Constraints for energy storage devices

Abstract

The present invention provides an energy storage device and an energy storage method. [Solution] An energy storage device comprising a unit cell in which an electrode and a counter electrode are stacked along the axial direction and separated from each other, and a restraint 130 including tension members 133, 135 having two opposing sides, wherein the tension members are planar, each side of which is coupled to compression members 132, 134, the compression members are arranged perpendicular to the tension members, and the restraint is configured to maintain a pressure on the unit cell greater than other pressures in two axial directions perpendicular to the axis and perpendicular to each other, (a) during use of the device and (b) in the axial direction, and the restraint is operably coupled to the unit cell.

Description

[Technical Field]

[0001] This disclosure relates, in general terms, to a structure for use in an energy storage device, an energy storage device incorporating the structure, and a method for creating the structure and the energy device. [Background technology]

[0002] A rocking chair or rechargeable battery is a type of energy storage device in which carrier ions, such as lithium, sodium, potassium, calcium, magnesium, or aluminum ions, move between a positive electrode and a negative electrode via an electrolyte. A rechargeable battery includes a single battery cell or two or more battery cells electrically coupled to form a battery, each battery cell containing a positive electrode, a negative electrode, a microporous separator, and an electrolyte.

[0003] In a rocking chair battery cell, both the positive and negative electrode structures contain material through which carrier ions enter and exit. When the cell is discharged, carrier ions are extracted from the negative electrode and inserted into the positive electrode. When the cell is charged, the reverse process occurs; that is, carrier ions are extracted from the positive electrode and inserted into the negative electrode.

[0004] Figure 1 shows a cross-sectional view of an electrochemical stack of an existing energy storage device, such as a non-aqueous secondary battery. The electrochemical stack 1 includes, within its stacked configuration, a positive electrode assembly 3, a positive electrode active material layer 5, a microporous separator 7, a negative electrode active material layer 9, and a negative electrode assembly 11. Each layer has a height measured in the electrode stack direction (i.e., from the positive electrode assembly 3 to the negative electrode assembly 11 as shown in Figure 1) that is significantly smaller (e.g., at least 10 times smaller) than the length and width of each layer measured in mutually orthogonal directions and in directions perpendicular to the electrode stack direction. Referring now to Figure 2, a roll 13 (sometimes called a "jelly roll") having a top 15 and a bottom 17 is formed by winding the electrochemical stack around a central axis 19, after which the roll 13 is packed into a can (not shown) and filled with a non-aqueous electrolyte to assemble the secondary battery. As shown in Figure 2, the electrode stack direction of the layers is perpendicular to the central axis 19.

[0005] Existing energy storage devices, such as batteries, fuel cells, and electrochemical capacitors, typically have a two-dimensional thin-layer architecture (e.g., planar or spiral stacking) as shown in Figures 1 and 2, where the surface area of ​​each stacking is approximately equal to the geometric footprint (neglecting porosity and surface roughness). Three-dimensional batteries have been proposed in the literature as a way to improve battery capacity and active material utilization. It has been proposed that three-dimensional architectures can be used to provide a larger surface area and higher energy compared to two-dimensional thin-layer battery architectures. There are advantages to fabricating three-dimensional energy storage devices due to the increased amount of energy obtained from a small geometric area. See, for example, Rust et al. WO2008 / 089110 (Patent Document 1) and Long et al. “Three-Dimensional Battery Architectures,” Chemical Reviews, (2004), 104, 4463-4492 (Non-Patent Document 1).

[0006] Conventional rolled batteries (see, for example, U.S. Patent No. 6,090,505 (Patent Document 2) and No. 6,235,427 (Patent Document 3) and Figure 2) typically have electrode material (active material, binder, conductive additive) coated on a single foil and compressed prior to cell assembly. The foil on which the electrodes are coated is typically part of the current collection path. In single jelly roll batteries such as 18650 or prism cells, the current collector foil is ultrasonically welded to electrode buses, tabs, tags, etc., which carry current from the active material through the current collector foil and tabs to the outside of the battery. Depending on the design, tabs may be present at multiple locations along the single jelly roll, or tabs may be present at one location along one or both ends of the current collector foil. Conventional stacked battery pouch cells have multiple plates (or foils) of active material sequentially gathered and welded to tabs, with areas on top of the individual foils. The plate then carries the current to the outside of the battery pouch (see, for example, U.S. Patent Application Publication No. 2005 / 0008939 (Patent Document 4)). [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] WO2008 / 089110 [Patent Document 2] U.S. Patent No. 6090505 [Patent Document 3] U.S. Patent No. 6,235,427 [Patent Document 4] U.S. Patent Application Publication No. 2005 / 0008939 [Non-patent literature]

[0008] [Non-Patent Document 1] Long et al., “3D Battery Architecture,” Chemical Reviews, (2004), 104, 4463-4492. [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] However, one of the challenges with secondary batteries is their reliability and cycle life. For example, the electrode structure of lithium-ion batteries tends to expand and contract when the battery is repeatedly charged and discharged, which can lead to electrical short circuits and equipment failures. [Means for solving the problem]

[0010] Among the various aspects of this disclosure, three-dimensional structures are provided for use in energy storage devices such as batteries, fuel cells, and electrochemical capacitors. Advantageously, according to one aspect of this disclosure, the proportion of electrode active material to other components of the energy storage device (i.e., the inactive material component of the energy storage device) can be increased. As a result, energy storage devices including the three-dimensional structures of this disclosure can have a higher energy density. They can also provide a higher energy recovery rate than two-dimensional energy storage devices for a given amount of energy stored, for example, by minimizing or reducing the transport distance for electron and ion transfer between the positive and negative electrodes. These devices may be better suited for miniaturization and for applications where the available geometric area for the device is limited and / or where the energy density requirements are higher than those that can be achieved with thin-layer devices.

[0011] Therefore, in short, according to one aspect of the present disclosure, an energy storage device is provided for cycling between a charged state and a discharged state. The energy storage device includes an enclosure, an electrode assembly and a non-aqueous liquid electrolyte within the enclosure, and a constraint that maintains pressure on the electrode assembly when the energy storage device cycles between a charged state and a discharged state. The electrode assembly has an assembly of electrode structures, an assembly of counter electrode structures, and an electrically insulating microporous separator material between the members of the electrode assembly and the counter electrode assembly. The electrode assembly has opposing first and second longitudinal end faces separated along a longitudinal axis, and an outer surface surrounding the longitudinal axis and connecting the first and second longitudinal end faces, wherein the combined surface area of ​​the first and second longitudinal end faces is less than 33% of the combined surface area of ​​the outer surface and the first and second longitudinal end faces. The members of the electrode assembly and the members of the counter electrode assembly are arranged alternately in a stacking direction parallel to the longitudinal axis within the electrode assembly. The constraint comprises first and second compression members connected by at least one tension member that pulls the compression members toward each other, and the constraint holds pressure on the electrode assembly in the stacking direction that exceeds the pressure held on the electrode assembly in each of two mutually orthogonal directions and orthogonal to the electrode stacking direction.

[0012] According to yet another aspect of the present disclosure, a secondary battery is provided for cycling between a charged state and a discharged state, the secondary battery comprising a battery enclosure, an electrode assembly and a non-aqueous liquid electrolyte within the battery enclosure, and a constraint that maintains pressure on the electrode assembly when the secondary battery cycles between a charged state and a discharged state. The electrode assembly comprises an assembly of electrode structures, an assembly of counter electrode structures, and an electrically insulating microporous separator material between the members of the electrode assembly and the counter electrode assembly. The electrode assembly has opposing first and second longitudinal end faces separated along a longitudinal axis, and an outer surface surrounding the longitudinal axis and connecting the first and second longitudinal end faces, wherein the surface area of ​​the first and second longitudinal end faces is less than 33% of the surface area of ​​the electrode assembly. The members of the electrode assembly and the members of the counter electrode assembly are arranged alternately in a stacking direction parallel to the longitudinal axis within the electrode assembly. The projection onto the first longitudinal plane of the electrode assembly and the counter electrode assembly members encloses a first projection region, and the projection onto the second longitudinal plane of the electrode assembly and the counter electrode assembly members encloses a second projection region. The constraint has first and second compression members that overlap the first and second projection regions, respectively, the compression members overlapping the outer surface of the electrode assembly and connected by tension members that pull the compression members toward each other, and the constraint holds pressure on the electrode assembly in the stacking direction that exceeds the pressure held on the electrode assembly in each of two mutually orthogonal directions and orthogonal to the electrode stacking direction.

[0013] Other objectives and components will be partially revealed and partially pointed out below. [Brief explanation of the drawing]

[0014] [Figure 1] This is a cross-sectional view of a cell in an electrochemical stack of a conventional two-dimensional energy storage device, such as a lithium-ion battery. [Figure 2] This is a cross-sectional view of a cell in a wound electrochemical stack of a conventional two-dimensional energy storage device, such as a lithium-ion battery. [Figure 3A]This is a schematic diagram of one embodiment of the electrode assembly of the present disclosure having a triangular prism shape. [Figure 3B] This is a schematic diagram of one embodiment of the electrode assembly of the present disclosure having a parallel pipe shape. [Figure 3C] This is a schematic diagram of one embodiment of the electrode assembly of the present disclosure having a rectangular prism shape. [Figure 3D] This is a schematic diagram of one embodiment of the electrode assembly of the present disclosure having a pentagonal prism shape. [Figure 3E] This is a schematic diagram of one embodiment of the electrode assembly of the present disclosure having a hexagonal prism shape. [Figure 4] This is a schematic exploded view of one embodiment of the secondary battery disclosed herein. [Figure 5A] Figure 4 is a schematic end view of one end of the electrode assembly of the secondary battery. [Figure 5B] Figure 5A is a schematic end view of the opposing ends of the electrode assembly. [Figure 5C] Figure 5A is a schematic top view of the outer surface of the electrode assembly. [Figure 5D] Figure 5A is a schematic bottom view of the opposite outer surface of the electrode assembly. [Figure 6A] Figure 4 is a schematic perspective view of the constraints on the secondary battery. [Figure 6B] This shows one embodiment of a cross-section of an electrode assembly having a constraint with an internal compression member. [Figure 6C] This shows one embodiment of a cross-section of an electrode assembly having constraints with multiple internal compression members. [Figure 7] This is a schematic exploded view of another embodiment of the secondary battery of the present disclosure. [Figure 8] This is a schematic diagram of another embodiment of an unfolded constraint for the electrode assembly of the secondary battery of the present disclosure. [Figure 9] This is a schematic diagram after the constraints in Figure 8 have been folded. [Figure 10A] This is a schematic diagram of another embodiment of the restraint and electrode assembly of the secondary battery of the present disclosure. [Figure 10B]Figure 10A is an enlarged view of the constraint and electrode assembly. [Figure 11A] This is a schematic diagram of another embodiment of constraint for the electrode assembly of the secondary battery of the present disclosure. [Figure 11B] This is an enlarged view of the constraint in Figure 11A. [Figure 12A] This is a perspective view of one embodiment of the electrode assembly of the secondary battery of the present disclosure, with a portion removed to show the internal structure. [Figure 12B] Figure 12A is an end view of one end of the electrode assembly. [Figure 12C] Figure 12A is an end view of the opposing ends of the electrode assembly. [Figure 13] This is a perspective view of another embodiment of the secondary battery of the present disclosure, with some parts removed to show the internal structure. [Figure 14] This is a perspective view of another embodiment of the secondary battery of the present disclosure, with some parts removed to show the internal structure. [Figure 15] This is a perspective view of another embodiment of the secondary battery of the present disclosure, with some parts removed to show the internal structure. [Figure 16] This is a cross-sectional view of another embodiment of the constraint and electrode assembly of the present disclosure.

[0015] Throughout the drawings, corresponding symbols indicate corresponding parts. [Modes for carrying out the invention]

[0016] definition

[0017] As used herein, singular nouns refer to multiple objects unless otherwise explicitly stated in the context. For example, in one instance, a reference to “electrode” includes both a single electrode and multiple similar electrodes.

[0018] As used herein, “about” and “approximately” mean ±10%, 5%, or 1% of the stated value. For example, in one example, about 250 μm includes 225 μm to 275 μm. In a further example, in one example, about 1000 μm includes 900 μm to 1100 μm. Unless otherwise specified, all numbers representing quantities (e.g., measured values, etc.) used herein and in the claims should be understood in all cases to be modified by “about.” Thus, unless otherwise indicated, the numerical parameters shown in the following specification and the appended claims are approximations. Each numerical parameter should be interpreted at least in light of the number of significant figures taken and by applying common rounding techniques.

[0019] As used herein in the context of describing the state of a secondary battery, “charged state” means a state in which a secondary battery has been charged to at least 75% of its rated capacity. For example, a battery can be charged to at least 80% of its rated capacity, at least 90% of its rated capacity, and even to at least 95% of its rated capacity (e.g., 100% of its rated capacity).

[0020] As used herein in the context of describing the state of a secondary battery, “discharged state” refers to a state in which a secondary battery has been discharged to less than 25% of its rated capacity. For example, a battery can be discharged to less than 20% of its rated capacity (e.g., less than 10%), and even less than 5% of its rated capacity (e.g., 0%).

[0021] As used herein in the context of describing a cycle of a secondary battery between a charged state and a discharged state, “cycle” means charging and / or discharging the battery to change the battery from a first state, which is either a charged state or a discharged state, to a second state opposite to the first state (i.e., a charged state if the first state was a discharged state, or a discharged state if the first state was a charged state), and then returning the battery to the first state to complete the cycle. For example, a single cycle of a secondary battery between a charged state and a discharged state may include charging from a discharged state to a charged state, and then discharging to a discharged state to complete the cycle. A single cycle may also include discharging the battery from a charged state to a discharged state, and then charging to a charged state to complete the cycle.

[0022] Where referred to herein in relation to an electrode assembly, the "ferret diameter" is defined as the distance between two planes that constrain the electrode assembly, measured in a direction perpendicular to the two parallel planes.

[0023] As used herein, “longitudinal axis,” “horizontal axis,” and “vertical axis” refer to mutually orthogonal axes (i.e., each is orthogonal to the others). For example, as used herein, “longitudinal axis,” “horizontal axis,” and “vertical axis” are analogous to the Cartesian coordinate system used to define a three-dimensional form or orientation. Thus, the description of the elements of the inventive features of this invention is not limited to one or more specific coordinate axes used to describe the three-dimensional orientation of the elements. In other words, the coordinate axes can be interchangeable when referring to the three-dimensional form of the inventive features of this invention.

[0024] As used herein, “longitudinal,” “horizontal,” and “vertical” refer to directions that are mutually orthogonal (i.e., each is orthogonal to the others). For example, as used herein, “longitudinal,” “horizontal,” and “vertical” may be substantially parallel to the longitudinal, transverse, and vertical axes of a Cartesian coordinate system used to define a three-dimensional form or orientation.

[0025] As used herein in the context of describing cycles between the charged state and the discharged state of a secondary battery, “repeated cycle” means two or more cycles from the discharged state to the charged state, or from the charged state to the discharged state. A repeating cycle between the charged state and the discharged state may include at least two cycles from the discharged state to the charged state (for example, charging from the discharged state to the charged state, discharging back to the discharged state, charging again to the charged state, and finally discharging back to the discharged state). As yet another example, at least two repeating cycles between the charged state and the discharged state may include discharging from the charged state to the discharged state, charging back to the charged state, discharging again to the discharged state, and finally charging back to the charged state. As yet another example, a repeating cycle between the charged state and the discharged state may include at least five cycles, and even at least ten cycles, from the discharged state to the charged state. As a further example, the recurring cycle between the charge state and the discharge state may include at least 25, 50, 100, 300, 500, and even 1000 cycles from the discharge state to the charge state.

[0026] In the context of describing secondary batteries, "rated output" as used herein refers to the capacity of a secondary battery to supply current over a certain period, measured at standard temperature conditions (25°C). For example, rated output can be measured in ampere-hours by determining the current output over a specific period, or by determining the time over which a particular current can be supplied and calculating the product of the current and time. For example, if the battery rating is 20 ampere-hours and the current is specified as 2 amperes relative to the rating, it can be understood that the battery will supply that current for 10 hours. Conversely, if the time is specified as 10 hours relative to the rating, it can be understood that the battery will output 2 amperes over 10 hours.

