Transfer of carrier ions from auxiliary electrodes

Abstract

A method for transferring carrier ions from an auxiliary electrode including a carrier ion source to an electrode assembly includes transferring carrier ions from the auxiliary electrode to a constituent unit of a unit cell group through a porous electrically insulating material. The electrode assembly includes a group of unit cells stacked continuously in a stacking direction and a porous electrically insulating material, each unit cell includes an electrode structure, a counter electrode structure, and an electrically insulating separator, the electrode structure, the counter electrode structure, and the electrically insulating separator having upper and lower end faces that are vertically separated and opposite to each other, and the porous electrically insulating material covers the upper or lower end faces of the electrode structure or the counter electrode structure of the constituent unit of the unit cell group. The porous electrically insulating material has a porosity in the range of 20% to 60%.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63 / 168,454, filed March 31, 2021, which is incorporated herein by reference in its entirety.

[0002] FIELD OF THE DISCLOSURE This disclosure relates generally to methods and 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, such as a solid electrolyte or a liquid 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, an electrically insulating separator, and an electrolyte. In a solid-state secondary battery, a single solid material may function as both the electrically insulating separator and the 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. Summary of the Invention [Problem to be solved by the invention]

[0005] However, as part of this carrier ion desorption and insertion process occurring during charging and / or discharging of the secondary battery, at least a portion of the carrier ions may be irreversibly lost to the electrochemical reaction. For example, a decomposition product containing lithium (or other carrier ions) and electrolyte components, known as a solid electrolyte interfacial phase (SEI), may form on the surface of the negative electrode. The formation of this SEI layer traps carrier ions and removes them from the cycling operation of the secondary battery, leading to irreversible capacity loss. Other chemical and electrochemical processes in the electrode assembly may also affect the loss of carrier ions. Such losses often occur during the initial charging step performed as part of the secondary battery formation process, for example due to the formation of an SEI layer in the initial charging step, resulting in a significantly lower capacity compared to the amount of carrier ions included in the secondary battery preformation.

[0006] Methods for replenishing electrodes in secondary batteries have been described (see, for example, U.S. Patent No. 10,770,760 to Castledine et al., which is incorporated herein by reference in its entirety), but there remains a need for new methods and structures for effectively and efficiently providing carrier ions to secondary batteries to replenish lost carrier ions.

[0007] Among the various aspects of the present disclosure is the provision of energy storage devices, such as secondary batteries, fuel cells, and electrochemical capacitors, that can restore capacity lost as a result of SEI formation and / or mechanical or electrical degradation of the negative and / or positive electrodes. Advantageously, energy storage devices according to the present disclosure provide increased cycle life, higher energy density, and / or increased discharge rates. [Means for solving the problem]

[0008] Briefly, therefore, one aspect of the present disclosure relates to a method for transporting carrier ions from an auxiliary electrode having a carrier ion source to an electrode assembly, the electrode assembly including a group of unit cells stacked in series in a stacking direction, and a porous electrically insulating material, (i) each unit cell includes an electrode structure, a counter electrode structure, and an electrically insulating separator between the electrode structure and the counter electrode structure, (ii) the electrode structure, the counter electrode structure, and the electrically insulating separator in each unit cell have upper and lower end faces that are vertically separated and opposite to each other, (iii) the vertical direction is perpendicular to the stacking direction, (iv) the porous electrically insulating material covers the upper or lower end faces of the electrode structure or the counter electrode structure of a constituent unit of the unit cell group, and (v) the porous electrically insulating material has a porosity in the range of 20% to 60%. The method includes transporting carrier ions from the auxiliary electrode to the constituent unit of the unit cell group through the porous electrically insulating material.

[0009] Another aspect of the present disclosure relates to an electrode assembly for a secondary battery for cycling between a charged state and a discharged state, the electrode assembly comprising a group of unit cells stacked in succession in a stacking direction, and a porous electrically insulating material, (i) each unit cell comprises an electrode structure, a counter electrode structure, and an electrically insulating separator between the electrode structure and the counter electrode structure, (ii) the electrode structure, the counter electrode structure, and the electrically insulating separator in each unit cell have upper and lower end faces that are vertically separated and on opposite sides, (iii) the vertical direction is perpendicular to the stacking direction, (iv) the porous electrically insulating material covers the upper or lower end faces of the electrode structure or the counter electrode structure of the constituent unit of the unit cell group, and (v) the porous electrically insulating material has a porosity in the range of 20% to 60%. Another aspect of the present disclosure relates to a secondary battery having the electrode assembly.

[0010] Another aspect of the present disclosure relates to a method for manufacturing an electrode assembly or a secondary battery, the method including: (1) stacking a group of unit cells stacked continuously in a stacking direction, (i) each unit cell including an electrode structure, a counter electrode structure, and an electrically insulating separator between the electrode structure and the counter electrode structure, (ii) the electrode structure, the counter electrode structure, and the electrically insulating separator in each unit cell have upper and lower end faces that are vertically separated and on opposite sides, (iii) the vertical direction is perpendicular to the stacking direction; and (2) covering the upper end face or the lower end face of the electrode structure or the counter electrode structure of a constituent unit of the unit cell group with a porous electrically insulating material, the porous electrically insulating material having a porosity in the range of 20% to 60%.

[0011] 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]

[0012] [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 set of electrode constraints with openings therein. [Figure 4] FIG. 1 is a cross-sectional view of one embodiment of an electrode assembly including a porous electrically insulating material. [Diagram 5] 1A-1D are perspective and cross-sectional views of an embodiment of a secondary battery comprising a wound electrode assembly. [Figure 6A] FIG. 2 is a top view with an inset of one embodiment of an electrode assembly prior to providing a porous electrically insulating material on the upper and / or lower end faces of the electrodes and / or counter electrodes of the electrode assembly. [Figure 6B] FIG. 2 is a top view with an inset of one embodiment of an electrode assembly after providing a porous electrically insulating material on the upper end surface and / or the lower end surface of the electrode and / or counter electrode of the electrode assembly. [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 8] FIG. 1 is a top view of an embodiment of an electrode assembly having a secondary growth constraint system and having a porous electrically insulating material on the upper end surface and / or the lower end surface of the electrode and / or counter electrode of the electrode assembly. [Figure 9] 1 is a schematic diagram illustrating a portion of a process for providing a porous electrically insulating material to an upper end surface and / or a lower end surface of an electrode and / or a counter electrode of an electrode assembly. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] 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.

[0014] 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.

[0015] 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". Thus, 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.

[0016] "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.

[0017] "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.

[0018] 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.

[0019] 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.

[0020] With respect to the term "electrode" as used in "electrode structure" or "electrode active material", it is to be understood that such structure and / or materials may, in certain embodiments, correspond to those of a "negative electrode", e.g., "anode" as used in "negative electrode structure", "anode structure", "negative electrode active material", and "anode active material". With respect to the term "counter electrode" as used in "counter electrode structure" or "counter electrode active material", it is to be understood that such structure and / or materials may, in certain embodiments, correspond to those of a "positive electrode", e.g., "cathode" as used in "positive electrode structure", "cathode structure", "cathode active material", and "cathode 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] "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.

[0025] 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.

[0026] 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.

[0027] 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.

[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 104. In certain embodiments, the secondary battery 102 also includes a set of electrode constraints 108 that constrain 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] According to embodiments of the present disclosure, a method is provided for the transfer of carrier ions from an auxiliary electrode 686 comprising a carrier ion source to an electrode assembly 106, for example as shown in FIG. 3A. As discussed in more detail herein, according to certain embodiments, the transfer of carrier ions occurs as part of an initial formation process performed to activate a secondary battery comprising the electrode assembly. According to other embodiments, the transfer of carrier ions occurs as part of a process to replenish carrier ions in the electrode assembly lost due to the formation of a solid electrolyte interfacial phase (SEI) during the initial formation process and / or during cycling between charged and discharged states.

[0030] 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 group of unit cells includes an electrode structure 110, a counter electrode structure 112, and an electrically insulating separator 130 between the electrode structure and the counter electrode structure, 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 includes stacked continuous unit cells 504 including the electrode structures 110 and the counter electrode structures 112 in an alternating arrangement. FIG. 1C is an inset view showing a secondary battery 102 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.

[0031] 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 to form 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 row, 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 112 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 the 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 adjacent unit cells in the stacked row, for example 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.

[0032] 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.

