Restraints on the conduction of electrical current

Abstract

An electrode assembly and method for a secondary battery is provided. The electrode assembly comprises a group of unit cells and a constraint system. The electrode assembly comprises a group of electrode structures, a group of counter electrode structures, and an electrically insulating separator material. The constraint system comprises (i) longitudinally separated first and second primary growth constraints, and (ii) vertically separated first and second connecting members connecting the first and second primary growth constraints and a subset of the constituent elements of the electrode group or counter electrode group. The first and second connecting members are adhered to the subset by an electrically insulating thermoplastic hot melt adhesive having (i) a melt temperature in the range of 75°C to 130°C and (ii) a melt index value measured according to ASTM D1238 in the range of at least 20 to 350.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63 / 168,742, filed March 31, 2021, which is incorporated herein by reference in its entirety.

[0002] FIELD OF THE DISCLOSURE The present disclosure relates generally to structures for use in energy storage devices, energy storage devices employing such structures, and methods for producing such structures and energy devices. [Background technology]

[0003] A rocking chair secondary battery, or insertion secondary battery, is a type of energy storage device in which carrier ions, such as lithium ions, sodium ions, potassium ions, calcium ions, or magnesium ions, migrate between a positive electrode and a negative electrode through an electrolyte. A secondary battery may include a single battery cell or two or more battery cells electrically coupled to form a battery, where each battery cell may include a positive electrode, a negative electrode, a microporous separator, and an electrolyte.

[0004] In a rocking chair battery cell, both the positive and negative electrodes contain materials into which carrier ions can be inserted and desorbed. When the cell is discharged, carrier ions are desorbed from the negative electrode and inserted into the positive electrode. When the cell is charged, the reverse process occurs, and carrier ions are desorbed from the positive electrode and inserted into the negative electrode.

[0005] As carrier ions move between the electrodes, one of the persistent challenges lies in the fact that the electrodes tend to expand and contract as the battery is repeatedly charged and discharged. Swelling and contraction during cycling tends to be problematic for the reliability and cycle life of the battery, as electrode expansion can lead to electrical shorts and battery failure.

[0006] Therefore, there remains a need to control the expansion and contraction of electrodes during battery cycling to improve battery reliability and cycle life. Summary of the Invention

[0007] Thus, in brief, one aspect of the present disclosure relates to the implementation of constraining adhesives to reliably hold constraining structures in place without losing adhesion under prolonged exposure to the electrolyte and other conditions of secondary battery cycling, thereby improving the energy density, reliability, and cycle life of the battery.

[0008] According to one aspect, an electrode assembly for a secondary battery is provided, the electrode assembly having a group of unit cells, a constraint system, and an adhesive, the electrode assembly having mutually perpendicular longitudinal, lateral, and vertical axes, first and second longitudinal end faces separated from each other in the longitudinal direction, and an electrode assembly longitudinal axis A. EA and a lateral surface connecting the first and second longitudinal end surfaces, the lateral surface having opposed first and second regions on opposite sides of the longitudinal axis and separated in a first direction perpendicular to the longitudinal axis, the electrode assembly having a maximum width W measured in the longitudinal direction. EA and the maximum length L measured laterally bounded by the lateral plane EA and the maximum height H bounded by the lateral surface and measured vertically EAThe electrode assembly further comprises a group of electrode structures, a group of counter electrode structures, and an electrically insulating separator material that electrically isolates the constituent units of the electrode structure group and the counter electrode structure group, the constituent units of the electrode structure group and the counter electrode structure group having upper and lower end faces that are vertically separated and on opposite sides, and each constituent unit of the unit cell group comprises an electrode structure, a counter electrode structure, and an electrically insulating separator between the electrode structure and the counter electrode structure. The constraint system comprises (i) vertically separated first and second primary growth constraints, and (ii) vertically separated first and second connecting members connecting the first and second primary growth constraints and a subset of the building blocks of the electrode structures or counter-electrode structures, the first and second connecting members having opposed upper and lower inner surfaces with upper and lower end faces, respectively, bonded to the subset by an electrically insulating thermoplastic hot melt adhesive having (i) a melt temperature in the range of 75° C. to 130° C. and (ii) a melt index value in the range of at least 20 to 350, as measured according to ASTM D1238. Another embodiment relates to a secondary having an electrode assembly.

[0009] According to another aspect, a process for manufacturing a secondary battery or electrode assembly is provided, the process including: (a) stacking in a stacked configuration a group of electrode structures, a group of counter electrode structures, and a group of electrically insulating separator materials that electrically isolate the constituent units of the electrode and counter electrode groups; (b) placing a first surface of at least one of the adhesive films comprising an electrically insulating thermoplastic hot melt adhesive in contact with an upper or lower inner surface of a first or second connecting member of a constraint system; (c) placing an upper or lower end surface of a subset of the constituent units of the electrode or counter electrode groups in contact with a second surface of the at least one adhesive film; and (d) at least partially melting or softening the at least one adhesive film by heating to adhere the subset of the constituent units of the electrode or counter electrode groups to the first and second connecting members.

[0010] Other aspects, features, and embodiments of the present disclosure will be discussed in part, and in part will be apparent from, the following description and drawings. [Brief description of the drawings]

[0011] [Figure 1A] FIG. 1 is a perspective view of one embodiment of an electrode assembly having a set of electrode constraints. [Figure 1B] FIG. 1 is a schematic diagram of one embodiment of a three-dimensional electrode assembly for a secondary battery. [Figure 1C] FIG. 1C is an inset cross-sectional view of the electrode assembly of FIG. [Figure 1D] 1C is a cross-sectional view of the electrode assembly of FIG. 1B taken along line D in FIG. 1B. [Diagram 2] 1 illustrates an exploded view of one embodiment of an energy storage device or secondary battery comprising an electrode assembly and a set of electrode constraints. [Figure 3A] 1 illustrates a cross section in the ZY plane of an embodiment of an electrode assembly having an auxiliary electrode. [Figure 3B] 1 illustrates a top view in the XY plane of an embodiment of an electrode assembly having a constraint system with an opening therein. [Figure 4] 1 is a cross-sectional view of one embodiment of an electrode assembly joined to a constraint system. [Diagram 5] FIG. 2 is a top view of one embodiment of an electrode assembly illustrating the upper end surface of the electrode current collector prior to bonding to a constraint system. [Figure 6] 6 is a top view of the embodiment of the electrode assembly of FIG. 5 after a constraint system has been adhered thereto. [Figure 7A] 1B illustrates a cross-section of an embodiment of an electrode assembly taken along line AA' as shown in FIG. 1A, illustrating elements of an embodiment of a primary growth constraint system and a secondary growth constraint system. [Figure 7B] 1B illustrates a cross-section of one embodiment of an electrode assembly taken along line BB' as shown in FIG. 1A, illustrating elements of an embodiment of a primary growth constraint system and a secondary growth constraint system. [Figure 7C] 1B illustrates a cross-section of one embodiment of an electrode assembly taken along line AA' as shown in FIG. 1A, further illustrating elements of an embodiment of a primary growth constraint system and a secondary growth constraint system. [Figure 8A] 1 illustrates a process for manufacturing a secondary battery and / or electrode assembly by using an electrically insulating thermoplastic hot melt adhesive. [Figure 8B] 1 illustrates a process for manufacturing a secondary battery and / or electrode assembly by using an electrically insulating thermoplastic hot melt adhesive. [Figure 8C] 1 illustrates a process for manufacturing a secondary battery and / or electrode assembly by using an electrically insulating thermoplastic hot melt adhesive. [Figure 8D] 1 illustrates a process for manufacturing a secondary battery and / or electrode assembly by using an electrically insulating thermoplastic hot melt adhesive. [Figure 8E] 1 illustrates a process for manufacturing a secondary battery and / or electrode assembly by using an electrically insulating thermoplastic hot melt adhesive. [Figure 9A] 1 illustrates another process for manufacturing a secondary battery and / or electrode assembly by using a form of electrically insulating thermoplastic hot melt adhesive. [Figure 9B] 1 illustrates another process for manufacturing a secondary battery and / or electrode assembly by using a form of electrically insulating thermoplastic hot melt adhesive. [Figure 9C] 1 illustrates another process for manufacturing a secondary battery and / or electrode assembly by using a form of electrically insulating thermoplastic hot melt adhesive. [Figure 9D] 1 illustrates another process for manufacturing a secondary battery and / or electrode assembly by using a form of electrically insulating thermoplastic hot melt adhesive. [Figure 9E] 1 illustrates another process for manufacturing a secondary battery and / or electrode assembly by using a form of electrically insulating thermoplastic hot melt adhesive. [Figure 10A] 1 illustrates an alternative process for manufacturing a secondary battery and / or electrode assembly by using an electrically insulating thermoplastic hot melt adhesive. [Figure 10B] 1 illustrates an alternative process for manufacturing a secondary battery and / or electrode assembly by using an electrically insulating thermoplastic hot melt adhesive. [Figure 10C] 1 illustrates an alternative process for manufacturing a secondary battery and / or electrode assembly by using an electrically insulating thermoplastic hot melt adhesive. [Figure 10D] 1 illustrates an alternative process for manufacturing a secondary battery and / or electrode assembly by using an electrically insulating thermoplastic hot melt adhesive. [Figure 10E] 1 illustrates an alternative process for manufacturing a secondary battery and / or electrode assembly by using an electrically insulating thermoplastic hot melt adhesive.

[0012] Other aspects, embodiments, and features of the inventive subject matter will become apparent from the following detailed description when considered in conjunction with the accompanying drawings, which are schematic and are not intended to be drawn to scale. For clarity, not every element or component will be labeled in every figure, and not every element or component of every embodiment of the inventive subject matter will be shown unless illustration is necessary to enable those skilled in the art to understand the inventive subject matter.

[0013] definition As used herein, "a," "an," and "the" (i.e., singular) refer to plural referents unless the context clearly dictates otherwise. For example, in one instance, reference to an "electrode" includes both a single electrode and a plurality of similar electrodes.

[0014] As used herein, "about" and "approximately" refer to plus or minus 10%, 5%, or 1% of the stated value. For example, in one case, about 250 μm includes 225 μm to 275 μm. As a further example, in one case, about 1,000 μm includes 900 μm to 1,100 μm. Unless otherwise indicated, all numbers expressing quantities (e.g., measurements, etc.) and the like used in the specification and claims should be understood to be modified in all cases by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximations. Each numerical parameter should be construed, at least in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0015] "State of charge," as used herein in the context of the state of a secondary battery, refers to a state in which a secondary battery is charged to at least 75% of its rated capacity. For example, a battery may be charged to at least 80% of its rated capacity, at least 90% of its rated capacity, and even at least 95% of its rated capacity, such as 100% of its rated capacity.

[0016] "C-rate," as used herein, refers to a measure of the rate at which a secondary battery is discharged and is defined as the discharge current divided by the theoretical current draw that the battery would deliver its nominal rated capacity in 1 hour. For example, a C-rate of 1C indicates a discharge current that will discharge the battery in 1 hour, a rate of 2C indicates a discharge current that will discharge the battery in ½ hour, a rate of C / 2 indicates a discharge current that will discharge the battery in 2 hours, etc.

[0017] As used herein in the context of the state of a secondary battery, a "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 may be discharged to less than 20% of its rated capacity, such as less than 10% of its rated capacity, and even less than 5% of its rated capacity, such as 0% of its rated capacity.

[0018] As used herein in the context of cycling a secondary battery between a charging state and a discharging state, "cycling" refers to charging and / or discharging the battery to move the battery from a first state, either a charging state or a discharging state, to a second state that is the opposite of the first state (i.e., the charging state if the first state was discharging, or the discharging state if the first state was charging), and then returning the battery to the first state to complete the cycle. For example, a single cycle of a secondary battery between a charging state and a discharging state can include charging the battery from the discharging state to the charging state and then returning it to the discharging state to complete the cycle, as in a charging cycle. A single cycle can also include discharging the battery from the charging state to the discharging state and then returning it to the charging state to complete the cycle, as in a discharging cycle.

[0019] The "ferret diameter" referred to herein with respect to an electrode assembly is defined as the distance between two parallel planes that bound the electrode assembly, measured in a direction perpendicular to the two planes. For example, the ferret diameter of an electrode assembly in a longitudinal direction is the distance measured in a longitudinal direction between two parallel planes that bound the electrode assembly perpendicular to the longitudinal direction. As another example, the ferret diameter of an electrode assembly in a transverse direction is the distance measured in a transverse direction between two parallel planes that bound the electrode assembly perpendicular to the transverse direction. As yet another example, the ferret diameter of an electrode assembly in a vertical direction is the distance measured in a vertical direction between two parallel planes that bound the electrode assembly perpendicular to the vertical direction.

[0020] As used herein, "longitudinal axis", "lateral axis", and "vertical axis" refer to mutually perpendicular axes (i.e., each is orthogonal to the other). For example, the "longitudinal axis", "lateral axis", and "vertical axis" used herein are similar to a Cartesian coordinate system used to define three-dimensional aspects or orientations. Thus, the description of the elements of the inventive subject matter herein is not limited to the particular axes used to describe the three-dimensional orientation of the elements. Alternatively stated, the axes may be interchangeable when referring to three-dimensional aspects of the inventive subject matter.

[0021] As used herein, "longitudinal," "lateral," and "vertical" refer to directions that are perpendicular to one another (i.e., each is orthogonal to the other). For example, as used herein, "longitudinal," "lateral," and "vertical" may generally be parallel to the longitudinal, lateral, and vertical axes, respectively, of a Cartesian coordinate system used to define three-dimensional aspects or orientations.

[0022] As used herein in the context of cycling between a charged state and a discharged state of a secondary battery, "repeated cycling" refers to cycling from a discharged state to a charged state or from a charged state to a discharged state two or more times. For example, repeated cycling between a charged state and a discharged state can include at least two cyclings from a discharged state to a charged state, such as charging from a discharged state to a charged state, discharging back to a discharged state, charging again to a charged state, and finally discharging back to a discharged state. As yet another example, repeated cycling between a charged state and a discharged state can include discharging from a charged state to a discharged state, charging back to a charged state, discharging again to a discharged state, and finally charging back to a charged state at least twice. As a further example, repeated cycling between a charged state and a discharged state can include at least five cyclings, and even at least ten cyclings from a discharged state to a charged state. As a further example, repeated cycling between a charged state and a discharged state can include cycling from a discharged state to a charged state at least 25, 50, 100, 300, 500, and even 1000 times.

[0023] "Rated capacity" as used herein in the context of secondary batteries refers to the capacity of a secondary battery to deliver a specified current over a period of time, measured under standard temperature conditions (25°C). For example, rated capacity may be measured in ampere-hours by determining the current output for a specified time, or by determining the time that current can be output for a specified current and taking the product of the current and time. For example, for a 20 ampere-hour rated battery, if the current is specified at 2 amperes for the rating, the battery may be understood to be one that will provide a current output for 10 hours, and conversely, if the time is specified at 10 hours for the rating, the battery may be understood to be one that will output 2 amperes for 10 hours. In particular, the rated capacity of a secondary battery may be given as the rated capacity at a specified discharge current, such as a C-rate, where the C-rate is a measure of the rate at which the battery is discharged relative to its capacity. For example, a C-rate of 1C indicates a discharge current that will discharge the battery in 1 hour, 2C indicates a discharge current that will discharge the battery in ½ hour, C / 2 indicates a discharge current that will discharge the battery in 2 hours, and so on. So, for example, a battery rated at 20 amp hours at a C-rate of 1C will provide a discharge current of 20 amps for 1 hour, a battery rated at 20 amp hours at a C-rate of 2C will provide a discharge current of 40 amps for 1 / 2 hour, and a battery rated at 20 amp hours at a C-rate of C / 2 will provide a discharge current of 10 amps for 2 hours.

[0024] As used herein in the context of the dimensions of an electrode assembly, "maximum width" (W EA ) corresponds to the maximum width of the electrode assembly measured longitudinally from a point opposite the longitudinal end face of the electrode assembly.

[0025] As used herein in the context of the dimensions of an electrode assembly, "maximum length" (L EA ) corresponds to the maximum length of the electrode assembly measured laterally from a point on the opposite side of the lateral surface of the electrode assembly.

[0026] As used herein in the context of the dimensions of an electrode assembly, "maximum height" (H EA) corresponds to the maximum height of the electrode assembly measured laterally from a point on the opposite side of the lateral surface of the electrode assembly.

[0027] Furthermore, as used herein, for each embodiment where the term "electrode" is used to describe a material or structure, such as "electrode structure" or "electrode active material," it is understood that such structure and / or material may, in certain embodiments, correspond to a "negative electrode" structure and / or material, such as "negative electrode structure" or "negative electrode active material." Similarly, as used herein, for each embodiment where the term "counter electrode" is used to describe a material or structure, such as "counter electrode structure" or "counter electrode active material," it is understood that such structure and / or material may, in certain embodiments, correspond to a "positive electrode" structure and / or material, such as "positive electrode structure" or "positive electrode active material." That is, where appropriate, any embodiment described with respect to an electrode and / or counter electrode may correspond to the same embodiment in which the electrode and / or counter electrode include the corresponding structure and materials, respectively, specifically the negative electrode and / or the positive electrode. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] In general, the present disclosure is directed to an energy storage device 100, such as a secondary battery 102, cycling between a charged state and a discharged state, for example as shown in Figures 1A-1D and 2. The secondary battery 102 includes a battery housing 104, an electrode assembly 106, carrier ions, and a non-aqueous liquid electrolyte within the battery housing. In certain embodiments, the secondary battery 102 also includes a constraining system 108 that constrains the growth of the electrode assembly 106. The constrained growth of the electrode assembly 106 can be a macroscopic increase in one or more dimensions of the electrode assembly 106.

