,812 to Lee et al., which is incorporated herein by reference in its entirety for all purposes.

[0099] In some embodiments, the electrolyte comprises one or more room temperature ionic liquids. Room temperature ionic liquids, when present, typically comprise one or more cations and one or more anions. Non-limiting examples of suitable cations include lithium cations and / or one or more quaternary ammonium cations, such as imidazolium, pyrrolidinium, pyridinium, tetraalkylammonium, pyrazolium, piperidinium, pyridazinium, pyrimidinium, pyrazinium, oxazolium, and trizolium cations. Non-limiting examples of suitable anions include trifluoromethylsulfonate (CF3SO3 - ), bis(fluorosulfonyl)imide (N(FSO2)2-), bis(trifluoromethylsulfonyl)imide ((CF3SO2)2N - , bis(perfluoroethylsulfonyl)imide ((CF3CF2SO2)2N) -and tris(trifluoromethylsulfonyl)imide ((CF3SO2)3C - Non-limiting examples of suitable ionic liquids include N-methyl-N-propylpyrrolidinium / bis(fluorosulfonyl)imide and 1,2-dimethyl-3-propylimidazolium / bis(trifluoromethanesulfonyl)imide. In some embodiments, the electrolyte comprises both a room temperature ionic liquid and a lithium salt. In some other embodiments, the electrolyte comprises a room temperature ionic liquid and does not include a lithium salt.

[0100] In some embodiments, the article and / or electrochemical device may further include a separator between the two electrode portions (e.g., the anode portion and the cathode portion). The separator may be a solid, non-conductive or insulating material that separates or insulates the anode and cathode from each other, prevents short circuits, and allows transport of ions between the anode and cathode. In some embodiments, the porous separator may be permeable to the electrolyte.

[0101] The pores of the separator can be partially or substantially filled with electrolyte. The separator can be supplied as a porous, free-standing film that is interleaved with the anode and cathode during cell fabrication. Alternatively, a porous separator layer can be applied directly to one surface of an electrode, as described, for example, in PCT Publication WO 99 / 33125 to Carlson et al. and U.S. Patent No. 5,194,341 to Bagley et al.

[0102] Various separator materials are known in the art. Examples of suitable solid porous separator materials include, but are not limited to, polyolefins such as polyethylene (e.g., SETELA™ from Tonen Chemical Corp.) and polypropylene, glass fiber filter paper, and ceramic materials. For example, in some embodiments, the separator comprises a microporous polyethylene film. Further examples of separators and separator materials suitable for use in the present invention include microporous xerogel layers, such as microporous pseudoboehmite layers, which can be provided as free-standing films or by coating directly onto one of the electrodes, as described in commonly assigned U.S. Patent Nos. 6,153,337 and 6,306,545 to Carlson et al. Solid and gel electrolytes may function as separators in addition to their electrolyte function.

[0103] According to certain embodiments, the electrode portions described herein may include pores. As used herein, "pore" refers to pores measured using ASTM Standard Test D4284-07 and generally refers to conduits, voids, or passageways, at least a portion of which is surrounded by the medium in which the pore is formed such that a continuous loop can be drawn around the pore while remaining within the medium. Generally, voids within a material that are completely surrounded by the material (and therefore inaccessible from outside the material, e.g., closed-cell) are not considered pores within the context of the present invention. When an article comprises an agglomeration of particles, it should be understood that the pores include both interparticle pores (i.e., pores, e.g., interstices, defined between particles when the particles are packed together) and intraparticle pores (i.e., those pores within the envelope of an individual particle). The pores may include any suitable cross-sectional shape, such as, for example, circular, elliptical, polygonal (e.g., rectangular, triangular, etc.), and irregular.

[0104] The porosity of different portions of the electrode portion can be measured by physically separating the different regions, for example, cutting out a specific area of ​​the electrode and then measuring the separated portion using the above-mentioned ASTM standard test D4284-07.

[0105] To protect an electrode (e.g., a lithium anode) from harmful interactions with the electrolyte material during operation of an electrochemical cell, a layer of ceramic or other inorganic protective material (e.g., glass, glassy ceramic) can be used. For example, a protected lithium anode (PLA) structure can be used.

[0106] The protective layers described herein can be formed from various types of materials. In certain embodiments, the material from which the protective layer is formed can be selected to allow ions (e.g., electrochemically active ions such as lithium ions) to pass through but substantially impede the passage of electrons. In this context, "substantially impede" means, in this embodiment, that the material allows a lithium ion flux that is at least 10 times greater than the electron passage.