[0033] 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 may 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 may 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 may have upper and lower end faces 502a and 502b that are separated on opposite sides in a vertical direction. According to yet another embodiment, the constituent elements of the unit cell group have upper edges 503a and lower edges 503b extending across and comprising the opposite upper and lower end faces of the electrode structure 110, the electrical insulating separator 130, and the counter electrode structure 112 in each unit cell constituent element. Referring to FIG. 3A and FIG. 4, according to yet another embodiment, the upper end faces 500a, 501a of the electrode structure 110 and the counter electrode structure 112 in the same unit cell group constituent element are vertically offset from each other to form an upper recess 505a, and the lower end faces 500b, 501b of the electrode structure 110 and the counter electrode structure 112 in the same unit cell group constituent element are vertically offset from each other to form a lower recess 505b. For example, the upper end faces and lower end faces of the counter electrodes can be recessed inward and / or offset with respect to the upper end faces and lower end faces of the respective electrodes in the same unit cell group constituent element. Referring to FIG. 3A , in one embodiment, a constituent unit of a unit cell group includes a counter electrode active material layer 138 having an upper end surface 501 a and a lower end surface 501 b recessed inward relative to the upper end surface and the lower end surface of the electrode active material layer 132 and / or the electrically insulating separator 130.

[0034] According to one embodiment, the electrode assembly 106 further comprises a porous electrically insulating material 508 covering the upper end surfaces 500a, 501a and / or the lower end surfaces 500b, 501b of the electrode structures 110 and / or the counter electrode structures 112 of the constituent elements of the unit cells 504. For example, as shown in FIG. 3A and FIG. 4, the porous electrically insulating material 508 may be located in one or more of the upper and lower recesses 505a, 505b formed by the vertical offset of the electrode structures and the counter electrode structures in the constituent elements of the unit cells. According to a particular embodiment, the porous electrically insulating material has a porosity in the range of 20% to 60% (percent of pore volume per total volume of the porous electrically insulating material). According to a particular embodiment, the porous electrically insulating material 508 may provide an ion conducting structure and may provide a path for carrier ions provided by the auxiliary electrode 686 to the constituent elements of the unit cells 504.

[0035] 3A-3B, according to certain embodiments, a method is provided for transporting carrier ions from the auxiliary electrode 686 to the constituent elements of the group of unit cells 504 through the porous electrical insulating material 508. As discussed above, carrier ions may be transported to provide carrier ions to the electrode structure 110 of the constituent elements of the unit cells to compensate for the formation of a solid electrolyte interface (SEI) layer that may be formed during the initial formation process or the loss of carrier ions resulting from a subsequent charge cycle of the secondary battery 102 having the electrode assembly 106. In certain embodiments, a portion of the carrier ions introduced into the unit cells from the counter electrode structure are irreversibly bound at this SEI layer and are therefore removed from the cycle operation, i.e., from the capacity available to the user. As a result, during the initial discharge, fewer carrier ions are returned from the electrode structure to the counter electrode structure than were initially provided by the cathode during the initial charge operation, leading to irreversible capacity loss. During each subsequent charge and discharge cycle of the secondary battery, the resulting capacity loss from mechanical and / or electrical degradation of the electrode structure and / or counter electrode structure tends to be much less per cycle, but even a relatively small carrier ion loss per cycle can significantly affect the degradation of the energy density and cycle life as the battery ages. In addition, the electrode structure and counter electrode structure can also undergo chemical and electrochemical degradation, causing capacity loss. Thus, embodiments of the present disclosure herein provide a method of activating an electrode assembly and / or a secondary battery, such as through an initial formation process that provides additional carrier ions from the auxiliary electrode to the constituent units of the unit cell, and / or during a refilling process that is performed to replenish the content of carrier ions lost during subsequent charge and / or discharge cycles of a secondary battery having the electrode assembly. According to certain embodiments, carrier ions are transferred to compensate for the loss of carrier ions during the initial or subsequent charge cycles of the electrode assembly.

[0036] According to one embodiment, the auxiliary electrode 686 includes a carrier ion source, such as any of lithium, sodium, potassium, calcium, magnesium, and aluminum ions. In the embodiment shown in FIG. 3A, the auxiliary electrode 686 is positioned on a vertical end surface of the electrode structure, counter electrode structure, and electrically insulating separator of the constituent elements of the unit cell, such as on the opening 176 in the first secondary growth constraint 158 ​​and / or the second secondary growth constraint 160. In a variation, one or more auxiliary electrodes 686 are positioned on both the upper and lower end surfaces, and / or alternatively, the auxiliary electrode 686 may be positioned on only one of the upper and lower end surfaces. For example, in one embodiment, a first auxiliary electrode 686a is positioned on an upper end surface of the electrode structure and / or the counter electrode structure, and a second auxiliary electrode 686b is positioned on a lower end surface of the electrode structure and / or the counter electrode structure. The auxiliary electrode 686 may 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, for example, 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 structures and / or electrode structures of the constituent elements of the unit cells to provide a flow of carrier ions from the auxiliary electrode to the electrode structures and / or counter electrode structures. By electrolytically coupled, it is meant that carrier ions may be transported through an electrolyte, such as from the auxiliary electrode 686 to the electrode structures 110 and / or counter electrode structures 112 and between the electrode structures 110 and the counter electrode structures 112. The auxiliary electrode 686 is also directly or indirectly coupled to the electrode structures and / or counter electrode structures, such as by a series of wires or other electrical connections.

[0037] In one embodiment, carrier ions are transported to a discharge voltage V ces eod , and the discharge voltage V at the end of a given electrode structure es,eod where, for the unit cells of the group, the discharge voltage V of the unit cells is cell,eod =V es,eod -Vces,eod For example, in one embodiment, the constituent elements of the unit cell and / or the secondary battery including the constituent elements of the unit cell are subjected to a discharge voltage V cell,eod When the discharge voltage V es,eod is less than 0.9 V (vs. Li) and greater than 0.4 V (vs. Li). Thus, for example, in one such embodiment, the secondary battery has a discharge voltage V cell,eod When the discharge voltage V es,eod can be in the range of about 0.5 V (vs. Li) to about 0.8 V (vs. Li). By way of further example, in one such embodiment, the secondary battery has a discharge voltage V cell,eod When the discharge voltage V es,eod can be in the range of about 0.6 V (vs. Li) to about 0.8 V (vs. Li). In one such embodiment, the secondary battery has a discharge voltage V cell,eod When the discharge voltage V es,eod can be in the range of about 0.6 V (vs. Li) to about 0.7 V (vs. Li).

[0038] According to yet another embodiment, the V ces,eod The value corresponds to the voltage at which the state of charge of the counter electrode structure is at least 95% of the reversible chronocapacity of the counter electrode structure, V ces,eod is at least 0.4 V (vs. Li) but less than 0.9 V (vs. Li). For example, in one such embodiment, V cell,eod When the voltage V reaches 1 V, the counter electrode structure is at a voltage V, which corresponds to a voltage at which the state of charge of the counter electrode structure is at least 96% of the reversible chronocapacity of the counter electrode structure. ces,eod has a value of V es,eod is at least 0.4 V (vs. Li) but less than 0.9 V (vs. Li). By way of further example, in one such embodiment, V cell,eodWhen the voltage V reaches 1 V, the counter electrode structure is at a voltage V corresponding to a voltage at which the state of charge of the counter electrode structure is at least 97% of the reversible chronocapacity of the counter electrode structure. ces,eod has a value of V es,eod is at least 0.4 V (vs. Li) but less than 0.9 V (vs. Li). By way of further example, in one such embodiment, V cell,eod When the voltage V reaches 1 V, the counter electrode structure is at a voltage V corresponding to a voltage at which the state of charge of the counter electrode structure is at least 98% of the reversible chronocapacity of the counter electrode structure. ces,eod has a value of V es,eod is at least 0.4 V (vs. Li) but less than 0.9 V (vs. Li). By way of further example, in one such embodiment, V cell,eod When the voltage V reaches 1 V, the counter electrode structure is at a voltage V, which corresponds to a voltage at which the state of charge of the counter electrode structure is at least 99% of the reversible chronocapacity of the counter electrode structure. ces,eod has a value of V es,eod is at least 0.4 V (vs. Li) but less than 0.9 V (vs. Li).

[0039] According to one embodiment, the method includes the steps of: (i) transferring carrier ions from the counter electrode structure to the electrode structure in the group of unit cells during an initial or subsequent charging cycle to at least partially charge the electrode assembly; and (ii) transferring carrier ions from the auxiliary electrode to the counter electrode structure and / or electrode structure through the porous electrically insulating material, such that the auxiliary electrode is electrolytically coupled to the counter electrode structure and / or electrode structure of the constituent units of the group of unit cells through the separator to provide the electrode assembly with a discharge voltage V at a predetermined counter electrode structure end. cos,eod and the discharge voltage V at the end of a given electrode structure es,eodand providing a method for producing a porous electrically insulating material comprising the steps of: (i) transferring carrier ions from the counter electrode structure of the unit cell group to the electrode structure of the unit cell group after (ii) to charge the electrode assembly; (iii) transferring carrier ions from the auxiliary electrode to the counter electrode structure during (ii) may then be transferred from the counter electrode structure to the electrode structure in (iii); (ii) is performed simultaneously with (i ...