[0029] 1A-1D, in one embodiment, the electrode assembly 106 includes a group of unit cells 504 stacked in series in a stacking direction (i.e., stacking direction D in FIG. 1B). Each unit of the unit cell group includes an electrode structure 110, a counter electrode structure 112, and an electrical insulating separator 130 between the electrode structure and the counter electrode structure for electrically insulating the electrode structure 110 and the counter electrode structure 112 from each other. In one example, as shown in FIG. 1B, the electrode assembly 106 includes stacked continuous unit cells 504 including the electrode structure 110 and the counter electrode structure in an alternating arrangement. FIG. 1C is an inset view showing a secondary battery having the electrode assembly 106 of FIG. 1B, and FIG. 1D is a cross-section of the secondary battery having the electrode assembly 106 of FIG. 1B. Other arrangements of stacked continuous unit cells 504a, 504b can also be provided. Thus, the electrode assembly can comprise a group of electrode structures, a group of counter electrode structures, and a group of electrically insulating separator materials that electrically isolate the electrode structure group and the constituent units of the counter electrode structure group, and each constituent unit of the unit cell group comprises an electrode structure, a counter electrode structure, and an electrically insulating separator between the electrode structure and the counter electrode structure.

[0030] In one embodiment, the electrode structure 110 includes an electrode active material layer 132 and an electrode current collector 136, as shown in, for example, FIGS. 1A-1D. For example, the electrode structure 110 can include an electrode current collector 136 disposed between one or more electrode active material layers 132. According to one embodiment, the electrode active material layer 132 includes an anode active material, and the electrode current collector 136 includes an anode current collector. Similarly, in one embodiment, the counter electrode structure 112 includes a counter electrode active material layer 138 and a counter electrode current collector 140. For example, the counter electrode structure 112 can include a counter electrode current collector 140 disposed between one or more counter electrode active material layers 138. According to one embodiment, the counter electrode active material layer 138 includes a cathode active material, and the counter electrode current collector 140 includes a cathode current collector. It should further be understood that the electrode structure 110 and the counter electrode structure 112, respectively, are not limited to the specific embodiments and structures described herein, and other configurations, structures, and / or materials than those specifically described herein may be provided for forming the electrode structure 110 and the counter electrode structure 112. According to a specific embodiment, each unit cell 504a, 504b in the group of unit cells comprises, in a stacked configuration, a unit cell portion of an electrode current collector 136, an electrode structure 110 comprising an electrode active material layer 132, an electrically insulating separator 130 between the electrode and the counter electrode active material layer, a counter electrode structure 113 comprising a counter electrode active material layer 138, and a unit cell portion of a counter electrode current collector 140. In certain embodiments, the order of unit cell portions of the electrode current collector, electrode active material layer, separator, counter electrode active material layer, and counter electrode current collector is reversed for unit cells adjacent to one another in the stacked configuration, such as shown in FIG. 1C, such that portions of the electrode current collector and / or counter electrode current collector are shared between adjacent unit cells.

[0031] According to the embodiment as shown in Figures 1A to 1D, the constituent units of the electrode structure group 110 and the counter electrode structure group 112 are respectively arranged in an alternating array having an alternating array direction corresponding to the stacking direction D. The electrode assembly 106 according to this embodiment further includes a longitudinal axis, a transverse axis, and a vertical axis that are perpendicular to each other, and the longitudinal axis A EAGenerally, the longitudinal axis A corresponds to or is parallel to the stacking direction D of the constituent units of the electrode structure group and the counter electrode structure group. As shown in the embodiment in FIG. EA is shown to correspond to the Y-axis, the horizontal axis is shown to correspond to the X-axis, and the vertical axis is shown to correspond to the Z-axis. According to the embodiment disclosed herein, the electrode structure 110, the counter electrode structure 112, and the electrical insulating separator 130 in each unit cell 504 of the unit cell group have upper and lower end faces that are separated on opposite sides in a vertical direction perpendicular to the stacking direction of the unit cell group. For example, referring to FIG. 1C and FIG. 4, the electrode structure 110 in each unit of the unit cell group can have upper and lower end faces 500a and 500b that are separated on opposite sides in a vertical direction, the counter electrode structure 112 in each unit of the unit cell group can have upper and lower end faces 501a and 501b that are separated on opposite sides in a vertical direction, and the electrical insulating separator 130 can have upper and lower end faces 502a and 502b that are separated on opposite sides in a vertical direction.

[0032] 1A-1D, according to one embodiment, the electrode assembly 106 has mutually perpendicular lateral, longitudinal, and vertical axes corresponding to the x-, y-, and z-axes, respectively, of a virtual three-dimensional Cartesian coordinate system, a first longitudinal end surface 116 and a second longitudinal end surface 118 separated from one another in the longitudinal direction, and an electrode assembly longitudinal axis A. EAand a lateral surface 142 surrounding the first longitudinal end surface 116 and the second longitudinal end surface 118 and connecting the first longitudinal end surface 116 and the second longitudinal end surface 118. In one embodiment, the surface area of ​​the first longitudinal end surface 116 and the second longitudinal end surface 118 is less than 33% of the surface area of ​​the electrode assembly 106. For example, in one such embodiment, the sum of the surface areas of the first longitudinal end surface 116 and the second longitudinal end surface 118, respectively, is less than 25% of the surface area of ​​the entire surface of the electrode assembly 106. By way of further example, in one embodiment, the sum of the surface areas of the first longitudinal end surface 116 and the second longitudinal end surface 118, respectively, is less than 20% of the surface area of ​​the entire surface of the electrode assembly. By way of further example, in one embodiment, the sum of the surface areas of the first longitudinal end surface 116 and the second longitudinal end surface 118, respectively, is less than 15% of the surface area of ​​the entire surface of the electrode assembly. As a further example, in one embodiment, the sum of the surface areas of the first longitudinal end face 116 and the second longitudinal end face 118 is each less than 10% of the surface area of ​​the total surface of the electrode assembly.

[0033] In one embodiment, the lateral surface 142 includes a first region and a second region on either side of a longitudinal axis, separated in a first direction perpendicular to the longitudinal axis. For example, the lateral surface 142 can include surface regions 144, 146 on opposite sides in the X direction (i.e., sides of a rectangular cylinder) and surface regions 148, 150 on opposite sides in the Z direction. In yet another embodiment, the lateral surface can include a cylindrical shape. The electrode assembly 106 has a maximum width W measured in the longitudinal direction. EA and the maximum length L bounded by the lateral surface and measured laterally EA and the maximum height H bounded by the lateral surface and measured vertically EA In one embodiment, the maximum length L EA and maximum height H EA may be at least 2:1. By way of further example, in one embodiment, the maximum length L EA and maximum height H EA By way of further example, in one embodiment, the ratio of maximum length L EA and maximum height H EABy way of further example, in one embodiment, the ratio of maximum length L EA and maximum height H EA By way of further example, in one embodiment, the ratio of maximum length L EA and maximum height H EA The ratio of may be at least 20: 1. The ratio of the various dimensions may allow for optimal configuration within the energy storage device to maximize the amount of active material, thereby increasing the energy density.

[0034] In some embodiments, the maximum width W EA is the maximum height H EA For example, in one embodiment, the maximum width W EA and maximum height H EA By way of further example, in one embodiment, the ratio of maximum width W EA and maximum height H EA By way of further example, in one embodiment, the ratio of maximum width W EA and maximum height H EA By way of further example, in one embodiment, the ratio of maximum width W EA and maximum height H EA By way of further example, in one embodiment, the ratio of maximum width W EA and maximum height H EA may be at least 20:1.

[0035] According to one embodiment, the maximum width W EA and maximum length L EA The ratio of the maximum width W to the maximum width W may be selected to be within a predetermined range that provides an optimal configuration. EA and maximum length L EA The ratio of maximum width W to maximum width W may range from 1:5 to 5:1. EA and maximum length L EA The ratio of maximum width WEA and maximum length L EA The ratio may range from 1:2 to 2:1.

[0036] According to an embodiment of the present disclosure, each electrode structure 110 of the constituent elements of the unit cell group has a length L measured in a lateral direction between a first opposing lateral end surface 601 a and a second opposing lateral end surface 601 b of the electrode structure 110. E and a height H measured in the vertical direction between the upper and lower opposing vertical end faces 500a and 500b of the electrode structure 110. E and a width W measured longitudinally between the first opposing surface 603a and the second opposing surface 603b of the electrode structure 110. E Each counter electrode structure 112 of the constituent units of the unit cell group includes a length L measured in the lateral direction between a first opposite lateral end surface 602a and a second opposite lateral end surface 602b of the counter electrode structure 112. CE and a height H measured in the vertical direction between the upper second opposite vertical end face 501a and the lower second opposite vertical end face 501b of the counter electrode structure 112. CE and a width W measured in the vertical direction between the first opposing surface 604a and the second opposing surface 604b of the counter electrode structure 112. CE Including,

[0037] According to one embodiment, the electrode structure 110 constituting the unit cell group is L E and W E and H E is at least 5:1 with each of H E and W E The ratio of L to L is in the range of about 2:1 to about 100:1, and for the counter electrode structure 112 constituting the unit cell group, CE and W CE and H CE is at least 5:1 with each of H CE and W CE In one embodiment, the ratio of L E and W E and HE is at least 10:1, and L CE and W CE and H CE and each of L is at least 10:1. E and W E and H E is at least 15:1, and L CE and W CE and H CE and each of L is at least 15:1. E and W E and H E is at least 20:1, and L CE and W CE and H CE Each of the ratios is at least 20:1.

[0038] In one embodiment, the height (H E ) and width (W E ) is at least 0.4:1. For example, in one embodiment, for each electrode structure 110 constituting the unit cell group, H E and W E and H may have a ratio of at least 2:1, respectively. E and W E and H may have a ratio of at least 10:1, respectively. E and W E The ratio of H to H, respectively, will be at least 20:1. E and W E The ratio of H to H will generally be less than 1,000:1, respectively. For example, in one embodiment, E and W E and H may have a ratio of less than 500:1, respectively. E and W E and H may have a ratio of less than 100:1, respectively. E and W Eand H may be less than 10:1, respectively. E and W E The ratio of may range from about 2:1 to about 100:1, respectively.

[0039] In one embodiment, the height (H CE ) and width (W CE ) is at least 0.4:1. For example, in one embodiment, for each counter electrode structure 112 of the unit cell group, CE and W CE and H may have a ratio of at least 2:1, respectively. CE and W CE and H may have a ratio of at least 10:1, respectively. CE and W CE The ratio of H to H, respectively, will be at least 20:1. CE and W CE The ratio of H to H will generally be less than 1,000:1, respectively. For example, in one embodiment, CE and W CE and H may have a ratio of less than 500:1, respectively. CE and W CE and H may have a ratio of less than 100:1, respectively. CE and W CE and H may be less than 10:1, respectively. CE and W CE The ratio of may range from about 2:1 to about 100:1, respectively.

[0040] In one embodiment, the group of unit cells can include an alternating arrangement of electrode structures 110 and counter electrode structures 112, and can include any number of building blocks depending on the energy storage device 100 and its intended use. By way of further example, in one embodiment, more generally, the group of electrode structures 110 and the group of counter electrode structures 112 each have N building blocks, each of the N-1 electrode structure building blocks 110 being between two counter electrode structure building blocks 112, each of the N-1 counter electrode structure building blocks 112 being between two electrode structure building blocks 110, and N being at least 2. By way of further example, in one embodiment, N is at least 4. By way of further example, in one embodiment, N is at least 5. By way of further example, in one embodiment, N is at least 10. By way of further example, in one embodiment, N is at least 25. By way of further example, in one embodiment, N is at least 50. By way of further example, in one embodiment, N is at least 100 or more.

[0041] In one embodiment, the electrode assembly 106 is enclosed within a volume V defined by a constraint system 108 that constrains the overall macroscopic growth of the electrode assembly 106, for example as illustrated in FIGS. 1A and 1B. The constraint system 108 may be capable of constraining the growth of the electrode assembly 106 along one or more dimensions to reduce swelling and deformation of the electrode assembly 106 and thereby improve the reliability and cycling life of the energy storage device 100 having the constraint system 108. Without being limited to any one particular theory, it is believed that carrier ions that migrate between the electrode structure 110 and the counter electrode structure 112 during charging and / or discharging of the secondary battery 102 and / or electrode assembly 106 may intercalate into the electrode active material, causing the electrode active material and / or the electrode structure 110 to expand. This expansion of the electrode structure 110 may cause the electrode and / or electrode assembly 106 to deform and swell, thereby compromising the structural integrity of the electrode assembly 106 and / or increasing the likelihood of electrical shorts or other failures. In one example, excessive swelling and / or expansion and contraction of the electrode active material layer 132 during cycling of the energy storage device 100 can cause pieces of the electrode active material to peel off and / or delaminate from the electrode active material layer 132, thereby compromising the efficiency and cycling life of the energy storage device 100. In yet another example, excessive swelling and / or expansion and contraction of the electrode active material layer 132 can cause the electrode active material to breach the electrically insulating microporous separator 130, thereby causing electrical shorts and other failures of the electrode assembly 106. Thus, the constraint system 108 prevents this swelling or growth from occurring upon cycling between charged and discharged states, improving the reliability, efficiency, and / or cycling life of the energy storage device 100.

[0042] In one embodiment, the constraint system 108 comprising the primary growth constraint system 151 is provided to mitigate and / or reduce at least one of the growth, expansion, and / or swelling of the electrode assembly 106 in the longitudinal direction (i.e., in a direction parallel to the Y-axis), for example as shown in FIG. 1A. For example, the primary growth constraint system 151 may include a structure configured to constrain growth by opposing expansion at the longitudinal end faces 116, 118 of the electrode assembly 106. In one embodiment, the primary growth constraint system 151 comprises a first primary growth constraint 154 and a second primary growth constraint 156 that are separated from each other in the longitudinal direction (stack direction) and can operate in conjunction with at least one primary connecting member 162 that connects the first primary growth constraint 154 and the second primary growth constraint 156 together to inhibit growth in the electrode assembly 106 in the stack direction. For example, the first and second primary growth constraints 154, 156 may at least partially cover the first and second longitudinal end faces 116, 118 of the electrode assembly 106 and may work in conjunction with the connecting members 162, 164 connecting the primary growth constraints 154, 156 to one another to impede and inhibit any growth in the electrode assembly 106 that occurs during repeated cycles of charging and / or discharging.

[0043] According to an embodiment herein, the primary growth constraint system 151 restricts the growth of the electrode assembly 106 in the vertical direction such that the increase in the ferret diameter of the electrode assembly 106 in the vertical direction that may occur after 20 consecutive cycles (cycles between a charged state and a discharged state) of the secondary battery 102 is less than 20%, or less than 10% after 10 consecutive cycles of the secondary battery, or less than 10% after 5 consecutive cycles, or less than 1% per cycle of the battery. In one embodiment, the increase in the ferret diameter of the electrode assembly in the stacking direction that may occur after 20 consecutive cycles and / or 50 consecutive cycles of the secondary battery is less than 3% and / or less than 2%.

[0044] According to one embodiment, the projection of the constituent units of the electrode structure group 110 and the counter electrode structure group 112 onto the first vertical surface surrounds a first projection area 700a, the projection of the constituent units of the electrode structure group 110 and the counter electrode structure group 112 onto the second vertical surface surrounds a second projection area 700b, and the first primary growth constraint 154 and the second primary growth constraint 156 comprise first and second compression members overlapping the first and second projection areas 700a and 700b.

[0045] In addition, repeated cycling of charge and discharge processes in the secondary battery 102 may induce growth and distortion not only in the longitudinal direction (e.g., Y-axis in FIG. 1A ) of the electrode assembly 106, but also in directions perpendicular to the longitudinal direction, such as the transverse and vertical directions (e.g., X-axis and Z-axis in FIG. 1A , respectively), as discussed above. Furthermore, in certain embodiments, the incorporation of a primary growth constraint system 151 to inhibit growth in one direction may even exacerbate growth and / or swelling in one or more other directions. For example, if a primary growth constraint system 151 is provided to inhibit longitudinal growth of the electrode assembly 106, the intercalation of carrier ions during charge and discharge cycles and the resulting swelling of the electrode structure may induce distortion in one or more other directions. In particular, in one embodiment, the strain generated by the combination of electrode growth / swelling and longitudinal growth constraints may result in buckling or other failure of the electrode assembly 106 in the vertical direction (e.g., Z-axis shown in FIG. 1A) or even in the lateral direction (e.g., X-axis shown in FIG. 1A). Thus, in one embodiment of the present disclosure, a secondary growth constraint system 152 is provided that may operate in conjunction with the primary growth constraint system 151 to constrain the growth of the electrode assembly 106 along multiple axes of the electrode assembly 106. For example, in one embodiment, the secondary growth constraint system 152 may be configured to operate in conjunction with or otherwise synergistically with the primary growth constraint system 151, thereby constraining the overall growth of the electrode assembly 106 to provide improved performance and reduced occurrence of failures of secondary batteries having the electrode assembly 106 and the primary growth constraint system 151 and secondary growth constraint system 152, respectively.

[0046] In one embodiment, the secondary growth restriction system 152, which includes the first connecting member 158 and the second connecting member 160, restricts the growth of the electrode assembly 106 in the vertical direction such that the increase in the ferret diameter of the electrode assembly in the vertical direction over 20 consecutive cycles of the secondary battery is less than 20%, or less than 10% over 10 consecutive cycles of the secondary battery, or less than 10% over 5 consecutive cycles, or less than 1% per cycle of the battery. In one embodiment, the increase in the ferret diameter of the electrode assembly in the vertical direction over 20 consecutive cycles and / or 50 consecutive cycles of the secondary battery is less than 3% and / or less than 2%.