[0107] In some embodiments, the material used for the protective layer has a sufficiently high electrical conductivity (e.g., at least 10 -6 S / cm, or another conductivity value described herein). The material may also be selected for its ability to form a smooth, dense, and uniform thin film, especially on a polymer layer such as a separator. Lithium oxysulfide may specifically include these properties.

[0108] In certain embodiments, the protective layer can be configured to be substantially electronically non-conductive, which can reduce the extent to which ionic conductors can cause short circuits in the electrochemical cell. In certain embodiments, all or a portion of the protective layer can be at least 10 4 Ohm meters, at least 10 5 Ohm meters, at least 10 10 Ohm meters, at least 10 15ohmmeter, or at least 10 20 The bulk electronic resistivity may be in the range of 10 ohms. 20 ohm meters or less, or 10 15 It may be in the ohm-meter range or less. Combinations of the above ranges are also possible. Other values ​​of bulk electronic resistivity are also possible.

[0109] In some embodiments, the average ionic conductivity (e.g., lithium ion conductivity) of the protective layer material is at least 10 -7 S / cm, at least 10 -6 S / cm, at least 10 -5 S / cm, at least 10 -4 S / cm, at least 10 -3 S / cm, at least 10 -2 S / cm, at least 10 -1 The average ionic conductivity may be 20 S / cm or less, 10 S / cm or less, or 1 S / cm or less. The conductivity may be measured at room temperature (e.g., 25 degrees Celsius).

[0110] In some embodiments, the protective layer can be solid. In some embodiments, the protective layer can comprise or be substantially formed of a non-polymeric material. For example, the protective layer can comprise or be substantially formed of an inorganic material.

[0111] While various materials can be used as the ion-conducting layer, in one set of embodiments, the protective layer is an inorganic ion-conducting layer. For example, the inorganic ion-conductor layer can be a ceramic, a glass, or a glass-like ceramic. Suitable glasses include, but are not limited to, those that can be characterized as including a "modifier" portion and a "network" portion, as known in the art. The modifier can include a metal oxide of the conductive metal ions in the glass. The network portion can include, for example, a metal oxide or a metal chalcogenide such as a sulfide. The protective layer may include a glassy material selected from one or more of lithium nitride, lithium silicate, lithium borate, lithium aluminate, lithium phosphate, lithium phosphorus oxynitride, lithium silicon sulfide, lithium germanosulfide, lithium oxide (e.g., LiO, LiO, LiO, LiRO, where R is a rare earth metal), lithium lanthanum oxide, lithium titanium oxide, lithium borosulfide, lithium aluminosulfide, and lithium phosphosulfide, and combinations thereof. In some embodiments, the protective layer comprises an oxysulfide, such as lithium oxysulfide. In one embodiment, the protective layer comprises lithium phosphorus oxynitride in the form of an electrolyte.

[0112] In certain embodiments in which the inorganic ion conductor material described herein comprises lithium oxysulfide, the lithium oxysulfide (or an ion conductor layer comprising lithium oxysulfide) may have an oxide content of 0.1 to 20 wt%. The oxide content may be measured with respect to the total weight of the lithium oxysulfide material or the total weight of the ion conductor layer comprising the lithium oxysulfide material. For example, the oxide content may be at least 0.1 wt%, at least 1 wt%, at least 2 wt%, at least 5 wt%, at least 10 wt%, at least 15 wt%, or at least 20 wt%. In some embodiments, the oxide content may be 20 wt% or less, 15 wt% or less, 10 wt% or less, 5 wt% or less, 2 wt% or less, or 1 wt% or less of lithium oxysulfide. Combinations of the above ranges are also possible. The elemental composition, including the oxide content, of the layer may be determined by methods such as energy dispersive X-ray spectroscopy.