[0040] 3A and 4, according to one embodiment, the porous electrically insulating material 508 substantially fills the upper and lower recesses 505a, 505b of the constituent units of the unit cell group 504. According to another embodiment, the porous electrically insulating material 508 is disposed such that at least a portion of the porous electrically insulating material 508 covering the upper end faces 500a, 501a and / or the lower end faces 500b, 501b of the electrode structure 110 and / or the counter electrode structure 112 of the constituent units of the unit cells is adjacent to the electrically insulating separator 130 of that unit cell. For example, in one embodiment, the porous electrically insulating material substantially fills the areas of the upper and lower recesses 505a, 505b that are disposed inwardly relative to the upper end surface 500a and the lower end surface 500b of the electrode structure 110 in the constituent unit of the unit cell group and abut the first side surface 131a of the electrically insulating separator 130 that faces the counter electrode structure 110. According to a particular embodiment, the porous electrically insulating material fills at least a portion of the upper recess 505a and / or the lower recess 505b recessed inwardly from the upper end surface 502a and the lower end surface 502b of the electrically insulating separator 130 to provide structural support to the electrically insulating separator 130. For example, the porous electrically insulating material, in certain embodiments, can provide a rigid material abutting the upper and lower vertical ends 133a, 133b of the electrically insulating separator 130 to maintain the upright position of the vertical ends relative to the upper and lower end faces of the counter electrode structure 112. Maintaining the position of the vertical ends 133a, 133b of the electrically insulating separator 130 can, in certain embodiments, reduce the possibility of electrical shorts between the electrode structure and the counter electrode structure, and other undesirable effects. The porous electrically insulating material, in certain embodiments, can also reduce undesirable electrical edge effects at portions of the upper and lower end faces of the counter electrode structure.

[0041] According to one embodiment, the electrode structure 110 constituting the unit cell group comprises an electrode active material layer 132 and an electrode current collector layer 136, the counter electrode structure 112 constituting the unit cell group comprises a counter electrode active material layer 138 and a counter electrode current collector layer 140, and the porous electrically insulating material 508 covers the counter electrode active material layer of the unit cell group on the upper end surface 507 a and the lower end surface 507 b. 3A and 4, the porous electrically insulating material extends in the stacking direction across and covers the upper end faces 501 a, 501 b of the counter electrode structure 112, including across one or more of the upper end faces 507 a, 507 b of the counter electrode active material layers 138 in adjacent unit cells 504 a, 504 b, and in certain embodiments across the upper end faces 509 a, 509 b of the counter electrode current collector 140 shared by adjacent unit cells 504. The porous electrically insulating material extending across portions of adjacent unit cells can, in this embodiment, abut and provide structural support to the vertical ends 133 a, 133 b of the electrically insulating separators 130 in adjacent unit cells. In still further embodiments, a porous electrically insulating material 508 can be provided on the upper and lower end faces of the electrode structure 110, such as on the upper end faces 511 a and lower end faces 511 b of the electrode active material layers 132 in adjacent unit cells 504 a, 504 b, and across the upper end faces 510 a and lower end faces 510 b of the electrode current collectors 136 shared by adjacent unit cells 504.

[0042] According to yet further embodiments, the porous electrically insulating material 508 is provided on those portions of the upper and lower end faces of the electrode structure and the counter electrode structure, where a path is provided for the flow of carrier ions from the auxiliary electrode to the constituent elements of the unit cell group. For example, in an embodiment where a flow of carrier ions is provided from the auxiliary electrode 686 to the counter electrode structure 112, the porous electrically insulating material 508 is disposed on the upper and lower end faces of the counter electrode structure to provide a path for the carrier ions to the counter electrode structure. As another example, in an embodiment where a flow of carrier ions is provided from the auxiliary electrode to the electrode structure 110, the porous electrically insulating material 508 is disposed on the upper and lower end faces of the electrode structure to provide a path for the carrier ions to the electrode structure.

[0043] According to certain embodiments, the porosity of the electrically insulating material can be selected to provide a predetermined conductivity of carrier ions through the material. In certain embodiments, the porous electrically insulating material comprises a porosity of at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, and / or at least 55%. Furthermore, in certain embodiments, the porous electrically insulating material comprises a porosity of 55% or less, 50% or less, 45% or less, 40% or less, and / or 35% or less. According to yet another embodiment, the porous electrically insulating material 508 comprises a ratio of porosity to the porosity of the electrically insulating separator 130 between the electrode structure and the counter electrode structure in the constituent units of the unit cell group in a range of 1:0.75 to 1:1.5.

[0044] In one embodiment, the porous electrically insulating material 508 includes particulate material dispersed in a binder material. For example, the specific material may include stable metal oxides and / or ceramics, such as one or more of alumina, boron nitride, titania, silica, zirconia, magnesium oxide, and calcium oxide. In another embodiment, the particulate material includes particles having a d50 particle size (median particle size) of at least 0.35 microns, at least 0.45 microns, at least 0.5 microns, and / or at least 0.75 microns. In yet another embodiment, the particulate material includes particles having a d50 particle size (median particle size) of 40 microns or less, 35 microns or less, 25 microns or less, and / or 20 microns or less. In one embodiment, at least 80%, at least 85%, at least 90%, and / or at least 95% by weight of the particles have a particle size of at least 0.35 microns, at least 0.45 microns, at least 0.5 microns, and / or at least 0.75 microns, and no more than 40 microns, no more than 35 microns, no more than 25 microns, and / or no more than 20 microns. Further, in one embodiment, the particulate material comprises at least 70%, at least 75%, at least 80%, and / or at least 85% by weight of the porous electrically insulating material. In further embodiments, the particulate material comprises no more than 99.5%, no more than 97%, no more than 95%, and / or no more than 90% by weight of the porous electrically insulating material. In one embodiment, the binder material comprises a polymeric material selected from any of the group consisting of polyvinylidene fluoride (PVDF), polyethylene, polypropylene, ethylene acrylic acid (EAA), ethylene methacrylic acid (EMAA), and copolymers thereof.

[0045] 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 electrode assembly 106 and connecting the first longitudinal end surface 116 and the second longitudinal end surface 118. The lateral surface 142 includes first and second regions on either side of the 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 of the X direction (i.e., sides of a rectangular prism) and surface regions 148, 150 on opposite sides of 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 EA By 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.

[0046] 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 WEA 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.

[0047] 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 W EA and maximum length L EA The ratio may range from 1:2 to 2:1.

[0048] 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. CEand 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,

[0049] According to one embodiment, the electrode structure of the constituent unit of 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 the counter electrode structure of the unit cell group is 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 H E 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.

[0050] In one embodiment, the height (HE ) and width (W E ) is at least 0.4:1. For example, in one embodiment, for each electrode structure of 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 E and 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.

[0051] 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 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.

[0052] 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.

[0053] 5, in one embodiment, the electrode assembly 106 includes a wound electrode assembly having a plurality of windings 205a, 205b of the constituent electrode structure 110 and counter electrode structure 112 of the unit cells about a central axis C of the wound electrode assembly, the vertical direction of the wound electrode assembly being parallel to the central axis (z direction), and further, the constituent electrode structure and counter electrode structure of the unit cells each have a length L extending from a first end 121a of the counter electrode structure at a central region 200 of the wound electrode assembly and along each winding to a second end 121b of the counter electrode structure at an outer region 202 of the electrode assembly. E and L CE In the embodiment shown, the wound electrode assembly comprises a generally cylindrical shape.

[0054] According to one embodiment, the porous electrically insulating material has a length L CE and / or the length L of the electrode structure of the unit cell group. E 6A-6B, embodiments may include an electrode assembly without a porous electrically insulating material 508 (FIG. 6A) and an electrode assembly in which the porous electrically insulating material 508 extends over at least the length L of the counter electrode structure (FIG. 6B). CE 6B shows a top view of an electrode assembly having a porous electrically insulating material 508 disposed to fill recesses 505a, 505b in the form of grooves extending along the length of the electrode structure 110. In the embodiment shown in Fig. 6B, the porous electrically insulating material 508 covers the counter electrode active material layer 138 and the counter electrode current collector 140. In addition to covering the upper end face 501a and the lower end face 501b of the counter electrode structure 112, the embodiment shown in Fig. 6B further includes a porous electrically insulating material covering the length of the electrode active material layer 132 of the electrode structure 110 such that only the electrode current collector 136 remains exposed.