[0047] 7A-7C, an embodiment of a constraint system 108 having a primary growth constraint system 151 and a secondary growth constraint system 152 for an electrode assembly 106 is shown. FIG. 7A shows a cross-section of the electrode assembly 106 in FIG. 1A taken along the longitudinal axis (Y-axis) such that the resulting 2D cross-section is illustrated with the vertical axis (Z-axis) and the longitudinal axis (Y-axis). FIG. 7B shows a cross-section of the electrode assembly 106 in FIG. 1A taken along the transverse axis (X-axis) such that the resulting 2D cross-section is illustrated with the vertical axis (Z-axis) and the transverse axis (X-axis). As shown in FIG. 7A, the primary growth constraint system 151 can generally comprise a first primary growth constraint 154 and a second primary growth constraint 156, respectively, separated from each other along the longitudinal axis (Y-axis). For example, in one embodiment, the first primary growth constraint 154 and the second primary growth constraint 156 each include a first primary growth constraint 154 at least partially or even completely covering a first longitudinal end surface 116 of the electrode assembly 106, and a second primary growth constraint 156 at least partially or even completely covering a second longitudinal end surface 118 of the electrode assembly 106. In yet another version, one or more of the first primary growth constraint 154 and the second primary growth constraint 156 can be internal to the longitudinal end surfaces 116, 118 of the electrode assembly 106, such as when one or more of the primary growth constraints include an internal structure of the electrode assembly 106. The primary growth constraint system 151 can further include at least one primary connecting member 162 connecting the first primary growth constraint 154 and the second primary growth constraint 156 and can have a major axis that is parallel to the longitudinal direction. For example, the primary growth constraint system 151 may include a first primary connection member 162 and a second primary connection member 164 separated from one another along an axis perpendicular to the longitudinal axis, such as along a vertical axis (Z-axis) as depicted in the embodiment. The first primary connection member 162 and the second primary connection member 164 may function to connect the first primary growth constraint 154 and the second primary growth constraint 156, respectively, to one another and to maintain the first primary growth constraint 154 and the second primary growth constraint 156, respectively, in tension with one another to inhibit growth along the longitudinal axis of the electrode assembly 106.

[0048] 7A-7C, the constraint system 108 can further include a secondary growth constraint system 152, which can generally comprise a first secondary growth constraint 158 ​​and a second secondary growth constraint 160, each separated from one another along a second direction perpendicular to the longitudinal direction, such as along a vertical axis (Z-axis) in the embodiment shown. For example, in one embodiment, the first secondary growth constraint 158 ​​extends at least partially across a first region 148 of the lateral surface 142 of the electrode assembly 106, and the second secondary growth constraint 160 extends at least partially across a second region 150 of the lateral surface 142 of the electrode assembly 106 opposite the first region 148. In yet another version, one or more of the first and second secondary growth constraints 158 and 160 may be internal to the lateral surface 142 of the electrode assembly 106, such as when one or more of the secondary growth constraints include an internal structure of the electrode assembly 106. In one embodiment, the first and second secondary growth constraints 158 and 160 are each connected by at least one secondary connection member 166, which may have a major axis that is parallel to a second direction, such as a vertical axis. The secondary connection member 166 may function to connect and hold the first and second secondary growth constraints 158 and 160, respectively, in tension with each other to constrain growth of the electrode assembly 106 along a direction perpendicular to the longitudinal direction, such as, for example, constraining growth in the vertical direction (e.g., along the Z axis). In the embodiment depicted in FIG. 7A, the at least one secondary connection member 166 may correspond to at least one of the first and second primary growth constraints 154 and 156. However, the secondary connecting members 166 are not so limited and may alternatively and / or additionally comprise other structures and / or configurations.

[0049] According to one embodiment, the primary growth constraint system 151 and the secondary growth constraint system 152 are each configured to operate in a coordinated manner such that portions of the primary growth constraint system 151 act in a coordinated manner as portions of the secondary growth constraint system 152 and / or portions of the secondary growth constraint system 152 act in a coordinated manner as portions of the primary growth constraint system 151. For example, in the embodiment shown in Figures 7A and 7B, the first primary connecting member 162 and the second primary connecting member 164 of the primary growth constraint system 151 can function as at least a portion, or even the entire structure, of the first secondary growth constraint 158 ​​and the second secondary growth constraint 160, respectively, that constrain growth in a second direction perpendicular to the longitudinal direction. In yet another embodiment, as discussed above, one or more of the first primary growth constraint 154 and the second primary growth constraint 156 can function as one or more secondary connecting members 166 for connecting the first secondary growth constraint 158 ​​and the second secondary growth constraint 160, respectively. Conversely, at least a portion of the first and second secondary growth constraints 158, 160 may act as the first and second primary connecting members 162, 164, respectively, of the primary growth constraint system 151, and at least one secondary connecting member 166 of the secondary growth constraint system 152 may act, in one embodiment, as one or more of the first and second primary growth constraints 154, 156, respectively. In yet another embodiment, at least a portion of each of the first and second primary connecting members 162, 164 of the primary growth constraint system 151 and / or at least one secondary connecting member 166 of the secondary growth constraint system 152 may function as at least a portion, or even the entire structure, of the first and second tertiary growth constraints 157, 159, respectively, that constrain growth in a lateral direction perpendicular to the vertical direction. Thus, the primary growth constraint system 151 and the secondary growth constraint system 152 may each share components and / or structures for exerting a constraint on the growth of the electrode assembly 106 .

[0050] In one embodiment, the constraint system 108 can comprise structures such as primary and secondary growth constraints and primary and secondary connecting members that can be structures external and / or internal to the battery housing 104 or can be part of the battery housing 104 itself. In certain embodiments, the battery housing 104 can be a sealed housing, for example, to seal the liquid electrolyte therein and / or to seal the electrode assembly 106 from the external environment. In one embodiment, the constraint system 108 can comprise a combination of structures including the battery housing 104 and other structural components. In one such embodiment, the battery housing 104 may be a component of the primary growth constraint system 151 and / or the secondary growth constraint system 152; stated differently, in one embodiment, the battery housing 104, alone or in combination with one or more other structures (within the battery housing 104 and / or outside the battery housing 104, e.g., the primary growth constraint system 151 and / or the secondary growth constraint system 152), constrains the growth of the electrode assembly 106 in the electrode stacking direction D and / or in a second direction orthogonal to the stacking direction D. In one embodiment, one or more of the primary growth constraints 154, 156 and the secondary growth constraints 158, 160 may comprise structures internal to the electrode assembly. In another embodiment, the primary growth constraint system 151 and / or the secondary growth constraint system 152 do not form any part of the battery housing 104, but instead, one or more separate structures (within the battery housing 104 and / or outside the battery housing 104) constrain the growth of the electrode assembly 106 in the electrode stacking direction D and / or in a second direction perpendicular to the stacking direction D. In another embodiment, the primary growth constraint system 151 and the secondary growth constraint system 152 are within the battery housing 104, which may be a sealed battery housing, such as a hermetically sealed battery housing. The electrode assembly 106 may be constrained by the constraint system 108 at a pressure greater than the pressure exerted by the growth and / or swelling of the electrode assembly 106 during repeated cycling of the energy storage device 100 or secondary battery having the electrode assembly 106.

[0051] In one exemplary embodiment, the primary growth constraint system 151 includes one or more separate structures within the battery housing 104 that constrain the growth of the electrode structure 110 in the stacking direction D by exerting a pressure in the stacking direction D that exceeds the pressure generated by the electrode structure 110 upon repeated cycling of a secondary battery 102 having the electrode structure 110 as part of an electrode assembly 106. In another exemplary embodiment, the primary growth constraint system 151 includes one or more separate structures within the battery housing 104 that constrain the growth of the counter electrode structure 112 in the stacking direction D by exerting a pressure in the stacking direction D that exceeds the pressure generated by the counter electrode structure 112 upon repeated cycling of a secondary battery 102 having the counter electrode structure 112 as part of an electrode assembly 106. The secondary growth constraint system 152 may similarly include one or more separate structures within the battery housing 104 that suppress growth of at least one of the electrode structure 110 and the counter electrode structure 112 in a second direction perpendicular to the stacking direction D, such as along a vertical axis (Z-axis), by exerting a pressure in the second direction that exceeds the pressure generated in the second direction by the electrode structure 110 or the counter electrode structure 112, respectively, upon repeated cycling of a secondary battery 102 having the electrode structure 110 or the counter electrode structure 112, respectively.

[0052] In yet another embodiment, the first and second primary growth constraints 154, 156 of the primary growth constraint system 151 constrain the growth of the electrode assembly 106 by exerting pressure on the first and second longitudinal end faces 116, 118 of the electrode assembly 106, respectively, in a longitudinal direction, i.e., pressure that exceeds the pressure exerted by the first and second primary growth constraints 154, 156 on other surfaces of the electrode assembly 106 that would be in a direction perpendicular to the longitudinal direction, such as first and second regions of the lateral surface 142 of the electrode assembly 106 that are on opposite sides along the transverse and / or vertical axis. That is, the first and second primary growth constraints 154, 156 may exert pressure in the longitudinal direction (Y-axis) that exceeds the pressure generated by the first and second primary growth constraints 154, 156 in a direction perpendicular to the longitudinal direction, such as the transverse (X-axis) and vertical (Z-axis) directions. For example, in one such embodiment, the primary growth constraint system 151 constrains the growth of the electrode assembly 106 in at least one of two directions perpendicular to the stacking direction D, or even in both, with a pressure against the first and second longitudinal end faces 116 and 118 (i.e., in the stacking direction D) that exceeds by a factor of at least three the pressure maintained by the primary growth constraint system 151 on the electrode assembly 106. As a further example, in one such embodiment, the primary growth constraint system 151 constrains the growth of the electrode assembly 106 in at least one of two directions perpendicular to the stacking direction D, or even in both, with a pressure against the first and second longitudinal end faces 116 and 118 (i.e., in the stacking direction D) that exceeds by a factor of at least four the pressure maintained by the primary growth constraint system 151 on the electrode assembly 106. As a further example, in one such embodiment, the primary growth constraint system 151 inhibits growth of the electrode assembly 106 with a pressure against the first longitudinal end surface 116 and the second longitudinal end surface 118 (i.e., in the stacking direction D) that exceeds the pressure maintained against the electrode assembly 106 by at least five times in at least one, or even both, of two directions perpendicular to the stacking direction D.

[0053] 7C, an embodiment of an electrode assembly 106 having a constraint system 108 is shown with a cross section taken along line A-A' shown in FIG. 1A. In the embodiment shown in FIG. 7C, the primary growth constraint system 151 can comprise a first primary growth constraint 154 and a second primary growth constraint 156 on the longitudinal end faces 116, 118 of the electrode assembly 106, respectively, and the secondary growth constraint system 152 can comprise a first secondary growth constraint 158 ​​and a second secondary growth constraint 160 on the opposing first surface region 148 and second surface region 150 of the lateral face 142 of the electrode assembly 106. According to this embodiment, the first primary growth constraint 154 and the second primary growth constraint 156 can function as at least one secondary connecting member 166 to connect the first secondary growth constraint 158 ​​and the second secondary growth constraint 160 and to maintain the growth constraints in tension with each other in a second direction perpendicular to the longitudinal direction (e.g., vertical direction). However, additionally and / or alternatively, the secondary growth constraint system 152 can include at least one secondary connection member 166 located in an area other than the longitudinal end faces 116, 118 of the electrode assembly 106. It can also be understood that the at least one secondary connection member 166 can act as at least one of the first and second primary growth constraints 154, 156 internal to the longitudinal ends 116, 118 of the electrode assembly and can act in conjunction with either another internal primary growth constraint and / or a primary growth constraint at the longitudinal ends 116, 118 of the electrode assembly 106 to inhibit growth. With reference to the embodiment shown in FIG. 7C, the secondary connection member 166 can be provided spaced apart along the longitudinal axis from the first and second longitudinal end faces 116, 118 of the electrode assembly 106, respectively, such as towards a central region of the electrode assembly 106. The secondary connection member 166 may connect the first secondary growth constraint 158 ​​and the second secondary growth constraint 160 at an interior location from the electrode assembly end faces 116, 118, respectively, and may be subjected to tension between the secondary growth constraints 158, 160 at that location.In one embodiment, the secondary connection members 166 connecting the secondary growth constraints 158, 160 at interior locations from the end faces 116, 118 are provided in addition to one or more secondary connection members 166 provided at the electrode assembly end faces 116, 118, such as secondary connection members 166 that also function as the primary growth constraints 154, 156 at the longitudinal end faces 116, 118. In another embodiment, the secondary growth constraint system 152 comprises one or more secondary connection members 166 connecting the first secondary growth constraint 158 ​​and the second secondary growth constraint 160, respectively, at interior locations spaced apart from the longitudinal end faces 116, 118, with or without the secondary connection members 166 at the longitudinal end faces 116, 118. The internal secondary connection members 166 may also be understood to act as the first primary growth constraint 154 and the second primary growth constraint 156, according to one embodiment. For example, in one embodiment, at least one of the secondary connection members 166 located at an internal location may include at least a portion of the electrode structure 110 or the counter electrode structure 112, as described in more detail below.

[0054] More specifically, with respect to the embodiment shown in FIG. 7C, the secondary growth constraint system 152 may include a first secondary growth constraint 158 ​​overlying the upper region 148 of the lateral surface 142 of the electrode assembly 106 and an opposing second secondary growth constraint 160 overlying the lower region 150 of the lateral surface 142 of the electrode assembly 106, the first secondary growth constraint 158 ​​and the second secondary growth constraint 160 being vertically separated from each other (i.e., along the Z-axis). Additionally, the secondary growth constraint system 152 may further include at least one internal secondary connecting member 166 spaced apart from the longitudinal end faces 116, 118 of the electrode assembly 106. The internal secondary connecting member 166 may be aligned parallel to the Z-axis and connect the first secondary growth constraint 158 ​​and the second secondary growth constraint 160, respectively, to maintain the growth constraints in tension with each other and form at least a portion of the secondary growth constraint system 152. In one embodiment, the at least one internal secondary connection member 166, either alone or together with the secondary connection members 166 located at the longitudinal end faces 116, 118 of the electrode assembly 106, may be subjected to tension between the first and secondary growth constraints 158, 160 in the vertical direction (i.e., along the Z-axis) during repeated charging and / or discharging of the energy storage device 100 and / or secondary battery 102 having the electrode assembly 106, to reduce the growth of the electrode assembly 106 in the vertical direction. Furthermore, in the embodiment shown in FIG. 7C, the constraint system 108 further comprises a primary growth constraint system 151 having a first primary growth constraint 154 and a second primary growth constraint 156, respectively, at the longitudinal ends 116, 118 of the electrode assembly 106 connected by a first primary connection member 162 and a second primary connection member 164, respectively, to the upper lateral surface region 148 and the lower lateral surface region 150 of the electrode assembly 106, respectively. In one embodiment, the secondary internal connection member 166 may itself be understood to act in coordination with one or more of the first primary growth constraint 154 and the second primary growth constraint 156, respectively, to exert a constraining pressure on each portion of the electrode assembly 106 that lies vertically between the secondary internal connection member 166 and the longitudinal ends 116, 118 of the electrode assembly 106, where the first primary growth constraint 154 and the second primary growth constraint 156, respectively, may be located.

[0055] According to one embodiment, the first primary connection member 162 and the second primary connection member 164 (which may be the same as the first secondary growth constraint 158 ​​and the second secondary growth constraint 160) are connected to the secondary connection member 166, which includes at least a portion of the electrode structure 110 or the counter electrode structure 112, or other internal structure, of the electrode assembly 106. In one embodiment, the first primary connection member 162 (which may be the first secondary growth constraint 158) is connected to the upper end surface 500a, 501a of the electrode structure 110 and / or the counter electrode structure 112 of the subset 515 of the building blocks of the unit cell group 504. In another embodiment, the second primary connection member 164 (which may be the second secondary growth constraint 160) is connected to the lower end surface 500b, 501b of the electrode structure 110 or the counter electrode structure 112 of the subset 515 of the building blocks of the unit cell group 504. The subset 515 of the building blocks of the unit cells connected at the upper end surface may be the same as or different from the subset of the building blocks of the unit cells connected at the lower end surface. In one embodiment, the first secondary growth constraint 158 ​​and / or the second secondary growth constraint 160 may be connected to other internal structures in the electrode assembly forming the secondary connection member 166. In one embodiment, the first secondary growth constraint 158 ​​and / or the second secondary growth constraint 160 may be connected to the upper end surface and / or the lower end surface of the electrode structure 110 and / or the counter electrode structure 112 including one or more of the electrode current collector 136, the electrode active material layer 132, the counter electrode current collector 140, and the counter electrode active material layer 138 in the building blocks of the unit cell group 504. In another example, the first secondary growth constraint 158 ​​and the second secondary growth constraint 160 may be connected to the upper end surface and / or the lower end surface of the electrical insulating separator 130. Thus, in certain embodiments, the secondary connection member 166 may comprise one or more of the electrode structures 110 and / or counter electrode structures 112 including one or more of the electrode current collector 136, electrode active material layer 132, counter electrode current collector 140, and counter electrode active material layer 138 of the constituent elements of the unit cell group 504. Referring to Figures 3A-3B, an embodiment is shown in which a first secondary growth constraint 158 ​​and a second secondary growth constraint 160 are connected to a secondary connection member 166 comprising the electrode current collector 136 of a subset of the constituent elements of the unit cell group.In Figures 1C and 4, the first secondary growth constraint 158 ​​and the second secondary growth constraint 160 are connected to a secondary connection member 166 with an electrode structure 110 including an electrode current collector 136. In one embodiment, a constituent element of the group of electrode structures 110 comprises an electrode current collector 136 having vertically opposite upper and lower end faces 510a, 510b, and a constituent element of the group of counter electrode structures comprises a counter electrode current collector 140 having vertically opposite upper and lower end faces 509a, 509b, and the first connection member 162 and the second connection member 164 are connected to the vertical end faces of the electrode current collectors and / or counter electrode current collectors of a subset of constituent elements of the electrode group and / or counter electrode group.