[0027] Detailed explanation

[0028] Generally, the secondary battery of this disclosure comprises a battery enclosure, an electrode assembly and a non-aqueous liquid electrolyte within the battery enclosure, and a constraint that maintains pressure on the electrode assembly as the secondary battery cycles between a charged state and a discharge state. As previously stated, during the formation of the secondary battery and / or the subsequent cycles between the charged and discharge states of the secondary battery, the electrodes and / or counter electrodes within the electrode assembly may expand in the direction in which the electrodes and counter electrodes are stacked (the electrode stacking direction). Such expansion becomes a challenge when the electrode assembly contains dozens (or more) stacked electrodes and counter electrodes. Advantageously, the constraint of this disclosure maintains pressure on the electrode assembly, suppressing expansion of the electrode assembly (in the stacking direction) during the formation of the battery and / or the subsequent cycles between the charged and discharge states of the battery. The constraint also further suppresses buckling of the electrode assembly that may potentially arise from the pressure differences exerted on different surfaces of the electrode assembly by the constraint.

[0029] The constraints of this disclosure may be embodied, for example, in a structure including the battery enclosure itself, a structure outside the battery enclosure, a structure inside the battery enclosure, or a combination of the battery enclosure and the structure inside and / or outside the battery enclosure. In one such embodiment, the battery enclosure is a component of the constraint; in other words, in this embodiment, the battery enclosure, by itself or in combination with one or more other structures (inside and / or outside the battery enclosure), applies a pressure to the electrode structure in the direction of the electrode stack that is greater than the pressure applied to the electrode structure in a mutually orthogonal and perpendicular direction to the electrode stack. In another embodiment, the constraints do not include the battery enclosure and one or more individual structures (inside and / or outside the battery enclosure) other than the battery enclosure that applies a pressure to the electrode structure in the direction of the electrode stack that is greater than the pressure applied to the electrode structure in a mutually orthogonal and perpendicular direction to the electrode stack.

[0030] In one exemplary embodiment, the constraint includes one or more individual structures inside the battery enclosure that apply a pressure to the electrode structure in the direction of the electrode stack that exceeds the pressure applied to the electrode structure in two directions that are perpendicular to and mutually orthogonal to the electrode stack direction.

[0031] In one exemplary embodiment, the constraint is located inside the battery enclosure and applies pressure to the electrode structure in the direction of the electrode stack that exceeds the pressure applied to the electrode structure in two directions that are perpendicular to and mutually orthogonal to the electrode stack direction.

[0032] In one exemplary embodiment, the constraints include a battery enclosure and one or more individual structures outside one or more individual structures inside the battery enclosure, which apply a combined pressure to the electrode structure in the electrode stack direction that exceeds the pressure applied to the electrode structure in two directions that are orthogonal to and mutually orthogonal to the electrode stack direction.

[0033] Regardless of the location of the constraint (e.g., inside or outside the battery enclosure, and / or included within the enclosure), it is preferable that the constraint and the battery enclosure together occupy only 75% of the volume enclosed by the outer surface of the battery enclosure (i.e., the battery drainage volume). For example, in one such embodiment, the constraint and the battery enclosure together occupy only 60% of the volume enclosed by the outer surface of the battery enclosure. As a further example, in one such embodiment, the constraint and the battery enclosure together occupy only 45% of the volume enclosed by the outer surface of the battery enclosure. As a further example, in one such embodiment, the constraint and the battery enclosure together occupy only 30% of the volume enclosed by the outer surface of the battery enclosure. As a further example, in one such embodiment, the constraint and the battery enclosure together occupy only 20% of the volume enclosed by the outer surface of the battery enclosure.

[0034] The electrode assemblies of this disclosure generally comprise two opposing longitudinal end faces (separated along the longitudinal axis of the electrode assembly) and an outer surface extending between the two opposing longitudinal end faces (enclosing the longitudinal axis). Generally, the longitudinal end faces may be planar or non-planar. For example, in one embodiment, the opposing longitudinal end faces are convex. In a further example, in one embodiment, the opposing longitudinal end faces are concave. In a further example, in one embodiment, the opposing longitudinal end faces are substantially planar.

[0035] The opposing longitudinal end faces may also have any range of two-dimensional shapes when projected onto a plane. For example, the longitudinal end faces may independently have a smooth curved shape (e.g., circular, elliptical, hyperbolic, or parabolic), and independently include a series of lines and vertices (e.g., polygons), or independently include a smooth curved shape and include one or more lines and vertices. Similarly, the outer surface of the electrode assembly may have a smooth curved shape (e.g., the electrode assembly has a circular, elliptical, hyperbolic, or parabolic cross-sectional shape), or the outer surface may include two or more faces connected at vertices (e.g., the electrode assembly may have a polygonal cross-section). For example, in one embodiment, the electrode assembly may have a cylindrical, elliptical cylindrical, parabolic cylindrical, or hyperbolic cylindrical shape. As a further example, in one such embodiment, the electrode assembly may have opposing longitudinal end faces of the same size and shape and a parallelogram outer surface (i.e., a surface extending between the opposing longitudinal end faces). As a further example, in one such embodiment, the electrode assembly has a shape corresponding to a triangular prism, and the electrode assembly has two opposing triangular longitudinal end faces and an outer surface consisting of three parallelograms (e.g., rectangles) extending between the two longitudinal end faces. As a further example, in one such embodiment, the electrode assembly has a shape corresponding to a rectangular prism, and the electrode assembly has two opposing rectangular longitudinal end faces and an outer surface including four parallelogram (e.g., rectangular) faces. As a further example, in one such embodiment, the electrode assembly has a shape corresponding to a pentagonal prism, a hexagonal prism, and so on, and the electrode assembly has two opposing longitudinal end faces such as a pentagon and a hexagon, and an outer surface including five, six, or so parallelogram (e.g., rectangular) faces, respectively.

[0036] Referring here to Figures 3A to 3E, several exemplary geometric shapes are schematically shown for the electrode assembly 120. In Figure 3A, the electrode assembly 120 has a triangular prism shape with opposing first and second longitudinal end faces 122, 124 separated along the longitudinal axis A, and an outer surface (unsigned) that connects the longitudinal end faces and includes three rectangular faces surrounding the longitudinal axis A. In Figure 3B, the electrode assembly 120 has a parallelepiped shape with opposing first and second parallelogram longitudinal end faces 122, 124 separated along the longitudinal axis A, and an outer surface (unsigned) that connects the two longitudinal end faces and includes four parallelogram faces surrounding the longitudinal axis A. In Figure 3C, the electrode assembly 120 has a rectangular prism shape with opposing first and second rectangular longitudinal end faces 122, 124 separated along the longitudinal axis A, and an outer surface (unsigned) that connects the two longitudinal end faces and includes four rectangular faces surrounding the longitudinal axis A. In Figure 3D, the electrode assembly 120 has a pentagonal prism shape having opposing first and second pentagonal vertical end faces 122, 124 separated along the vertical axis A, and an outer surface (unsigned) that connects the two vertical end faces and includes five rectangular faces surrounding the vertical axis A. In Figure 3E, the electrode assembly 120 has a hexagonal prism shape having opposing first and second hexagonal vertical end faces 122, 124 separated along the vertical axis A, and an outer surface (unsigned) that connects the two vertical end faces and includes six rectangular faces surrounding the vertical axis A.

[0037] Regardless of the overall geometric shape of the electrode assembly, the opposing first and second longitudinal end faces of the electrode assembly have a combined surface area of ​​less than 50% of the total surface area of ​​the electrode assembly (i.e., the total surface area is the sum of the surface areas of the first and second longitudinal end faces and the surface area of ​​the outer surface of the electrode assembly). For example, the first and second opposing longitudinal end faces 122, 124 of each electrode assembly 120 in Figures 3A to 3E have a combined surface area (i.e., the sum of the surface areas of the first and second longitudinal end faces) of less than 50% of the total surface area of ​​a triangular prism (Figure 3A), parallelepiped (Figure 3B), rectangular prism (Figure 3C), pentagonal prism (Figure 3D), or hexagonal prism (Figure 3E), respectively. For example, in one such embodiment, the opposing first and second longitudinal end faces of the electrode assembly have a surface area of ​​less than 33% of the total surface area of ​​the electrode assembly. As a further example, in one such embodiment, the opposing first and second longitudinal end faces of the electrode assembly have a surface area of ​​less than 25% of the total surface area of ​​the electrode assembly. As a further example, in one such embodiment, the opposing first and second longitudinal end faces of the electrode assembly have a surface area of ​​less than 20% of the total surface area of ​​the electrode assembly. As a further example, in one such embodiment, the opposing first and second longitudinal end faces of the electrode assembly have a surface area of ​​less than 15% of the total surface area of ​​the electrode assembly. As a further example, in one such embodiment, the opposing first and second longitudinal end faces of the electrode assembly have a surface area of ​​less than 10% of the total surface area of ​​the electrode assembly.

[0038] In some embodiments, the electrode assembly is a rectangular prism, and the first and second opposing longitudinal end faces have a combined surface area smaller than the combined surface area of ​​at least two opposing faces on the outer surface (i.e., the sum of the surface areas of the two opposing rectangular outer surfaces connecting the opposing longitudinal end faces). In some embodiments, the electrode assembly is a rectangular prism, and the rectangular prism has first and second opposing longitudinal end faces and an outer surface containing two pairs of opposing surfaces, and the two opposing longitudinal end faces have a combined surface area smaller than the combined surface area of ​​at least one pair of opposing surfaces included on the outer surface. In some embodiments, the electrode assembly is a rectangular prism, and the rectangular prism has two opposing first and second longitudinal end faces and an outer surface containing two pairs of opposing surfaces, and the two opposing longitudinal end faces have a combined surface area smaller than the combined surface area of ​​each pair of opposing surfaces included on the outer surface.

[0039] Generally, an electrode assembly includes an electrode assembly and a counter electrode assembly stacked in a direction coinciding with the longitudinal axis of the electrode assembly (i.e., the electrode stacking direction) (see, for example, Figures 3A to 3E). In other words, the electrodes and counter electrodes are stacked in a direction extending from a first opposing longitudinal end face to a second opposing longitudinal end face of the electrode assembly. In one embodiment, the members of the electrode assembly and / or the members of the counter electrode assembly are substantially thin (see, for example, Figures 1 and 2). In another embodiment, the members of the electrode assembly and / or the members of the counter electrode assembly are substantially non-thin; in other words, in one embodiment, the members of the electrode assembly and / or the counter electrode assembly extend sufficiently from a virtual backplane (e.g., a plane substantially coinciding with the surface of the electrode assembly) to have a surface area (neglecting porosity) greater than twice the geometric footprint (i.e., projection) of the members in the backplane. In certain embodiments, the ratio of the surface area of ​​the non-thin (i.e., three-dimensional) electrode and / or counter-electrode structure to its non-geometric footprint in the virtual backplane can be at least about 5, at least about 10, at least about 50, at least about 100, or even at least about 500. However, generally, this ratio is about 2 to about 1000. In one such embodiment, the members of the electrode assembly are substantially non-thin. As a further example, in one such embodiment, the members of the counter-electrode assembly are substantially non-thin. As a further example, in one such embodiment, the members of the electrode assembly and the members of the counter-electrode assembly are substantially non-thin.

[0040] During the formation and / or cycling of a secondary battery incorporating an electrode assembly, expansion of the electrode assembly in the longitudinal direction (e.g., the direction parallel to longitudinal axis A in each of Figures 3A to 3E) can be suppressed by the constraints of this disclosure. Generally, the constraint comprises compression members (adapted to overlap the first and second projection regions, respectively) connected by a tension member (adapted to overlap the outer surface of the electrode assembly). The tension member pulls the compression member toward each other, thereby applying compressive forces to the opposing first and second longitudinal end faces of the electrode assembly, thereby suppressing expansion of the electrode assembly in the longitudinal direction (which coincides with the electrode stacking direction, as further described herein). After the battery is formed, the constraint also applies pressure to the electrode assembly in the longitudinal direction (i.e., the electrode stacking direction) that exceeds the pressure held in the electrode assembly in each of two mutually orthogonal and longitudinal directions.

[0041] Referring here to Figure 4, an exploded view of one embodiment of the secondary battery of the present disclosure, shown overall as 100. The secondary battery includes a battery enclosure 102 and a set 110 of electrode assemblies 120 within the battery enclosure 102, each electrode assembly having a first longitudinal end face 122, an opposing second longitudinal end face 124 (separated from the first longitudinal end face 122 along a longitudinal axis (not shown) parallel to the "Y-axis" of the hypothetical Cartesian coordinate system in Figure 4), and outer surfaces including outer surfaces 123, 125, 126, 127 (see Figure 12A). Each electrode assembly includes an assembly of electrode structures and an assembly of counter electrode structures stacked on top of each other within each electrode assembly (see, for example, Figure 12A) in the electrode stacking direction D. In other words, the assembly of electrode structures and counter electrode structures is arranged in an alternating series of electrodes and counter electrodes progressing in direction D between a first longitudinal end face 122 and a second longitudinal end face 124 (see, for example, Figure 12A; as shown in Figure 4, the electrode stacking direction D is parallel to the Y-axis of the hypothetical Cartesian coordinate system in Figure 4). Furthermore, the stacking direction D of the electrodes within each electrode assembly 120 is orthogonal to the stacking direction of the assembly of electrode assemblies 120 within the set 110 (i.e., the stacking direction of the electrode assemblies). In other words, the electrode assemblies are arranged relative to each other in a set 110 that is orthogonal to the electrode stacking direction D within each electrode assembly (for example, the stacking direction of the electrode assemblies is in the direction corresponding to the Z-axis of the virtual Cartesian coordinate system, while the electrode stacking direction D within each electrode assembly is in the direction corresponding to the Y-axis of the virtual Cartesian coordinate system).

[0042] Tabs 141 and 142 protrude from the battery enclosure and provide an electrical connection between the electrode assembly of set 110 and an energy supply or consumption device (not shown). More specifically, in this embodiment, tab 141 is electrically connected to tab extension 143 (e.g., using conductive adhesive), and tab extension 143 is electrically connected to an electrode included in each of the electrode assemblies 120. Similarly, tab 142 is electrically connected to tab extension 144 (e.g., using conductive adhesive), and tab extension 144 is electrically connected to a counter electrode included in each of the electrode assemblies 120.

[0043] Each electrode assembly 120 in the embodiment shown in Figure 4 has associated constraints 130 to suppress longitudinal expansion (i.e., electrode stack direction D). Each constraint 130 includes compression members 132, 134 (see Figures 5A and 5B) that overlap the first and second longitudinal end faces 122, 124, respectively, and tension members 133, 135 (see Figures 5C and 5D) that overlap the outer surfaces 123, 125, respectively. The tension members 133, 135 pull the compression members 132, 134 toward each other, and the compression members 132, 134 apply a compressive force to the opposing first and second longitudinal end faces 122, 124. As a result, longitudinal expansion of the electrode assembly during battery formation and / or the battery's charging and discharging cycles is suppressed. Furthermore, the constraint 130 applies a pressure to the electrode assembly in the longitudinal direction (i.e., the electrode stacking direction D) that exceeds the pressure held on the electrode assembly in one of two mutually orthogonal directions that are also orthogonal to the longitudinal direction. (As shown in the figure, the longitudinal direction corresponds to the direction of the "Y" axis, and the two mutually orthogonal directions that are also orthogonal to the longitudinal direction correspond to the X and Z axes of the illustrated virtual Cartesian coordinate system, respectively.)

[0044] Referring now to Figures 5A, 5B, 5C, and 5D, each electrode assembly 120 in the embodiment of Figure 4 has a geometric shape corresponding to the shape of a rectangular prism, having first and second vertical end faces 122, 124 having dimensions X1 × Z1, outer surfaces 123, 125 having dimensions X1 × Y1, and outer surfaces 126, 127 having dimensions Y1 × Z1. (wherein X1, Y1, and Z1 are dimensions measured in the directions corresponding to the X, Y, and Z axes of the Cartesian coordinate system, respectively.) Therefore, the first and second vertical end faces 122, 124 have a surface area corresponding to the product of X1 and Z1, the outer surfaces 123, 125 each have a surface area corresponding to the product of X1 and Y1, and the outer surfaces 126, 127 each have a surface area corresponding to the product of Y1 and Z1. According to one aspect of the present disclosure, the sum of the surface areas of the first and second longitudinal end faces is less than 33% of the total surface area of ​​the electrode assembly, the electrode assembly is a rectangular prism, the combined surface area of ​​the first and second longitudinal end faces is equal to (X1×Z1)+(X1×Z1), and the surface area of ​​the outer face is equal to (X1×Y1)+(X1×Y1)+(Y1×Z1)+(Y1×Z1). For example, in one such embodiment, the sum of the surface areas of the first and second longitudinal end faces is less than 25% of the total surface area of ​​the electrode assembly, the combined surface area of ​​the first and second longitudinal end faces is equal to (X1×Z1)+(X1×Z1), and the total surface area of ​​the electrode assembly is equal to (X1×Y1)+(X1×Y1)+(Y1×Z1)+(Y1×Z1)+(X1×Z1).