[0055] In one embodiment, the electrode assembly 106 is enclosed within a volume V defined by a set of electrode constraints 108 that constrain the overall macroscopic growth of the electrode assembly 106, for example as illustrated in FIG. 1A. The set of electrode constraints 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 set of electrode constraints 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 set of electrode constraints 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.

[0056] In one embodiment, the set of electrode constraints 108 comprising a 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.

[0057] 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 110 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.

[0058] 7A-7C, an embodiment of a set of electrode constraints 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 in 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 in 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.

[0059] 7A-7C, the set of electrode constraints 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.

[0060] According to one embodiment, the primary growth constraint system 151 and the secondary growth constraint system 152 are each configured to operate cooperatively such that portions of the primary growth constraint system 151 function cooperatively as part of the secondary growth constraint system 152 and / or portions of the secondary growth constraint system 152 act cooperatively as part 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 secondary growth constraint 158 ​​and the second secondary growth constraint 160 can act as the first primary connection member 162 and the second primary connection member 164, respectively, of the primary growth constraint system 151, and at least one secondary connection member 166 of the secondary growth constraint system 152 can, in one embodiment, act as one or more of the first primary growth constraint 154 and the second primary growth constraint 156, respectively. Thus, the primary growth constraint system 151 and the secondary growth constraint system 152 can each share components and / or structures for exerting restraint on the growth of the electrode assembly 106.

[0061] In one embodiment, the set of electrode constraints 108 can comprise structures such as primary and secondary growth constraints 154, 156, and primary and secondary connection members 162, 164, 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 set of electrode constraints 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 and the secondary growth constraint system are within the battery housing, which may be a sealed battery housing, such as a hermetically sealed battery housing. The electrode assembly 106 may be constrained by the set of electrode constraints 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 102 having the electrode assembly 106.

[0062] 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 a 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.

[0063] 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 in both, with a pressure against the first vertical end surface 116 and the second vertical end surface 118 (i.e., in the stacking direction D) that exceeds by at least a factor of 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 in both, with a pressure against the first vertical end surface 116 and the second vertical end surface 118 (i.e., in the stacking direction D) that exceeds by at least a factor of 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 both of two directions perpendicular to the stacking direction D.

[0064] 7C, an embodiment of an electrode assembly 106 having a set of electrode constraints 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., vertically). 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 internal secondary connection members 166 may include at least a portion of the electrode structure 110 or the counter electrode structure 112, as described in more detail below.

[0065] 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 on 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, thereby reducing the growth of the electrode assembly 106 in the vertical direction. Furthermore, in the embodiment shown in FIG. 7C, the set of electrode constraints 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.

[0066] According to one embodiment, the first secondary growth constraint 158 ​​and the second secondary growth constraint 160 are each connected to a secondary connection member 166 that 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. The first secondary growth constraint 158 ​​and the second secondary growth constraint 160 may each be connected to an upper end surface and / or a lower end surface of the counter electrode structure 112 and / or the electrode structure 110, or other internal structure, which in one embodiment forms the secondary connection member 166. In one embodiment, the first secondary growth constraint 158 ​​is connected to an upper end surface 500a, 501a of the electrode structure 110 and / or the counter electrode structure 112 of the constituent elements of the unit cell group 504. In another embodiment, the second secondary growth constraint 160 is connected to a lower end surface 500b, 501b of the electrode structure 110 or the counter electrode structure 112 of the constituent elements of the unit cell group 504. The constituent units of the unit cells connected at the upper end surface may be the same as or different from the constituent units of the unit cells connected at the lower end surface. The first secondary growth constraint and / or the second secondary growth constraint may be connected to the upper end surface and / or the lower end surface away from the electrode structure and / or the counter electrode structure including one or more of the electrode current collector, the electrode active material layer, the counter electrode current collector, and the counter electrode active material layer in the constituent units of the unit cells. In another example, the first and second secondary growth constraints may be connected to the upper end surface and / or the lower end surface of the electrical insulating separator. Thus, in certain embodiments, the secondary connection member 166 may comprise one or more of the structures of the electrode structure and / or the counter electrode structure including one or more of the electrode current collector, the electrode active material layer, the counter electrode current collector, and the counter electrode active material layer in the constituent units of the unit cells. 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 including an electrode current collector 136 in a constituent unit of a group of unit cells. In FIG. 4, the first secondary growth constraint 158 ​​and the second secondary growth constraint 160 are connected to a secondary connection member 166 including an electrode structure 110 including an electrode current collector 136.

[0067] 3A-3B, in one embodiment, the first secondary growth constraint 158 ​​and / or the second secondary growth constraint 160 are each configured to have a vertical thickness T C The electrode assembly 106 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 secondary growth constraints 158 and / or 160 to the building blocks of the unit cells. For example, for an auxiliary electrode 686 located outside the volume V enclosed by the set of electrode constraints 108, e.g., outside the first and / or second secondary growth constraints 158 and / or 160, carrier ions provided from the auxiliary electrode 686 can access the building blocks of the unit cells of the electrode assembly inside the constraints via a passage through the opening 176. In the embodiment shown in FIG. 8 , which depicts a top view of the electrode assembly 106 showing the first secondary growth constraint 158, the opening 176 includes a slot shape having a long dimension oriented in the vertical and / or stacking direction (Y direction) and extending across the building blocks of the unit cells. Other shapes and / or configurations of the opening 176 can also be provided. According to certain embodiments, at least a portion of the opening 176 is vertically aligned over the porous electrically insulating material 508, such that carrier ions entering the electrode assembly 106 through the opening 176 pass through the porous electrically insulating material 508 to the constituent elements of the unit cells. According to certain embodiments, the process for transporting carrier ions from the auxiliary electrode 686 to the constituent elements of the unit cells can include transporting carrier ions from the auxiliary electrode 686 through the opening 176, through the porous electrically insulating material 508, to one or more of the electrode structure 110 and the counter electrode structure 112. In the embodiment shown in FIG. 8, the porous electrically insulating material 508 extends over the upper and lower end faces of the electrode structure and the counter electrode structure within the first and second secondary growth constraints, while leaving the upper and lower end faces of the electrode current collector 136 exposed.

[0068] According to a further embodiment of the present disclosure, a method for manufacturing an electrode assembly and / or a secondary battery is provided. According to one embodiment, the method includes providing a group of unit cells stacked in a stacking direction, (i) each unit cell includes an electrode structure, a counter electrode structure, and an electrically insulating separator between the electrode structure and the counter electrode structure, (ii) the electrode structure, the counter electrode structure, and the electrically insulating separator in each unit cell have upper and lower end faces that are vertically separated and on opposite sides, and (iii) the vertical direction is perpendicular to the stacking direction. The method further includes providing a porous electrically insulating material covering the upper end face and / or the lower end face of the electrode structure or the counter electrode structure of the constituent unit of the group of unit cells, the porous electrically insulating material having a porosity in the range of 20% to 60%. According to one embodiment, the porous electrically insulating material is provided by coating the upper and / or lower end faces with a slurry or paste including a particulate binder material in a solvent and allowing the solvent to evaporate, leaving the particulate material dispersed in the binder material on the upper and / or lower end faces. For example, in the embodiment shown in Figure 9, a slurry and / or paste 900 is applied to the upper end faces 500a, 501a and / or lower end faces 500b, 501b of the electrode structure 110 and / or counter electrode structure 112.

[0069] In one embodiment, the binder material is soluble in a solvent, and the solvent is evaporated by heating and / or drying the solvent with a gas flow. For example, the solvent can include any of N-methyl-2-pyrrolidone (NMP), heptane, octane, toluene, xylene, or mixed hydrocarbon solvents. Furthermore, according to certain embodiments, the slurry and / or paste includes at least 50% by weight, at least 55% by weight, at least 60% by weight, at least 65% by weight, at least 70% by weight, at least 75% by weight, and / or at least 80% by weight of particulate material, and 90% by weight or less, 85% by weight or less, 80% by weight or less, and / or 75% by weight or less of particulate material. According to one embodiment, the density of the porous electrically insulating material provided on the upper and lower end faces of the counter electrode structure per surface area of ​​the upper and lower end faces of the counter electrode is 15 mg / cm. 2 ~25mg / cm2 is in the range.