[0056] 3A and 4, in one embodiment, vertically separated first and second primary connection members 162 and 164 connect the first and second primary growth constraints 154 and 156, respectively, and further connect to a subset of the constituent elements of the electrode group 110 or counter electrode group 112. According to embodiments herein, the first and second connection members 158 and 160 have opposing upper and lower inner surfaces 400a and 400b, respectively, bonded at the upper and lower end faces of the subsets 500a, 501a, 500b, 501b by an electrically insulating thermoplastic hot melt adhesive 511. In some embodiments, the hot melt adhesive 511 has a melting temperature in the range of 75°C to 130°C, preferably in the range of 77°C to 100°C. In further embodiments, the hot melt adhesive has a melt index value, measured according to ASTM D1238, ranging from at least 20 to 350, preferably ranging from at least 70 to 350. In some embodiments, the hot melt adhesive 511 includes, but is not limited to, a material selected from EAA (ethylene-co-acrylic acid), EMAA (ethylene-co-methacrylic acid), functionalized polyethylene, and functionalized polypropylene, and combinations thereof. For example, in one embodiment, the hot melt adhesive includes a mixture of EAA copolymer and EMAA copolymer. In some embodiments, the hot melt adhesive 511 does not significantly react or lose adhesive strength at temperatures of about 80° C. or greater. In some embodiments, the hot melt adhesive 511 does not significantly lose adhesive strength after 200 continuous cycles, 500 continuous cycles, 800 continuous cycles, and / or 1000 continuous cycles of the secondary battery. In one embodiment, the hot melt adhesive 511 has a film shape having a thickness in the range of about 10 to about 100 micrometers and a predetermined pattern geometry.

[0057] 3A-3B, in one embodiment, the first primary connection member 162 and / or the second primary connection member 164 (which may be the same as or different from the first secondary growth constraint 158 ​​and / or the second secondary growth constraint 160) have their respective vertical thicknesses T CThe auxiliary electrode 686 includes an opening 176 formed therethrough. According to embodiments herein, the opening 176 can provide a passage for the flow of carrier ions from the auxiliary electrode 686 through the first and / or second primary connection members 162 and / or 164 to the constituent elements of the group of unit cells. For example, for an auxiliary electrode 686 located outside the volume V enclosed by the constraint system 108, e.g., outside the first and / or second primary connection members 162 and / or 164, carrier ions provided from the auxiliary electrode 686 can access the constituent elements of the unit cells of the electrode assembly inside the constraint via a passage through the opening. The auxiliary electrode 686 can be selectively electrically connected or coupled to one or more of the electrode structures 110 and / or counter electrode structures 112 of the constituent elements of the unit cells, e.g., by a switch and / or a control unit (not shown). According to certain embodiments, the auxiliary electrode is electrolytically or otherwise coupled (e.g., through a separator) to the counter electrode structure and / or electrode structure of the constituent elements of the group of unit cells to provide a flow of carrier ions from the auxiliary electrode to the electrode structure and / or the counter electrode structure. Electrolytically coupled means that carrier ions may be transported through an electrolyte, such as from the auxiliary electrode to the electrode structure 110 and / or the counter electrode structure 112 and between the electrode structure 110 and the counter electrode structure 112. The auxiliary electrode 686 is also directly or indirectly coupled to the electrode structure 110 and / or the counter electrode structure 112, such as by a series of wires or other electrical connections.

[0058] In the embodiment shown in FIG. 6 , which depicts a top view of the electrode assembly 106 showing the first primary connection member 162, the opening 176 comprises a slot shape having a long dimension oriented in the vertical and / or stacking direction (Y direction) and extending across the constituent elements of the plurality of unit cells. Other shapes and / or configurations of the opening 176 may also be provided. For example, in one embodiment, the plurality of openings comprises a plurality of slots 178 spaced apart from one another in a laterally-spaced direction perpendicular to the stacking and vertical directions, each slot 178 extending along a vertical axis L oriented in the stacking direction. S10C and 10D, in some embodiments, the opening 176 comprises a plurality of slots extending longitudinally, and the bonding areas 901a, 901b for bonding to the subset of the constituent units of the electrode group 110 and / or the counter electrode group 112 are located on the inner surface areas 400a, 400b between the slots of the first connection member 158 and / or the second connection member 160. In some embodiments, the opening 176 comprises a plurality of slots extending longitudinally, and the bonding areas 901a, 901b for bonding to the subset of the constituent units of the electrode group 110 and / or the counter electrode group 112 are located on the inner surface areas 400a, 400b between the slots of the first connection member 158 and / or the second connection member 160.

[0059] In one embodiment, a method is provided for preparing an electrode assembly 106 with a constraint system 108, which may be used as part of a secondary battery configured to cycle between charged and discharged states. The method may generally include forming a sheet structure, cutting the sheet structure into pieces (and / or pieces), stacking the pieces, and applying the constraint system. By strip, it is understood that pieces other than those in the shape of a strip may be used. The pieces may include an electrode active material layer 132, an electrode current collector 136, a counter electrode active material layer 138, a counter electrode current collector 140, and a separator 130, and may be stacked to provide an alternating arrangement of electrode active material and / or counter electrode active material. The sheet may include, for example, a unit cell 504 and / or at least one of the components of a unit cell 504. For example, the sheet may include a group of unit cells, which may be cut to a predetermined size (such as a size suitable for a 3D battery), and then the sheets of unit cells may be stacked to form the electrode assembly 106. In another example, the sheet can include one or more components of a unit cell, such as, for example, at least one of electrode current collector 136, electrode active material layer 132, separator 130, counter electrode active material layer 138, and counter electrode current collector 140. Sheets of components can be cut to size to form pieces (such as a size suitable for a 3D battery) and then stacked to form an alternating arrangement of electrode active material layer components and counter electrode active material layer components.

[0060] In yet another embodiment, the applied constraint system 108 may correspond to any of those described herein, such as a constraint system 108 comprising a primary growth constraint system 151 comprising a first primary growth constraint 154 and a second primary growth constraint 156 and at least one primary connecting member 162, where the first primary growth constraint 154 and the second primary growth constraint 156 are separated from each other in the vertical direction, and the at least one primary connecting member 162 connects the first primary growth constraint 154 and the second primary growth constraint 156. Furthermore, the constraint system 108 may comprise a secondary growth constraint system 152 comprising a first secondary growth constraint 158 ​​and a second secondary growth constraint 160 separated in a direction perpendicular to the vertical direction (such as vertical or horizontal) and connected by at least one secondary connecting member 166, where the secondary growth constraint system 152 at least partially restrains the growth of the electrode assembly in the vertical direction upon cycling of the secondary battery 102. At least one of the primary connection member 162, or the first primary growth constraint 154 and / or the second primary growth constraint 156 of the primary growth constraint system 151, and the secondary connection member 166, or the first secondary growth constraint 158 ​​and / or the second secondary growth constraint 160 of the secondary growth constraint system 152, may be one or more of the assembly components that make up the piece, such as, for example, at least one of the electrode active material layer 132, the electrode current collector 136, the counter electrode active material layer 138, the counter electrode current collector 140, and the separator 130. For example, in one embodiment, the primary connection member 162 of the primary growth constraint system 151 may be one or more of the assembly components that make up the piece, such as, for example, at least one of the electrode active material layer 132, the electrode current collector 136, the counter electrode active material layer 138, the counter electrode current collector 140, and the separator 130. That is, applying the constraints may include applying a first primary growth constraint 154 and a second primary growth constraint 156 to a primary building block connecting member 162 that is one of the structures in the stack of fragments.

[0061] 2, an exploded view of one embodiment of a secondary battery 102 having a constraint system 108 of the present disclosure is illustrated. The secondary battery 102 includes a battery housing 104 and an electrode assembly 106 within the battery housing 104, the electrode assembly 106 having a first longitudinal end 116 and an opposing second longitudinal end 118 (i.e., separated from the first longitudinal end 116 along the Y-axis Cartesian coordinate system shown). Alternatively, the secondary battery 102 may include only a single electrode assembly 106 having a constraint system 108. Each electrode assembly 106 includes a group of electrode structures 110 and a group of counter electrode structures 112 stacked relative to each other in a stacking direction D within each of the electrode assemblies 106, or in other words, the groups of electrode structures 110 and counter electrode structures 112 are arranged in a series of alternating electrodes 110 and counter electrodes 112, which series proceeds in the stacking direction D between a first longitudinal end surface 116 and a second longitudinal end surface 118, respectively.

[0062] According to the embodiment shown in Fig. 2, tabs 190, 192 protrude out of the battery housing 104 and provide electrical connection between the electrode assemblies 106 and an energy source or consumer (not shown). More specifically, in this embodiment, the tab 190 is electrically connected (e.g., using a conductive adhesive) to a tab extension 191, which is electrically connected to the electrode 110 of each of the electrode assemblies 106. Similarly, the tab 192 is electrically connected (e.g., using a conductive adhesive) to a tab extension 193, which is electrically connected to the counter electrode 112 of each of the electrode assemblies 106. The tab extensions 191, 193 may also function as bus bars to pool current from each of the respective electrode and counter electrode structures to which the tab extensions 191, 193 are electrically connected.

[0063] Each electrode assembly 106 in the embodiment illustrated in FIG. 2 has an associated primary growth constraint system 151 for constraining growth in the vertical direction (i.e., stacking direction D). Alternatively, in one embodiment, multiple electrode assemblies 106 may share at least a portion of the primary growth constraint system 151. In the embodiment shown, each primary growth constraint system 151 includes first and second primary growth constraints 154, 156 that may overlie first and second vertical end faces 116, 118, respectively, as described above, and opposing first and second primary connection members 162, 164 that may overlie lateral surface 142, respectively, as described above. The opposing first and second primary connection members 162, 164 may pull the first and second primary growth constraints 154, 156, respectively, toward one another, or alternatively, may help constrain the growth of the electrode assembly 106 in the longitudinal direction, and the primary growth constraints 154, 156 may exert a compressive or constraining force on the opposing first and second longitudinal end faces 116, 118, respectively. As a result, expansion of the electrode assembly 106 in the longitudinal direction is prevented during formation and / or cycling of the battery 102 between charged and discharged states. Additionally, the primary growth constraint system 151 exerts a pressure on the electrode assembly 106 in a vertical direction (i.e., stacking direction D) that exceeds the pressure maintained on the electrode assembly 106 in either of two directions that are mutually perpendicular to each other and perpendicular to the vertical direction (e.g., as illustrated, the vertical direction corresponds to the direction of the Y axis, and the two directions that are mutually perpendicular to each other and to the vertical direction correspond to the directions of the X axis and Z axis, respectively, of the illustrated Cartesian coordinate system).

[0064] 2 has an associated secondary growth constraint system 152 for constraining vertical growth (i.e., expansion of the electrode assembly 106, electrode 110, and / or counter electrode 112 in the vertical direction (i.e., along the Z-axis of the Cartesian coordinate system). Alternatively, in one embodiment, multiple electrode assemblies 106 share at least a portion of the secondary growth constraint system 152. Each secondary growth constraint system 152 includes a first secondary growth constraint 158 ​​and a second secondary growth constraint 160, each of which may overlie a corresponding lateral surface 142, and at least one secondary connection member 166, each of which is described in more detail above. The secondary connecting member 166 may pull the first and second secondary growth constraints 158, 160, respectively, toward one another, or alternatively, may help constrain growth of the electrode assembly 106 in the vertical direction, and the first and second secondary growth constraints 158, 160 may apply a compressive or constraining force to the lateral surface 142, each of which is described in more detail above. As a result, expansion of the electrode assembly 106 in the vertical direction is prevented during formation and / or cycling of the battery 102 between charged and discharged states. Additionally, the secondary growth constraint system 152 exerts a pressure on the electrode assembly 106 in a vertical direction (i.e., parallel to the Z-axis of a Cartesian coordinate system) that exceeds the pressure maintained on the electrode assembly 106 in either of two directions that are mutually perpendicular to each other and perpendicular to the vertical direction (e.g., as illustrated, the vertical direction corresponds to the direction of the Z-axis, and the two directions that are mutually perpendicular to each other and perpendicular to the vertical direction correspond to the directions of the X-axis and Y-axis, respectively, of the illustrated Cartesian coordinate system).

[0065] According to certain embodiments, to complete the assembly of the secondary battery 102, the battery housing 104 can be filled with a non-aqueous electrolyte (not shown), and the lid 104a can be folded (along the fold line, FL) and sealed against the top surface 104b. When fully assembled, the sealed secondary battery 102 occupies a volume bounded by the exterior surfaces of the secondary battery 102 (i.e., the displaced volume), the secondary battery housing 104 occupies a volume corresponding to the displaced volume of the battery (including the lid 104a) less the interior volume of the battery (i.e., the prismatic volume bounded by the interior surfaces 104c, 104d, 104e, 104f, 104g, and the lid 104a), and each of the primary growth constraint system 151 and the secondary growth constraint system 152 occupies a volume corresponding to its respective displaced volume. Thus, in combination, the battery housing 104 and the primary growth constraint system 151 and the secondary growth constraint system 152 occupy 75% or less of the volume bounded by the exterior surface of the battery housing 104 (i.e., the displacement volume of the battery). For example, in one such embodiment, the primary growth constraint system 151 and the secondary growth constraint system 152 and the battery housing 104 in combination occupy 60% or less of the volume bounded by the exterior surface of the battery housing 104. By way of further example, in one such embodiment, the primary growth constraint system 151 and the secondary growth constraint system 152 and the battery housing 104 in combination occupy 45% or less of the volume bounded by the exterior surface of the battery housing 104. By way of further example, in one such embodiment, the primary growth constraint system 151 and the second growth constraint system 152 and the battery housing 104 in combination occupy 30% or less of the volume bounded by the exterior surface of the battery housing 104. As a further example, in one such embodiment, the primary growth constraint system 151 and the secondary growth constraint system 152 and the battery housing 104 in combination occupy 20% or less of the volume bounded by the exterior surface of the battery housing.

[0066] In general, the primary growth constraint system 151 and / or the secondary growth constraint system 152 will typically comprise a material that has a tensile strength of at least 10,000 psi (greater than 70 MPa), comparable to the battery electrolyte, and that does not significantly corrode at the floating or anodic potential of the battery 102, and does not significantly react or lose mechanical strength up to 45° C. and even 70° C. For example, the primary growth constraint system 151 and / or the secondary growth constraint system 152 may comprise any of a wide range of metals, alloys, ceramics, glasses, plastics, or combinations thereof (e.g., composite materials). In one exemplary embodiment, the primary growth constraining system 151 and / or the secondary growth constraining system 152 include a metal such as 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, etc.; however, in general, when the primary growth constraining system 151 and / or the secondary growth constraining system 152 include a metal, it is generally preferred that the metal be incorporated to limit corrosion and to limit the creation of an electrical short between the electrode structure 110 and the counter electrode structure 112. In another exemplary embodiment, the primary growth constraining system 151 and / or the secondary growth constraining system 152 include a ceramic such as alumina (e.g., sintered or Coorstek AD96), zirconia (e.g., Coorstek YZTP), yttria stabilized zirconia (e.g., ENrG E-Strate®), etc. In another exemplary embodiment, the primary growth constraint system 151 includes glass, such as Schott D263 tempered glass.In another exemplary embodiment, the primary growth constraint system 151 and / or the secondary growth constraint system 152 include a plastic such as polyetheretherketone (PEEK) (e.g., Aptiv 1102), PEEK with carbon (e.g., Victrex 90HMF40 or Xycomp 1000-04), polyphenylene sulfide (PPS) with carbon (e.g., Tepex Dynalite 207), polyetheretherketone (PEEK) with 30% glass (e.g., Victrex 90HMF40 or Xycomp 1000-04), polyimide (e.g., Kapton®), or the like. In another exemplary embodiment, the primary growth constraint system 151 and / or the secondary growth constraint system include composite materials such as E-glass standard cloth / epoxy, 0°, E-glass UD / epoxy, 0°, Kevlar standard cloth / epoxy, 0°, Kevlar UD / epoxy, 0°, Carbon standard cloth / epoxy, 0°, Carbon UD / epoxy, 0°, Toyobo Zylon® HM fiber / epoxy, etc. In another exemplary embodiment, the primary growth constraint system 151 and / or the secondary growth constraint system 152 include fibers such as Kevlar 49 aramid fiber, S-glass fiber, carbon fiber, Vectran UM LCP fiber, Dyneema, Zylon, etc. In yet another embodiment, the primary growth constraint system 151 and / or the secondary growth constraint system 152 comprise a coating of an insulating material, such as an insulating polymeric material, on an inner and / or outer surface of the primary growth constraint system 151 and / or the secondary growth constraint system 152, such as the inner surfaces 400a, 400b and outer surfaces 401a, 401b of the first primary connection member 162 and the second primary connection member 164.

[0067] The constituent elements of the electrode structures 110 and the counter electrode structures 112 include an electroactive material capable of absorbing and releasing carrier ions, such as lithium ions, sodium ions, potassium ions, calcium ions, magnesium ions, or aluminum ions. In some embodiments, the constituent elements of the electrode structures 110 include an anode active electroactive material (sometimes referred to as a negative electrode) and the constituent elements of the counter electrode structures 112 include a cathode active electroactive material (sometimes referred to as a positive electrode). In other embodiments, the constituent elements of the electrode structures 110 include a cathode active electroactive material and the constituent elements of the counter electrode structures 112 include an anode active electroactive material. In each of the embodiments and examples listed in this paragraph, the anode active material can be, for example, a particle agglomerate electrode, an electrode active material formed from a particulate material, such as by forming a slurry of particulate material and casting it into a layer shape, or a monolithic electrode.

[0068] According to one embodiment, the electrode active material used in the electrode structure 110 corresponding to the anode of the electrode assembly 106 includes a material that expands upon insertion of carrier ions into the electrode active material during charging of the secondary battery 102 and / or the electrode assembly 106. For example, the electrode active material may include an anode active material that accepts carrier ions during charging of the secondary battery, such as by intercalation or alloying with the carrier ions, in an amount sufficient to generate an increase in the volume of the electrode active material. For example, in one embodiment, the electrode active material may include a material that has a capacity to accept 2 or more moles of carrier ions per mole of electrode active material when the secondary battery 102 is charged from a discharged state to a charged state. As a further example, the electrode active material may include a material that has a capacity to accept 1.5 or more moles of carrier ions per mole of electrode active material, such as 2.0 or more moles of carrier ions per mole of electrode active material, and even 2.5 or more moles of carrier ions per mole of electrode active material, such as 3.5 or more moles of carrier ions per mole of electrode active material. The carrier ions accepted by the electrode active material may be at least one of lithium, potassium, sodium, calcium, and magnesium. Examples of electrode active materials that expand to provide such a volume change include one or more of silicon (e.g., SiO), aluminum, tin, zinc, silver, antimony, bismuth, gold, platinum, germanium, palladium, and alloys and compounds thereof. For example, in one embodiment, the electrode active material may include a silicon-containing material in particulate form, such as one or more of particulate silicon, particulate silicon oxide, and mixtures thereof. In yet another embodiment, the electrode active material may include a material that exhibits a smaller or even negligible volume change. For example, in one embodiment, the electrode active material may include a carbon-containing material, such as graphite. In yet another embodiment, the electrode structure may function as an electrode current collector and include a layer of lithium metal on which the electrode active material is deposited via the transfer of carrier ions to the lithium metal layer during the charging process.