[0045] Each restraint 130 in this embodiment includes compression members 132, 134 that overlap the first and second longitudinal end faces 122, 124, respectively, and at least one tension member that pulls the compression members toward each other. For example, the restraint may include tension members 133, 135 that overlap the respective outer surfaces 123, 125 of the outer surface. Generally, the compression members 132, 134 apply pressure to the first and second longitudinal end faces 122, 124 (i.e., in the electrode stacking direction D) that exceeds the pressure held against the outer surfaces 123, 125 and outer surfaces 126, 127 of the electrode assembly (i.e., in each of the two directions that are mutually orthogonal and perpendicular to the electrode stacking direction). For example, in one such embodiment, the constraint applies a pressure to the first and second longitudinal end faces 122, 124 (i.e., in the electrode stacking direction D) at least three times the pressure that is held in the electrode assembly (in at least one or more of two directions that are orthogonal to the electrode stacking direction and mutually orthogonal). As a further example, in one such embodiment, the constraint applies a pressure to the first and second longitudinal end faces 122, 124 (i.e., in the electrode stacking direction D) at least four times the pressure that is held in the electrode assembly (in at least one or more of two directions that are orthogonal to the electrode stacking direction and mutually orthogonal). As a further example, in one such embodiment, the constraint applies a pressure to the first and second longitudinal end faces 122, 124 (i.e., in the electrode stacking direction D) at least five times the pressure that is held in the electrode assembly (in at least one or more of two directions that are orthogonal to the electrode stacking direction and mutually orthogonal).

[0046] Referring here to Figure 6A, in one embodiment, the constraint 130 may be derived from a sheet 107 having a length L1, a width W1, and a thickness t1. To form the constraint, the sheet 107 is simply wrapped around the electrode structure 120 (see Figures 4 and 5A-5D) and folded along the fold line 113 to enclose the electrode structure. The edges 115, 117 overlap each other and are welded, glued, or otherwise fixed to each other to form a constraint including compression members 132, 134 (compression member 134 including the overlapping edges 115, 117 fixed to each other) and tension members 133, 135. In this embodiment, the constraint has a volume corresponding to the drainage volume of the sheet 107 (i.e., the product of L1, W1, and t1).

[0047] Sheet 107 may include any of a wide range of compatible materials that can apply the desired force to the electrode structure. Generally, the restraint typically includes a material that has an ultimate tensile strength of at least 10,000 psi (>70 MPa), is compatible with the battery electrolyte, does not corrode significantly at the battery's floating potential or anode potential, and does not react significantly or lose mechanical strength at 45°C. For example, the restraint may include any of a wide range of metals, alloys, ceramics, glass, plastics, or combinations thereof (i.e., composite materials). In one exemplary embodiment, the restraint includes metals (e.g., stainless steel (e.g., SS316, 440C, or 440C hard), aluminum (e.g., aluminum 7075-T6, hard H18), titanium (e.g., 6Al-4V), beryllium, beryllium copper (hard), copper (O2-free, hard), nickel). However, generally, if the restraint includes metal, it is generally preferred that it be incorporated in a manner that limits corrosion and limits the generation of electrical short circuits between the electrode and the counter electrode. In another exemplary embodiment, the constraint includes ceramics (e.g., alumina (e.g., sintered or Coorstek AD96), zirconia (e.g., Coorstek YZTP), yttria-stabilized zirconia (e.g., ENRG E-Strate®)). In yet another exemplary embodiment, the constraint includes glass (e.g., Schott D263 tempered glass). In another exemplary embodiment, the constraint includes plastics (e.g., polyetheretherketone (PEEK) (e.g., Aptiv 1102), carbon-containing PEEK (e.g., Victrex 90HMF40 or Xycomp 1000-04), carbon-containing polyphenylene sulfide (PPS) (e.g., Tepex Dynalite 207), polyetheretherketone (PEEK) with 30% glass (e.g., Victrex 90HMF40 or Xycomp 1000-04), and polyimide (e.g., Kapton®)).In another exemplary embodiment, the constraint includes composite materials (e.g., E-glass standard fabric / epoxy, 0 degrees, E-glass UD / epoxy, 0 degrees, Kevlar® standard fabric / epoxy, 0 degrees, Kevlar UD / epoxy, 0 degrees, carbon standard fabric / epoxy, 0 degrees, carbon UD / epoxy, 0 degrees, Toyobo Zylon® HM fiber / epoxy). In another exemplary embodiment, the constraint includes fibers (e.g., Kevlar 49 aramid fiber, S-glass fiber, carbon fiber, Vectran UM LCP fiber, Dyneema, Zylon).

[0048] The thickness (t1) of the restraint depends on a range of factors including, for example, the constituent material of the restraint, the overall dimensions of the electrode assembly, and the composition of the anode and cathode of the battery. In some embodiments, for example, the restraint includes a sheet having a thickness in the range of about 10 to about 100 micrometers. For example, in one such embodiment, the restraint includes a stainless steel sheet (e.g., SS316) having a thickness of about 30 μm. As a further example, in another such embodiment, the restraint includes an aluminum sheet (e.g., 7075-T6) having a thickness of about 40 μm. As yet another such embodiment, the restraint includes a zirconia sheet (e.g., Coorstek YZTP) having a thickness of about 30 μm. As yet another such embodiment, the restraint includes an E-glass UD / epoxy 0 degree sheet having a thickness of about 75 μm. As yet another such embodiment, the restraint includes 12 μm carbon fibers with a packing density of >50%.

[0049] In certain embodiments, the compression and / or tension members of the constraint include a porous material. Generally, the porous material facilitates access to the electrode assembly of the electrolyte. For example, in some embodiments, the compression and / or tension members may have a porosity of at least 0.25. As a further example, in some embodiments, the compression and / or tension members may have a porosity of at least 0.375. As a further example, in some embodiments, the compression and / or tension members may have a porosity of at least 0.5. As a further example, in some embodiments, the compression and / or tension members may have a porosity of at least 0.625. As a further example, in some embodiments, the compression and / or tension members may have a porosity of at least 0.75.

[0050] In yet another embodiment, the restraint 130 includes one or more compression members located inside the electrode assembly 120. For example, referring here to Figure 6B, a cross-sectional view of one embodiment of an electrode assembly 120 having a restraint 130 with an internal compression member 132a is shown. In the embodiment shown in Figure 6B, the restraint 130 may comprise first and second compression members 132 and 134 on the longitudinal end faces 122 and 124 of the electrode assembly 120, respectively. However, additionally and / or alternatively, the restraint 130 may further include at least one internal compression member 132a located in an internal region other than the longitudinal end faces 122 and 124 of the electrode assembly. The internal compression member 132a is connected to the tension members 133, 135 and imposes compressive pressure between the internal compression member 132a and other compression members (e.g., one or more compression members 132, 134 on the longitudinal end faces 122, 124 of the electrode assembly 120) and / or on a portion of the electrode assembly 120 having one or more other internal compression members 132. Referring to the embodiment shown in Figure 6B, it is possible to provide internal compression members 132a that are spaced apart along the longitudinal axis (in the stacking direction D) away from the first and second longitudinal end faces 122, 124 of the electrode assembly 120 (e.g., towards the central region of the electrode assembly 120). The internal compression member 132a can be connected to the tension members 133, 135 at a position inward from the electrode assembly end faces 122, 124. In one embodiment, at least one internal compression member 132a located inward from the end faces 122, 124 is provided in addition to the compression members 132, 134 provided to the electrode assembly end faces 122, 124. In another embodiment, the restraint 130 includes an internal compression member 132a located inward from the longitudinal end faces 122, 124, in an internal position of the electrode assembly 120, spaced inward from the longitudinal end faces 122, 124, with or without the compression members 132, 134 on the longitudinal end faces 122, 124. In yet another embodiment, the restraint 130 includes an internal compression member 132a located inward from the longitudinal end faces 122, 124, in an internal position of the electrode assembly spaced inward from the longitudinal end faces 122, 124, without the compression members 132, 134 on the longitudinal end faces 122, 124.In one embodiment, the internal compression member 132a can be understood as cooperating with one or more compression members 132, 134 and / or other internal compression members 132a to apply compressive pressure to portions of the electrode assembly 120 that are longitudinally located between the internal compression member 132a and the longitudinal surfaces 122, 124 of the electrode assembly 120, and / or to apply compressive pressure to portions of the electrode assembly 120 that are longitudinally located between the internal compression member 132a and another internal compression member 132a. In one version, at least one of the internal compression members 132a includes at least a portion of the electrode structure 151 or the counter electrode structure 152, as will be described in more detail below. For example, the internal compression member 132a may include at least a portion of the counter electrode active material, separator, electrode current collector, counter electrode current collector, electrode backbone, and counter electrode backbone.

[0051] According to one embodiment, as described above, the constraint 130 may include an internal compression member 132a which is part of the internal structure of the electrode assembly 106 (e.g., part of the electrode 151 and / or counter electrode structure 152). In one embodiment, by providing compression between the structures within the electrode assembly 120, a tightly constrained structure can be realized that adequately compensates for the strain generated by the elongation of the electrode structure 120. For example, in one embodiment, one or more internal compression members 132 may work in cooperation with the compression members 132, 134 at the longitudinal end faces 122, 124 of the electrode assembly 120, by being positioned under tension to one another via connecting tension members 133, 134, in order to suppress elongation in a direction parallel to the longitudinal direction. In yet another embodiment, the elongation of the electrode structure 151 (e.g., the anode structure) may be neutralized by compression via one or more internal compression members 132a corresponding to a portion of the counter electrode structure 152 (e.g., the cathode) which is positioned under tension to one another via tension members 133, 135.

[0052] Generally, in certain embodiments, the components of the constraint 130 can be embodied as electrodes 151 and / or counter electrode structures 152 within the electrode assembly 120, respectively, not only providing effective constraint but also enabling more efficient utilization of the volume of the electrode assembly 120 without excessively increasing the size of the secondary battery having the electrode assembly 120. For example, in one embodiment, the constraint 130 may include tension members 133, 135 that function as internal compression members 132a attached to one or more electrode structures 151 and / or counter electrode structures 152. As a further example, in certain embodiments, at least one internal compression member 132a may be embodied as an assembly of electrode structures 151. As a further example, in certain embodiments, at least one internal compression member 132a may be embodied as an assembly of counter electrode structures 152.

[0053] Referring here to Figure 6C, a Cartesian coordinate system for reference is shown, having a vertical axis (Z-axis), a longitudinal axis (Y-axis), and a transverse axis (X-axis), where the X-axis is oriented to extend beyond the plane of the page, and the symbolic representation of the stacking direction D as described above is parallel to the Y-axis. More specifically, Figure 7 shows a cross-sectional view of an electrode assembly 120 having a constraint 130 with compression members 132, 134 on its longitudinal surface, and at least one internal compression member 132a. The constraint 130 includes the compression members 132, 134, and the internal compression member embodied as an assembly of electrode structures 151 and / or counter electrode structures 152. Thus, in this embodiment, it can be understood that at least one internal compression member 132a, electrode structures 151, and / or counter electrode structures 152 are interchangeable. Furthermore, the separator 150 can also form part of the internal compression member 132a. More specifically, Figure 6C shows one embodiment of a flush connection of an internal compression member 132a corresponding to an electrode 151 or counter electrode structure 152. The flush connection may further include a layer of adhesive 182 of other bonding means between the tension members 133, 135 and the internal compression member 132a. The layer of adhesive 182 fixes the internal compression member 132a to the tension members 133, 135 so that the internal compression member 132a can be held under tension with other compression members (e.g., other internal compression members or compression members on the longitudinal end faces of the electrode assembly 120).

[0054] In one embodiment, a component of an electrode assembly 151 having an electrode active material layer 160, an electrode current collector 163 (for example, an ionic porous electrode current collector), and an electrode backbone 165 supporting the electrode active material layer 160 and the electrode current collector 163 is further shown in Figure 6C. Similarly, in one embodiment, a component of a counter electrode assembly 152 having a counter electrode active material layer 167, a counter electrode current collector 169, and a counter electrode backbone 171 supporting the counter electrode active material layer 167 and the counter electrode current collector 169 is shown in Figure 6C.

[0055] Without being bound by a particular theory (for example, as shown in Figure 6C), in a particular embodiment, the components of electrode assembly 151 include an electrode active material layer 160, an electrode current collector 163, and an electrode backbone 165 supporting the electrode active material layer 160 and the electrode current collector 163. Similarly, in a particular embodiment, the components of counter electrode assembly 152 include a counter electrode active material layer 167, a counter electrode current collector 169, and a counter electrode backbone 171 supporting the counter electrode active material layer 167 and the counter electrode current collector 169. In one embodiment, at least a portion of either the electrode structure or the counter electrode structure 151, 152 (e.g., current collectors 163, 169, backbones 165, 171, counter electrode active material layer 167, and separator 130) can function as part or as a whole of the internal compression member 132a (e.g., by being connected to tension members 133, 135, or by being tensioned with one or more other internal or external compression members 132, 134 in other ways). In one embodiment, the internal compression member 132a can be connected to the tension members 133, 135 by at least one of adhesive, welding, joining, bonding, or similar connecting means. The embodiment shown in Figure 6C shows an internal compression member 132a that corresponds to both the electrode structure and the counter electrode structures 151, 152 (i.e., both the electrode structure and the counter electrode structure are arranged under tension from each other by being connected to the tension members 133, 135). However, in other embodiments, only one of the electrode and / or counter electrode structures functions as an internal compression member 132a (for example, by being bonded to the tension members 133, 135), and / or only a portion of the electrode or counter electrode structures 151, 152 can function as an internal compression member 132a. For example, in one embodiment, a current collector (e.g., at least one of the electrode current collector 163 and / or counter electrode current collector 152) can function as an internal compression member 132 (for example, by being bonded to the tension members 133, 135).

[0056] Referring again to Figure 4, to complete the manufacture of the secondary battery 100, the battery enclosure 102 is filled with a non-aqueous electrolyte (not shown), the lid 104 is folded (along the fold 106) and sealed to the top surface 108. When the sealed secondary battery is fully assembled, it occupies a volume bounded by its outer surface (i.e., drainage volume), the secondary battery enclosure 102 occupies a volume corresponding to the drainage volume of the battery (including the lid 104) which is smaller than its internal volume (i.e., the columnar volume bounded by the inner surfaces 103A, 103B, 103C, 103D, 103E, and the lid 104), and each restraint 130 of the set 110 occupies a volume corresponding to its respective drainage volume. Thus, combined, the battery enclosure and restraints occupy only 75% of the volume bounded by the outer surface of the battery enclosure (i.e., the drainage volume of the battery). For example, in one such embodiment, the constraint and battery enclosure together occupy only 60% of the volume bounded by the outer surface of the battery enclosure. As a further example, in one such embodiment, the constraint and battery enclosure together occupy only 45% of the volume bounded by the outer surface of the battery enclosure. As a further example, in one such embodiment, the constraint and battery enclosure together occupy only 30% of the volume bounded by the outer surface of the battery enclosure. As a further example, in one such embodiment, the constraint and battery enclosure together occupy only 20% of the volume bounded by the outer surface of the battery enclosure.

[0057] For the sake of clarity in the explanation of Figure 4, the secondary battery 100 includes only one set of electrode assemblies 110, and the set includes only six electrode assemblies 120. In practice, a secondary battery may include two or more sets of electrode assemblies, and each set may be arranged laterally (e.g., in the relative direction within the XY plane of the Cartesian coordinate system in Figure 4) or perpendicularly (e.g., substantially parallel to the Z axis of the Cartesian coordinate system in Figure 4). Also, in each of these embodiments, each set of electrode assemblies may comprise one or more electrode assemblies. For example, in a particular embodiment, a secondary battery may comprise one, two, or more sets of electrode assemblies, each such set comprising one or more electrode assemblies (e.g., each such set contains 1, 2, 3, 4, 5, 6, 10, 15 or more electrode assemblies), and if the battery includes two or more such sets, the sets may be arranged laterally or perpendicularly with respect to the electrode assemblies of the other sets constituting the secondary battery. In each of these various embodiments, each individual electrode assembly may have its own constraints (i.e., a one-to-one relationship between the electrode assembly and the constraint), two or more electrode assemblies may have a common constraint (i.e., one constraint for two or more electrode assemblies), or two or more electrode assemblies may share components of a constraint (i.e., two or more electrode assemblies may have a common compression member and / or tension member).