[0070] According to one embodiment, the method further includes connecting vertically separated first and second secondary growth constraints to the constituent electrode current collectors of the electrode structure, the first and second secondary growth constraints having openings formed through their respective vertical thicknesses, the secondary growth constraint system at least partially inhibiting growth of the electrode assembly in the vertical direction upon cycling of the electrode assembly. For example, the growth constraints can be connected to the exposed upper and lower end faces of the electrode current collectors as shown in FIG. 8 after the porous electrically insulating material is applied to the upper and / or lower end faces of the electrode structure 110 and / or counter electrode structure 112.

[0071] In yet another embodiment, a method for manufacturing an electrode assembly and / or a secondary battery includes: (1) providing an auxiliary electrode including a carrier ion source external to a porous electrically insulating material; and (2) applying a bias voltage between the auxiliary electrode and the constituent units of the electrode group or the constituent units of the counter electrode group to provide a flow of carrier ions through the openings in the first and second secondary growth constraints and through the porous electrically insulating material to the electrode group and / or the counter electrode structure of the constituent units of the unit cell group. For example, the manufacturing method can include a process for forming a secondary battery including an initial charging process for charging the secondary battery and / or charging the electrode structure, and a process for replenishing carriers lost in the initial charging process. According to certain embodiments, the manufacturing method for an electrode assembly and / or a secondary battery can include any of the methods for providing carrier ions to the constituent units of the unit cell group described herein. According to further embodiments, a method for transferring carrier ions from the auxiliary electrode including a source of carrier ions to the electrode assembly can be performed during an initial or subsequent charging cycle of the secondary battery and / or electrode assembly.

[0072] In one embodiment, a method is provided for preparing an electrode assembly 106 with a set of electrode constraints 108, which can be used as part of a secondary battery configured to cycle between charged and discharged states. The method can generally include forming a sheet structure, cutting the sheet structure into pieces (and / or pieces), stacking the pieces, and applying a set of constraints. By strip, it is understood that pieces other than those in the shape of a strip can be used. The pieces can include an electrode active material layer, an electrode current collector, a counter electrode active material layer, a counter electrode current collector, and a separator, and can be stacked to provide an alternating arrangement of electrode active material and / or counter electrode active material. The sheet can include, for example, a unit cell 504 and / or at least one of the components of a unit cell 504. For example, the sheet can include a group of unit cells, which can be cut to a predetermined size (such as a size suitable for a 3D battery), and then the sheets of unit cells can 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.

[0073] In yet another embodiment, the set of applied electrode constraints 108 may correspond to any of those described herein, such as a set of constraints including a primary growth constraint system comprising first and second primary growth constraints, at least one primary connecting member, the first and second primary growth constraints separated from one another in a vertical direction, and at least one primary connecting member connecting the first and second primary growth constraints. Additionally, the set of electrode constraints may include a secondary growth constraint system comprising first and second secondary growth constraints separated in a direction perpendicular to the vertical direction (e.g., vertical or horizontal) and connected by at least one secondary connecting member, the secondary growth constraint system at least partially restraining growth of the electrode assembly in a vertical direction upon cycling of the secondary battery. At least one of the primary connection member, or the first and / or second primary growth constraints of the primary growth constraint system, and the secondary connection member, or the first and / or second secondary growth constraints of the secondary growth constraint system, may be one or more of the assembly components constituting the pieces, such as, for example, at least one of an electrode active material layer, an electrode current collector, a counter electrode active material layer, a counter electrode current collector, and a separator. For example, in one embodiment, the primary connection member of the primary growth constraint system may be one or more of the assembly components constituting the pieces, such as, for example, at least one of an electrode active material layer, an electrode current collector, a counter electrode active material layer, a counter electrode current collector, and a separator. That is, applying the constraints may include applying the first and second primary growth constraints to the primary building block connection members that are one of the structures in the stack of pieces.

[0074] 2, an exploded view of one embodiment of a secondary battery 102 having a set of electrode constraints 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, as described above, the electrode assembly 106 having a first longitudinal end surface 116 and an opposing second longitudinal end surface 118 (i.e., separated from the first longitudinal end surface 116 along the Y-axis Cartesian coordinate system shown). Alternatively, the secondary battery 102 may include multiple electrode assemblies 106 having a set of electrode constraints 108 provided within the housing. The electrode assemblies 106 include 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 group of electrode structures 110 and counter electrode structures 112 are arranged in a series of alternating electrode structures 110 and counter electrode structures 112, which series proceeds in the stacking direction D between a first longitudinal end surface 116 and a second longitudinal end surface 118, respectively.

[0075] According to the embodiment shown in Fig. 2, tabs 190, 192 protrude outwardly from the battery housing 104 and provide electrical connection between the electrode assembly 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 structure 110 that the electrode assembly 106 comprises. 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 that the electrode assembly 106 comprises. The tab extensions 191, 193 may also function as bus bars to pool currents from each of the respective electrodes and counter electrode structures to which the tab extensions 191, 193 are electrically connected.

[0076] 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 a first primary growth constraint 154 and a second primary growth constraint 156 that may overlie the first vertical end surface 116 and the second vertical end surface 118, respectively, as described above, and opposing first primary connection members 162 and second primary connection members 164 that may overlie the 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).

[0077] 2 has an associated secondary growth constraint system 152 for constraining vertical growth (i.e., expansion of the electrode assembly 106, electrode structure 110, and / or counter electrode structure 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, respectively, that may overlie the 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).

[0078] 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 upper 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 systems 151 and secondary growth constraint systems 152 of the set 106a occupies a volume corresponding to its respective displaced volume. Thus, in combination, the battery housing 104 and the primary and secondary growth constraint systems 151 and 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 and secondary growth constraint systems 151 and 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 and secondary growth constraint systems 151 and 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 and secondary growth constraint systems 151 and 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.

[0079] 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, 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 can comprise any of a wide range of metals, alloys, ceramics, glasses, plastics, or combinations thereof (i.e., composites). 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 152 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.

[0080] The constituent elements of the electrode structures 110 and the counter electrode structures 112 can 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.

[0081] 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 can include a silicon-containing material in particulate form, such as one or more of particulate silicon, particulate silicon oxide, and mixtures thereof. In another embodiment, the electrode active material consists of silicon or silicon oxide. In yet another embodiment, the electrode active material can include a material that exhibits a smaller or even negligible volume change. For example, in one embodiment, the electrode active material can include a carbon-containing material, such as graphite. In yet another embodiment, the electrode structure includes a layer of lithium metal, such as, for example, an electrode structure including an electrode current collector, on which a layer of lithium metal is deposited during the charging process as a result of the transfer of carrier ions from the counter electrode structure to the electrode structure.

[0082] Further, according to certain embodiments, 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.

[0083] 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), 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 and synthetic graphite, and amorphous carbon such as soft carbon and hard carbon. 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 an alloy thereof, a transition metal oxide such as Li₄ / ₃Ti₅ / ₃O₄ or SnO, and a carbonaceous material 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.

[0084] 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.

[0085] 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, and 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 The cathode active material may include one or more of lithium manganese complex oxides 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), LiMn2O4 in which a portion of Li is replaced with an alkaline earth metal ion, disulfide compounds, Fe2(MoO4)3, etc. In one embodiment, the cathode active material may include one or more of lithium manganese complex oxides represented by the chemical formula Li2Mn3MO8 (wherein M=Fe, Co, Ni, Cu, or Zn), LiMn2O4 in which a portion of Li is replaced with an alkaline earth metal ion, disulfide compounds, Fe2(MoO4)3, etc. Li 1+a 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, and a + b + c = 2), LiMn 2-z Ni z O4, LiMn 2-z Co z O4(0 < z < 2), LiCoPO4, and LiFePO4, or at least one of mixtures of two or more of them.

[0086] In another embodiment, the cathode active material can include elemental sulfur (S8), sulfur - based compounds, or mixtures 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 include oxides of lithium and zirconium.

[0087] In another embodiment, the cathode active material can include at least one composite oxide of lithium and at least one metal such as cobalt, manganese, nickel, or combinations thereof, and can be used. Examples thereof are 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(Wherein, 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 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 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 bO4 (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) and LiFePO4. In the above 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 may 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 a lithium compound such as lithium iron phosphate, nickel sulfide, copper sulfide, sulfur, iron oxide, or vanadium oxide.

[0088] In one embodiment, the cathode active material has the formula NaM, such as NaFeO, NaMnO, NaNiO, or NaCoO. 1 a At least one of the oxides of O2 or the chemical formula NaMn 1-a M 1 aThe oxide may include a sodium-containing material, such as an oxide represented by the formula M 1 is at least one transition metal element, and 0≦a<1. Representative positive active materials include 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 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), Na such as Na2FeSiO6 f M 4 g The oxide represented by Si2O6 (wherein, M 4is 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 5 is 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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%.