[0069] Exemplary anode active electroactive materials include carbon materials such as graphite and soft or hard carbon, or any of a range of metals, metalloids, alloys, oxides, and compounds that can form alloys with lithium. Specific examples of metals or metalloids that can constitute the anode material include graphite, tin, lead, magnesium, aluminum, boron, gallium, silicon, Si / C composites, Si / graphite blends, SiOx, porous Si, intermetallic Si alloys, indium, zirconium, germanium, bismuth, cadmium, antimony, silver, zinc, arsenic, hafnium, yttrium, lithium, sodium, graphite, carbon, lithium titanate, palladium, and mixtures thereof. In one exemplary embodiment, the anode active material includes aluminum, tin, or silicon, or oxides thereof, nitrides thereof, fluorides thereof, or other alloys thereof. In another exemplary embodiment, the anode active material includes silicon, silicon oxide, or alloys thereof.

[0070] In yet another embodiment, the anode active material can include lithium metal, lithium alloys, carbon, petroleum coke, activated carbon, graphite, silicon compounds, tin compounds, and alloys thereof. In one embodiment, the anode active material can include carbon, such as non-graphitizable carbon, graphitic carbon, and the like; Li x Fe2O3(0≦x≦1), Li x WO2(0≦x≦1), Sn x Me 1-x Me' y O z(Me: Mn, Fe, Pb, Ge; Me’: Al, B, P, Si, elements found in Groups 1, 2, and 3 of the periodic table, halogens, 0 < x ≦ 1, 1 ≦ y ≦ 3, 1 ≦ z ≦ 8), etc., such as metal composite oxides, lithium metal, lithium alloys, silicon-based alloys, tin-based alloys, SnO, SnO2, PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O4, Sb2O5, GeO, GeO2, Bi2O3, Bi2O4, Bi2O5, etc., such as metal oxides, conductive polymers such as polyacetylene, Li-Co-Ni-based materials, etc. In one embodiment, the anode active material can include a carbon-based active material including crystalline graphite such as natural graphite, synthetic graphite, etc., and amorphous carbon such as soft carbon, hard carbon, etc. Other examples of carbon materials suitable for the anode active material can include graphite, kish graphite, pyrolytic carbon, mesophase pitch-based carbon fibers, mesocarbon microbeads, mesophase pitch, graphitized carbon fibers, and high-temperature sintered carbon such as coke derived from petroleum or coal tar pitch. In one embodiment, the negative electrode active material can include tin oxide, titanium nitrate, and silicon. In another embodiment, the negative electrode can include lithium metal such as a lithium metal film, or a lithium alloy such as an alloy of lithium, and one or more types of metals selected from the group consisting of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al, and Sn. In yet another embodiment, the anode active material is a metal compound capable of alloying and / or intercalating with lithium, such as Si, Al, C, Pt, Sn, Pb, Ir, Ni, Cu, Ti, Na, K, Rb, Cs, Fr, Be, Ca, Sr, Sb, Ba, Ra, Ge, Zn, Bi, In, Mg, Ga, Cd, Si alloy, Sn alloy, Al alloy, etc., SiO v(0 < v < 2), it can include metal oxides capable of doping and undoping lithium ions, such as SnO₂, vanadium oxide, or lithium vanadium oxide, and composite materials containing metal compounds and carbon materials, such as Si-C composite materials or Sn-C composite materials. For example, in one embodiment, it can be a metal such as lithium, indium, tin, aluminum, or silicon, or their alloys, transition metal oxides such as Li₄ / ₃Ti₅ / ₃O₄ or SnO, and carbonaceous materials such as artificial graphite, graphite carbon fiber, resin-fired carbon, pyrolytic vapor-grown carbon, cork, mesocarbon microbeads ("MCMB"), furfuryl alcohol resin-fired carbon, polyacene, pitch-based carbon fiber, vapor-grown carbon fiber, or natural graphite. In another embodiment, the negative electrode active material can include a composition suitable for carrier ions such as sodium or magnesium. For example, in one embodiment, the negative electrode active material includes a layered carbonaceous material and a chemical formula Na x Sn y-z M z composition disposed between the layers of the layered carbonaceous material, where M is Ti, K, Ge, P, or a combination thereof, 0 < x ≦ 15, 1 ≦ y ≦ 5, and 0 ≦ z ≦ 1.

[0071] In one embodiment, the negative electrode active material may further include a conductive material such as a carbon-based material, carbon black, graphite, graphene, activated carbon, carbon fiber, and / or a conductive assistant, carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, and the like, conductive fibers such as carbon fibers, metal fibers, and the like, conductive tubes such as carbon nanotubes, fluorocarbon powder, metal powder such as aluminum powder, nickel powder, and the like, conductive whiskers such as zinc oxide, titanium potassium oxide, and the like, conductive metal oxides such as titanium oxide, and the like, or polyphenylene derivatives, and the like. In addition, metal fibers such as metal meshes, metal powders such as copper, silver, nickel, and aluminum, and organic conductive materials such as polyphenylene derivatives may also be used. In yet another embodiment, a binder such as one or more of, for example, polyethylene, polyethylene oxide, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene-butadiene rubber, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, vinylidene fluoride-pentafluoropropylene copolymer, propylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-perfluoromethyl vinyl ether tetrafluoroethylene copolymer, ethylene-acrylic acid copolymer, and the like, may be provided and may be used alone or in mixtures.

[0072] Exemplary cathode active materials include any of a wide range of cathode active materials. For example, for lithium ion batteries, the cathode active material may include a cathode material 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 of these transition metal oxides, transition metal sulfides, and transition metal nitrides may include metal elements having a d-shell or an 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, LiNi 0.5 Mn 1.5 O4, Li(Ni x Co y Al z )O2, LiFePO4, Li2MnO4, V2O5, molybdate oxysulfide, phosphates, silicates, vanadates, sulfur, sulfur compounds, oxygen (air), Li(Ni x Mn y Co z )O2, and combinations thereof. Additionally, compounds for the cathode active material layer can include lithium-containing compounds further including metal oxides or metal phosphates, such as compounds including lithium, cobalt, and oxygen (e.g., LiCoO2), compounds including lithium, manganese, and oxygen (e.g., LiMn2O4), and compounds including lithium iron and phosphate (e.g., LiFePO). In one embodiment, the cathode active material includes at least one of lithium manganese oxide, lithium cobalt oxide, lithium nickel oxide, lithium iron phosphate, or composite oxides formed from combinations of the foregoing oxides. In another embodiment, the cathode active material includes one or more of lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2), and the like, or substituted compounds having one or more transition metals, Li 1+x Mn 2-xO4 (wherein x is 0 to 0.33), lithium manganese oxides such as LiMnO3, LiMn2O3, and LiMnO2, lithium copper oxide (Li2CuO2), vanadium oxides such as LiV3O8, LiFe3O4, V2O5, and Cu2V2O7, LiNi 1-x M x LiMnO2 (wherein M=Co, Mn, Al, Cu, Fe, Mg, B, or Ga, and x=0.01 to 0.3) 2ーx M x LiMn2O4, in which a portion of Li is replaced with an alkaline earth metal ion, a disulfide compound, Fe2(MoO4), or the like. In one embodiment, the cathode active material can include one or more of the following: a lithium manganese complex oxide represented by the chemical formula LiMn2O4 (wherein M=Co, Ni, Fe, Cr, Zn, or Ta, and x=0.01 to 0.1) or Li2Mn3MO8 (wherein M=Fe, Co, Ni, Cu, or Zn). 1+x Fe 1-x M' x (PO 4-b )X b The cathode active material may include lithium metal phosphates having an olivine crystal structure of, where M' is at least one selected from Al, Mg, Ni, Co, Mn, Ti, Ga, Cu, V, Nb, Zr, Ce, In, Zn, and Y, and X is at least one selected from F, S, and N, with -0.5≦a≦+0.5, 0≦x≦0.5, and 0≦b≦0.1, such as LiFePO4, Li(Fe,Mn)PO4, Li(Fe,Co)PO4, Li(Fe,Ni)PO4, etc. In one embodiment, the cathode active material is LiCoO2, LiNiO2, LiMnO2, LiMn2O4, LiNi 1-y Co y O2, LiCo 1-y Mn y O2, LiNi 1-y Mn y O2(0≦y≦1), Li(Ni a Co b Mn c )O4(0 <a<2,0<b<2,0<c<2、かつa+b+c=2)、LiMn 2-zNi z O4, LiMn 2-z Co z O4 (0 < z < 2), LiCoPO4, and LiFePO4, or a mixture of two or more of them, contains at least one of them.

[0073] In another embodiment, the cathode active material can contain elemental sulfur (S8), sulfur-based compounds, or a mixture thereof. Sulfur-based compounds specifically include Li2S n (n ≥ 1), organic sulfur compounds, carbon-sulfur polymers ((C2S x ) n :x = 2.5 - 50, n ≥ 2), etc. In another embodiment, the cathode active material can contain oxides of lithium and zirconium.

[0074] In another embodiment, the cathode active material can contain at least one composite oxide of lithium and at least one metal such as cobalt, manganese, nickel, or a combination thereof, and can be used. Examples thereof include Li a A 1-b M b D2 (where 0.90 ≤ a ≤ 1 and 0 ≤ b ≤ 0.5), Li a E 1-b M b O 2-c D c (where 0.90 ≤ a ≤ 1, 0 ≤ b ≤ 0.5, and 0 ≤ c ≤ 0.05), LiE 2-b M b O 4-c D c (where 0 ≤ b ≤ 0.5 and 0 ≤ c ≤ 0.05), Li a Ni 1-b-c Co b M c D a (where 0.90 ≤ a ≤ 1, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, and 0 < a ≤ 2), Li a Ni 1-b-c Co b M c O 2-a X a (where 0.90 ≤ a ≤ 1, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, and 0 < a < 2), Li a Ni1-b-c Co b M c O 2-a X2 (wherein, 0.90≦a≦1, 0≦b≦0.5, 0≦c≦0.05, and 0 <a<2)、Li a Ni 1-b-c Mn b M c O 2-a X a (Wherein, 0.90≦a≦1, 0≦b≦0.5, 0≦c≦0.05, and 0 <a<2)、Li a Ni 1-b-c Mn b M c O 2-a X2 (wherein, 0.90≦a≦1, 0≦b≦0.5, 0≦c≦0.05, and 0 <a<2)、Li a Ni b E c G d O2 (wherein 0.90≦a≦1, 0≦b≦0.9, 0≦c≦0.5, and 0.001≦d≦0.1), Li a Ni b Co c Mn d G e O2 (wherein, 0.90≦a≦1, 0≦b≦0.9, 0≦c≦0.5, 0≦d≦0.5, and 0.001≦e≦0.1), Li a NiG b O2 (wherein 0.90≦a≦1 and 0.001≦b≦0.1), Li a CoG b O2 (wherein 0.90≦a≦1 and 0.001≦b≦0.1), Li a MnG b O2 (wherein 0.90≦a≦1 and 0.001≦b≦0.1), Li a Mn2G b O4 (wherein 0.90≦a≦1 and 0.001≦b≦0.1), QO2, QS2, LiQS2, V2O5, LiV2O5, LiX'O2, LiNiVO4, Li (3-f) J2(PO4)3(0≦f≦2), Li (3-f)It is Fe2(PO4)3(0≦f≦2) and LiFePO4. In the above chemical formula, A is Ni, Co, Mn, or a combination thereof, M is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof, D is O, F, S, P, or a combination thereof, E is Co, Mn, or a combination thereof, X is F, S, P, or a combination thereof, G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof, Q is Ti, Mo, Mn, or a combination thereof, X’ is Cr, V, Fe, Sc, Y, or a combination thereof, and J is V, Cr, Mn, Co, Ni, Cu, or a combination thereof. For example, LiCoO2, LiMn x O 2x (x = 1 or 2), LiNi 1-x Mn x O 2x (0 < x < 1), LiNi 1-x-y Co x Mn y O2(0≦x≦0.5, 0≦y≦0.5), or FePO4 can be used. In one embodiment, the cathode active material includes at least one of lithium cobalt oxide, lithium nickel oxide, lithium nickel cobalt oxide, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, lithium manganese oxide, or lithium iron phosphate, nickel sulfide, copper sulfide, sulfur, iron oxide, or vanadium oxide and other lithium compounds.

[0075] In one embodiment, the cathode active material can include at least one of oxides of chemical formula N a M 1 a O2 such as NaFeO2, NaMnO2, NaNiO2, or NaCoO2, or a sodium-containing material such as an oxide represented by chemical formula NaMn 1-a M 1 a O2, where M 1 is at least one transition metal element and 0 < a < 1. Representative positive active materials include Na[Ni 1 / 2Mn 1 / 2 ]O2, Na 2 / 3 [Fe 1 / 2 Mn 1 / 2 ]O2, Na 0.44 Mn 1-a M 1 a Oxide represented by O2, Na 0.7 Mn 1-a M 1 a O 2.05 (wherein, M 1 is at least one transition metal element, 0≦a<1), Na6Fe2Si 12 O 30 or Na2Fe5Si 12 Na as O b M 2 c S 12 O 30 (wherein M 2 is at least one transition metal element, 2≦b≦6, and 2≦c≦5), Na2Fe2Si6O 18 or Na2MnFeSi6O 18 Such as Na d M 3 e SiO 18 (wherein, M 3 is at least one transition metal element, 3≦d≦6, and 1≦e≦2), NaFeSiO6, etc. f M 4 g The oxide represented by Si2O6 (wherein, M 4 is at least one element selected from transition metal elements, magnesium (Mg), and aluminum (Al), where 1≦f≦2 and 1≦g≦2; phosphates such as NaFePO4, Na3Fe2(PO4)3, Na3V2(PO4)3, Na4Co3(PO4)2P2O7, and the like; borates such as NaFeBO4 or Na3Fe2(BO4)3, NaFeF6, Na2MnF6, and the like; h M 5 Fluorides represented by F6 (wherein M 5is at least one transition metal element, 2≦h≦3), fluorophosphates such as Na3V2(PO4)2F3, Na3V2(PO4)2FO2, etc. The positive active material is not limited to the above, and any suitable positive active material used in the art can be used. In one embodiment, the positive active material is preferably NaMnO2, Na[Ni 1 / 2 Mn 1 / 2 ]O2 and Na 2 / 3 [Fe 1 / 2 Mns 1 / 2 ]O2, phosphate cathodes such as Na3V2(PO4)3 and Na4Co3(PO4)2P2O7, or fluorophosphate cathodes such as Na3V2(PO4)2F3 and Na3V2(PO4)2FO2.

[0076] In one embodiment, the electrode current collector may include a negative electrode current collector and may include a suitable conductive material, such as a metallic material. For example, in one embodiment, the negative electrode current collector may include at least one of copper, nickel, aluminum, stainless steel, titanium, palladium, calcined carbon, calcined carbon, indium, iron, magnesium, cobalt, germanium, copper or stainless steel surface treatment material (with lithium, carbon, nickel, titanium, silver, aluminum-cadmium alloy, and / or other alloys thereof). As another example, in one embodiment, the negative electrode current collector includes at least one of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel surface treatment material (with carbon, nickel, titanium, silver, aluminum-cadmium alloy, and / or other alloys thereof). In one embodiment, the negative electrode current collector includes at least one of copper and stainless steel.

[0077] In one embodiment, the counter electrode current collector may include a positive current collector and may include a suitable conductive material, such as a metallic material. In one embodiment, the positive current collector includes at least one of stainless steel, aluminum, nickel, titanium, sintered carbon, aluminum or stainless steel surface treatment materials (with carbon, nickel, titanium, silver, and / or alloys thereof). In one embodiment, the positive current collector includes aluminum.

[0078] In yet another embodiment, the cathode active material can further include one or more conductive additives and / or binders, which can be, for example, any of the conductive additives and / or binders described herein for the anode active material.

[0079] According to certain embodiments, an electrically insulating separator layer 130 may electrically insulate each component of the electrode structure 110 from each component of the counter electrode structure 112. The electrically insulating separator layer is designed to prevent electrical shorts while also allowing the transport of ionic charge carriers necessary to close the circuit during the passage of current in the electrochemical cell. In one embodiment, the electrically insulating separator layer is microporous and permeable to an electrolyte, such as a non-aqueous liquid electrolyte or a gel electrolyte. Alternatively, the electrically insulating separator layer may include a solid electrolyte, i.e., a solid ionic conductor, which may function as both a separator and an electrolyte in the battery.

[0080] In certain embodiments, the electrically insulating separator layer 130 will typically comprise a microporous separator material that is permeable to a non-aqueous electrolyte. For example, in one embodiment, the microporous separator material comprises pores having diameters of at least 50 Å, more typically in the range of about 2,500 Å, and a porosity in the range of about 25% to about 75%, more typically in the range of about 35% to 55%. Additionally, the microporous separator material may be permeable to a non-aqueous electrolyte to allow conduction of carrier ions between adjacent units of the electrode and counter electrodes. In certain embodiments, for example, disregarding the multi-efficiency of the microporous separator material, at least 70 volume % of the electrically insulating separator material between the constituent units of the electrode structures 110 and the nearest constituent units of the counter electrode structures 112 (i.e., the "adjacent pairs") for ion exchange during a charge or discharge cycle is microporous separator material, or stated another way, the microporous separator material constitutes at least 70 volume % of the electrically insulating material between the constituent units of the electrode structures 110 and the nearest constituent units of the counter electrode structures 112.