[0058] Referring here to Figure 12A, in one exemplary embodiment, the electrode assembly 120 comprises first and second longitudinal end faces 121, 122 and outer surfaces including outer surfaces 123, 124, 125, 126. The electrode assembly 120 further comprises an assembly of electrode structures 151 and an assembly of counter electrode structures 152 stacked in an electrode stacking direction D parallel to a longitudinal axis A extending between the opposing first and second longitudinal end faces 121, 122. The electrode structures and counter electrode structures 151, 152 are stacked alternately (e.g., intersecting), with each member of the electrode assembly substantially between two members of the counter electrode assembly, and each member of the counter electrode assembly substantially between two members of the electrode assembly. For example, except for the first and last electrode or counter electrode structures in the alternating sequence, in one embodiment, each electrode structure in the alternating sequence is between two counter electrode structures, and each counter electrode structure in the sequence is between two electrode structures. Furthermore, the ratio of the surface area of ​​the non-thin electrode and counter-electrode structures to the respective geometric footprints on the virtual backplane (e.g., outer surfaces 126 and 127, respectively) can be at least about 5, at least about 10, at least about 50, at least about 100, and even at least about 500.

[0059] As shown in Figure 12A, with one exception, each member 151 of the electrode structure assembly lies between two members 152 of the counter electrode assembly, and with one exception, each member 152 of the counter electrode structure assembly lies between two members 151 of the electrode structure assembly. More generally, in one embodiment, the electrode and the counter electrode assembly each have N members, each of the N-1 electrode assembly members lies between two counter electrode structures, and each of the N-1 counter electrode assembly members lies between electrode structures, where N is at least 2. For example, in one embodiment, N is at least 4, at least 5, at least 10, at least 25, at least 50, and even at least 100 (as shown in Figure 4).

[0060] Referring here to Figures 12B and 12C, the projection onto the first longitudinal end face 122 of the electrode and counter-electrode assembly members encloses the first projection region 162, and the projection onto the second longitudinal end face 124 of the electrode and counter-electrode assembly members encloses the second projection region 164. Generally, the first and second projection regions 162, 164 typically include a substantial portion of the surface area of ​​the first and second longitudinal end faces 122, 124, respectively. For example, in one embodiment, the first and second projection regions each include at least 50% of the surface area of ​​the first and second longitudinal end faces. As a further example, in one such embodiment, the first and second projection regions each include at least 75% of the surface area of ​​the first and second longitudinal end faces, respectively. As a further example, in one such embodiment, the first and second projection regions each include at least 90% of the surface area of ​​the first and second longitudinal end faces, respectively.

[0061] The electrode and counter electrode assemblies contain an electroactive material capable of absorbing and releasing carrier ions (e.g., lithium ions, sodium ions, potassium ions, calcium ions, magnesium ions, or aluminum ions). In some embodiments, the electrode structure assembly member 151 contains an anode-active electroactive material (sometimes called the negative electrode), and the counter electrode structure assembly member 152 contains a cathode-active electroactive material (sometimes called the positive electrode). In other embodiments, the electrode structure assembly member 151 contains a cathode-active electroactive material, and the counter electrode structure assembly member 152 contains an anode-active electroactive material. In each of the embodiments and examples described in this paragraph, the negative electrode active material can be a granular aggregate electrode or a monolithic electrode.

[0062] Exemplary anodic active materials include carbon materials (e.g., graphite, and soft or hard carbon), or any of the metals, metalloids, alloys, oxides, and compounds that can form alloys with lithium. Specific examples of metals or metalloids that can constitute an anode material include tin, lead, magnesium, aluminum, boron, gallium, silicon, indium, zirconium, germanium, bismuth, cadmium, antimony, silver, zinc, arsenic, hafnium, yttrium, and palladium. In one exemplary embodiment, the anode active material includes aluminum, tin, or silicon, or their oxides, nitrides, fluorides, or other alloys. In another exemplary embodiment, the anode active material includes silicon or an alloy thereof.

[0063] Exemplary cathode active materials include any of the broad range of cathode active materials. For example, in lithium-ion batteries, the cathode active material may include cathode materials selected from transition metal oxides, transition metal sulfides, transition metal nitrides, lithium transition metal oxides, lithium transition metal sulfides, and lithium transition metal nitrides. The transition metal elements in these transition metal oxides, transition metal sulfides, and transition metal nitrides may include metal elements having a d-shell or f-shell. Specific examples of such metal elements are Sc, Y, lanthanides, actinides, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pb, Pt, Cu, Ag, and Au. Additional cathode active materials include LiCoO2 and LiNi 0.5 Mn 1.5 O4, Li(Ni x Co y This includes Al2)O2, LiFePO4, Li2MnO4, V2O5, molybdenum oxysulfide, phosphates, silicates, vanadates, and combinations thereof.

[0064] In one embodiment, the anode active material is microstructured to accommodate volume expansion and contraction when lithium ions (or other carrier ions) are incorporated into or detach from the negative electrode active material during the charge and discharge processes, thereby providing a high porosity. Generally, the porosity of the negative electrode active material is at least 0.1. However, typically, the porosity of the negative electrode active material is 0.8 or less. For example, in one embodiment, the porosity of the negative electrode active material is about 0.15 to about 0.75. As a further example, in one embodiment, the porosity of the negative electrode active material is about 0.2 to about 0.7. As a further example, in one embodiment, the porosity of the negative electrode active material is about 0.25 to about 0.6.

[0065] Depending on the composition and method of forming the microstructured negative electrode active material, the microstructured negative electrode active material may include macroporous, microporous, or mesoporous material layers, or combinations thereof (e.g., a combination of microporous and mesoporous, or a combination of mesoporous and macroporous). Microporous materials are typically characterized by a pore morphology characterized by pore dimensions of less than 10 nm, wall dimensions of less than 10 nm, pore depths of 1 to 50 micrometers, and generally a spongy, irregular appearance (smooth, non-branched pore walls). Mesoporous materials are typically characterized by a pore morphology generally characterized by pore dimensions of 10 to 50 nm, wall dimensions of 10 to 50 nm, pore depths of 1 to 100 micrometers, and somewhat clearly defined branched or dendritic pores. Macroporous materials are typically characterized by pore dimensions greater than 50 nm, wall dimensions greater than 50 nm, pore depths of 1 to 500 micrometers, and pore morphologies that can be linear, branched, or dendritic, and have smooth or rough walls. The void volume can also include open or closed voids, or a combination thereof. In one embodiment, the void volume includes open voids; that is, the negative electrode active material includes voids having openings on the outer surface of the negative electrode active material, through which lithium ions (or other carrier ions) can enter and exit the negative electrode active material, for example, lithium ions can enter the negative electrode active material through the void openings after leaving the positive electrode active material. In another embodiment, the void volume includes closed voids; that is, the negative electrode active material includes voids surrounded by the negative electrode active material. Generally, open voids can provide a larger interfacial surface area for carrier ions, while closed voids are less affected by the solid electrolyte interface and, at the same time, provide space for the negative electrode active material to expand upon carrier ion intrusion. Therefore, in certain embodiments, the negative electrode active material preferably includes a combination of open and closed voids.

[0066] In one embodiment, the negative electrode active material comprises porous aluminum, tin, or silicon, or an alloy thereof. The porous silicon layer can be formed, for example, by anodizing, etching (e.g., depositing a precious metal (e.g., gold, platinum, silver, or gold / palladium) onto the (100) surface of single-crystal silicon and etching the surface with a mixture of hydrofluoric acid and hydrogen peroxide), or by other methods known in the art (e.g., patterned chemical etching). Furthermore, the porous negative electrode active material generally has a porosity of at least about 0.1 and less than 0.8 and a thickness of about 1 to about 100 micrometers. For example, in one embodiment, the negative electrode active material comprises porous silicon and has a thickness of about 5 to about 100 micrometers and a porosity of about 0.15 to about 0.75. As a further example, in one embodiment, the negative electrode active material comprises porous silicon and has a thickness of about 10 to about 80 micrometers and a porosity of about 0.15 to about 0.7. As a further example, in one such embodiment, the negative electrode active material comprises porous silicon, having a thickness of about 20 to about 50 micrometers and a porosity of about 0.25 to about 0.6. As a further example, in one embodiment, the negative electrode active material comprises a porous silicon alloy (e.g., nickel silicide), having a thickness of about 5 to about 100 micrometers and a porosity of about 0.15 to about 0.75.

[0067] In another embodiment, the negative electrode active material comprises fibers of aluminum, tin, or silicon, or alloys thereof. Individual fibers may have a diameter (thickness dimension) of about 5 nm to about 10,000 nm and a length approximately corresponding to the thickness of the negative electrode active material. Silicon fibers (nanowires) can be formed by chemical vapor deposition or other techniques known in the art (e.g., VLS (Vapor Liquid Solid) growth and SLS (Solid Liquid Solid) growth). The negative electrode active material generally has a porosity of at least about 0.1 and less than 0.8, and a thickness of about 1 to about 200 micrometers. For example, in one embodiment, the negative electrode active material comprises silicon nanowires, has a thickness of about 5 to about 100 micrometers, and a porosity of about 0.15 to about 0.75. As a further example, in one embodiment, the negative electrode active material comprises silicon nanowires, has a thickness of about 10 to about 80 micrometers, and a porosity of about 0.15 to about 0.7. As a further example, in one such embodiment, the negative electrode active material comprises silicon nanowires having a thickness of about 20 to about 50 micrometers and a porosity of about 0.25 to about 0.6. As a further example, in one embodiment, the negative electrode active material comprises nanowires of a silicon alloy (e.g., nickel silicide) having a thickness of about 5 to about 100 micrometers and a porosity of about 0.15 to about 0.75.

[0068] In one embodiment, the components of the electrode assembly include an electrode active material layer, an electrode current collector, and an electrode backbone supporting the electrode active material layer and the electrode current collector. Similarly, in one embodiment, the components of the counter electrode assembly include a counter electrode active material layer, a counter electrode current collector, and a counter electrode backbone supporting the counter electrode active material layer and the counter electrode current collector.

[0069] In one embodiment, each member of the electrode assembly has a bottom, a top, and a longitudinal axis (A) extending from the bottom to the top, and in a direction substantially perpendicular to the direction in which the alternating arrangement of the electrode structure and counter electrode structure progresses. E ) has. In addition, each member of the electrode assembly has a vertical axis (A EThe length (L E ) measured along , the width (W E ) measured in the direction in which the alternating arrangement of the electrode structure and the counter electrode structure proceeds, and the height (H E ) measured in a direction perpendicular to each of the measurement directions of the length (L E ) and the width (W E ). Each member of the electrode assembly also has a perimeter (P E ) corresponding to the sum of the lengths of the sides of the projection of the electrodes in a plane perpendicular to its longitudinal axis.

[0070] The length (L E ) of the members of the electrode assembly varies depending on the energy storage device and its intended use. However, generally, the members of the electrode assembly typically have a length (L E ) in the range of about 5 mm to about 500 mm. For example, in one such embodiment, the members of the electrode assembly have a length (L E ) of about 10 mm to about 250 mm. As a further example, in one such embodiment, the members of the electrode assembly have a length (L E ) of about 25 mm to about 100 mm.

[0071] The width (W E ) of the members of the electrode assembly also varies depending on the energy storage device and its intended use. However, generally, each member of the electrode assembly typically has a width (W E ) within the range of about 0.01 mm to 2.5 mm. For example, in one embodiment, the width (W E ) of each member of the electrode assembly is in the range of about 0.025 mm to about 2 mm. As a further example, in one embodiment, the width (W E ) of each member of the electrode assembly is in the range of about 0.05 mm to about 1 mm.

[0072] The height (H E ) of the members of the electrode assembly also varies depending on the energy storage device and its intended use. However, generally, the members of the electrode assembly typically have a height (H E) has. For example, in one embodiment, the height (H) of each member of the electrode assembly is E The height (H) of each component of the electrode assembly is within the range of approximately 0.05 mm to approximately 5 mm. As a further example, in one embodiment, the height (H) of each component of the electrode assembly is within the range of approximately 0.05 mm to approximately 5 mm. E ) is within the range of approximately 0.1 mm to approximately 1 mm.

[0073] Around the component of the electrode assembly (P E Similarly, this also varies depending on the energy storage device and its intended use. However, generally, the components of the electrode assembly are typically within a range of about 0.025 mm to about 25 mm around the periphery (P E ) has. For example, in one embodiment, the periphery of each member of the electrode assembly (P E ) is within a range of approximately 0.1 mm to approximately 15 mm. As a further example, in one embodiment, the periphery of each component of the electrode assembly (P E ) is within a range of approximately 0.5 mm to 10 mm.

[0074] Generally, the components of an electrode assembly have a width (W E ) and its height (H E (L) is substantially larger than each of the above. E ) has. For example, in one embodiment, L E W E and H E The ratio for each of the electrodes is at least 5:1 for each component of the electrode assembly (i.e., L E W E The ratios to L are at least 5:1, and E H E The ratios to each are at least 5:1). As a further example, in one embodiment, L E W E and H E The ratio of each to is at least 10:1. As a further example, in one embodiment, L E W E and H E The ratio of each to is at least 15:1. As a further example, in one embodiment, L E W Eand H E The ratio of each to the others is at least 20:1 for each component of the electrode assembly.

[0075] Furthermore, the electrode assembly component is located around (P E (L) is effectively larger than E It is generally preferable to have ). For example, in one embodiment, L E P E The ratio to is at least 1.25:1 for each component of the electrode assembly. As a further example, in one embodiment, L E P E The ratio to is at least 2.5:1 for each component of the electrode assembly. As a further example, in one embodiment, L E P E The ratio to is at least 3.75:1 for each component of the electrode assembly.

[0076] In one embodiment, the height (H) of the electrode assembly member is E ) width (W E The ratios to ) are at least 0.4:1, respectively. For example, in one embodiment, H E W E The ratio to is at least 2:1 for each component of the electrode assembly. As a further example, in one embodiment, H E W E The ratios to each are at least 10:1. As a further example, in one embodiment, H E W E The ratios to each are at least 20:1. However, typically, H E W E The ratios to are generally less than 1000:1 for each. For example, in one embodiment, H E W E The ratios to each are less than 500:1. As a further example, in one embodiment, H E W E The ratios to each are less than 100:1. As a further example, in one embodiment, H E WE The ratios to each are less than 10:1. As a further example, in one embodiment, H E W E The ratio to each component of the electrode assembly is in the range of approximately 2:1 to approximately 100:1.

[0077] Each member of the counter electrode assembly has a bottom, a top, and a longitudinal axis (A) extending from the bottom to the top, and in a direction substantially perpendicular to the direction in which the alternating arrangement of the electrode structure and the counter electrode structure progresses. CE ) has. In addition, each member of the counter electrode assembly has a vertical axis (A CE Length (L) measured along ) CE ), width (W) measured in the direction in which the alternating arrangement of electrode structures and counter-electrode structures progresses CE ), and length (L CE ) and width (W CE Height (H) measured in a direction perpendicular to each of the measurement directions CE Each member of the counter electrode assembly also has a circumference (P) corresponding to the sum of the side lengths of the projection of the electrodes in a plane perpendicular to its longitudinal axis. CE ) has.

[0078] Length of the counter electrode assembly component (L CE ) varies depending on the energy storage device and its intended use. However, generally, the components of the counter electrode assembly typically have a length (L) ranging from about 5 mm to about 500 mm. CE ) has. For example, in one such embodiment, each member of the counter electrode assembly has a length (L) of about 10 mm to about 250 mm. CE ) has. As a further example, in one such embodiment, each member of the counter electrode assembly has a length (L) of about 25 mm to about 100 mm. CE ) has.

[0079] Width of the counter electrode assembly member (W CE ) also varies depending on the energy storage device and its intended use. However, generally, each component of the counter electrode assembly typically has a width (W) in the range of approximately 0.01 mm to 2.5 mm. CE) has. For example, in one embodiment, the width (W CE ) of each member of the counter electrode assembly is in the range of about 0.025 mm to about 2 mm. As a further example, in one embodiment, the width (W CE ) of each member of the counter electrode assembly is in the range of about 0.05 mm to about 1 mm.

[0080] The height (H CE ) of the members of the counter electrode assembly also varies depending on the energy storage device and its intended use. However, generally, the members of the counter electrode assembly typically have a height (H CE ) in the range of about 0.05 mm to about 10 mm. For example, in one embodiment, the height (H CE ) of each member of the counter electrode assembly is in the range of about 0.05 mm to about 5 mm. As a further example, in one embodiment, the height (H CE ) of each member of the counter electrode assembly is in the range of about 0.1 mm to about 1 mm.