[0095] Binders for microporous separator materials can be selected from a wide range of inorganic or polymeric materials. For example, in one embodiment, the binder can 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.

[0096] 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 binder has a conductivity for carrier ions of less than S / cm. For example, in one embodiment, the binder is an organic 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 aerogel, fumed silica, silica gel, silica hydrogel, silica xerogel, silica sol, 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.

[0097] According to one embodiment of the assembled energy storage device, the microporous separator material 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 15 As 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.

[0098] 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.

[0099] 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.

[0100] Embodiment The following enumerated embodiments 1-157 describe embodiments according to the present disclosure.

[0101] Embodiment 1: A method for transferring carrier ions from an auxiliary electrode including a source of carrier ions to an electrode assembly, comprising: The electrode assembly includes a group of unit cells stacked in succession in a stacking direction, and a porous electrically insulating material, (i) each unit cell includes an electrode structure, a counter electrode structure, and an electrically insulating separator between the electrode structure and the counter electrode structure, (ii) the electrode structure, the counter electrode structure, and the electrically insulating separator in each unit cell have upper and lower end faces that are vertically separated and on opposite sides, (iii) the vertical direction is perpendicular to the stacking direction, (iv) the porous electrically insulating material covers the upper end face or the lower end face of the electrode structure or the counter electrode structure of a constituent unit of the group of unit cells, and (v) the porous electrically insulating material has porosity, The method includes transporting carrier ions from an auxiliary electrode to a constituent unit of the group of unit cells through a porous electrically insulating material.

[0102] Embodiment 2: An electrode assembly for a secondary battery for cycling between a charged state and a discharged state, the electrode assembly comprising: An electrode assembly comprising: a group of unit cells stacked in succession in a stacking direction; and a porous electrically insulating material, (i) each unit cell comprises an electrode structure, a counter electrode structure, and an electrically insulating separator between the electrode structure and the counter electrode structure, (ii) the electrode structure, the counter electrode structure, and the electrically insulating separator in each unit cell have upper and lower end faces that are separated in a vertical direction and are on opposite sides, (iii) the vertical direction is perpendicular to the stacking direction, (iv) the porous electrically insulating material covers the upper end face or the lower end face of the electrode structure or the counter electrode structure of a constituent unit of the group of unit cells, and (v) the porous electrically insulating material has porosity.

[0103] Embodiment 3: A secondary battery comprising the electrode assembly according to embodiment 2.

[0104] Embodiment 4: The method, electrode assembly, or secondary battery according to any one of embodiments 1 to 3, wherein the porous electrically insulating material covers both the upper end surface and the lower end surface of the electrode structure or counter electrode structure of the unit cell group.

[0105] Embodiment 5: The method, electrode assembly, or secondary battery according to any one of embodiments 1 to 4, wherein the porous electrically insulating material covers both the upper vertical end faces or the lower vertical end faces of the electrode structure or the counter electrode structure of the constituent unit of the unit cell group.

[0106] Embodiment 6: The method, electrode assembly, or secondary battery according to any one of embodiments 1 to 5, wherein the porous electrically insulating material covers both the upper end surface and the lower end surface of both the electrode structure or the counter electrode structure of the unit cell group.

[0107] Embodiment 7: Carrier ions are transferred to a discharge voltage V ces eod and the discharge voltage V at the end of a given electrode structure es,eod and, the method according to any one of embodiments 1 and 4 to 6, achieving and / or restoring.

[0108] Embodiment 8: The method of any one of embodiments 1 and 4-7, wherein carrier ions are transported to replenish carrier ions lost in the formation of the SEI.

[0109] Embodiment 9: The method of any one of embodiments 1 and 4-8, wherein carrier ions are transported to compensate for loss of carrier ions during an initial or subsequent charging cycle performed by the electrode assembly.

[0110] Embodiment 10: A method comprising: (i) transferring carrier ions from a counter electrode structure to an electrode structure in a group of unit cells during an initial or subsequent charging cycle to at least partially charge an electrode assembly; and (ii) transferring carrier ions from an auxiliary electrode to the counter electrode structure and / or the electrode structure through a porous electrically insulating material to charge the electrode assembly to a discharge voltage V at a predetermined counter electrode structure end. ces,eod and the discharge voltage V at the end of a given electrode structure es,eod 10. The method of any one of embodiments 1 and 4-9, comprising providing:

[0111] Embodiment 11: The method according to any one of embodiments 1 and 4 to 10, wherein the process further comprises, after (iii)(ii), transferring carrier ions from the counter electrode structure of the constituent unit of the unit cell group to the electrode structure to charge the electrode assembly.

[0112] Embodiment 12: The method of any one of embodiments 1 and 4 to 11, wherein (ii) is performed simultaneously with (i).

[0113] Embodiment 13: In (ii), a bias voltage is applied between the auxiliary electrode and the electrode structure and / or the counter electrode structure of the unit cell group to provide a flow of carrier ions through the porous electrically insulating material member.

[0114] Embodiment 14: The method, electrode assembly, or secondary battery according to any one of the preceding embodiments, wherein the unit cell group components have upper and lower edges including upper and lower vertical end faces that are on opposite sides, the upper vertical end faces of the electrode structure and the counter electrode structure in the same unit cell group components are vertically offset from each other to form an upper recess, the lower vertical end faces of the electrode structure and the counter electrode structure in the same unit cell group components are vertically offset from each other to form a lower recess, the upper end faces and the lower end faces of the counter electrode structure are vertically offset inwardly relative to the upper and lower vertical end faces of the respective electrode structures in the same unit cell group components, and the porous electrically insulating material is located in at least one of the upper recess and the lower recess.

[0115] Embodiment 15: The method, electrode assembly, or secondary battery according to embodiment 14, wherein the porous electrically insulating material substantially fills the upper recess and the lower recess of the constituent unit of the unit cell group.

[0116] Embodiment 16: The method, electrode assembly, or secondary battery according to any one of the preceding embodiments, wherein, for a constituent unit of a unit cell group, at least a portion of the porous electrically insulating material covering the upper end surface and / or the lower end surface of the electrode structure and / or the counter electrode structure is adjacent to an electrically insulating separator.

[0117] Embodiment 17: A method, electrode assembly, or secondary battery according to any one of the preceding embodiments, wherein the porous electrically insulating material substantially fills the areas of the upper and lower recesses that are disposed inwardly relative to the upper and lower end faces of the electrode structure in the constituent unit of the unit cell group and abut against the side of the electrically insulating separator facing the counter electrode structure.

[0118] Embodiment 18: The method, electrode assembly, or secondary battery according to any one of the preceding embodiments, wherein the electrode structure of the unit of the unit cell group comprises an electrode active material layer and an electrode current collector layer, the counter electrode structure of the unit of the unit cell group comprises a counter electrode active material layer and a counter electrode current collector layer, and the porous electrically insulating material covers the upper and lower end faces of the counter electrode active material layer of the unit of the unit cell group.

[0119] Embodiment 19: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the porous electrically insulating material comprises a porosity of at least 25%.

[0120] Embodiment 20: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the porous electrically insulating material comprises a porosity of at least 30%.

[0121] Embodiment 21: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the porous electrically insulating material comprises a porosity of at least 35%.

[0122] Embodiment 22: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the porous electrically insulating material comprises a porosity of at least 40%.

[0123] Embodiment 23: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the porous electrically insulating material comprises a porosity of at least 45%.

[0124] Embodiment 24: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the porous electrically insulating material comprises a porosity of at least 50%.

[0125] Embodiment 25: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the porous electrically insulating material comprises a porosity of at least 55%.

[0126] Embodiment 26: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the porous electrically insulating material comprises a porosity of 55% or less.

[0127] Embodiment 27: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the porous electrically insulating material comprises a porosity of 50% or less.

[0128] Embodiment 28: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the porous electrically insulating material comprises a porosity of 45% or less.

[0129] Embodiment 29: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the porous electrically insulating material comprises a porosity of 40% or less.

[0130] Embodiment 30: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the porous electrically insulating material comprises a porosity of 35% or less.

[0131] Embodiment 31: The method, electrode assembly, or secondary battery according to any one of the preceding embodiments, wherein the electrically insulating separator is microporous and the ratio of the porosity of the porous electrically insulating material to the porosity of the electrically insulating separator is in the range of 1:0.75 to 1:1.5.

[0132] Embodiment 32: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the porous electrically insulating material comprises a particulate material dispersed in a binder material.

[0133] Embodiment 33: The method, electrode assembly, or secondary battery of embodiment 32, wherein the particulate material comprises a stable metal oxide and / or ceramic.