[0113] In some embodiments in which the inorganic ion conductor material described herein comprises lithium oxysulfide, the lithium oxysulfide material (or an ion conductor layer comprising lithium oxysulfide) has an atomic ratio between sulfur atoms and oxygen atoms (S:O), for example, from 0.5:1 to 1000:1. For example, the atomic ratio between sulfur atoms and oxygen atoms (S:O) in the lithium oxysulfide material (or an ion conductor layer comprising lithium oxysulfide) can be at least 0.5:1, at least 0.667:1, at least 1:1, at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 10:1, at least 20:1, at least 50:1, at least 70:1, at least 90:1, at least 100:1, at least 200:1, at least 500:1, or at least 1000:1. The atomic ratio between sulfur atoms and oxygen atoms (S:O) in the lithium oxysulfide material (or ion conductor layer comprising lithium oxysulfide) can be 1000:1 or less, 500:1 or less, 200:1 or less, 100:1 or less, 90:1 or less, 70:1 or less, 50:1 or less, 20:1 or less, 10:1 or less, 5:1 or less, 3:1 or less, or 2:1 or less. Combinations of the above ranges are also possible (e.g., an S:O atomic ratio of 0.67:1 to 1000:1, or 4:1 to 100:1). Other ranges are also possible. The elemental composition of the layer can be determined by methods such as energy dispersive X-ray spectroscopy.

[0114] In some embodiments, the lithium oxysulfide materials described herein can have a formula of x(yLi2S+zLi2O)+MS2, where M is Si, Ge, or Sn, y+z=1, and x is between 0.5 and 3.3. In certain embodiments, x is at least 0.5, at least 1.0, at least 1.5, at least 2.0, or at least 2.5. In other embodiments, x is 3.0 or less, 2.5 or less, 2.0 or less, 1.5 or less, 1.0 or less, or 0.5 or less. Combinations of the above ranges are also possible. Other values ​​of x are also possible.

[0115] The protective layer, in some embodiments, can include an amorphous lithium ion conductive oxysulfide, a crystalline lithium ion conductive oxysulfide, or a mixture of an amorphous lithium ion conductive oxysulfide and a crystalline lithium ion conductive oxysulfide, such as amorphous lithium oxysulfide, crystalline lithium oxysulfide, or a mixture of an amorphous lithium oxysulfide and a crystalline lithium oxysulfide.

[0116] In some embodiments, protective layer materials, such as lithium oxysulfide, described above, comprise a glass-forming additive in the range of 0 wt% to 30 wt% of the inorganic ionic conductor material. Examples of glass-forming additives include, for example, SiO2, Li2SiO3, Li4SiO4, Li3PO4, LiPO3, Li3PS4, LiPS3, BO3, and BS3. Other glass-forming additives are possible. In certain embodiments, the glass-forming additive can be at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, or at least 30 wt% of the inorganic ionic conductor. In certain embodiments, the glass-forming additive can be up to 30 wt%, up to 25 wt%, up to 20 wt%, up to 15 wt%, or up to 10 wt% of the inorganic ionic conductor material. Combinations of the above ranges are also possible. Other values ​​of the glass-forming additive are also possible.

[0117] In some embodiments, one or more additional salts (e.g., lithium salts such as LiI, LiBr, LiCl, Li2CO3, or Li2SO4) can be added to the inorganic ion conductor material, for example, in the range of 0 to 50 mol%. Other salts are possible. In certain embodiments, the additional salt is at least 0 mol%, at least 10 mol%, at least 20 mol%, at least 30 mol%, at least 40 mol%, or at least 50 mol%. In certain embodiments, the additional salt is no more than 50 mol%, no more than 40 mol%, no more than 30 mol%, no more than 20 mol%, or no more than 10 mol%. Combinations of the above ranges are also possible. Other values ​​are also possible.

[0118] Additional examples of protective layer materials include lithium nitride, lithium silicate, lithium borate, lithium aluminate, lithium phosphate, lithium phosphorus oxynitride, lithium silicon sulfide, lithium germanosulfide, lithium oxide (e.g., Li2O, LiO2, LiO2, LiRO2, where R is a rare earth metal), lithium lanthanum oxide, lithium titanium oxide, lithium borosulfide, lithium aluminosulfide, and lithium phosphosulfide, and combinations thereof.

[0119] In certain embodiments, the protective layer is formed of a single-ion conductive material (eg, a single-ion conductive ceramic material).

[0120] Other suitable materials that can be used to form all or part of the protective layer include the ionically conductive materials described in U.S. Patent Publication No. 2010 / 0327811, filed July 1, 2010, published December 30, 2010, entitled "Aqueous and Non-Aqueous Electromechanical Cells, Including Rechargeable Lithium Batteries," which is incorporated herein by reference in its entirety for all purposes.