[0081] The perimeter (P CE ) of the members of the counter electrode assembly also varies depending on the energy storage device and its intended use. However, generally, the members of the counter electrode assembly typically have a perimeter (P CE ) in the range of about 0.025 mm to about 25 mm. For example, in one embodiment, the perimeter (P CE ) of each member of the counter electrode assembly is in the range of about 0.1 mm to about 15 mm. As a further example, in one embodiment, the perimeter (P CE ) of each member of the counter electrode assembly is in the range of about 0.5 mm to about 10 mm.

[0082] Generally, each member of the counter electrode assembly has a length (L CE ) that is substantially greater than each of its width (W and its height (H CE ). For example, in one embodiment, the ratio of L CE to each of W CE and H CE is at least 5:1 for each member of the counter electrode assembly (i.e., L CE to W CE of each of which is at least 5:1 for each member of the counter electrode assembly (i.e., LCE The ratios to L are at least 5:1, and CE H CE The ratios to each are at least 5:1). As a further example, in one embodiment, L CE W CE and H CE The ratio of each to each is at least 10:1 for each member of the counter electrode assembly. As a further example, in one embodiment, L CE W CE and H CE The ratio of each to each component of the counter electrode assembly is at least 15:1. As a further example, in one embodiment, L CE W CE and H CE The ratio of each to the others is at least 20:1 for each component of the electrode assembly.

[0083] Furthermore, the counter electrode assembly component is located around its surroundings (P CE (L) is effectively larger than CE It is generally preferable to have ). For example, in one embodiment, L CE P CE The ratio to is at least 1.25:1 for each member of the counter electrode assembly. As a further example, in one embodiment, L CE P CE The ratio to is at least 2.5:1 for each member of the counter electrode assembly. As a further example, in one embodiment, L CE P CE The ratio to is at least 3.75:1 for each component of the counter electrode assembly.

[0084] In one embodiment, the height (H) of the counter electrode assembly member is CE ) width (W CE The ratios to ) are at least 0.4:1, respectively. For example, in one embodiment, H CE W CE The ratio to is at least 2:1 for each member of the counter electrode assembly. As a further example, in one embodiment, H CEW CE The ratio to is at least 10:1 for each member of the counter electrode assembly. As a further example, in one embodiment, H CE W CE The ratio to is at least 20:1 for each component of the counter electrode assembly. However, typically, H CE W CE The ratio to is generally less than 1000:1 for each component of the electrode assembly. For example, in one embodiment, H CE W CE The ratio to is less than 500:1 for each component of the counter electrode assembly. As a further example, in one embodiment, H CE W CE The ratios to each are less than 100:1. As a further example, in one embodiment, H CE W CE The ratios to each are less than 10:1. As a further example, in one embodiment, H CE W CE The ratio to each component of the counter electrode assembly is in the range of approximately 2:1 to approximately 100:1.

[0085] Referring again to Figure 12A, the electrical insulating separator layer 153 surrounds each member 151 of the electrode structure assembly and electrically insulates it from each member 152 of the counter electrode structure assembly. The electrical insulating separator layer 153 typically includes a microporous separator material that can be permeated with a non-aqueous electrolyte. For example, in one embodiment, the microporous separator material includes pores having a diameter in the range of at least 50 Å, more typically in the range of about 2500 Å, and a porosity in the range of about 25% to about 75%, more typically in the range of about 35% to 55%. The microporous separator material also allows for the permeation of a non-aqueous electrolyte, enabling the conduction of carrier ions between adjacent members of the electrode and counter electrode assemblies. In one embodiment, for example, neglecting the porosity of the microporous separator material, at least 70 volume percent of the electrical insulating separator material layer 153 between member 151 of the electrode structure assembly for ion exchange and the nearest member 152 of the counter electrode structure (i.e., "adjacent pair") during charging or discharge is the microporous separator material. In other words, the microporous separator material constitutes at least 70 volume percent of the electrical insulating material between member 151 of the electrode structure assembly and the nearest member 152 of the counter electrode structure assembly. As a further example, in one embodiment, neglecting the porosity of the microporous separator material, the microporous separator material constitutes at least 75 volume percent of the electrical insulating separator material layer between adjacent pairs of members 151 and 152 of the electrode structure assembly and the counter electrode structure assembly. As a further example, in one embodiment, neglecting the porosity of the microporous separator material, the microporous separator material constitutes at least 80 volume% of the electrical insulating separator material layer between adjacent pairs of members 151 and 152 of the electrode structure assembly and the counter electrode structure assembly. As a further example, in one embodiment, neglecting the porosity of the microporous separator material, the microporous separator material constitutes at least 85 volume% of the electrical insulating separator material layer between adjacent pairs of members 151 and 152 of the electrode structure assembly and the counter electrode structure assembly.As a further example, in one embodiment, neglecting the porosity of the microporous separator material, the microporous separator material constitutes at least 90 volume% of the electrical insulating separator material layer between adjacent pairs of members 151 and 152 of the electrode structure assembly and the counter electrode structure assembly. As a further example, in one embodiment, neglecting the porosity of the microporous separator material, the microporous separator material constitutes at least 95 volume% of the electrical insulating separator material layer between adjacent pairs of members 151 and 152 of the electrode structure assembly and the counter electrode structure assembly. As a further example, in one embodiment, neglecting the porosity of the microporous separator material, the microporous separator material constitutes at least 99 volume% of the electrical insulating separator material layer between adjacent pairs of members 151 and 152 of the electrode structure assembly and the counter electrode structure assembly.

[0086] In one embodiment, the microporous separator material comprises a granular material and a binder and has a porosity (void fraction) of at least about 20 volume%. The pores of the microporous separator material have a diameter of at least 50 Å and are typically in the range of about 250 to 2500 Å. The microporous separator material typically has a porosity of less than about 75%. In one embodiment, the microporous separator material has a porosity (void fraction) of at least about 25 volume%. In one embodiment, the microporous separator material has a porosity of about 35 to 55%.

[0087] Binders for microporous separator materials can be selected from a wide range of inorganic or polymeric materials. For example, in one embodiment, the binder is an organic material selected from the group consisting of silicates, phosphates, aluminates, aluminosilicates, and hydroxides (e.g., magnesium hydroxide, calcium hydroxide, etc.). For example, in one embodiment, the binder is a fluorinated polymer derived from monomers including vinylidene fluoride, hexafluoropropylene, tetrafluoropropene, etc. In another embodiment, the binder is a polyolefin (e.g., polyethylene, polypropylene, or polybutene) having any range of molecular weights and densities. In yet another embodiment, the binder is selected from the group consisting of ethylene-diene-propenter polymers, polystyrene, polymethyl methacrylate, polyethylene glycol, polyvinyl acetate, polyvinyl butyral, polyacetal, and polyethylene glycol diacrylate. In another embodiment, the binder is selected from the group consisting of methylcellulose, carboxymethylcellulose, styrene rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, polyacrylamide, polyvinyl ether, polyacrylic acid, polymethacrylic acid, and polyethylene oxide. In yet another embodiment, the binder is selected from the group consisting of acrylate, styrene, epoxy, and silicone. In yet another embodiment, the binder is a copolymer or blend of two or more of the above-mentioned polymers.

[0088] The granular material contained in the microporous separator material can also be selected from a wide range of materials. Generally, such materials have relatively low electronic and ionic conductivity at the operating temperature and do not corrode under the operating voltage of the battery electrodes or current collector that come into contact with the microporous separator material. For example, in one embodiment, the granular material is 1 × 10⁻¹⁶ -4 It has a conductivity for carrier ions (e.g., lithium) of less than S / cm. As a further example, in one embodiment, the granular material is 1 × 10 -5It has a conductivity for carrier ions of less than S / cm. As a further example, in one embodiment, the granular material is 1 × 10 -6 It has a conductivity to carrier ions of less than S / cm. Exemplary granular materials include granular polyethylene, polypropylene, TiO2-polymer composites, silica aerogels, fumed silica, silica gel, silica hydrogels, silica xerogels, silica sols, colloidal silica, alumina, titania, magnesia, kaolin, talc, diatomaceous earth, calcium silicate, aluminum silicate, calcium carbonate, magnesium carbonate, or combinations thereof. For example, in one embodiment, the granular material includes fine particle oxides or nitrides (e.g., TiO2, SiO2, Al2O3, GeO2, B2O3, Bi2O3, BaO, ZnO, ZrO2, BN, Si3N4, Ge3N4). (See, for example, P. Arora and J. Zhang, “Battery Separators,” Chemical Review 2004, 104, 4419-4462). In one embodiment, the granular material has an average particle size of about 20 nm to 2 micrometers, more typically 200 nm to 1.5 micrometers. In another embodiment, the granular material has an average particle size of about 500 nm to 1 micrometer.

[0089] In another embodiment, the granular material contained in the microporous separator material may be bonded by techniques such as sintering, bonding, and curing, while maintaining a desirable porosity for electrolyte intrusion to provide ion conductivity for the function of the battery.

[0090] Microporous separator materials can be deposited, for example, by electrophoretic deposition of particle separator materials in which particles are internally bonded by surface energy (e.g., electrostatic attraction or van der Waals forces), slurry deposition of particle separator materials (including spin or spray coating), screen printing, dipping coating, and electrostatic spray deposition. Binders may be included in the deposition process, for example, the particle material can be slurry deposited with a dissolved binder that precipitates by solvent evaporation, electrophoretically deposited in the presence of a dissolved binder material, or simultaneously electrophoretically deposited with a binder and insulating particles. Alternatively or additionally, the binder may be added after the particles have been deposited in or on the electrode structure. For example, the particle material can be dispersed in an organic binder solution, dipping or spray coating it, and then the binder material can be dried, dissolved, or crosslinked to provide adhesive strength.

[0091] In assembled energy storage devices, the microporous separator material is impregnated with a non-aqueous electrolyte suitable for use as a secondary battery electrolyte. Typically, the non-aqueous electrolyte contains lithium salts dissolved in an organic solvent. Exemplary lithium salts include inorganic lithium salts (e.g., LiClO4, LiBF4, LiPF6, LiAsF6, LiCl, and LiBr) and organolithium salts (e.g., LiB(C6H5)4, LiN(SO2CF3)2, LiN(SO2CF3)3, LiNSO2CF3, LiNSO2CF5, LiNSO2C4F9, LiNSO2C5F 11 LiNSO2C6F 13 , and LiNSO2C7F 15) are included. Exemplary organic solvents for dissolving lithium salts include cyclic esters, linear esters, cyclic ethers, and linear ethers. Specific examples of cyclic esters include propylene carbonate, butylene carbonate, γ-butyrolactone, vinylene carbonate, 2-methyl-γ-butyrolactone, acetyl-γ-butyrolactone, and γ-valerolactone. Specific examples of linear esters include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl butyl carbonate, methyl propyl carbonate, ethyl butyl carbonate, ethyl propyl carbonate, butyl propyl carbonate, alkylpropionates, dialkyl malonates, and alkyl acetates. Specific examples of cyclic ethers include tetrahydrofuran, alkyltetrahydrofuran, dialkyltetrahydrofuran, alkoxytetrahydrofuran, dialkoxytetrahydrofuran, 1,3-dioxolane, alkyl-1,3-dioxolane, and 1,4-dioxolane. Specific examples of linear ethers include 1,2-dimethoxyethane, 1,2-diethoxyethane, diethyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, and tetraethylene glycol dialkyl ether.

[0092] Referring again to Figures 12A, 12B, and 12C, the regions of the longitudinal end faces 122, 124 of the electrode assembly that coincide with the projection onto the longitudinal end faces 162, 164 of the electrode and counter-electrode assembly members (i.e., the “projected surface regions”) will each be subjected to a considerable compressive load imposed by the constraint 130 (see Figure 4). For example, in one embodiment, the regions of the longitudinal end faces of the electrode assembly that coincide with the projection onto the longitudinal end faces of the electrode and counter-electrode assembly members are each under a compressive load of at least 0.7 kPa (averaged over the respective surface areas of the first and second projection surface regions). As a further example, in one such embodiment, the regions of the longitudinal end faces of the electrode assembly that coincide with the projection onto the longitudinal end faces of the electrode and counter-electrode assembly members are each under a compressive load of at least 1.75 kPa (averaged over the respective surface areas of the first and second projection surface regions). As a further example, in one such embodiment, the longitudinal end face regions of the electrode assembly, coinciding with the projection onto the longitudinal end faces of the electrode and counter-electrode assembly members, are each under a compressive load of at least 2.8 kPa (averaged over the respective surface areas of the first and second projection surface regions). As a further example, in one such embodiment, the longitudinal end face regions of the electrode assembly, coinciding with the projection onto the longitudinal end faces of the electrode and counter-electrode assembly members, are each under a compressive load of at least 3.5 kPa (averaged over the respective surface areas of the first and second projection surface regions). As a further example, in one such embodiment, the longitudinal end face regions of the electrode assembly, coinciding with the projection onto the longitudinal end faces of the electrode and counter-electrode assembly members, are each under a compressive load of at least 5.25 kPa (averaged over the respective surface areas of the first and second projection surface regions). As a further example, in one such embodiment, the regions of the longitudinal end faces of the electrode assembly, which coincide with the projections onto the longitudinal end faces of the electrode and counter-electrode assembly members, are each under a compressive load of at least 7 kPa (averaged over the respective surface areas of the first and second projected surface regions).As a further example, in one such embodiment, the longitudinal end face regions of the electrode assembly, coinciding with the projections onto the longitudinal end faces of the electrode and counter-electrode assembly members, are each under a compressive load of at least 8.75 kPa (averaged over the surface area of ​​the first and second projection surface regions, respectively). However, generally, the longitudinal end face regions of the electrode assembly, coinciding with the projections onto the longitudinal end faces of the electrode and counter-electrode assembly members, are each subjected to a compressive load of only about 10 kPa (averaged over the surface area of ​​the first and second projection surface regions, respectively). In each of the exemplary embodiments described above, the longitudinal end face of the secondary battery of the present disclosure is under such a compressive load when the battery is charged to at least about 80% of its rated capacity.

[0093] In certain embodiments, substantially the entire longitudinal end face of the electrode assembly is under considerable compressive load (not necessarily just the first and second projected surface areas). For example, in some embodiments, each longitudinal end face of the electrode assembly is generally under a compressive load of at least 0.7 kPa (averaged over the total surface area of ​​each longitudinal end face). For example, in one embodiment, each longitudinal end face of the electrode assembly is under a compressive load of at least 1.75 kPa (averaged over the total surface area of ​​each longitudinal end face). As a further example, in one such embodiment, each longitudinal end face of the electrode assembly is under a compressive load of at least 2.8 kPa (averaged over the total surface area of ​​each longitudinal end face). As a further example, in one such embodiment, each longitudinal end face of the electrode assembly is under a compressive load of at least 3.5 kPa (averaged over the total surface area of ​​each longitudinal end face). As a further example, in one such embodiment, each longitudinal end face of the electrode assembly is under a compressive load of at least 5.25 kPa (averaged over the total surface area of ​​each longitudinal end face). As a further example, in one such embodiment, each of the longitudinal end faces of the electrode assembly is under a compressive load of at least 7 kPa (averaged over the entire surface area of ​​each longitudinal end face). As a further example, in one such embodiment, each of the longitudinal end faces of the electrode assembly is under a compressive load of at least 8.75 kPa (averaged over the entire surface area of ​​each longitudinal end face). However, generally, the longitudinal end faces of the electrode assembly are subjected to a compressive load of only about 10 kPa (averaged over the entire surface area of ​​each longitudinal end face). In each of the exemplary embodiments described above, the longitudinal end faces of the electrode assembly are under such compressive loads when the battery is charged to at least about 80% of its rated capacity.

[0094] In one embodiment, each of the first and second longitudinal end faces of the electrode assembly is under a compressive load of at least 100 psi. For example, in one embodiment, each of the first and second longitudinal end faces is under a compressive load of at least 200 psi. As a further example, in one embodiment, each of the first and second longitudinal end faces is under a compressive load of at least 300 psi. As a further example, in one embodiment, each of the first and second longitudinal end faces is under a compressive load of at least 400 psi. As yet another example, in one embodiment, each of the first and second longitudinal end faces is under a compressive load of at least 500 psi. As yet another example, in one embodiment, each of the first and second longitudinal end faces is under a compressive load of at least 600 psi. As yet another example, in one embodiment, each of the first and second longitudinal end faces is under a compressive load of at least 700 psi. As yet another example, in one embodiment, each of the first and second longitudinal end faces is under a compressive load of at least 800 psi. As a further example, in one embodiment, each of the first and second longitudinal end faces is under a compressive load of at least 900 psi. In yet another example, each of the first and second longitudinal end faces is under a compressive load of at least 1000 psi.