[0081] In one embodiment, the microporous separator material includes a particulate material and a binder and has a porosity (void volume fraction) of at least about 20% by volume. The pores of the microporous separator material will have a diameter of at least 50 Å and will typically be in the range of about 250-2,500 Å. The microporous separator material will typically have a porosity of less than about 75%. In one embodiment, the microporous separator material will have a porosity (void volume fraction) of at least about 25% by volume. In one embodiment, the microporous separator material will have a porosity of about 35-55%.

[0082] Binders for the microporous separator material may be selected from a wide range of inorganic or polymeric materials. For example, in one embodiment, the binder may be an organic polymeric material such as a fluoropolymer derived from monomers containing vinylidene fluoride, hexafluoropropylene, tetrafluoropropene, and the like. In another embodiment, the binder is a polyolefin such as polyethylene, polypropylene, or polybutene having any of a variety of molecular weight and density ranges. In another embodiment, the binder is selected from the group consisting of ethylene-diene-propene terpolymer, polystyrene, polymethylmethacrylate, polyethylene glycol, polyvinyl acetate, polyvinylbutyral, 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, polyacrylonitrile, polyvinylidene fluoride polyacrylonitrile, and polyethylene oxide. In another embodiment, the binder is selected from the group consisting of acrylate, styrene, epoxy, and silicone. Other suitable binders may be selected from polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene, polymethylmethacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinyl acetate, polyethylene-co-vinyl acetate, polyethylene oxide, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cyanoethyl pullulan, cyanoethyl polyvinyl alcohol, cyanoethyl cellulose, cyanoethyl sucrose, pullulan, carboxymethyl cellulose, acrylonitrile-styrene-butadiene copolymer, polyimide, or mixtures thereof.In yet another embodiment, the binder may be selected from polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trichloroethylene, polymethylmethacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinyl acetate, ethylene vinyl acetate copolymer, polyethylene oxide, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cyanoethyl pullulan, cyanoethyl polyvinyl alcohol, cyanoethyl cellulose, pullulan, carboxyl methyl cellulose, acrylonitrile styrene butadiene copolymer, polyimide, polyethylene terephthalate, polybutylene terephthalate, polyester, polyacetal, polyamide, polyether ether ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, polyethylene naphthalene, and / or any combination thereof. In another embodiment, the binder is a copolymer or blend of two or more of the aforementioned polymers.

[0083] The particulate material comprising the microporous separator material may also be selected from a wide range of materials. Generally, such materials have relatively low electronic and ionic conductivity at operating temperatures and do not corrode under the operating voltages of the battery electrodes or current collectors that contact the microporous separator material. For example, in one embodiment, the particulate material has a molecular weight of 1×10 -4 By way of further example, in one embodiment, the particulate material has a conductivity for carrier ions (e.g., lithium) of less than 1×10 -5 By way of further example, in one embodiment, the particulate material has a conductivity for carrier ions of less than 1×10 -6The particulate material has a conductivity for carrier ions of less than S / cm. For example, in one embodiment, the particulate material is an inorganic material selected from the group consisting of silicates, phosphates, aluminates, aluminosilicates, and hydroxides such as magnesium hydroxide, calcium hydroxide, etc. Exemplary particulate materials include particulate polyethylene, polypropylene, TiO2-polymer composites, silica aerogels, fumed silica, silica gels, 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 particulate material includes particulate oxides or nitrides such as TiO2, SiO2, Al2O3, GeO2, B2O3, Bi2O3, BaO, ZnO, ZrO2, BN, Si3N4, Ge3N4, etc. (See, for example, P. Arora and J. Zhang, "Battery Separators," Chemical Reviews 2004, 104, 4419-4462.) Other suitable particles include BaTiO3, Pb(Zr,Ti)O3 (PZT), Pb 1-x La x Zr 1-y Ti y O3(PLZT), PB(Mg3Nb 2 / 3 The particulate material may include, for example, ZnO-PbTiO3 (PMN-PT), hafnia (HfO2), SrTiO3, SnO2, CeO2, MgO, NiO, CaO, ZnO, ZrO2, YO3, Al2O3, TiO2, SiC, or mixtures thereof. In one embodiment, the particulate material will have an average particle size of about 20 nm to 2 micrometers, more typically 200 nm to 1.5 micrometers. In one embodiment, the particulate material will have an average particle size of about 500 nm to 1 micrometer.

[0084] In yet another embodiment, the electrically insulating separator 130 includes a solid electrolyte, for example, as in a solid-state battery. Generally speaking, a solid electrolyte can facilitate the transport of carrier ions without the need for the addition of a liquid or gel electrolyte. According to certain embodiments, when a solid electrolyte is provided, the solid electrolyte may itself be capable of providing an insulator between the electrodes and allowing the passage of carrier ions through the insulator, and may not require the addition of a liquid electrolyte that permeates the structure.

[0085] In one embodiment, the secondary battery 102 may include an electrolyte, which may be any of organic liquid electrolytes, inorganic liquid electrolytes, aqueous electrolytes, non-aqueous electrolytes, solid polymer electrolytes, solid ceramic electrolytes, solid glass electrolytes, garnet electrolytes, gel polymer electrolytes, inorganic solid electrolytes, fused inorganic electrolytes, and the like. Other arrangements and / or configurations of the electrically insulating separator 130 may also be provided, with or without a liquid electrolyte. In one embodiment, the solid electrolyte may include a ceramic or glass material that can conduct carrier ions therethrough while providing electrical insulation. Examples of ion conducting materials may include garnet materials, sulfide glasses, lithium ion conducting glass ceramics, or phosphate ceramic materials. In one embodiment, the solid polymer electrolyte may include any of polyethylene oxide (PEO)-based, polyvinyl acetate (PVA)-based, polyethyleneimine (PEI)-based, polyvinylidene fluoride (PVDF)-based, polyacrylonitrile (PAN)-based, LiPON (lithium phosphorus oxide), and polymethyl methacrylate (PMMA)-based polymers or copolymers thereof. In another embodiment, a sulfide-based solid electrolyte may be provided, such as a sulfide-based solid electrolyte comprising at least one of lithium and / or phosphorus, such as Li2S and P2S5, and / or at least one of SiS2, GeS2, Li3PS4, Li4P2S7, Li4SiS4, Li2S-P2S5, and other sulfides such as 50Li4SiO4.50Li3BO3, and / or B2S3. Other embodiments of the solid electrolyte include Li3N, LiI, Li5NI2, Li3N-LiI-LiOH, LiSiO4, LiSiO4-LiI-LiOH, Li2SiS3, Li4SiO4, Li4SiO4-LiI-LiOH, and Li3PO4-Li2S-SiS2, Li2S-P2S5, Li2S-P2S5-L4SiO4, Li2S-Ga2S3-GeS2, Li2S-Sb2S3-GeS2, Li 3.25 -Ge 0.25 -P 0.75 S4, (La,Li)TiO3(LLTO), Li6La2CaTa2O 12 , Li6La2ANb2O 12(A=Ca, Sr), Li2Nd3TeSbO 12 , LiBO 2.5 N 0.5 , Li9SiAlO8, Li 1+x Al x Ge 2-x (PO4)3(LAGP), Li 1+x Al x Ti 2-x (PO4)3(LATP), Li 1+x Ti 2-x Al x S y (PO4) 3-y , LiAl x Zr 2-x (PO4)3, LiTi x Zr 2-x Lithium (Li) nitrides, halides, and sulfides, such as (PO4)3, and other embodiments of the solid electrolyte may include garnet materials, such as those described in U.S. Patent No. 10,361,455, which is incorporated herein in its entirety. In one embodiment, the garnet solid electrolyte is a nesosilicate having the general formula X3Y2(SiO4)3, where X can be a divalent cation, such as Ca, Mg, Fe, or Mn, or Y can be a trivalent cation, such as Al, Fe, or Cr.

[0086] According to one embodiment of the assembled energy storage device, the electrically insulating separator is permeable to a non-aqueous electrolyte suitable for use as a secondary battery electrolyte. Typically, the non-aqueous electrolyte comprises a lithium salt and / or mixture of salts dissolved in an organic solvent and / or solvent mixture. Exemplary lithium salts include inorganic lithium salts such as LiClO4, LiBF4, LiPF6, LiAsF6, LiCl, and LiBr, as well as inorganic lithium salts such as LiB(CH5)4, LiN(SO2CF3)2, LiN(SO2CF3)3, LiNSO2CF3, LiNSO2CF5, LiNSO2C4F9, LiNSO2C5F 11 , LiNSO2C6F 13 , and LiNSO2C7F 15As yet another example, the electrolyte can include sodium ions dissolved in the electrolyte, such as, for example, any one or more of NaClO4, NaPF6, NaBF4, NaCF3SO3, NaN(CF3SO2)2, NaN(C2F5SO2)2, NaC(CF3SO2)3. Salts of magnesium and / or potassium can be provided as well. For example, magnesium salts such as magnesium chloride (MgCl), magnesium bromide (MgBr), or magnesium iodide (MgI) may be provided, and / or magnesium perchlorate (Mg(ClO)), magnesium nitrate (Mg(NO), magnesium sulfate (MgSO), magnesium tetrafluoroborate (Mg(BF), magnesium tetraphenylborate (Mg(B(CH), magnesium hexafluorophosphate (Mg(PF), magnesium hexafluoroarsenate (Mg(AsF), magnesium perfluoroalkylsulfonate (Mg(R ... f1 SO3)2) where R f1 is a perfluoroalkyl group), magnesium perfluoroalkylsulfonylimide (Mg((R f2 SO2)2N)2, where R f2As well as magnesium salts, which may be at least one selected from the group consisting of hexaalkyldisilazides ((Mg(HRDS)2), where R is a perfluoroalkyl group) and hexaalkyldisilazides ((Mg(HRDS)2), where R is an alkyl group). Exemplary organic solvents for dissolving the lithium salts include cyclic esters, linear esters, cyclic ethers, and linear ethers. Specific examples of cyclic esters include propylene carbonate, ethylene carbonate, butylene carbonate, γ-butyrolactone, vinylene carbonate, 2-methyl-γ-butyrolactone, acetyl-γ-butyrolactone, and γ-valerolactone. Specific examples of chain 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, alkyl propionate, dialkyl malonate, and alkyl acetate. Specific examples of cyclic ethers include tetrahydrofuran, alkyl tetrahydrofuran, dialkyl tetrahydrofuran, alkoxy tetrahydrofuran, dialkoxy tetrahydrofuran, 1,3-dioxolane, alkyl-1,3-dioxolane, and 1,4-dioxolane. Specific examples of chain 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.

[0087] 8A-10E, in one embodiment, a process for manufacturing a secondary battery and / or electrode assembly as disclosed herein is provided. In particular, an electrically insulating thermoplastic hot melt adhesive 511 is used to bond a subset of the constituent elements of the electrode group and / or counter electrode group to the first connection member 162 and / or the second connection member 164 of the constraint system 108. The hot melt adhesive 511 may be applied to the inner surface of the first connection member 400a and the second connection member 400b by any suitable method, such as by providing a blown or cast film of the adhesive, by extruding the adhesive, and / or by using a glue gun. In some embodiments, the hot melt adhesive 511 is provided in the form of a film having a predetermined thickness and pattern. According to embodiments herein, the predetermined pattern may conform to the shape of the inner surface of the first connection member 510a and the second connection member 510b. The predetermined pattern may be cut using a laser or a die. In some embodiments, the first connecting member 162 and / or the second connecting member 164 (which may be the same as or different from the first secondary growth constraint 158 ​​and the second secondary growth constraint 160) includes an opening 176 formed through the vertical thickness of the respective member, and the adhesive film cutout 513 is disposed along the bonding area 901 a, 901 b of the inner surface 400 a, 400 b of the first connecting member 162 and / or the second connecting member 164 adjacent the opening 176. In some embodiments, the hot melt adhesive is melted and / or softened by heating at a temperature of at least 75° C. and not more than 130° C. In some embodiments, a constituent unit of the group 110 of electrode structures comprises an electrode current collector 136 having upper and lower end faces that are opposite in the vertical direction 510a, 510b, and a constituent unit of the group 112 of counter electrodes comprises a counter electrode current collector 140 having upper and lower end faces that are opposite in the vertical direction 509a, 509b, and the adhesive film cutout is arranged in contact with the vertical end faces of the electrode current collectors and / or counter electrode current collectors of a subset of the constituent units of the electrode group and / or counter electrode group.

[0088] According to one embodiment, a process for manufacturing a secondary battery and / or electrode assembly according to any one of the preceding claims includes providing an electrode assembly, providing a constraint system, and providing an electrically insulating thermoplastic hot melt adhesive film having (i) a melting temperature in the range of 75° C. to 130° C. and (ii) a melt index value in the range of at least 20 to 350, measured according to ASTM D1238. The process further includes placing the first surface 514a of the adhesive film in contact with the upper inner surface 400a or the lower inner surface 400b of the first connecting member 162 and the second connecting member 164, and placing the upper end surface or the lower end surface of a subset of the constituent elements of the electrode group and / or counter electrode group in contact with the second surface 514b of the adhesive film 511. For example, the upper inner surface 400a of the first connection member 162 can be placed in contact with the first surface 514a of the first adhesive film 511a, and the lower inner surface 400b of the second connection member 164 can be placed in contact with the first surface 514a of the second adhesive film 511b. The first adhesive film 511a and the second adhesive film 511b can be placed in contact with the upper end surface or the lower end surface of the subset of the constituent units of the electrode group and / or counter electrode group. The process can further include melting and / or softening the adhesive film by heating to bond the subset of the constituent units of the electrode group and / or counter electrode group to the first connection member and the second connection member. According to an embodiment, pressure is applied during, before, and / or after heating to facilitate adhesion of the film. For example, a pressure of at least 3 psi may be applied, and even at least 5 psi may be applied, such as a pressure in the range of 3 psi to 10 psi. EXAMPLES

[0089] Example 1 This example demonstrates an exemplary process for manufacturing a secondary battery 102 and / or an electrode assembly 10, with an emphasis on the application of a hot melt adhesive. Figures 8A-8E are referred to herein as one embodiment of the process.

[0090] In this embodiment, the hot melt adhesive 511 is provided in the form of an adhesive film shape having a predetermined thickness and a first adhesive portion 511a and a second adhesive portion 511b (FIG. 10A). The adhesive film 511 is then cut to form cutouts having a predetermined pattern that at least partially covers and / or follows the shape of the inner surfaces of the first connecting member 400a and the second connecting member 400b, as shown in FIG. 8B. The first portion 511a of the adhesive film cutout and the second portion 511b of the adhesive film cutout are then placed in contact with the upper inner surface 400a and the lower inner surface 400b of the first connecting member 510a and the second connecting member 510b, leaving the opening (slot) 176 open, as shown in FIG. 8C. The upper and lower end faces of the subset of constituent units of the electrode group 110 and / or counter electrode group 112 are then placed in contact with the second first and second portions of the adhesive film cutouts 511a, 511b (FIG. 8D) on the surface of the adhesive film opposite the surface of the film placed in contact with the inner surface 400a, 400b. The adhesive film cutouts are melted and / or softened by heating at a temperature of at least 75° C. and not more than 130° C. to bond the subset of constituent units of the electrode group 110 and / or counter electrode group 112 to the first and second connecting members 162, 164. During the heating process, pressure can be applied to the outer surfaces 401a, 401b of the first and second connecting members 162, 164 to improve adhesion. The assembled product is shown in FIG. 8E.

[0091] Example 2 This example demonstrates another exemplary process for manufacturing a secondary battery 102 and / or an electrode assembly 10, with an emphasis on the application of a hot melt adhesive. Figures 9A-9E are referred to herein as one embodiment of the process.

[0092] In this embodiment, the process differs from that of Example 1 by first placing the first and second portions of the adhesive film 511a, 511b in contact with the upper and lower inner surfaces 400a, 400b of the first and second connecting members 162, 164 (FIG. 9B) and then cutting to form a predetermined desired pattern, as shown in FIG. 9C. The first and second secondary connecting members 162, 164 can then be connected to a subset of the constituent elements of the electrode group 110 and / or counter electrode group 112, for example, as described for Example 1 and depicted in FIGS. 9D-9E.

[0093] Example 3 This example demonstrates another exemplary process for manufacturing a secondary battery 102 and / or an electrode assembly 10, with an emphasis on the application of a hot melt adhesive. Figures 10A-10E are referred to herein as one embodiment of the process.

[0094] In this embodiment, the adhesive film 511 is cut into several strips 513, as illustrated in FIG. 10B. A first portion of the strips 513a is then placed in contact with the upper inner surface 400a of the first connecting member 162, and a second portion of the strips 513b is placed in contact with the lower inner surface 400b of the second connecting member 164, between the openings (slots) 176 (FIG. 10C). The first secondary connecting member 162 and the second secondary connecting member 164 can then be connected to a subset of the constituent elements of the electrode group 110 and / or the counter electrode group 112, for example, as described for embodiment 1 and depicted in FIGS. 10D-10E. Alternatively, similar to the process demonstrated in embodiment 2, the adhesive film 511 can be placed on the upper inner surface 400a and the lower inner surface 400b of the first connecting member 162 and the second connecting member 164, and then cut, leaving the strips 513 in contact. Other methods of applying and / or connecting the adhesive film 511 to the first primary connection member and / or the second primary connection member may also be provided.

[0095] The following embodiments are provided to illustrate aspects of the disclosure, but the embodiments are not intended to be limiting, and other aspects and / or embodiments may be provided.