[0134] Embodiment 34: The method, electrode assembly, or secondary battery of embodiment 32 or 33, wherein the particulate material comprises any one or more of alumina, boron nitride, titania, silica, zirconia, magnesium oxide, and calcium oxide.

[0135] Embodiment 35: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 34, wherein the particulate material comprises alumina.

[0136] Embodiment 36: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 35, wherein the particulate material comprises particles having a d50 particle size (median particle size) of at least 0.35 microns.

[0137] Embodiment 37: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 36, wherein the particulate material comprises particles having a d50 particle size (median particle size) of at least 0.45 microns.

[0138] Embodiment 38: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 37, wherein the particulate material comprises particles having a d50 particle size (median particle size) of at least 0.5 microns.

[0139] Embodiment 39: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 38, wherein the particulate material comprises particles having a d50 particle size (median particle size) of at least 0.75 microns.

[0140] Embodiment 40: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 39, wherein the particulate material comprises particles having a d50 particle size (median particle size) of 40 microns or less.

[0141] Embodiment 41: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 40, wherein the particulate material comprises particles having a d50 particle size (median particle size) of 35 microns or less.

[0142] Embodiment 42: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 41, wherein the particulate material comprises particles having a d50 particle size (median particle size) of 25 microns or less.

[0143] Embodiment 43: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 42, wherein the particulate material comprises particles having a d50 particle size (median particle size) of 20 microns or less.

[0144] Embodiment 44: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 43, wherein at least 80% by weight of the particles have a particle size of at least 0.35 microns.

[0145] Embodiment 45: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 44, wherein at least 85% by weight of the particles have a particle size of at least 0.35 microns.

[0146] Embodiment 46: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 45, wherein at least 90% by weight of the particles have a particle size of at least 0.35 microns.

[0147] Embodiment 47: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 46, wherein at least 95% by weight of the particles have a particle size of at least 0.35 microns.

[0148] Embodiment 48: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 47, wherein at least 80% by weight of the particles have a particle size of at least 0.45 microns.

[0149] Embodiment 49: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 48, wherein at least 85% by weight of the particles have a particle size of at least 0.45 microns.

[0150] Embodiment 50: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 49, wherein at least 90% by weight of the particles have a particle size of at least 0.45 microns.

[0151] Embodiment 51: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 50, wherein at least 95% by weight of the particles have a particle size of at least 0.45 microns.

[0152] Embodiment 52: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 51, wherein at least 80% by weight of the particles have a particle size of at least 0.5 microns.

[0153] Embodiment 53: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 52, wherein at least 85% by weight of the particles have a particle size of at least 0.5 microns.

[0154] Embodiment 54: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 53, wherein at least 90% by weight of the particles have a particle size of at least 0.5 microns.

[0155] Embodiment 55: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 54, wherein at least 95% by weight of the particles have a particle size of at least 0.5 microns.

[0156] Embodiment 56: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 55, wherein at least 80% by weight of the particles have a particle size of at least 0.75 microns.

[0157] Embodiment 57: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 56, wherein at least 85% by weight of the particles have a particle size of at least 0.75 microns.

[0158] Embodiment 58: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 57, wherein at least 90% by weight of the particles have a particle size of at least 0.75 microns.

[0159] Embodiment 59: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 58, wherein at least 95% by weight of the particles have a particle size of at least 0.75 microns.

[0160] Embodiment 60: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 59, wherein at least 80% by weight of the particles have a particle size of 40 microns or less.

[0161] Embodiment 61: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 60, wherein at least 85% by weight of the particles have a particle size of 40 microns or less.

[0162] Embodiment 62: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 61, wherein at least 90% by weight of the particles have a particle size of 40 microns or less.

[0163] Embodiment 63: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 62, wherein at least 95% by weight of the particles have a particle size of 40 microns or less.

[0164] Embodiment 64: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 63, wherein at least 80% by weight of the particles have a particle size of 35 microns or less.

[0165] Embodiment 65: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 64, wherein at least 85% by weight of the particles have a particle size of 35 microns or less.

[0166] Embodiment 66: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 65, wherein at least 90% by weight of the particles have a particle size of 35 microns or less.

[0167] Embodiment 67: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 66, wherein at least 95% by weight of the particles have a particle size of 35 microns or less.

[0168] Embodiment 68: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 67, wherein at least 80% by weight of the particles have a particle size of 25 microns or less.

[0169] Embodiment 69: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 68, wherein at least 85% by weight of the particles have a particle size of 25 microns or less.

[0170] Embodiment 70: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 69, wherein at least 90% by weight of the particles have a particle size of 25 microns or less.

[0171] Embodiment 71: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 70, wherein at least 95% by weight of the particles have a particle size of 25 microns or less.

[0172] Embodiment 72: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 71, wherein at least 80% by weight of the particles have a particle size of 20 microns or less.

[0173] Embodiment 73: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 72, wherein at least 85% by weight of the particles have a particle size of 25 microns or less.

[0174] Embodiment 74: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 73, wherein at least 90% by weight of the particles have a particle size of 25 microns or less.

[0175] Embodiment 75: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 74, wherein at least 95% by weight of the particles have a particle size of 25 microns or less.

[0176] Embodiment 76: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 75, wherein the particulate material comprises at least 70% by weight of a porous electrically insulating material.

[0177] Embodiment 77: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 76, wherein the particulate material comprises at least 75% by weight of a porous electrically insulating material.

[0178] Embodiment 78: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 77, wherein the particulate material comprises at least 80% by weight of a porous electrically insulating material.

[0179] Embodiment 79: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 78, wherein the particulate material comprises at least 85% by weight of a porous electrically insulating material.

[0180] Embodiment 80: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 79, wherein the particulate material comprises 99.5% by weight or less of the porous electrically insulating material.

[0181] Embodiment 81: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 80, wherein the particulate material comprises 97% by weight or less of a porous electrically insulating material.

[0182] Embodiment 82: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 81, wherein the particulate material comprises 95% by weight or less of a porous electrically insulating material.

[0183] Embodiment 83: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 82, wherein the particulate material comprises 90% by weight or less of the porous electrically insulating material.

[0184] Embodiment 84: The method, electrode assembly, or secondary battery according to any one of embodiments 32 to 83, wherein the binder material comprises a polymer material selected from the group consisting of polyvinylidene fluoride (PVDF), polyethylene, polypropylene, ethylene acrylic acid (EAA), ethylene methacrylic acid (EMAA), and copolymers thereof.

[0185]

[0081] Embodiment 85: An electrode assembly includes a wound electrode assembly having a plurality of turns of the constituent electrode structures and counter electrode structures of the unit cells around a central axis of the wound electrode assembly, the vertical direction of the wound electrode assembly being parallel to the central axis, and further, the constituent counter electrode structures of the unit cells having a length L extending from a first end of the counter electrode structure in a central region of the wound electrode assembly and along each turn to a second end of the counter electrode structure in an outer region of the electrode assembly. CE 4. The method, electrode assembly, or secondary battery of any one of the preceding embodiments, comprising:

[0186] Embodiment 86: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the wound electrode assembly has a cylindrical shape.

[0187]

[0081] Embodiment 87: An electrode assembly is provided having mutually perpendicular transverse, longitudinal, and vertical axes, which correspond to the x-axis, y-axis, and z-axis, respectively, of a virtual three-dimensional Cartesian coordinate system, and a first longitudinal end surface and a second longitudinal end surface are separated from each other in the longitudinal direction, and a longitudinal axis A of the electrode assembly is provided. EAa lateral surface surrounding the first and second longitudinal end surfaces and connecting the first and second longitudinal end surfaces, the lateral surface having opposed first and second regions on either side 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 bounded by the lateral plane and measured laterally EA and the maximum height H bounded by the lateral surface and measured vertically EA and a lateral surface having Each electrode structure of the constituent units of the unit cell group has a length L measured in the lateral direction between the first and second opposite lateral end faces of the electrode structure. E and the height H measured vertically between the opposite vertical end faces of the upper and lower sides of the electrode structure. E and a width W measured longitudinally between the first and second opposing surfaces of the electrode structure. E and each counter electrode structure of the constituent units of the unit cell group has a length L measured in a lateral direction between first and second opposite lateral end faces of the counter electrode structure. CE and the height H measured vertically between the upper and lower vertical edges of the counter electrode structure. CE and a width W measured longitudinally between the first and second opposing surfaces of the counter electrode structure. CE and Regarding the electrode structure of the unit cell group, 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 the counter electrode structure of the unit cell group is CE and W CE and H CE is at least 5:1 with each of H CE and W CE The method, electrode assembly, or secondary battery according to any one of the preceding embodiments, wherein the ratio of

[0188] Embodiment 88: The method, electrode assembly, or secondary battery according to any one of embodiments 85 to 87, wherein the porous electrically insulating material extends over at least 50% of the counter electrode structure of the constituent unit of the unit cell group.