[0095] Referring again to Figures 4 and 5A, 5B, 5C and 5D, according to one aspect of the present disclosure, the tension members 133 and 135 are preferably relatively close to the outer surface in order to suppress buckling of the electrode assembly in response to a compressive force applied to the longitudinal end face. In the embodiments shown in Figures 5A to 5D, for example, the tension members 133 and 135 are in contact with the outer surfaces 123 and 125, respectively. However, in other embodiments, a gap may exist between the tension members and the outer surfaces. However, generally, the distance between the tension members and the outer surfaces of the electrode assembly is less than 50% of the minimum ferret diameter of the electrode assembly, and the ferret diameter is measured in the same direction as the distance between the tension members and the outer surfaces of the electrode assembly. As a further example, in one such embodiment, the distance between the tension members and the outer surfaces of the electrode assembly is less than 40% of the minimum ferret diameter of the electrode assembly, and the ferret diameter is measured in the same direction as the distance between the tension members and the outer surfaces of the electrode assembly. As a further example, in one such embodiment, the distance between the tension member and the outer surface of the electrode assembly is less than 30% of the minimum ferret diameter of the electrode assembly, and the ferret diameter is measured in the same direction as the distance between the tension member and the outer surface of the electrode assembly. As a further example, in one such embodiment, the distance between the tension member and the outer surface of the electrode assembly is less than 20% of the minimum ferret diameter of the electrode assembly, and the ferret diameter is measured in the same direction as the distance between the tension member and the outer surface of the electrode assembly. As a further example, in one such embodiment, the distance between the tension member and the outer surface of the electrode assembly is less than 10% of the minimum ferret diameter of the electrode assembly, and the ferret diameter is measured in the same direction as the distance between the tension member and the outer surface of the electrode assembly. As a further example, in one such embodiment, the distance between the tension member and the outer surface of the electrode assembly is less than 5% of the minimum ferret diameter of the electrode assembly, and the ferret diameter is measured in the same direction as the distance between the tension member and the outer surface of the electrode assembly.

[0096] Referring now to Figure 7, we can see an exploded view of a secondary battery of another embodiment of the present disclosure, shown as 100 in total. The secondary battery comprises a battery enclosure 102 and a set 110 of electrode assemblies 120 within the battery enclosure 102, each electrode assembly having a first longitudinal end face 122, an opposing second longitudinal end face 124 (separated from the first longitudinal end face 122 along a longitudinal axis (not shown) parallel to the "Y-axis" of the hypothetical Cartesian coordinate system in Figure 7), and outer surfaces including outer surfaces 123, 125, 126, 127 (see Figure 4). In contrast to the embodiment shown in Figure 4, in this embodiment, individual constraints 130 impose compressive forces on the first and second longitudinal surfaces of each electrode assembly in the set 110. As previously stated, the combined surface area of ​​the opposing first and second longitudinal end faces of each electrode assembly in the set 110 is less than 50% of the total surface area of ​​each electrode assembly in the set. The tension members of the restraint 130 pull the compression members toward each other, thereby applying compressive forces to the opposing first and second longitudinal end faces of each electrode assembly in the set 110, which then suppresses longitudinal expansion of each electrode assembly in the set 110 (coinciding with the electrode stack direction of each electrode assembly as described herein). Furthermore, after the battery is formed, the restraint applies pressure to each electrode assembly in the set 110 in the longitudinal direction (i.e., the electrode stack direction) that exceeds the pressure held to each electrode assembly in either of two mutually orthogonal directions and perpendicular to the longitudinal direction.

[0097] Referring here to Figures 8, 9, 10A, and 10B, in another embodiment, the constraint 130 is formed from a sheet 107 including a slot 109, a connecting region 111, and a folding region 113. To form the constraint, the sheet 107 is simply wrapped around the electrode structure 120 (shown in Figure 9 without the electrode structure 120) folded along the folding region 113, and the overlapping edges 115, 117 are fixed to each other by welding, bonding, or other means to form a constraint including compression members 132, 134 (compression member 134 including the overlapping edges 115, 117 when fixed to each other) and tension members 133, 135. In one such embodiment, the constraint 130 is stretched in the stacking direction D, applying tension to the connecting region 111, and as a result, applying compressive force to the longitudinal end faces 122, 124. In another embodiment, instead of stretching the connection regions 111 and applying tension to them, the connection regions are pre-tensioned before being mounted on the electrode assembly. In yet another alternative embodiment, the connection regions 111 are not under tension when initially placed on the electrode assembly, but rather, the formation of the battery causes the electrode assembly to expand, inducing tension (i.e., self-tensioning) within the connection tension member.

[0098] Referring here to Figures 11A and 11B, in another embodiment, the constraint 130 comprises one or more meandering tension members 121 in addition to the slots 109 and connection regions 111. The meandering tension members 121 provide secondary tensile forces in embodiments where the forces are greater during formation than during the cycle. In such embodiments, the linear members provide greater resistance and yield during formation, while the meandering tension members apply less tension during the cycle. As previously described, the constraint 130 can be formed by wrapping the sheet 107 around the electrode structure 120, folding it along the folding region 113, and securing the overlapping edges 115, 117 (shown in Figures 11A and 11B without the electrode structure 20). Once the sheet 107 is wrapped around the electrode structure, the constraint 130 is stretched in the stacking direction D, applying tension to the connection regions 111 and the meandering tension members 121, and then a compressive force in the stacking direction D acts on the electrode structure 120.

[0099] Generally, restraints with high strength and rigidity can suppress the rapid growth of electrode assemblies during battery formation, while restraints with much lower strength and rigidity allow for volume changes in electrode assemblies due to lithiation changes occurring under different charge conditions. Furthermore, restraints with low rigidity and high preload (or starting load) help control cell impedance by maintaining a minimum force between the cathode and anode. One approach to address these conflicting requirements, according to one embodiment of this disclosure, is to construct the restraint from two components. These components can be made from (i) similar materials with different geometric shapes, or (ii) materials with different moduli and the same geometric shape, or (iii) a combination of moduli and geometric properties to achieve the desired rigidity. In any case, the first component ("Element 1") utilizes a higher rigidity design (material or geometric shape driven) than the second component ("Element 2"), and is elastically and plastically deformable but does not shatter under the loads received during battery formation. Element 2 preferably deforms only elastically. In any case, the first element should prevent the second element from being displaced more than itself by containing the second element or by supporting it in any other way.

[0100] In one embodiment, the constraint includes an elastically deformable material positioned between the longitudinal surface of the electrode assembly and a compression member. In this embodiment, the elastically deformable material elastically deforms to adapt to the expansion of the electrodes and elastically returns to its original thickness and shape when the electrodes contract. As a result, minimal longitudinal force can be maintained on the electrode assembly as the electrodes and / or counter electrodes expand and contract during the secondary battery cycle.

[0101] Referring now to Figure 16, in one exemplary embodiment, the constraint 130 includes first and second elements 136 and 137. In this embodiment, the compression member 132 includes the compression regions 132A and 132B of the first and second elements 136 and 137, respectively, which overlap the longitudinal end face 122, and the compression member 134 includes the compression regions 134A and 134B of the first and second elements 136 and 137, respectively, which overlap the longitudinal end face 124. The tension member 133 includes the tension member regions 133A and 133B of the first and second elements 136 and 137, respectively, which overlap the outer surface 123, and the tension member 135 includes the tension member regions 135A and 135B of the first and second elements 136 and 137, respectively, which overlap the outer surface 125. In this exemplary embodiment, the first element 136 is used to limit the maximum growth of the electrode assembly during cell formation or cell cycling, while element 137 is used to maintain a preload in the direction of the electrode stack direction D during the discharge state. In this exemplary embodiment, element 136 has no preload before formation (no force is applied to the electrode assembly). Element 137 is preloaded to the electrode assembly to impose compressive forces on the first and second longitudinal end faces 122, 124. As the electrode assembly expands (for example, when the silicon-containing anode expands during carrier ion uptake in the charging process), the force on element 136 grows rapidly due to its high stiffness, while the force on the less stiff element 137 increases slowly because its displacement is limited by element 136. Beyond a certain force, element 136 yields or transitions from elastic to plastic (permanent), while element 137 remains within the elastic range. As the force continues to increase, the length of element 136 increases permanently. Subsequently, as the force decreases to a small value (for example, when the insertion of carrier ions is released during the discharge step and the silicon-containing anode contracts), element 136 is permanently deformed and can no longer contact the electrode assembly 120, and can return to near its initial pre-load level.

[0102] Referring here to Figure 13, in another embodiment, the secondary battery 100 includes a battery enclosure 102 and a set of electrode assemblies 120 within the battery enclosure 102. As previously stated, each electrode assembly has a first longitudinal end face and a second opposing longitudinal end face separated along the longitudinal axis, and a transverse surface surrounding the longitudinal axis (see Figures 4 and 12A). Furthermore, the set has associated constraints 130, including an upper constraint member 130T and a bottom constraint member 130B, to restrain the expansion of each electrode stack direction D of the electrode assemblies within the set. The upper constraint member 130T and the bottom constraint member 130B each include interlocking tabs 132D and 132C, respectively, which together constitute a compression member 132. The upper constraint member 130T and the bottom constraint member 130B each include interlocking tabs, which together constitute a compression member 134 (not shown). Similar to other embodiments, each of the compression members applies a compressive force to opposing first and second longitudinal end faces, and the tension member comprises the slot 109 and connection region 111 as described above.

[0103] Referring now to Figure 14, in another embodiment, the secondary battery 100 comprises a battery enclosure 102, a set of electrode assemblies (not shown) within the battery enclosure 102, and associated constraints 130 that prevent each electrode assembly within the set from expanding in the electrode stack direction. The constraints 130 comprise first and second shells 130R, 130L that enclose first and second longitudinal halves, respectively, of each set of electrode assemblies. As in other embodiments, a first compression member 132 comprising elements 132E and 132F overlaps a first longitudinal end face (not shown) of the electrode assembly within the set, a second compression member (not shown) overlaps a second longitudinal end face (not shown) of the electrode assembly within the set, and a tension member overlaps the outer surface of the electrode assembly. As in other embodiments, each compression member applies compressive force to the opposing first and second longitudinal end faces, and the tension member comprises slots 109 and connection regions 111 as described above.

[0104] Referring now to Figure 15, in another embodiment, the secondary battery 100 comprises a battery enclosure 102, a set of electrode assemblies 120 within the battery enclosure 102, and associated constraints 130 that prevent each electrode assembly within the set from expanding in the electrode stack direction. The constraints 130 comprises a series of bands 151 that surround each of the electrode assemblies and a cap 153 inserted between the bands 151 and the first and second longitudinal end faces (not shown) of each electrode assembly 120 within the set. In this embodiment, the portion of the bands over the longitudinal end faces and caps constitutes the compression member of the disclosure, and the portion of the bands covering the outer surfaces of the electrode assemblies constitutes the tension member. As in other embodiments, each of the compression members applies a compressive force to the opposing first and second longitudinal end faces, as described above.

[0105] In the following further embodiments numbered 1 to 122, aspects of the present disclosure include:

[0106] Embodiment 1 A secondary battery for cycling between a charged state and a discharged state, the secondary battery comprising a battery enclosure, an electrode assembly and a non-aqueous liquid electrolyte within the battery enclosure, and a restraint for maintaining pressure on the electrode assembly when the secondary battery cycles between a charged state and a discharged state, wherein the electrode assembly includes an assembly of electrode structures, an assembly of counter electrode structures, and an electrically insulating microporous separator material between the members of the electrode assembly and the counter electrode assembly,

[0107] The electrode assembly has opposing first and second longitudinal end faces separated along the longitudinal axis, and an outer surface surrounding the longitudinal axis and connecting the first and second longitudinal end faces, wherein the surface area of ​​the first and second longitudinal end faces is less than 33% of the surface area of ​​the electrode assembly.

[0108] The components of the electrode assembly and the counter electrode assembly are arranged alternately in a stacking direction parallel to the longitudinal axis within the electrode assembly.

[0109] The projection onto the first longitudinal plane of the electrode assembly and counter electrode assembly members encloses the first projection area, and the projection onto the second longitudinal plane of the electrode assembly and counter electrode assembly members encloses the second projection area.

[0110] The constraint comprises first and second compression members that overlap the first and second projection regions, respectively, the compression members overlapping the outer surfaces of the electrode assembly and connected by tension members that pull the compression members toward each other.

[0111] The constraints maintain pressure on the electrode assembly in the stacking direction that exceeds the pressure held on the electrode assembly in each of two mutually orthogonal directions and orthogonal to the electrode stacking direction.

[0112] Embodiment 2 The secondary battery according to Embodiment 1, wherein the constraint imposes an average compressive force of at least 0.7 kPa on each of the first and second projection regions, averaged over the surface areas of the first and second projection regions.

[0113] Embodiment 3 The secondary battery according to Embodiment 1, wherein the constraint imposes an average compressive force of at least 1.75 kPa on each of the first and second projection regions, averaged over the surface areas of the first and second projection regions.

[0114] Embodiment 4 The secondary battery according to Embodiment 1, wherein the constraint imposes an average compressive force of at least 2.8 kPa on each of the first and second projection regions, averaged over the surface areas of the first and second projection regions.

[0115] Embodiment 5 The secondary battery according to Embodiment 1, wherein the constraint imposes an average compressive force of at least 3.5 kPa on each of the first and second projection regions, averaged over the surface areas of the first and second projection regions.

[0116] Embodiment 6 The secondary battery according to Embodiment 1, wherein the constraint imposes an average compressive force of at least 5.25 kPa on each of the first and second projection regions, averaged over the surface areas of the first and second projection regions.

[0117] Embodiment 7 The secondary battery according to Embodiment 1, wherein the constraint imposes an average compressive force of at least 7 kPa on each of the first and second projection regions, averaged over the surface areas of the first and second projection regions.

[0118] Embodiment 8 The secondary battery according to Embodiment 1, wherein the constraint imposes an average compressive force of at least 8.75 kPa on each of the first and second projection regions, averaged over the surface areas of the first and second projection regions.

[0119] Embodiment 9 The secondary battery according to Embodiment 1, wherein the constraint imposes an average compressive force of at least 10 kPa on each of the first and second projection regions, averaged over the surface areas of the first and second projection regions.

[0120] Embodiment 10 The secondary battery according to any of the above embodiments, wherein the surface areas of the first and second longitudinal end faces are less than 25% of the surface area of ​​the electrode assembly.

[0121] Embodiment 11 The secondary battery according to any of the above embodiments, wherein the surface areas of the first and second longitudinal end faces are less than 20% of the surface area of ​​the electrode assembly.

[0122] Embodiment 12 The secondary battery according to any of the above embodiments, wherein the surface areas of the first and second longitudinal end faces are less than 15% of the surface area of ​​the electrode assembly.

[0123] Embodiment 13 The secondary battery according to any of the above embodiments, wherein the surface areas of the first and second longitudinal end faces are less than 10% of the surface area of ​​the electrode assembly.

[0124] Embodiment 14 The secondary battery according to any of the above embodiments, wherein the restraint and enclosure have a combined volume of less than 60% of the volume enclosed by the battery enclosure.

[0125] Embodiment 15 The secondary battery according to any of the above embodiments, wherein the restraint and enclosure have a combined volume of less than 45% of the volume enclosed by the battery enclosure.

[0126] Embodiment 16 The secondary battery according to any of the above embodiments, wherein the restraint and enclosure have a combined volume of less than 30% of the volume enclosed by the battery enclosure.

[0127] Embodiment 17 The secondary battery according to any of the above embodiments, wherein the restraint and enclosure have a combined volume of less than 20% of the volume enclosed by the battery enclosure.

[0128] Embodiment 18 Each component of the electrode assembly has a bottom, a top, and a length L. E , width W E Height H E , and a central vertical axis A extending from the bottom to the top of each member in a direction that is approximately transverse to the stacking direction E The electrode assembly has a length L of each member. E The central vertical axis A E The width W of each component of the electrode assembly is measured in the direction of the electrode assembly. E This is measured in the stacking direction, and the height H of each component of the electrode assembly. E The central vertical axis A of each component E And measured in a direction perpendicular to the stacking direction, the W of each member of the electrode assembly E and H E L for each of E The ratio of each component of the electrode assembly is at least 5:1, and the H E and WE The secondary battery according to any of the embodiments described above, wherein the ratios are 0.4:1 to 1000:1, respectively.

[0129] Embodiment 19 The secondary battery according to any of the above embodiments, wherein the microporous separator material comprises a granular material and a binder, has a porosity of at least 20 volume%, and is impregnated with a non-aqueous liquid electrolyte.