[0121] Given this disclosure, one skilled in the art will be able to select an appropriate material for use as a protective layer. Relevant factors that may be considered when making such a selection include the ionic conductivity of the material; the ability to deposit, etch, or otherwise form the material on or with other materials in an electrochemical cell; the brittleness of the material; the compatibility of the material with the polymer or separator material; the compatibility of the material with the electrolyte of the electrochemical cell; the ionic conductivity of the material (e.g., lithium ion conductivity); and / or the ability to adhere the material to the separator material.

[0122] The protective layer material may be deposited by any suitable method, such as sputtering, electron beam evaporation, vacuum thermal evaporation, laser ablation, chemical vapor deposition (CVD), thermal evaporation, plasma-assisted chemical vacuum deposition (PECVD), laser-assisted chemical vapor deposition, and jet evaporation. The technique used may depend on the type of material being deposited, the thickness of the layer, etc. In certain embodiments, at least a portion of the protective layer material may be etched or otherwise removed, after which a separator material (e.g., a polymeric separator material) may be formed over the protective layer material.

[0123] As described herein, in certain embodiments, the protective layer material can be deposited on the separator using a vacuum deposition process (e.g., sputtering, CVD, thermal, or E-beam evaporation). Vacuum deposition allows for the deposition of a smooth, dense, and uniform thin layer. In other embodiments, the ionic conductor (e.g., ceramic) can be coated by drawing and casting the ionic conductor from a slurry or gel.

[0124] In some embodiments (e.g., when the protective layer is adjacent to and / or attached to a polymer layer (e.g., a separator)), the thickness of the protective layer can vary. The thickness of the protective layer can vary, for example, over a range of 1 nm to 7 microns. For example, the thickness of the ion conductor layer can be between 1 and 10 nm, between 10 and 100 nm, between 10 and 50 nm, between 30 and 70 nm, between 100 and 1000 nm, or between 1 and 7 microns. The thickness of the ion conductor layer can be, for example, 7 microns or less, 5 microns or less, 2 microns or less, 1000 nm or less, 600 nm or less, 500 nm or less, 250 nm or less, 100 nm or less, 70 nm or less, 50 nm or less, 25 nm or less, or 10 nm or less. In some embodiments, the ion conductor layer is at least 10 nm thick, at least 20 nm thick, at least 30 nm thick, at least 100 nm thick, at least 400 nm thick, at least 1 micron thick, at least 2.5 microns thick, or at least 5 microns thick. Other thicknesses are possible. Combinations of the above ranges are also possible.