[0096] Embodiment 1. An electrode assembly for a secondary battery comprising a group of unit cells, a constraint system, and an adhesive, The electrode assembly has a longitudinal axis, a transverse axis, and a vertical axis perpendicular to each other, a first longitudinal end surface and a second longitudinal end surface separated from each other in a longitudinal direction, and an electrode assembly longitudinal axis A. EA and a lateral surface connecting the first and second longitudinal end surfaces, the lateral surface having opposed first and second regions on opposite sides of the longitudinal axis and separated in a first direction perpendicular to the longitudinal axis, the electrode assembly having a maximum width W measured in the longitudinal direction. EA and the maximum length L measured laterally bounded by the lateral plane EA and the maximum height H bounded by the lateral surface and measured vertically EA and a lateral surface having the electrode assembly further comprises a group of electrode structures, a group of counter electrode structures, and an electrically insulating separator material that electrically separates the constituent units of the electrode group and the counter electrode group, the constituent units of the electrode structure group and the counter electrode structure group having upper and lower end faces that are vertically separated and on opposite sides, and each constituent unit of the unit cell group comprises an electrode structure, a counter electrode structure, and an electrically insulating separator between the electrode structure and the counter electrode structure, An electrode assembly, wherein the constraint system comprises: (i) vertically separated first and second primary growth constraints; and (ii) vertically separated first and second connecting members connecting the first and second primary growth constraints and a subset of constituent units of the electrode group or counter electrode group, the first and second connecting members having opposed upper and lower inner surfaces to which upper and lower end surfaces of the subset are respectively adhered by an electrically insulating thermoplastic hot melt adhesive having (i) a melting temperature in the range of 75°C to 130°C and (ii) a melt index value.

[0097] Embodiment 2: A secondary battery comprising the electrode assembly according to embodiment 1.

[0098] Embodiment 3. The electrode assembly or secondary battery according to embodiment 1 or 2, wherein the melting temperature of the hot melt adhesive is in the range of 77°C to 100°C.

[0099] Embodiment 4. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the melt index value, measured according to ASTM D1238, is in the range of at least 70 to 350.

[0100] Embodiment 5. An electrode assembly or secondary battery according to any one of the preceding embodiments, wherein the constituent units of the group of electrode structures comprise electrode current collectors having upper and lower end faces that are vertically opposite, and the constituent units of the group of counter electrode structures comprise counter electrode current collectors having upper and lower end faces that are vertically opposite, and the first connection member and the second connection member are bonded to the vertical end faces of the electrode current collectors or counter electrode current collectors of a subset of the constituent units of the electrode group or counter electrode group.

[0101] Embodiment 6. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the hot melt adhesive comprises a material selected from EAA (ethylene-co-acrylic acid), EMAA (ethylene-co-methacrylic acid), functionalized polyethylene and functionalized polypropylene, and combinations thereof.

[0102] Embodiment 7. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the hot melt adhesive comprises a mixture of an EAA copolymer and an EMAA copolymer.

[0103] Embodiment 8. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the hot melt adhesive does not significantly react or lose adhesive strength at a temperature of about 80° C. or higher.

[0104] Embodiment 9. An electrode assembly or secondary battery according to any one of the preceding embodiments, wherein the hot melt adhesive does not significantly lose adhesion over 1000 continuous cycles of the secondary battery.

[0105] Embodiment 10. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the hot melt adhesive has a film shape having a thickness in the range of about 10 to about 100 micrometers and a predetermined pattern geometry.

[0106] Embodiment 11. An electrode assembly or secondary battery according to any one of the preceding embodiments, wherein the first connecting member or the second connecting member includes an opening formed through the vertical thickness of the respective member, the first connecting member or the second connecting member including a bonding area on an inner surface adjacent the opening, and a hot melt adhesive is provided for adhesion to a subset of the constituent elements of the electrode group or counter electrode group.

[0107] Embodiment 12. The electrode assembly or secondary battery of embodiment 11, wherein both the first connecting member and the second connecting member include an opening through the vertical thickness of the first connecting member and the second connecting member.

[0108] Embodiment 13. The electrode assembly or secondary battery according to embodiment 11 or 12, wherein the opening comprises a plurality of slots extending in the longitudinal direction, and the bonding area for bonding the subset is located on the inner surface area between the slots of the first connection member or the second connection member.

[0109] Embodiment 14. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein a surface area of ​​the first longitudinal end face and the second longitudinal end face is less than 33% of a surface area of ​​the electrode assembly.

[0110] Embodiment 15. Length L of each constituent unit of the electrode structure group E and the length L of each constituent unit of the counter electrode structure group CE and the central longitudinal axis A of these units. E and A CE The width W of each component of the electrode structure group is measured in the horizontal direction.E and the width W of each constituent unit of the counter electrode structure group CE and are measured vertically, and the height H of each constituent unit of the electrode structure group is E and the height H of each constituent unit of the counter electrode structure group CE and the central longitudinal axis A of each such unit. E Or A CE The L of each component unit of the electrode structure group is measured in the vertical direction, which is perpendicular to the longitudinal direction. E and W E and H E and H for each unit of the electrode structure group is at least 5:1, E and W E The ratio of L of each constituent unit of the counter electrode structure group is 0.4:1 to 1000:1. CE and W CE and H CE and H for each of the constituent units of the counter electrode structure group is at least 5:1, CE and W CE The electrode assembly or secondary battery according to any one of the preceding embodiments, wherein the ratio of

[0111] Embodiment 16. L EA and W EA Each of and H EA 4. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the ratio of

[0112] Embodiment 17. The electrode assembly or secondary battery according to any one of the preceding embodiments, wherein the projection of the constituent elements of the electrode structure group and the counter-electrode structure group onto the first longitudinal surface surrounds a first projected area, the projection of the constituent elements of the electrode structure group and the counter-electrode structure group onto the second longitudinal surface surrounds a second projected area, and the first primary growth constraint and the second primary growth constraint comprise a first compression member and a second compression member overlapping the first projected area and the second projected area.

[0113] Embodiment 18. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the first primary growth constraint and the second primary growth constraint maintain a pressure in the longitudinal direction on the electrode assembly that exceeds a pressure maintained on the electrode assembly in each of two directions that are mutually perpendicular and perpendicular to the longitudinal direction, and that exceeds a pressure maintained on the electrode assembly in each of two directions that are mutually perpendicular and perpendicular to the longitudinal direction.

[0114] Embodiment 19. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the first primary growth constraint and the second primary growth constraint maintain a pressure in the longitudinal direction on the electrode assembly that is at least three times greater than the pressure maintained on the electrode assembly in each of two directions that are mutually perpendicular and perpendicular to the longitudinal direction.

[0115] Embodiment 20. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the first primary growth constraint and the second primary growth constraint maintain a pressure in the longitudinal direction on the electrode assembly that is at least four times greater than the pressure maintained on the electrode assembly in each of two directions that are mutually perpendicular and perpendicular to the longitudinal direction.

[0116] Embodiment 21. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the first primary growth constraint and the second primary growth constraint maintain a pressure in the longitudinal direction on the electrode assembly that is at least 5 times greater than the pressure maintained on the electrode assembly in each of two directions that are mutually perpendicular and perpendicular to the longitudinal direction.

[0117] Embodiment 22. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the primary growth constraint system inhibits the growth of the electrode assembly in the vertical direction such that the increase in the ferret diameter of the electrode assembly in the vertical direction over 20 consecutive cycles is less than 20%.

[0118] Embodiment 23. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the primary growth constraint system inhibits the growth of the electrode assembly in the vertical direction such that the increase in ferret diameter of the electrode assembly in the vertical direction can be less than 10% over 10 consecutive cycles.

[0119] Embodiment 24. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the primary growth constraint system inhibits the growth of the electrode assembly in the vertical direction such that the increase in ferret diameter of the electrode assembly in the vertical direction can be less than 10% over five consecutive cycles.

[0120] Embodiment 25. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the primary growth constraint system inhibits the growth of the electrode assembly in the vertical direction such that the increase in the ferret diameter of the electrode assembly in the vertical direction is less than 1% per cycle.

[0121] Embodiment 26. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the first connecting member and the second connecting member comprise a secondary growth constraint system that constrains the growth of the electrode assembly in the vertical direction such that the increase in ferret diameter of the electrode assembly in the vertical direction can be less than 20% over 20 consecutive cycles.

[0122] Embodiment 27. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the first connecting member and the second connecting member comprise a secondary growth constraint system that constrains the growth of the electrode assembly in the vertical direction such that the increase in ferret diameter of the electrode assembly in the vertical direction can be less than 10% over 10 consecutive cycles.

[0123] Embodiment 28. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the first connecting member and the second connecting member comprise a secondary growth constraint system that constrains the growth of the electrode assembly in the vertical direction such that the increase in ferret diameter of the electrode assembly in the vertical direction can be less than 10% over five consecutive cycles.

[0124] Embodiment 29. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the first connecting member and the second connecting member comprise a secondary growth constraint system that constrains the growth of the electrode assembly in the vertical direction such that the increase in the ferret diameter of the electrode assembly in the vertical direction can be less than 1% per cycle.

[0125] Embodiment 30. An electrode assembly or a secondary battery according to any one of the preceding embodiments, wherein (i) the constituent unit of the group of electrode structures is an anode structure and the constituent unit of the group of counter electrode structures is a cathode structure, or (ii) the constituent unit of the group of electrode structures is a cathode structure and the constituent unit of the group of counter electrode structures is an anode structure.

[0126] Embodiment 31. An electrode assembly or secondary battery according to embodiment 31, wherein the constituent unit of the group of electrode structures is an anode structure comprising an anode active material layer, and the constituent unit of the group of counter electrode structures is a cathode structure comprising a cathode active material layer.

[0127] Embodiment 32. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the electrode assembly is contained in a sealed battery housing.

[0128] Embodiment 33. An electrode assembly or a secondary battery according to embodiment 33, wherein the set of carrier ions and electrode constraints are contained within a sealed battery housing.

[0129] Embodiment 34. The constituent units of the group of electrode structures are anode active materials, which are carbon materials, graphite, soft or hard carbon, metals, metalloids, alloys, oxides, compounds capable of forming alloys with lithium, tin, lead, magnesium, aluminum, boron, gallium, silicon, Si / C composites, Si / graphite blends, SiOx, porous Si, intermetallic Si alloys, indium, zirconium, germanium, bismuth, cadmium, antimony, silver, zinc, arsenic, hafnium, yttrium, lithium, sodium, lithium titanate, palladium, lithium metal, carbon, petroleum coke, activated carbon, graphite, silicon compounds, silicon alloys, tin compounds, non-graphitizable carbon, graphitic carbon, Li x Fe2O3(0≦x≦1), Li x WO2(0≦x≦1), Sn x Me 1-x Me' y O z(Me: Mn, Fe, Pb, Ge; Me’: Al, B, P, Si, elements found in Group 1, Group 2, and Group 3 of the periodic table, halogens, 0 < x ≤ 1, 1 ≤ y ≤ 3, 1 ≤ z ≤ 8), lithium alloys, silicon-based alloys, tin-based alloys, metal oxides, SnO, SnO2, PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O4, Sb2O5, GeO, GeO2, Bi2O3, Bi2O4, Bi2O5, conductive polymers, polyacetylene, Li-Co-Ni-based materials, crystalline graphite, natural graphite, synthetic graphite, amorphous carbon, kish graphite, pyrolytic carbon, mesophase pitch-based carbon fibers, mesocarbon microbeads, mesophase pitch, graphitized carbon fibers, high-temperature sintered carbon, petroleum, coke derived from coal tar pitch, tin oxide, titanium nitrate, lithium metal film, an alloy of lithium and one or more metals selected from the group consisting of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al, and Sn, a metal compound selected from any of Si, Al, C, Pt, Sn, Pb, Ir, Ni, Cu, Ti, Na, K, Rb, Cs, Fr, Be, Ca, Sr, Sb, Ba, Ra, Ge, Zn, Bi, In, Mg, Ga, Cd that can be alloyed with and / or intercalated with lithium, Sn alloys, Al alloys, metal oxides capable of doping and undoping lithium ions, SiO v (0 < v < 2), a composite material containing SnO2, vanadium oxides, lithium vanadium oxides, metal compounds, and carbon materials, Si-C composite materials, Sn-C composite materials, transition metal oxides, Li4 / 3Ti5 / 3O4, SnO, carbonaceous materials, graphite carbon fibers, resin-fired carbon, pyrolytic vapor-grown carbon, cork, mesocarbon microbeads (“MCMB”), furfuryl alcohol resin-fired carbon, polyacene, pitch-based carbon fibers, vapor-grown carbon fibers, or natural graphite, and the chemical formula Na disposed between layers of a layered carbonaceous material x Sn y-z M zA composition wherein M is Ti, K, Ge, P, or a combination thereof, and 0 < x ≦ 15, 1 ≦ y ≦ 5, and 0 ≦ z ≦ 1, and an anode active material containing any one or more of the foregoing oxides, alloys, nitrides, fluorides, and any arbitrary combination of the foregoing, an electrode assembly or a secondary battery according to any one of the preceding embodiments.

[0130] Embodiment 35. The electrode assembly or secondary battery according to Embodiment 34, wherein the anode active material contains at least one of lithium metal, a lithium metal alloy, silicon, a silicon alloy, silicon oxide, tin, a tin alloy, tin oxide, and a carbon-containing material.

[0131] Embodiment 36. The electrode assembly or secondary battery according to Embodiment 35, wherein the negative electrode active material contains at least one of silicon and silicon oxide.

[0132] Embodiment 37. The electrode assembly or secondary battery according to Embodiment 35, wherein the anode active material contains at least one of lithium and a lithium metal alloy.

[0133] Embodiment 38. The electrode assembly or secondary battery according to Embodiment 35, wherein the anode active material contains a carbon-containing substance.

[0134] Embodiment 39. The electrode assembly or secondary battery according to any one of the preceding embodiments, wherein the constituent unit of the group of electrical insulation separators contains a microporous separator material permeated with a non-aqueous liquid electrolyte.

[0135] Embodiment 40. The electrode assembly or secondary battery according to any one of Embodiments 1 to 39, wherein the constituent unit of the group of electrical insulation separators contains a solid electrolyte.

[0136] Embodiment 41. The electrode assembly or secondary battery according to Embodiment 40, wherein the constituent unit of the group of electrical insulation separators contains a ceramic material, glass, or a garnet material.

[0137] Embodiment 42. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the electrode assembly comprises an electrolyte selected from the group consisting of a non-aqueous liquid electrolyte, a gel electrolyte, a solid electrolyte, and combinations thereof.

[0138] Embodiment 43. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the electrode assembly comprises a liquid electrolyte.

[0139] Embodiment 44. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the electrode assembly comprises an aqueous liquid electrolyte.

[0140] Embodiment 45. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the electrode assembly comprises a non-aqueous liquid electrolyte.

[0141] Embodiment 46. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the electrode assembly comprises a gel electrolyte.

[0142] Embodiment 47. An electrode assembly or a secondary battery according to any one of the preceding embodiments, wherein the electrically insulating separator comprises a solid electrolyte.

[0143] Embodiment 48. An electrode assembly or a secondary battery according to any one of the preceding embodiments, wherein the electrically insulating separator comprises a solid polymer electrolyte.

[0144] Embodiment 49. An electrode assembly or a secondary battery according to any one of the preceding embodiments, wherein the electrically insulating separator comprises a solid inorganic electrolyte.

[0145] Embodiment 50. An electrode assembly or a secondary battery according to any one of the preceding embodiments, wherein the electrically insulating separator comprises a solid organic electrolyte.

[0146] Embodiment 51. An electrode assembly or a secondary battery according to any one of the preceding embodiments, wherein the electrically insulating separator comprises a ceramic electrolyte.

[0147] Embodiment 52. An electrode assembly or a secondary battery according to any one of the preceding embodiments, wherein the electrically insulating separator comprises an inorganic electrolyte.

[0148] Embodiment 53. An electrode assembly or a secondary battery according to any one of the preceding embodiments, wherein the electrically insulating separator comprises a ceramic.

[0149] Embodiment 54. An electrode assembly or a secondary battery according to any one of the preceding embodiments, wherein the electrically insulating separator comprises a garnet material.

[0150] Embodiment 55. The electrode assembly or secondary battery of any one of the preceding embodiments, comprising an electrolyte selected from the group consisting of an aqueous electrolyte, a non-aqueous liquid electrolyte, a solid polymer electrolyte, a solid ceramic electrolyte, a solid glass electrolyte, a solid garnet electrolyte, a gel polymer electrolyte, an inorganic solid electrolyte, and a fused inorganic electrolyte.