[0130] Embodiment 20 A secondary battery according to any of the above embodiments, wherein the tension member is sufficiently close to the outer surface to suppress buckling of the electrode assembly when the secondary battery is cycled between a charged state and a discharge state.

[0131] Embodiment 21 The secondary battery according to any of the above embodiments, wherein the distance between the tension member and the outer surface is less than 50% of the minimum ferret diameter of the electrode assembly, and the ferret diameter is measured in the same direction as the distance between the tension member and the outer surface of the electrode assembly.

[0132] Embodiment 22 The secondary battery according to any of the above embodiments, wherein the distance between the tension member and the outer surface is less than 40% of the minimum ferret diameter of the electrode assembly, and the ferret diameter is measured in the same direction as the distance between the tension member and the outer surface of the electrode assembly.

[0133] Embodiment 23 The secondary battery according to any of the above embodiments, wherein the distance between the tension member and the outer surface is less than 30% of the minimum ferret diameter of the electrode assembly, and the ferret diameter is measured in the same direction as the distance between the tension member and the outer surface of the electrode assembly.

[0134] Embodiment 24 The secondary battery according to any of the above embodiments, wherein the distance between the tension member and the outer surface is less than 20% of the minimum ferret diameter of the electrode assembly, and the ferret diameter is measured in the same direction as the distance between the tension member and the outer surface of the electrode assembly.

[0135] Embodiment 25 The secondary battery according to any of the above embodiments, wherein the distance between the tension member and the outer surface is less than 10% of the minimum ferret diameter of the electrode assembly, and the ferret diameter is measured in the same direction as the distance between the tension member and the outer surface of the electrode assembly.

[0136] Embodiment 26 The secondary battery according to any of the above embodiments, wherein the distance between the tension member and the outer surface is less than 5% of the minimum ferret diameter of the electrode assembly, and the ferret diameter is measured in the same direction as the distance between the tension member and the outer surface of the electrode assembly.

[0137] Embodiment 27 The secondary battery according to any of the above embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 100 psi.

[0138] Embodiment 28 A secondary battery according to any of the above embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 200 psi.

[0139] Embodiment 29 The secondary battery according to any of the above embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 300 psi.

[0140] Embodiment 30 The secondary battery according to any of the above embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 400 psi.

[0141] Embodiment 31 The secondary battery according to any of the above embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 500 psi.

[0142] Embodiment 32 The secondary battery according to any of the above embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 600 psi.

[0143] Embodiment 33 The secondary battery according to any of the above embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 700 psi.

[0144] Embodiment 34 The secondary battery according to any of the above embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 800 psi.

[0145] Embodiment 35 The secondary battery according to any of the above embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 900 psi.

[0146] Embodiment 36 The secondary battery according to any of the above embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 1000 psi.

[0147] Embodiment 37 The secondary battery according to any of the above embodiments, wherein the secondary battery has a rated capacity, and when the secondary battery is charged to at least 80% of its rated capacity, the first and second longitudinal end faces are under such compressive load.

[0148] Embodiment 38 A secondary battery according to any of the above embodiments, wherein the electrode structure includes an anode-active electroactive material, and the counter electrode structure includes a cathode-active electroactive material.

[0149] Embodiment 39 A secondary battery according to any of the above embodiments, wherein the electrode structure includes an anode-active electroactive material containing silicon, and the counter electrode structure includes a cathode-active electroactive material.

[0150] Embodiment 40 The secondary battery is the secondary battery according to any of the above embodiments, comprising a set of electrode assemblies including at least two electrode assemblies.

[0151] Embodiment 41 The secondary battery comprises a set of at least two electrode assemblies, and when the secondary battery is cycled between a charged state and a discharge state, the constraint maintains pressure on the electrode assemblies within the set, as described in any of Embodiments 1 to 39.

[0152] Embodiment 42 A secondary battery according to any of Embodiments 1 to 39, comprising a set of at least two electrode assemblies, wherein the secondary battery includes a corresponding number of constraints, each of which maintains pressure on one of the electrode assemblies in the set when the secondary battery is cycled between a charged state and a discharge state.

[0153] Embodiment 43 The electrode assembly comprises at least five electrode structures and at least five counter electrode structures, as described in any of the above embodiments of the secondary battery.

[0154] Embodiment 44 The electrode assembly comprises at least 10 electrode structures and at least 10 counter electrode structures, as described in any of the above embodiments of the secondary battery.

[0155] Embodiment 45 The electrode assembly comprises at least 50 electrode structures and at least 50 counter electrode structures, as described in any of the above embodiments of the secondary battery.

[0156] Embodiment 46 The electrode assembly comprises at least 100 electrode structures and at least 100 counter electrode structures, as described in any of the above embodiments of the secondary battery.

[0157] Embodiment 47 The electrode assembly comprises at least 500 electrode structures and at least 500 counter electrode structures, as described in any of the above embodiments of the secondary battery.

[0158] Embodiment 48 The restraint is a secondary battery according to any of the above embodiments, comprising a material having an ultimate tensile strength of at least 10,000 psi (>70 MPa).

[0159] Embodiment 49 The restraint is a secondary battery according to any of the above embodiments, comprising a material compatible with the electrolyte of the battery.

[0160] Embodiment 50 The restraint is a secondary battery according to any of the above embodiments, comprising a material that does not corrode significantly at the floating potential or anode potential of the battery.

[0161] Embodiment 51 The restraint is a secondary battery according to any of the above embodiments, comprising a material that does not react significantly or lose mechanical strength at 45°C.

[0162] Embodiment 52 The restraint is a secondary battery according to any of the above embodiments, including metal, metal alloy, ceramics, glass, plastic, or a combination thereof.

[0163] Embodiment 53 The restraint is a secondary battery according to any of the above embodiments, comprising a sheet of material having a thickness in the range of about 10 to about 100 micrometers.

[0164] Embodiment 54 The restraint is a secondary battery according to any of the above embodiments, comprising a sheet of material having a thickness in the range of about 30 to about 75 micrometers.

[0165] Embodiment 55 The restraint is a secondary battery according to any of the above embodiments, comprising carbon fibers with a packing density of >50%.

[0166] Embodiment 56 The secondary battery according to any of the above embodiments, wherein the compression member applies a pressure to the first and second longitudinal end faces in two mutually orthogonal directions and perpendicular to the stacking direction, at least three times the pressure held by the electrode assembly.

[0167] Embodiment 57 The secondary battery according to any of the above embodiments, wherein the compression member applies a pressure to the first and second longitudinal end faces in two mutually orthogonal directions and perpendicular to the stacking direction, at least three times the pressure held by the electrode assembly.

[0168] Embodiment 58 The secondary battery according to any of the above embodiments, wherein the compression member applies a pressure to the first and second longitudinal end faces in two mutually orthogonal directions and perpendicular to the stacking direction, at least four times the pressure held by the electrode assembly.

[0169] Embodiment 59 The secondary battery according to any of the above embodiments, wherein the compression member applies a pressure to the first and second longitudinal end faces in two mutually orthogonal directions and perpendicular to the stacking direction, at least five times the pressure held by the electrode assembly.

[0170] Embodiment 60 An energy storage device for cycling between a charge state and a discharge state, the energy storage device comprising an enclosure, an electrode assembly within the enclosure and a non-aqueous liquid electrolyte, and a restraint for maintaining pressure on the electrode assembly when the energy storage device cycles between a charge state and a discharge state, wherein the electrode assembly includes an assembly of electrode structures, an assembly of counter electrode structures, and an electrically insulating microporous separator material between the members of the electrode assembly and the counter electrode assembly,

[0171] The electrode assembly has opposing first and second longitudinal end faces separated along the longitudinal axis, and an outer surface surrounding the longitudinal axis and connecting the first and second longitudinal end faces, wherein the combined surface area of ​​the first and second longitudinal end faces is less than 33% of the combined surface area of ​​the outer surface and the first and second longitudinal end faces.

[0172] The components of the electrode assembly and the counter electrode assembly are arranged alternately in a stacking direction parallel to the longitudinal axis within the electrode assembly.

[0173] The restraint comprises first and second compression members connected by at least one tension member that pulls the compression members toward each other.

[0174] The constraints maintain pressure on the electrode assembly in the stacking direction that exceeds the pressure held on the electrode assembly in each of two mutually orthogonal directions and orthogonal to the electrode stacking direction.

[0175] Embodiment 61 The energy storage device is a secondary battery, as described in Embodiment 60.

[0176] Embodiment 62 The energy storage device according to embodiment 60, wherein the constraint includes first and second compression members that overlap the longitudinal end faces of the electrode assembly.

[0177] Embodiment 63 The restraint includes at least one compression member located inside the longitudinal end face, as described in any of the above embodiments of the energy storage device.

[0178] Embodiment 64 An energy storage device according to any of the above embodiments, wherein projection onto a first longitudinal surface of the electrode assembly and counter electrode assembly members encloses a first projection region, and projection onto a second longitudinal surface of the electrode assembly and counter electrode assembly members encloses a second projection region, and the first and second projection regions each include at least 50% of the surface area of ​​the first and second longitudinal end faces, respectively.

[0179] Embodiment 65 An energy storage device according to any of the above embodiments, wherein projection onto a first longitudinal plane of the members of the electrode assembly and counter electrode assembly surrounds a first projection region, projection onto a second longitudinal plane of the members of the electrode assembly and counter electrode assembly surrounds a second projection region, and constraints impose an average compressive force of at least 0.7 kPa on each of the first and second projection regions.

[0180] Embodiment 66 The energy storage device according to any of the above embodiments, wherein the constraint imposes an average compressive force of at least 1.75 kPa on each of the first and second projection regions, averaged over the surface areas of the first and second projection regions.

[0181] Embodiment 67 The energy storage device according to any of the above embodiments, wherein the constraint imposes an average compressive force of at least 2.8 kPa on each of the first and second projection regions, averaged over the surface areas of the first and second projection regions.

[0182] Embodiment 68 The energy storage device according to any of the above embodiments, wherein the constraint imposes an average compressive force of at least 3.5 kPa on each of the first and second projection regions, averaged over the surface areas of the first and second projection regions.

[0183] Embodiment 69 The restraint is an energy storage device according to any of the preceding embodiments that imposes an average compressive force of at least 5.25 kPa averaged over the surface area of the first and second projection regions on each of the first and second projection regions.

[0184] Embodiment 70 The restraint is an energy storage device according to any of the preceding embodiments that imposes an average compressive force of at least 7 kPa averaged over the surface area of the first and second projection regions on each of the first and second projection regions.

[0185] Embodiment 71 The restraint is an energy storage device according to any of the preceding embodiments that imposes an average compressive force of at least 8.75 kPa on each of the first and second projection regions averaged over the surface area of the first and second projection regions.

[0186] Embodiment 72 The restraint is an energy storage device according to any of the preceding embodiments that imposes an average compressive force of at least 10 kPa averaged over the surface area of the first and second projection regions on each of the first and second projection regions.

[0187] Embodiment 73 The combined surface area of the first and second longitudinal end faces is less than 25% of the surface area of the electrode assembly, and the energy storage device is according to any of the preceding embodiments.

[0188] Embodiment 74 The combined surface area of the first and second longitudinal end faces is less than 20% of the surface area of the electrode assembly, and the energy storage device is according to any of the preceding embodiments.

[0189] Embodiment 75 The combined surface area of the first and second longitudinal end faces is less than 15% of the surface area of the electrode assembly, the energy storage device according to any of the foregoing embodiments.

[0190] Embodiment 76 The combined surface area of the first and second longitudinal end faces is less than 10% of the surface area of the electrode assembly, the energy storage device according to any of the foregoing embodiments.

[0191] Embodiment 77 The restraint and enclosure have a combined volume less than 60% of the volume enclosed by the enclosure, the energy storage device according to any of the foregoing embodiments.

[0192] Embodiment 78 The restraint and enclosure have a combined volume less than 45% of the volume enclosed by the enclosure, the energy storage device according to any of the foregoing embodiments.

[0193] Embodiment 79 The restraint and enclosure have a combined volume less than 30% of the volume enclosed by the enclosure, the energy storage device according to any of the foregoing embodiments.

[0194] Embodiment 80 The restraint and enclosure have a combined volume less than 20% of the volume enclosed by the enclosure, the energy storage device according to any of the foregoing embodiments.

[0195] Embodiment 81 Each member of the electrode assembly has a bottom, a top, a length L E , a width W E , a height H E , and a central longitudinal axis A extending in a direction substantially transverse to the stacking direction from the bottom to the top of each member E and the length L of each member of the electrode assembly E is its central longitudinal axis A EThe width W of each component of the electrode assembly is measured in the direction of the electrode assembly. E This is measured in the stacking direction, and the height H of each component of the electrode assembly. E The central vertical axis A of each component E And measured in a direction perpendicular to the stacking direction, the W of each member of the electrode assembly E and H E L for each of E The ratios of each component of the electrode assembly are at least 5:1, and the W of each component of the electrode assembly E H E An energy storage device according to any of the embodiments described above, wherein the ratio to is 0.4:1 to 1000:1, respectively.

[0196] Embodiment 82 The energy storage device according to any of the above embodiments, wherein the microporous separator material comprises a granular material and a binder, has a porosity of at least 20 volume%, and is impregnated with a non-aqueous liquid electrolyte.

[0197] Embodiment 83 An energy storage device according to any of the above embodiments, wherein the tension member is sufficiently close to the outer surface to suppress buckling of the electrode assembly when the energy storage device is cycled between a charged state and a discharge state.

[0198] Embodiment 84 An energy storage device according to any of the above embodiments, wherein the distance between the tension member and the outer surface is less than 50% of the minimum ferret diameter of the electrode assembly.

[0199] Embodiment 85 An energy storage device according to any of the above embodiments, wherein the distance between the tension member and the outer surface is less than 40% of the minimum ferret diameter of the electrode assembly.

[0200] Embodiment 86 An energy storage device according to any of the above embodiments, wherein the distance between the tension member and the outer surface is less than 30% of the minimum ferret diameter of the electrode assembly.

[0201] Embodiment 87 The energy storage device according to any one of the foregoing embodiments, wherein the distance between the tension member and the outer surface is less than 20% of the minimum ferret diameter of the electrode assembly.

[0202] Embodiment 88 The energy storage device according to any one of the foregoing embodiments, wherein the distance between the tension member and the outer surface is less than 10% of the minimum ferret diameter of the electrode assembly.

[0203] Embodiment 89 The energy storage device according to any one of the foregoing embodiments, wherein the distance between the tension member and the outer surface is less than 5% of the minimum ferret diameter of the electrode assembly.

[0204] Embodiment 90 The energy storage device according to any one of the foregoing embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 100 psi.

[0205] Embodiment 91 The energy storage device according to any one of the foregoing embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 200 psi.

[0206] Embodiment 92 The energy storage device according to any one of the foregoing embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 300 psi.

[0207] Embodiment 93 The energy storage device according to any one of the foregoing embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 400 psi.

[0208] Embodiment 94 The energy storage device according to any one of the foregoing embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 500 psi.

[0209] Embodiment 95 The energy storage device according to any of the above embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 600 psi.

[0210] Embodiment 96 The energy storage device according to any of the above embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 700 psi.

[0211] Embodiment 97 The energy storage device according to any of the above embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 800 psi.

[0212] Embodiment 98 The energy storage device according to any of the above embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 900 psi.

[0213] Embodiment 99 The energy storage device according to any of the above embodiments, wherein each of the first and second longitudinal end faces is under a compressive load of at least 1000 psi.

[0214] Embodiment 100 The energy storage device has a rated capacity, and when the energy storage device is charged to at least 80% of its rated capacity, the first and second longitudinal end faces are under such compressive load, as described in any of the above embodiments of the energy storage device.

[0215] Embodiment 101 An energy storage device according to any of the above embodiments, wherein the electrode structure comprises an anode-active electroactive material, and the counter electrode structure comprises a cathode-active electroactive material.

[0216] Embodiment 102 An energy storage device according to any of the above embodiments, wherein the electrode structure comprises an anodically active electroactive material containing silicon, and the counter electrode structure comprises a cathodeically active electroactive material.

[0217] Embodiment 103 The energy storage device is an energy storage device according to any of the embodiments described above, comprising a set of electrode assemblies including at least two electrode assemblies.

[0218] Embodiment 104 The energy storage device comprises a set of at least two electrode assemblies, and when the energy storage device is cycled between a charged state and a discharge state, a constraint maintains pressure on the electrode assemblies in the set, as described in any of embodiments 60 to 103.

[0219] Embodiment 105 An energy storage device according to any of embodiments 60 to 103, comprising a set of at least two electrode assemblies, the energy storage device including a corresponding number of constraints, each of which maintains pressure on one of the electrode assemblies in the set when the energy storage device is cycled between a charged state and a discharge state.