[0125] The following applications are incorporated herein by reference in their entirety for all purposes: U.S. Patent Publication No. US2007 / 0221265, filed April 6, 2006 as Application No. 11 / 400,781, entitled "Rechargeable Lithium / Water, Lithium / Air Battery," published September 27, 2007; U.S. Patent Publication No. US2009 / 0221265, filed July 31, 2007 as Application No. 11 / 888,339, entitled "Battery Swelling Inhibition," published February 5, 2009; No. 035646; filed February 2, 2010 as application serial number 12 / 312,674, patented December 31, 2013 as U.S. Patent No. 8,617,748, entitled "Separation of Electrolytes," published May 17, 2010 as U.S. Patent Publication No. US2010 / 0129699; filed July 30, 2010 as application serial number 12 / 682,011, patented October 28, 2014 as U.S. Patent No. 8,871,387, entitled "Primer for Battery Electrodes" U.S. Patent Publication No. US2010 / 0291442, published November 18, 2010; U.S. Patent Publication No. 2009 / 0200986, filed February 8, 2008 as application No. 12 / 069,335, patented September 11, 2012 as U.S. Patent No. 8,264,205, entitled "Circuit for Charging and / or Discharging Protection in an Energy Storage Device," published August 31, 2009; U.S. Patent Publication No. 2009 / 0200986, filed April 6, 2006 as application No. 11 / 400,025, patented September 11, 2012 as U.S. Patent No. 8,264,205, entitled "Circuit for Charging and / or Discharging Protection in an Energy Storage Device," published August 31, 2009; and U.S. Patent Publication No. US2007 / 0224502, filed on August 10, 2010, as U.S. Patent No. 7,771,870, entitled "Electrode Protection in Both Aqueous and Non-Aqueous Electrochemical Cells, Including Rechargeable Lithium Batteries," published on September 27, 2007; and U.S. Patent Publication No. US2008 / 0318128, filed on June 22, 2007, as application No. 11 / 821,576, entitled "Lithium Alloy / Sulfur Battery," published on December 25, 2008;U.S. Patent Publication No. US2002 / 0055040, filed on February 27, 2001 as application serial number 09 / 795,915 and patented on May 10, 2011 as U.S. Patent No. 7,939,198, entitled "Novel Composite Cathode, Electrochemical Cell Including the Novel Composite Cathode, and Process for Manufacturing the Same," published on May 9, 2002; U.S. Patent Publication No. 11 / 111,262, filed on April 20, 2005 as application serial number 11 / 111,262 and patented on March 30, 2010 as U.S. Patent No. 7,688,075; and patented U.S. Patent Publication No. US2006 / 0238203, entitled "System and Method for Lithium-Sulfur Rechargeable Battery Fuel Gauge," published October 26, 2006; U.S. Patent Publication No. 11 / 728,197, filed March 23, 2007, patented December 27, 2011, U.S. Patent No. 8,084,102, entitled "Method for Co-Flash Evaporation of Polymerizable Monomer and Non-Polymerizable Carrier Solvent / Salt Mixture / Solution," published August 7, 2008; Ta U.S. Patent Publication No. US2008 / 0187663; U.S. Patent Publication No. US2011 / 0006738, filed September 23, 2010 as Application No. 12 / 679,371, entitled "Electrolyte Additive for Lithium Batteries and Related Methods," and published January 13, 2011; 2 The application was filed on September 23, 2010 under application number 12 / 811,576, and was granted a patent on May 19, 2015 under U.S. Patent No. 9,034,421, entitled "Method for forming an electrode containing sulfur and a porous material containing carbon." 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[0126] When a part (e.g., a layer, structure, region) is said to be "on," "adjacent to," "above," "over," "overlying," or "supported by" another part, it is understood that this can be directly on the part, or intervening parts (e.g., layers, structures, regions) can also be present. Similarly, when a part is "below" or "underneath" another part, it can be directly below the part, or intervening parts (e.g., layers, structures, regions) can also be present. A part that is "directly on," "directly adjacent to," "immediately adjacent to," "in direct contact with," or "directly supported by" another part means that there are no intervening parts. Also, when an element is "on," "above," "adjacent," "over," "overlying," "in contact with," "below," or "supported by" another element, it is understood that the entire element or a portion of the element is covered.

[0127] U.S. Provisional Application No. 62 / 851,162, filed May 22, 2019, and entitled "Electrically Connected Electrodes and Related Articles and Methods," is hereby incorporated by reference in its entirety for all purposes.

[0128] The following examples are intended to illustrate certain embodiments of the present invention, but do not exemplify the full scope of the invention. [Example]

[0129] Example In the following examples, articles comprising double-sided anodes were prepared in the following manner. The anodes were formed by vacuum-depositing a lithium layer onto a PVOH release layer (having a thickness of 6 μm) on a polyethylene terephthalate (PET) substrate (having a thickness of 25 μm). The lithium and release layer were released from the PET substrate during assembly. The double-sided anode layers were assembled by stacking two anodes so that the associated release layers of each anode faced away from each other and were in contact. The double-sided anode stack was assembled and connected to a copper tab, and a pin was inserted into the double-sided anode and copper tab assembly so that the pin passed through multiple double-sided anodes.

[0130] The following examples describe the electrical resistance evaluated for these stacked double-sided anode and copper tab assemblies and a foil control assembly, which was constructed in the same manner as the stacked double-sided anode and copper tab assemblies, except that a stack of layers of lithium metal foil was used instead of the stacked double-sided anodes.

[0131] Example 1 In this example, the effect of the number of pins used to penetrate an assembly of stacked double-sided anodes and copper tabs was evaluated. Sample 1 included a stack of 41 double-sided anodes with copper tabs connected to the exterior of the stack, and Sample 1 was penetrated by six pins. Sample 2 included a stack of 41 double-sided anodes with copper tabs connected to the exterior of the stack, and Sample 2 was penetrated by 12 pins. Comparative Sample 1 was a foil-controlled assembly that was not penetrated by pins. The electrical resistance of each of Samples 1, 2, and 3 was measured, and the results are shown in Table 1.