[0151] Embodiment 56. The constituent unit of the group of the counter electrode structure is a cathode active material, and includes transition metal oxides, transition metal sulfides, transition metal nitrides, lithium transition metal oxides, lithium transition metal sulfides, lithium transition metal nitrides, LiCoO2, LiNi, which have a metal element having a d-shell or an f-shell, and the metal element is any one selected from 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. 0.5 Mn 1.5 O4, Li(Ni x Co y Al z )O2, LiFePO4, Li2MnO4, V2O5, molybdate oxysulfides, phosphates, silicates, vanadates, sulfur, sulfur compounds, oxygen (air), Li(Ni x Mn y Co z)O2, lithium-containing compounds including metal oxides or metal phosphates, compounds including lithium, cobalt, and oxygen (e.g., LiCoO2), compounds including lithium, manganese, and oxygen (e.g., LiMn2O4), compounds including lithium iron and phosphates (e.g., LiFePO), lithium manganese oxide, lithium cobalt oxide, lithium nickel oxide, lithium iron phosphate, lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2), substituted compounds having one or more transition metals, lithium manganese oxide, Li 1+x Mn 2-x O4 (wherein x is 0 to 0.33), LiMnO3, LiMn2O3, LiMnO2, lithium copper oxide (Li2CuO2), vanadium oxide, LiV3O8, LiFe3O4, V2O5, Cu2V2O7, LiNi 1-x M x Lithium nickel oxide with Ni site represented by the chemical formula of LiMnO2 (wherein M=Co, Mn, Al, Cu, Fe, Mg, B, or Ga, and x=0.01 to 0.3). 2-x M x Lithium manganese composite oxides represented by the chemical formula Li2Mn3MO8 (wherein M=Co, Ni, Fe, Cr, Zn, or Ta, and x=0.01 to 0.1), Li2Mn3MO8 (wherein M=Fe, Co, Ni, Cu, or Zn), LiMn2O4 in which a portion of Li is replaced by an alkaline earth metal ion, disulfide compounds, Fe2(MoO4)3, and lithium metal phosphates having an olivine crystal structure represented by the chemical formula 2: Li 1+a Fe 1-x M' x (PO 4-b )X b (wherein M' is at least one selected from Al, Mg, Ni, Co, Mn, Ti, Ga, Cu, V, Nb, Zr, Ce, In, Zn, and Y, and X is at least one selected from F, S, and N, and -0.5≦a≦+0.5, 0≦x≦0.5, and 0≦b≦0.1), LiFePO4, Li(Fe,Mn)PO4, Li(Fe,Co)PO4, Li(Fe,Ni)PO4, LiCoO2, LiNiO2, LiMnO2, LiMn2O4, LiNi 1-y Co yO2, LiCo 1-y Mn y O2, LiNi 1-y Mn y O2(0≦y≦1), Li(Ni a Co b Mn c )O4(0<a<2, 0<b<2, 0<c<2, and a + b + c = 2), LiMn 2-z Ni z O4, LiMn 2-z Co z O4(0<z<2), LiCoPO4 and LiFePO4, elemental sulfur (S8), sulfur - based compounds, Li2S n (n≧1), organic sulfur compounds, carbon - sulfur polymer ((C2S x ) n : x = 2.5~50, n≧2), lithium and zirconium oxides, composite oxides of lithium and metals (cobalt, manganese, nickel, or combinations thereof), Li a A 1-b M b D2 (where 0.90≦a≦1, and 0≦b≦0.5), Li a E 1-b M b O 2-c D c (where 0.90≦a≦1, 0≦b≦0.5, and 0≦c≦0.05), LiE 2-b M b O 4-c D c (where 0≦b≦0.5, and 0≦c≦0.05), Li a Ni 1-b-c Co b M c D a (where 0.90≦a≦1, 0≦b≦0.5, 0≦c≦0.05, and 0<a≦2), Li a Ni 1-b-c Co b M c O 2-a X a (where 0.90≦a≦1, 0≦b≦0.5, 0≦c≦0.05, and 0<a<2), Li a Ni 1-b-c Co b M c O 2-aX2 (wherein, 0.90≦a≦1, 0≦b≦0.5, 0≦c≦0.05, and 0 <a<2)、Li a Ni 1-b-c Mn b M c D a (Wherein, 0.90≦a≦1, 0≦b≦0.5, 0≦c≦0.05, and 0 <a≦2)、Li a Ni 1-b-c Mn b M c O 2-a X a (Wherein, 0.90≦a≦1, 0≦b≦0.5, 0≦c≦0.05, and 0 <a<2)、Li a Ni 1-b-c Mn b M c O 2-a X2 (wherein, 0.90≦a≦1, 0≦b≦0.5, 0≦c≦0.05, and 0 <a<2)、Li a Ni b E c G d O2 (wherein 0.90≦a≦1, 0≦b≦0.9, 0≦c≦0.5, and 0.001≦d≦0.1), Li a Ni b Co c Mn d GeO2 (wherein 0.90≦a≦1, 0≦b≦0.9, 0≦c≦0.5, 0≦d≦0.5, and 0.001≦e≦0.1), Li a NiG b O2 (wherein 0.90≦a≦1 and 0.001≦b≦0.1), Li a CoG b O2 (wherein 0.90≦a≦1 and 0.001≦b≦0.1), Li a MnG b O2 (wherein 0.90≦a≦1 and 0.001≦b≦0.1), Li a Mn2G b O4 (wherein 0.90≦a≦1 and 0.001≦b≦0.1), QO2, QS2, LiQS2, V2O5, LiV2O5, LiX′O2, LiNiVO4, Li (3-f) J2(PO4)3(0≦f≦2), Li (3-f)Fe2(PO4)3 (0≦f≦2), LiFePO4 (A is Ni, Co, Mn, or a combination thereof, M is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof, D is O, F, S, P, or a combination thereof, E is Co, Mn, or a combination thereof, X is F, S, P, or a combination thereof, G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof, Q is Ti, Mo, Mn, or a combination thereof, X' is Cr, V, Fe, Sc, Y, or a combination thereof, and J is V, Cr, Mn, Co, Ni, Cu, or a combination thereof), LiCoO2, LiMn x O 2x (x=1 or 2), LiNi 1-x Mn x O 2x (0 <x<1)、LiNi 1-x-y Co x Mn y O2 (0≦x≦0.5, 0≦y≦0.5), FePO4, lithium compounds, lithium cobalt oxide, lithium nickel oxide, lithium nickel cobalt oxide, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, lithium manganese oxide, lithium iron phosphate, nickel sulfide, copper sulfide, sulfur, iron oxide, vanadium oxide, sodium-containing materials, chemical formula NaM 1 a O2 (in the formula, M 1 is at least one transition metal element, and has the oxides with 0≦a<1), NaFeO2, NaMnO2, NaNiO2, NaCoO2, and the chemical formula NaMn 1-a M 1 a O2 (in the formula, M 1 is at least one transition metal element, and is an oxide represented by 0≦a<1), Na[Ni 1 / 2 Mn 1 / 2 ]O2, Na 2 / 3 [Fe 1 / 2 Mn 1 / 2 ]O2, Na 0.44 Mn 1-a M 1 aO2 (in the formula, M 1 is at least one transition metal element, and is an oxide represented by 0≦a<1), Na 0.7 Mn 1-a M 1 a O 2.05 (In the formula, M 1 is at least one transition metal element, and is an oxide represented by 0≦a<1), Na b M 2 c S 12 O 30 (In the formula, M 2 is at least one transition metal element, 2≦b≦6, and 2≦c≦5), an oxide represented by 12 O 30 , Na2Fe5Si 12 O (where M 2 is at least one transition metal element, 2≦b≦6, and 2≦c≦5), Na d M 3 e S 6O 18 (In the formula, M 3 is at least one transition metal element, 3≦d≦6, and 1≦e≦2), Na2Fe2Si6O 18 , Na2MnFeSi6O 18 (In the formula, M 3 is at least one transition metal element, 3≦d≦6, and 1≦e≦2), Na f M 4 g Si2O6 (in the formula, M 4 is at least one element selected from transition metal elements, magnesium (Mg), and aluminum (Al), and is represented by 1≦f≦2 and 1≦g≦2), oxide, phosphate, Na2FeSiO6, NaFePO4, Na3Fe2(PO4)3, Na3V2(PO4)3, Na4Co3(PO4)2P2O7, borate, NaFeBO4 or Na3Fe2(BO4)3, fluoride, Na h M 5 F6 (in the formula, M 5is at least one transition metal element, 2≦h≦3), Na3FeF6, Na2MnF6, fluorophosphates, Na3V2(PO4)2F3, Na3V2(PO4)2FO2, NaMnO2, Na[Ni 1 / 2 Mn 1 / 2 ]O2, Na 2 / 3 [Fe 1 / 2 Mn 1 / 2 ]O2, Na3V2(PO4)3, Na4Co3(PO4)2P2O7, Na3V2(PO4)2F3, and / or Na3V2(PO4)2FO2, and any composite oxides and / or other combinations of the above.

[0152] Embodiment 57. An electrode assembly or secondary battery as described in embodiment 56, wherein the cathode active material comprises at least one of a transition metal oxide, a transition metal sulfide, a transition metal nitride, a transition metal phosphate, and a transition metal nitride.

[0153] Embodiment 58. An electrode assembly or a secondary battery according to embodiment 56 or 57, wherein the cathode active material comprises a lithium-containing transition metal oxide and at least one of cobalt and nickel.

[0154] Embodiment 59. An electrode assembly or secondary battery according to any one of the preceding embodiments, wherein the constituent members of the group of electrode structures comprise an anode current collector comprising at least one of copper, nickel, aluminum, stainless steel, titanium, palladium, sintered carbon, calcined carbon, indium, iron, magnesium, cobalt, germanium, lithium, copper or stainless steel surface treatment materials (having carbon, nickel, titanium, silver, aluminum-cadmium alloy, and / or alloys thereof).

[0155] Embodiment 60. The electrode assembly or secondary battery of embodiment 59, wherein the constituent units of the group of electrode structures comprise an anode current collector comprising at least one of copper, nickel, stainless steel, and alloys thereof.

[0156] Embodiment 61. An electrode assembly or secondary battery according to any one of the preceding embodiments, wherein the counter electrode structure comprises a cathode current collector comprising at least one of stainless steel, aluminum, nickel, titanium, calcined carbon, sintered carbon, aluminum, or stainless steel surface treatment material (having carbon, nickel, titanium, silver, or alloys thereof).

[0157] Embodiment 62. The electrode assembly or secondary battery of any one of embodiments 61, wherein the cathode current collector comprises at least one of stainless steel, aluminum, nickel, titanium, calcined carbon, sintered carbon, aluminum, or stainless steel surface treatment materials (with carbon, silver, or alloys thereof).

[0158] Embodiment 63. An electrode assembly or a secondary battery according to embodiment 61 or 62, wherein the cathode current collector comprises aluminum.

[0159] Embodiment 64. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the first connecting member and the second connecting member of the constraint system comprise any of stainless steel, titanium, or a fiberglass composite material.

[0160] Embodiment 65. The electrode assembly or secondary battery of embodiment 64, wherein the first connecting member and the second connecting member of the constraint system comprise stainless steel.

[0161] Embodiment 66. The electrode assembly or secondary battery of any one of the preceding embodiments, wherein the first and second connecting members of the constraint system include a coating of insulating material on the inner and outer surfaces of the first and second connecting members.

[0162] Embodiment 67. An electrode assembly or a secondary battery according to any one of the preceding embodiments, wherein the electrode assembly comprises at least five electrode structures and at least five counter electrode structures.

[0163] Embodiment 68. An electrode assembly or a secondary battery according to any one of the preceding embodiments, wherein the electrode assembly comprises at least 10 electrode structures and at least 10 counter electrode structures.

[0164] Embodiment 69. An electrode assembly or a secondary battery according to any one of the preceding embodiments, wherein the electrode assembly comprises at least 50 electrode structures and at least 50 counter electrode structures.

[0165] Embodiment 70. An electrode assembly or a secondary battery according to any one of the preceding embodiments, wherein the electrode assembly comprises at least 100 electrode structures and at least 100 counter electrode structures.

[0166] Embodiment 71. An electrode assembly or a secondary battery according to any one of the preceding embodiments, wherein the electrode assembly comprises at least 500 electrode structures and at least 500 counter electrode structures.

[0167] Embodiment 72. A process for manufacturing a secondary battery or electrode assembly according to any one of the preceding embodiments, comprising: (a) stacking in a stacked configuration a group of electrode structures, a group of counter-electrode structures, and a group of electrically insulating separator materials electrically isolating the constituent elements of the electrode and counter-electrode groups, (b) placing a first surface of at least one of the adhesive films comprising an electrically insulating thermoplastic hot melt adhesive in contact with an upper or lower inner surface of a first or second connection member of a constraint system, (c) placing an upper or lower end surface of a subset of the constituent elements of the electrode or counter-electrode groups in contact with a second surface of the at least one adhesive film, and (d) at least partially melting or softening the at least one adhesive film by heating to bond the subset of the constituent elements of the electrode or counter-electrode groups to the first and second connection members.

[0168] Embodiment 73. The process of embodiment 72, wherein a first adhesive film adheres the upper inner surface of the first connection member to the upper end surface of the subset of constituent elements of the electrode group or counter-electrode group, and a second adhesive film adheres the lower inner surface of the second connection member to the lower end surface of the subset of constituent elements of the electrode group or counter-electrode group.

[0169] Embodiment 74. The process of embodiment 72 or 73, further comprising cutting at least one adhesive film to form a film cutout having a predetermined pattern, and attaching the film cutout to the upper and lower inner surfaces of the first and second connecting members.

[0170] Embodiment 75. The process of any one of embodiments 72-74, further comprising applying pressure to one or more of a subset of the constituent elements of the group of the first connecting member and the second connecting member, and the electrode structure and the counter-electrode structure to facilitate adhesion.

[0171] Embodiment 76. The process of embodiment 75, comprising applying a pressure of at least 3 psi.

[0172] Embodiment 77. The process of any one of embodiments 72-76, wherein at least one adhesive film is provided by extrusion, cast film, or blown film methods.

[0173] Embodiment 78. The process of any one of embodiments 72-77, wherein at least one adhesive film is cut into a film notch using a laser or a die.

[0174] Embodiment 79. The process of any one of embodiments 72-78, wherein at least one adhesive film is cut into a film cutout conforming to the shape of the upper and lower inner surfaces of the first and second connecting members.

[0175] Embodiment 80. The process of embodiment 79, wherein the first and second connecting members have openings formed through the vertical thickness of each member, comprising disposing adhesive film cutouts along bonding areas of the inner surfaces of the first and second connecting members adjacent the openings.

[0176] Embodiment 81. The process according to any one of embodiments 72 to 80, wherein the constituent elements of the group of electrode structures comprise electrode current collectors having vertically opposite upper and lower end faces, and the constituent elements of the group of counter-electrode structures comprise counter-electrode current collectors having vertically opposite upper and lower end faces, and the process comprises placing an adhesive film cutout in contact with the vertical end faces of the electrode current collectors or counter-electrode current collectors of a subset of the constituent elements of the electrode group or counter-electrode group.

[0177] Embodiment 82. The process according to any one of embodiments 72 to 81, comprising heating at least one adhesive film to a temperature of at least 75° C. and not more than 130° C. before, during or after contacting the at least one adhesive film with the first connection member or the second connection member and the subset of constituent elements of the electrode group or counter-electrode group.

[0178] Embodiment 83. The electrode assembly, secondary battery, or process according to any one of embodiments 1 to 3 and 5 to 82, wherein the melt index value of the electrically insulating thermoplastic hot melt adhesive, measured according to ASTM D1238, is at least in the range of 20 to 350.

[0179] Incorporation by Reference All publications and patents mentioned herein are hereby incorporated by reference in their entirety for all purposes as if each individual publication or patent was specifically and individually indicated to be incorporated by reference. In case of conflict, the present application, including any definitions herein, will control.

[0180] Equivalent While specific embodiments have been discussed, the above specification is illustrative and not restrictive. Many variations will become apparent to those skilled in the art upon review of this specification. The full scope of the invention should be determined by reference to the claims, along with their full scope of equivalents, and the specification, along with such variations.

[0181] Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless otherwise indicated to the contrary, the numerical parameters set forth in this specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained.

Claims

1. An apparatus for current conductance, comprising: The apparatus comprises: a unit cell having an electrode separated from a counter electrode, the counter electrode being stacked along a first axis, the unit cell comprising an electrolyte; a constraint system operably coupled to the unit cell, the constraint system being configured to (a) constrain a volumetric change of the unit cell during use of the device, (b) provide a passageway for a flow of carrier ions therethrough, the carrier ions being configured to be at least partially transported by the electrolyte during use of the device, or (c) a combination of (a) and (b); an adhesive operably coupled to the constraint system and the unit cell, the adhesive being disposed between the constraint system and the unit cell, the adhesive being either (A) configured to securely hold the constraint system in place while maintaining adhesive strength upon exposure of the adhesive to the electrolyte or (B) being thermoplastic; 16. An apparatus for current conductance comprising:

2. The apparatus of claim 1, comprising a secondary battery having the unit cell, the constraint system, and the adhesive.

3. The device of claim 1, wherein a change in temperature causes the adhesive to at least partially melt or soften.

4. The apparatus of claim 1, wherein the constraint system is configured to maintain a pressure on the unit cell in a direction that exceeds the pressure maintained on the unit cell in each of two other mutually perpendicular directions, the direction and the two other mutually perpendicular directions being axial directions of a Cartesian coordinate system.

5. The device of claim 1, wherein the adhesive does not significantly react or lose significant adhesive strength at temperatures above about 80°C.

6. 10. The device of claim 1, wherein the adhesive maintains adhesion through 200, 500, 800, and / or 1000 consecutive cycles of the device.

7. The apparatus of claim 1, wherein the constraint system suppresses growth of the unit cell in a direction such that the increase in ferret diameter of the cell in that direction after 20 consecutive cycles is less than 20%.

8. The device of claim 1, wherein the electrode comprises silicon, a silicon carbon composite, a silicon oxide, a porous silicon, a silicon alloy, a silicon-containing material in particulate form, or any combination thereof.

9. The apparatus of claim 1, wherein the electrodes comprise soft carbon and hard carbon.

10. The device of claim 1, wherein the unit cell comprises a carbon nanotube.

11. The device of claim 1, wherein the adhesive comprises a polyethylene derivative, a polyacrylic acid derivative, any salt thereof, any copolymer thereof, any mixture thereof, or any other combination thereof.

12. The apparatus of claim 11, wherein the adhesive comprises ethylene-co-acrylic acid (EAA), ethylene-co-methacrylic acid (EMAA), functionalized polyethylene, functionalized polypropylene, or a combination thereof.

13. The apparatus of claim 11, wherein the adhesive comprises a mixture of EAA and EMAA, each of the EAA and the EMAA being a copolymer.

14. The device of claim 1, wherein the adhesive has a film shape having a thickness in the range of about 10 to about 100 micrometers.

15. The apparatus of claim 1, wherein the constraint system has an opening.

16. The apparatus of claim 15, wherein the openings (a) have a curvature, (b) are elongated in a direction perpendicular to the first axis, (c) are evenly spaced along the constraint system, (d) are aligned with each other and with the constraint system, and / or (e) provide a passageway for the flow of carrier ions.

17. The device of claim 1, wherein a cell stack comprises the unit cell and other unit cells similar to the unit cell, the device comprises the cell stack, the unit cells of the cell stack are stacked along the first axis, and the cell stack comprises at least about 2, 4, 5, 10, 25, 50, or 100 unit cells.

18. The device described in claim 17, wherein each of the electrodes and / or counter electrodes in the cell stack has a length, a width and a height, the height, the length and the width are aligned along axes of a Cartesian coordinate system, and the ratio of maximum length to maximum height is at least 2:1, the ratio of maximum width to maximum height is at least 2:1, and the ratio of height to width is at least 0.4:

1.

19. A method for current conductance, the method comprising: (a) forming the device described in any one of claims 1 to 18; (b) flowing the carrier ions into the device; and / or (c) using the device for current conductance.

20. An apparatus for current conductance, comprising a control unit electrically coupled to the unit cell of the apparatus described in any one of claims 1 to 18, the control unit configured to control the flow of carrier ions into the unit cell.

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