[0220] Embodiment 106 The electrode assembly comprises at least five electrode structures and at least five counter electrode structures, wherein the energy storage device is according to any of the embodiments described above.

[0221] Embodiment 107 The electrode assembly comprises at least 10 electrode structures and at least 10 counter electrode structures, wherein the energy storage device is according to any of the embodiments described above.

[0222] Embodiment 108 The electrode assembly comprises at least 50 electrode structures and at least 50 counter electrode structures, wherein the energy storage device is according to any of the embodiments described above.

[0223] Embodiment 109 The electrode assembly comprises at least 100 electrode structures and at least 100 counter electrode structures, wherein the energy storage device is according to any of the embodiments described above.

[0224] Embodiment 110 The electrode assembly comprises at least 500 electrode structures and at least 500 counter electrode structures, wherein the energy storage device is according to any of the embodiments described above.

[0225] Embodiment 111 The restraint is an energy storage device according to any of the above embodiments, comprising a material having an ultimate tensile strength of at least 10,000 psi (>70 MPa).

[0226] Embodiment 112 The restraint is an energy storage device according to any of the above embodiments, comprising a material compatible with the electrolyte.

[0227] Embodiment 113 The restraint is an energy storage device according to any of the above embodiments, comprising a material that does not significantly corrode at the floating potential or anode potential of the energy storage device.

[0228] Embodiment 114 The restraint is an energy storage device according to any of the above embodiments, comprising a material that does not react significantly or lose mechanical strength at 45°C.

[0229] Embodiment 115 The energy storage device according to any of the above embodiments includes a restraint made of metal, a metal alloy, ceramics, glass, plastic, or a combination thereof.

[0230] Embodiment 116 The energy storage device according to any of the above embodiments includes a sheet of material having a thickness in the range of about 10 to about 100 micrometers.

[0231] Embodiment 117 The energy storage device according to any of the above embodiments includes a sheet of material having a thickness in the range of about 30 to about 75 micrometers.

[0232] Embodiment 118 The restraint is an energy storage device according to any of the above embodiments, comprising carbon fibers with a packing density of >50%.

[0233] Embodiment 119 An energy storage device according to any of the above embodiments, wherein the compression member applies a pressure to the first and second longitudinal end faces in two mutually orthogonal directions and perpendicular to the stacking direction, at least three times the pressure held by the electrode assembly.

[0234] Embodiment 120 An energy storage device according to any of the above embodiments, wherein the compression member applies a pressure to the first and second longitudinal end faces in two mutually orthogonal directions and perpendicular to the stacking direction, at least three times the pressure held by the electrode assembly.

[0235] Embodiment 121 An energy storage device according to any of the above embodiments, wherein the compression member applies a pressure to the first and second longitudinal end faces in two mutually orthogonal directions and perpendicular to the stacking direction, at least four times the pressure held by the electrode assembly.

[0236] Embodiment 122 An energy storage device according to any of the above embodiments, wherein the compression member applies a pressure to the first and second longitudinal end faces in two mutually orthogonal directions and perpendicular to the stacking direction, at least five times the pressure held by the electrode assembly.

[0237] Various modifications can be made to the above articles, compositions, and methods without departing from the scope of this disclosure; therefore, all matters shown in the above description and accompanying drawings are intended to be illustrative and not limiting.

[0238] All directional descriptors (e.g., top, bottom, left, right, etc.) are used solely to facilitate references to drawings and are not intended as limitations.

Claims

1. An energy storage device for cycling between a charge state and a discharge state, the energy storage device comprising an enclosure, an electrode assembly and a non-aqueous liquid electrolyte within the enclosure, and a restraint for maintaining pressure on the electrode assembly when the energy storage device cycles between a charge state and a discharge state, wherein the electrode assembly includes an assembly of electrode structures, an assembly of counter electrode structures, and an electrically insulating microporous separator material between the members of the electrode assembly and the counter electrode assembly, The electrode assembly has opposing first and second longitudinal end faces separated along the longitudinal axis, and an outer surface surrounding the longitudinal axis and connecting the first and second longitudinal end faces, wherein the combined surface area of ​​the first and second longitudinal end faces is less than 33% of the combined surface area of ​​the outer surface and the first and second longitudinal end faces. The members of the electrode assembly and the members of the counter electrode assembly are arranged alternately in a stacking direction parallel to the vertical axis within the electrode assembly. The restraint comprises first and second compression members connected by at least one tension member that pulls the compression members toward each other. The constraint is an energy storage device that maintains pressure on the electrode assembly in the stacking direction that exceeds the pressure held on the electrode assembly in each of two mutually orthogonal directions and orthogonal to the electrode stacking direction.

2. The energy storage device according to claim 1, wherein the energy storage device is a secondary battery.

3. The energy storage device according to claim 1, wherein the constraint includes first and second compression members that overlap the longitudinal end face of the electrode assembly.

4. The energy storage device according to any one of claims 1 to 3, wherein the constraint includes at least one compression member located inside the longitudinal end face.

5. The energy storage device according to any one of claims 1 to 4, wherein the projection of the members of the electrode assembly and the counter electrode assembly onto the first longitudinal surface encloses a first projection region, and the projection of the members of the electrode assembly and the counter electrode assembly onto the second longitudinal surface encloses a second projection region, and the first and second projection regions each include at least 50% of the surface area of ​​the first and second longitudinal end faces, respectively.

6. The energy storage device according to any one of claims 1 to 5, wherein the projection of the members of the electrode assembly and the counter electrode assembly onto the first longitudinal plane surrounds a first projection region, the projection of the members of the electrode assembly and the counter electrode assembly onto the second longitudinal plane surrounds a second projection region, and the constraint imposes on each of the first and second projection regions an average compressive force of at least 0.7 kPa averaged over the surface areas of the first and second projection regions.

7. The energy storage device according to any one of claims 1 to 6, wherein the constraint imposes on each of the first and second projection regions an average compressive force of at least 1.75 kPa averaged over the surface area of ​​the first and second projection regions.

8. The energy storage device according to any one of claims 1 to 7, wherein the constraint imposes on each of the first and second projection regions an average compressive force of at least 2.8 kPa averaged over the surface area of ​​the first and second projection regions.

9. The energy storage device according to any one of claims 1 to 8, wherein the constraint imposes on each of the first and second projection regions an average compressive force of at least 3.5 kPa averaged over the surface area of ​​the first and second projection regions.

10. The energy storage device according to any one of claims 1 to 9, wherein the constraint imposes on each of the first and second projection regions an average compressive force of at least 5.25 kPa averaged over the surface area of ​​the first and second projection regions.

11. The energy storage device according to any one of claims 1 to 10, wherein the constraint imposes on each of the first and second projection regions an average compressive force of at least 7 kPa averaged over the surface area of ​​the first and second projection regions.

12. The energy storage device according to any one of claims 1 to 11, wherein the constraint imposes on each of the first and second projection regions an average compressive force of at least 8.75 kPa averaged over the surface area of ​​the first and second projection regions.

13. The energy storage device according to any one of claims 1 to 12, wherein the constraint imposes on each of the first and second projection regions an average compressive force of at least 10 kPa averaged over the surface area of ​​the first and second projection regions.

14. The energy storage device according to any one of claims 1 to 13, wherein the combined surface area of ​​the first and second longitudinal end faces is less than 25% of the surface area of ​​the electrode assembly.

15. The energy storage device according to any one of claims 1 to 14, wherein the combined surface area of ​​the first and second longitudinal end faces is less than 20% of the surface area of ​​the electrode assembly.

16. The energy storage device according to any one of claims 1 to 15, wherein the combined surface area of ​​the first and second longitudinal end faces is less than 15% of the surface area of ​​the electrode assembly.

17. The energy storage device according to any one of claims 1 to 16, wherein the combined surface area of ​​the first and second longitudinal end faces is less than 10% of the surface area of ​​the electrode assembly.

18. The energy storage device according to any one of claims 1 to 17, wherein the restraint and enclosure have a combined volume of less than 60% of the volume enclosed by the enclosure.

19. The energy storage device according to any one of claims 1 to 18, wherein the restraint and enclosure have a combined volume of less than 45% of the volume enclosed by the enclosure.

20. The energy storage device according to any one of claims 1 to 19, wherein the restraint and enclosure have a combined volume of less than 30% of the volume enclosed by the enclosure.

21. The energy storage device according to any one of claims 1 to 20, wherein the restraint and enclosure have a combined volume of less than 20% of the volume enclosed by the enclosure.

22. Each member of the electrode assembly has a bottom, a top, a length L Ｅ , Ｅ , Ｅ , a width W Ｅ , a height H Ｅ , and a central longitudinal axis A that extends in a direction substantially transverse to the stacking direction from the bottom to the top of each member Ｅ . The length L of each member of the electrode assembly Ｅ is measured in the direction of its central longitudinal axis A Ｅ . The width W of each member of the electrode assembly Ｅ is measured in the stacking direction. The height H of each member of the electrode assembly Ｅ is measured in a direction orthogonal to the central longitudinal axis A of each member Ｅ and the stacking direction. The ratio of L to each of W Ｅ and H Ｅ of each member of the electrode assembly is at least 5:1 respectively. The ratio of W to H Ｅ of each member of the electrode assembly is 0.4:1 to 1000:1 respectively. The energy storage device according to any one of claims 1 to 21​​​​

23. The energy storage device according to any one of claims 1 to 22, wherein the microporous separator material comprises a granular material and a binder, has a porosity of at least 20 volume%, and is impregnated with the non-aqueous liquid electrolyte.

24. The energy storage device according to any one of claims 1 to 23, wherein the tension member is sufficiently close to the outer surface to suppress buckling of the electrode assembly when the energy storage device is cycled between a charged state and a discharge state.

25. The energy storage device according to any one of claims 1 to 24, wherein the distance between the tension member and the outer surface is less than 50% of the minimum ferret diameter of the electrode assembly, and the ferret diameter is measured in the same direction as the distance between the tension member and the outer surface of the electrode assembly.

26. The energy storage device according to any one of claims 1 to 25, wherein the distance between the tension member and the outer surface is less than 40% of the minimum ferret diameter of the electrode assembly, and the ferret diameter is measured in the same direction as the distance between the tension member and the outer surface of the electrode assembly.

27. The energy storage device according to any one of claims 1 to 26, wherein the distance between the tension member and the outer surface is less than 30% of the minimum ferret diameter of the electrode assembly, and the ferret diameter is measured in the same direction as the distance between the tension member and the outer surface of the electrode assembly.

28. The energy storage device according to any one of claims 1 to 27, wherein the distance between the tension member and the outer surface is less than 20% of the minimum ferret diameter of the electrode assembly, and the ferret diameter is measured in the same direction as the distance between the tension member and the outer surface of the electrode assembly.

29. The energy storage device according to any one of claims 1 to 28, wherein the distance between the tension member and the outer surface is less than 10% of the minimum ferret diameter of the electrode assembly, and the ferret diameter is measured in the same direction as the distance between the tension member and the outer surface of the electrode assembly.

30. The energy storage device according to any one of claims 1 to 29, wherein the distance between the tension member and the outer surface is less than 5% of the minimum ferret diameter of the electrode assembly, and the ferret diameter is measured in the same direction as the distance between the tension member and the outer surface of the electrode assembly.

31. The energy storage device according to any one of claims 1 to 30, wherein each of the first and second longitudinal end faces is under a compressive load of at least 100 psi.

32. The energy storage device according to any one of claims 1 to 31, wherein each of the first and second longitudinal end faces is under a compressive load of at least 200 psi.

33. The energy storage device according to any one of claims 1 to 32, wherein each of the first and second longitudinal end faces is under a compressive load of at least 300 psi.

34. The energy storage device according to any one of claims 1 to 33, wherein each of the first and second longitudinal end faces is under a compressive load of at least 400 psi.

35. The energy storage device according to any one of claims 1 to 34, wherein each of the first and second longitudinal end faces is under a compressive load of at least 500 psi.

36. The energy storage device according to any one of claims 1 to 35, wherein each of the first and second longitudinal end faces is under a compressive load of at least 600 psi.

37. The energy storage device according to any one of claims 1 to 36, wherein each of the first and second longitudinal end faces is under a compressive load of at least 700 psi.

38. The energy storage device according to any one of claims 1 to 37, wherein each of the first and second longitudinal end faces is under a compressive load of at least 800 psi.

39. The energy storage device according to any one of claims 1 to 38, wherein each of the first and second longitudinal end faces is under a compressive load of at least 900 psi.

40. The energy storage device according to any one of claims 1 to 39, wherein each of the first and second longitudinal end faces is under a compressive load of at least 1000 psi.

41. The energy storage device according to any one of claims 1 to 40, wherein the energy storage device has a rated capacity, and when the energy storage device is charged to at least 80% of its rated capacity, the first and second longitudinal end faces are under such compressive load.

42. The energy storage device according to any one of claims 1 to 41, wherein the electrode structure comprises an anode-active electroactive material, and the counter electrode structure comprises a cathode-active electroactive material.

43. The energy storage device according to any one of claims 1 to 42, wherein the electrode structure comprises an anode-active electroactive material containing silicon, and the counter electrode structure comprises a cathode-active electroactive material.

44. The energy storage device according to any one of claims 1 to 43, wherein the energy storage device includes a set of electrode assemblies comprising at least two electrode assemblies.

45. The energy storage device according to any one of claims 1 to 44, wherein the energy storage device comprises a set of at least two electrode assemblies, and when the energy storage device is cycled between a charged state and a discharge state, the constraint maintains pressure on the electrode assemblies in the set.

46. The energy storage device according to any one of claims 1 to 44, wherein the energy storage device comprises a set of at least two electrode assemblies, the energy storage device includes a corresponding number of constraints, each of which maintains pressure on one of the electrode assemblies in the set when the energy storage device is cycled between a charged state and a discharge state.

47. The energy storage device according to any one of claims 1 to 46, wherein the electrode assembly comprises at least five electrode structures and at least five counter electrode structures.

48. The energy storage device according to any one of claims 1 to 47, wherein the electrode assembly comprises at least 10 electrode structures and at least 10 counter electrode structures.

49. The energy storage device according to any one of claims 1 to 48, wherein the electrode assembly comprises at least 50 electrode structures and at least 50 counter electrode structures.

50. The energy storage device according to any one of claims 1 to 49, wherein the electrode assembly comprises at least 100 electrode structures and at least 100 counter electrode structures.

51. The energy storage device according to any one of claims 1 to 50, wherein the electrode assembly comprises at least 500 electrode structures and at least 500 counter electrode structures.

52. The energy storage device according to any one of claims 1 to 51, wherein the constraint comprises a material having an ultimate tensile strength of at least 10,000 psi (>70 MPa).

53. The energy storage device according to any one of claims 1 to 52, wherein the constraint comprises a material compatible with the electrolyte.

54. The energy storage device according to any one of claims 1 to 53, wherein the constraint includes a material that does not corrode significantly at the floating potential or the anode potential of the energy storage device.

55. The energy storage device according to any one of claims 1 to 54, wherein the constraint comprises a material that does not react significantly or lose mechanical strength at 45°C.

56. The energy storage device according to any one of claims 1 to 55, wherein the constraint includes metal, metal alloy, ceramics, glass, plastic, or a combination thereof.

57. The energy storage device according to any one of claims 1 to 56, wherein the constraint comprises a sheet of material having a thickness in the range of about 10 to about 100 micrometers.

58. The energy storage device according to any one of claims 1 to 57, wherein the constraint comprises a sheet of material having a thickness in the range of about 30 to about 75 micrometers.

59. The energy storage device according to any one of claims 1 to 58, wherein the constraint comprises carbon fibers having a packing density of >50%.

60. The energy storage device according to any one of claims 1 to 59, wherein the compression member applies a pressure to the first and second longitudinal end faces in each of two mutually orthogonal directions and orthogonal to the stacking direction, at least three times the pressure held by the electrode assembly.

61. The energy storage device according to any one of claims 1 to 60, wherein the compression member applies a pressure to the first and second longitudinal end faces in each of two mutually orthogonal directions and orthogonal to the stacking direction, at least three times the pressure held by the electrode assembly.

62. The energy storage device according to any one of claims 1 to 61, wherein the compression member applies a pressure to the first and second longitudinal end faces in each of two mutually orthogonal directions and orthogonal to the stacking direction that is at least four times the pressure held by the electrode assembly.

63. The energy storage device according to any one of claims 1 to 62, wherein the compression member applies a pressure to the first and second longitudinal end faces in each of two mutually orthogonal directions and orthogonal to the stacking direction that is at least five times the pressure held by the electrode assembly.

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