[0132] [Table 1]

[0133] The results, shown in Table 1, indicate that increasing the number of pins used to penetrate the sample decreases the resistance of the sample. The resistance of Sample 2 approaches that of Comparative Sample 1. These results demonstrate that relatively low resistance can be achieved for a double-sided lithium stack, even when each double-sided anode comprises a non-conductive release layer.

[0134] Example 2 In this example, the effect of the cross-sectional shape of the pins used to penetrate an assembly of stacked double-sided anodes and copper tabs was evaluated. Sample 3 included a stack of 21 double-sided anodes with copper tabs connected to the exterior of the stack, and was penetrated by six pins with a circular cross-sectional shape. Sample 4 included a stack of 21 double-sided anodes with copper tabs connected to the exterior of the stack, and was penetrated by six pins with a TORX® cross-sectional shape. Comparative Sample 2 was a foil-controlled assembly that was not penetrated by pins. The electrical resistance of Samples 3, 4, and 2 was measured, and the results are shown in Table 2.

[0135] [Table 2]

[0136] The results shown in Table 2 indicate that when a pin having a TORX® cross-sectional shape is used to penetrate the sample, the resistance of the sample is reduced compared to when a pin having a circular cross-sectional shape is used to penetrate the sample. The resistance of Sample 4 approaches the resistance of Comparative Sample 2. These results indicate that using a pin with a relatively high perimeter-to-area ratio (such as TORX® compared to a circle) can reduce the electrical resistance of the article.

[0137] While several embodiments of the present invention have been described and illustrated herein, those skilled in the art will readily envision various other means and / or structures for performing the functions and / or obtaining the results and / or one or more advantages described herein, and each such variation and / or modification is deemed to be within the scope of the present invention. More generally, those skilled in the art will readily appreciate that all parameters, dimensions, materials, and configurations described herein are intended to be exemplary, and that the actual parameters, dimensions, materials, and / or configurations will depend on the particular application for which the teachings of the present invention are used. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Accordingly, the foregoing embodiments are presented by way of example only, and it should be understood that, within the scope of the appended claims and their equivalents, the invention may be practiced otherwise than as specifically described and claimed. The present invention is directed to each individual feature (or function), system, article, material, and / or method described herein. Furthermore, any combination of two or more of such features, systems, articles, materials, and / or methods, where such features, systems, articles, materials, and / or methods are not mutually inconsistent, is within the scope of the present invention.

[0138] The indefinite articles "a" and "an," as used in the specification and claims, unless clearly indicated to the contrary, should be understood to mean "at least one."

[0139] The phrase "and / or," as used in the specification and claims, should be understood to mean "either or both" of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Other elements other than those specifically identified by the "and / or" clause may optionally be present, whether related to the elements specifically identified or not, unless clearly indicated to the contrary. Thus, as a non-limiting example, a reference to "A and / or B," when used in combination with open-ended language such as "comprising," can, in one embodiment, refer to A (optionally including other elements) without B; in another embodiment, refer to B (optionally including elements other than A) without A; and in yet another embodiment, refer to both A and B (optionally including other elements).

[0140] As used in this specification and the claims, "or" should be understood to have the same meaning as "and / or" as defined above. For example, when separating items in a list, "or" or "and / or" shall be interpreted as inclusive, i.e., the inclusion of at least one, but including a plurality, of a number or list of elements, and optionally additional unlisted items. It refers to the inclusion of only a term clearly indicated to the contrary, such as "only one of" or "exactly one," or, when used in the claims, "consisting of," exactly one element of a number or list. In general, the term "or" as used herein, when preceded by exclusive terms such as "either," "one," "only one of," or "exactly one," shall be interpreted as indicating exclusive alternatives (i.e., "one or the other, but not both"). "Consisting essentially of," when used in the claims, shall have its ordinary meaning as used in the field of patent law.

[0141] As used herein and in the claims, the phrase "at least one" in reference to a list of one or more elements means at least one element selected from one or more elements in the list of elements, but necessarily including at least one of all elements specifically listed in the list of elements, and not necessarily excluding combinations of elements in the list of elements. This definition also allows for elements other than those specifically identified in the list of elements to which the phrase "at least one" refers, whether related to the specifically identified elements or not, to be optionally present. Thus, as a non-limiting example, "at least one of A and B" (or, equivalently, "at least one of A or B," or, equivalently, "at least one of A and / or B") refers, in one embodiment, to at least one, optionally two or more, A, and no B (and optionally including elements other than B); in another embodiment, to at least one, optionally two or more, B, and no A (and optionally including elements other than A); in yet another embodiment, to at least one, optionally two or more, A, and at least one, optionally two or more, B (and optionally including other elements), etc.

[0142] In the claims and the foregoing specification, all transitional phrases such as "comprising," "including," "carrying," "having," "containing," "involving," "holding," and the like, shall be understood to be open-ended, meaning to include, but not be limited to. Only the transitional phrases "consisting of" and "consisting essentially of" shall be closed or semi-closed transitional phrases, respectively, as set forth in Section 2111.03 of the United States Patent Office Manual of Patent Examining Procedure.

Claims

1. a non-conductive layer including a first surface and a second surface; a first electrode portion adjacent to the first surface of the non-conductive layer; a second electrode portion adjacent to the second surface of the non-conductive layer; such that an electrical connection is established between the first electrode portion and the second electrode portion; The method, wherein the first electrode portion comprises an electrode active material and the second electrode portion comprises the same electrode active material.

2. A non-conductive layer including a first surface and a second surface; a first electrode portion adjacent to the first surface of the non-conductive layer; a second electrode portion adjacent to the second surface of the non-conductive layer; such that an electrical connection is established between the first electrode portion and the second electrode portion; the penetrating forms a conductive solid material region extending from the first electrode portion through the non-conductive layer to the second electrode portion, the conductive solid material region electrically connecting the first electrode portion and the second electrode portion; The method, wherein the conductive solid material region also comprises an electrode active material present in the first electrode portion and the second electrode portion.

3. 3. The method of claim 1 or 2, wherein said penetrating comprises piercing said article with a solid object.

4. The method of claim 3 , wherein the solid object is or comprises a pin.

5. 5. The method of claim 3 or 4, further comprising removing the solid object.

6. the first electrode portion has a polarity, The method according to any one of claims 1 to 5, wherein the second electrode portion has the same polarity as the polarity of the first electrode portion.

7. 7. The method of claim 1, wherein the penetrating forms a conductive solid material region extending from the first electrode portion through the non-conductive layer to the second electrode portion, the conductive solid material region electrically connecting the first electrode portion and the second electrode portion.

8. The method according to any one of claims 1 to 7, wherein the first electrode portion comprises an electrode active material and the second electrode portion comprises the same electrode active material.

9. 8. The method of claim 7, wherein the conductive solid material region also comprises an electrode active material present in the first electrode portion and the second electrode portion.

10. The method of any one of claims 1 to 8, wherein the penetrating forms a cavity extending from the first electrode portion through the non-conductive layer to the second electrode portion.

11. The method of claim 10 , wherein the penetrating forms a region of conductive solid material along a wall of the cavity.

12. The method of claim 10 further comprising filling at least a portion of the cavity with a conductive material.

13. a non-conductive layer comprising a first surface and a second surface; a first electrode portion adjacent to the first surface of the non-conductive layer and having polarity; a second electrode portion adjacent to the second surface of the non-conductive layer and having the same polarity as the polarity of the first electrode portion; a cavity extending from the first electrode portion through the non-conductive layer to the second electrode portion; and the first electrode portion is electrically connected to the second electrode portion by a conductive solid material region extending from the first electrode portion through the non-conductive layer to the second electrode portion; At least a portion of the region of conductive solid material is disposed along a wall of the cavity.

14. A non-conductive layer comprising a first surface and a second surface; a first electrode portion adjacent to the first surface of the non-conductive layer and having polarity; a second electrode portion adjacent to the second surface of the non-conductive layer and having the same polarity as the polarity of the first electrode portion; and the first electrode portion is electrically connected to the second electrode portion by a conductive solid material region extending from the first electrode portion through the non-conductive layer to the second electrode portion; The article, wherein the first electrode portion comprises an electrode active material and the second electrode portion comprises the same electrode active material.

15. 15. The article of claim 13 or 14, further comprising a cavity extending from the first electrode portion through the non-conductive layer to the second electrode portion, at least a portion of the conductive solid material region being disposed along a wall of the cavity.

16. The article according to any one of claims 13 to 15, wherein the first electrode portion comprises an electrode active material and the second electrode portion comprises the same electrode active material.

17. 17. The article of claim 16, wherein the conductive solid material region also comprises the electrode active material present in the first electrode portion and the second electrode portion.

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