[0189] Embodiment 89: The method, electrode assembly, or secondary battery according to any one of embodiments 85 to 88, wherein the porous electrically insulating material extends over at least 60% of the counter electrode structure of the constituent unit of the unit cell group.

[0190] Embodiment 90: The method, electrode assembly, or secondary battery according to any one of embodiments 85 to 89, wherein the porous electrically insulating material extends over at least 75% of the counter electrode structure of the component of the unit cell group.

[0191] Embodiment 91: The method, electrode assembly, or secondary battery according to any one of embodiments 85 to 90, wherein the porous electrically insulating material extends over at least 85% of the counter electrode structure of the constituent unit of the unit cell group.

[0192] Embodiment 92: The method, electrode assembly, or secondary battery according to any one of embodiments 85 to 91, wherein the porous electrically insulating material extends over at least 90% of the counter electrode structure of the constituent unit of the unit cell group.

[0193] Embodiment 93: Each electrode structure of the constituent unit of the unit cell group has a layer of an electrode active material, and each counter electrode structure of the constituent unit of the unit cell group has a layer of a counter electrode active material, and the adjacent electrode active material layers and counter electrode active material layers in the constituent unit of the unit cell are a. an upper vertical end surface of the counter electrode active material layer has a first recess disposed inwardly relative to the upper vertical end surfaces of the electrode active material layer and the separator; b. a lower vertical end surface of the counter electrode active material layer has a second recess disposed inwardly relative to the lower vertical end surfaces of the electrode active material layer and the separator; c. The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein a porous electrically insulating material is disposed adjacent to the electrically insulating separator and within a first recess in an upper vertical end face of the counter electrode active material layer, and a porous electrically insulating material is disposed adjacent to the electrically insulating separator and within a second recess in a lower vertical end face of the counter electrode active material layer.

[0194] Embodiment 94: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the secondary battery further comprises a set of electrode constraints.

[0195] Embodiment 95: The method, electrode assembly, or secondary battery according to embodiment 94, wherein the set of electrode constraints comprises a primary growth constraint system comprising first and second primary growth constraints and at least one primary connecting member, the first and second primary growth constraints being separated from each other in the stacking direction, and the at least one primary connecting member connecting the first and second primary growth constraints, and the primary growth constraint system suppresses growth of the electrode assembly in the stacking direction.

[0196] Embodiment 96: The method, electrode assembly, or secondary battery according to embodiment 94 or 95, wherein the set of electrode constraints comprises a secondary growth constraint system comprising first and second secondary growth constraints separated in the vertical direction and connected to the electrode current collectors of the constituent units of the group of unit cells, and the secondary growth constraint system at least partially suppresses growth of the electrode assembly in the vertical direction upon cycling of the electrode assembly.

[0197] Embodiment 97: The method, electrode assembly, or secondary battery according to any one of embodiments 94 to 96, wherein the first and second secondary growth constraints have openings formed through the vertical thickness of each of the first and second secondary growth constraints, at least a portion of the openings being vertically aligned on the porous electrically insulating material, and carrier ions are transported from the auxiliary electrode through the openings, through the porous electrically insulating material, to the electrode structure and / or the counter electrode structure.

[0198] Embodiment 98: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein (i) the electrode structure is an anode structure and the counter electrode structure is a cathode structure, or (ii) the electrode structure is a cathode structure and the counter electrode structure is an anode structure.

[0199] Embodiment 99: The method, electrode assembly, or secondary battery of embodiment 98, wherein the electrode structure is an anode structure comprising an anode active material layer, and the counter electrode structure is a cathode structure comprising a cathode active material layer.

[0200] Embodiment 100: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrode assembly is contained in a sealed battery housing.

[0201] Embodiment 101: The method, electrode assembly, or secondary battery of embodiment 100, wherein the set of carrier ions and electrode constraints are contained within a sealed battery housing.

[0202] Embodiment 102: The electrode structure is an anode active material that is selected from the group consisting of 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 and / or intercalated with lithium, Sn alloy, Al alloy, a metal oxide capable of doping and undoping lithium ions, SiO v (0 < v < 2), a composite material containing SnO2, vanadium oxide, lithium vanadium oxide, a metal compound, and a carbon material, Si-C composite material, Sn-C composite material, transition metal oxide, Li4 / 3Ti5 / 3O4, SnO, a carbonaceous material, 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, and a 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, a method, an electrode assembly, or a secondary battery according to any one of the preceding embodiments.

[0203] Embodiment 103: A method, an electrode assembly, or a secondary battery according to any one of the preceding embodiments, wherein the electrode structure includes an anode active material containing at least one of lithium metal, lithium metal alloy, silicon, silicon alloy, silicon oxide, tin, tin alloy, tin oxide, and a carbon-containing material.

[0204] Embodiment 104: A method, an electrode assembly, or a secondary battery according to any one of the preceding embodiments, wherein the electrode structure includes an anode active material containing at least one of silicon and silicon oxide.

[0205] Embodiment 105: A method, an electrode assembly, or a secondary battery according to any one of the preceding embodiments, wherein the electrode structure includes an anode active material containing at least one of lithium and lithium metal alloy.

[0206] Embodiment 106. A secondary battery and / or a method according to any one of the preceding embodiments, wherein the electrode structure includes an anode active material containing a carbon-containing material.

[0207] Embodiment 107: A method, an electrode assembly, or a secondary battery according to any one of the preceding embodiments, wherein the electrical insulation separator includes a microporous separator material permeated with a non-aqueous liquid electrolyte.

[0208] Embodiment 108: A method, an electrode assembly, or a secondary battery according to any one of the preceding embodiments, wherein the electrical insulation separator includes a solid separator containing a solid electrolyte.

[0209] Embodiment 109: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrically insulating separator comprises a ceramic material, a glass, or a garnet material.

[0210] Embodiment 110: The method, 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.

[0211] Embodiment 111: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrode assembly includes a liquid electrolyte.

[0212] Embodiment 112: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrode assembly comprises an aqueous liquid electrolyte.

[0213] Embodiment 113: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrode assembly comprises a non-aqueous liquid electrolyte.

[0214] Embodiment 114: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrode assembly includes a gel electrolyte.

[0215] Embodiment 115: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrically insulating separator comprises a solid electrolyte.

[0216] Embodiment 116: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrically insulating separator comprises a solid polymer electrolyte.

[0217] Embodiment 117: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrically insulating separator comprises a solid inorganic electrolyte.

[0218] Embodiment 118: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrically insulating separator comprises a solid organic electrolyte.

[0219] Embodiment 119: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrically insulating separator comprises a ceramic electrolyte.

[0220] Embodiment 120: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrically insulating separator comprises an inorganic electrolyte.

[0221] Embodiment 121: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrically insulating separator comprises a ceramic.

[0222] Embodiment 122: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrically insulating separator comprises a garnet material.

[0223] Embodiment 123: The method, 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 molten inorganic electrolyte.

[0224] Embodiment 124: A counter electrode structure is a cathode active material having a metal element having a d-shell or an f-shell, and the metal element is any one selected from Sc, Y, a lanthanide, an actinide, 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, including transition metal oxides, transition metal sulfides, transition metal nitrides, lithium transition metal oxides, lithium transition metal sulfides, lithium transition metal nitrides, LiCoO2, LiNi 0.5 Mn 1.5 O4, Li(Nix 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(where M’ is at least one selected from Al, Mg, Ni, Co, Mn, Ti, Ga, Cu, V, Nb, Zr, Ce, In, Zn, and Y; X is at least one selected from F, S, and N; -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 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, 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 polymers ((C2S x ) n :x = 2.5~50, n ≧ 2), oxides of lithium and zirconium, 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(Wherein, 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 (Wherein, 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 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 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 bO2 (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 1is 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 a O2 (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 SiO 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 4is 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 5 is 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 complex oxides and / or other combinations of the foregoing.

[0225] Embodiment 125: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the counter electrode structure comprises a cathode active material comprising 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.

[0226] Embodiment 126: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the counter electrode structure comprises a cathode active material comprising a lithium-containing transition metal oxide and at least one of cobalt and nickel.

[0227] Embodiment 127: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrode structure comprises 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).

[0228] Embodiment 128: The method, electrode assembly, or secondary battery of embodiment 119, wherein the electrode structure comprises an anode current collector comprising at least one of copper, nickel, stainless steel, and alloys thereof.

[0229] Embodiment 129: The method, electrode assembly, or secondary battery of 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, and / or alloys thereof).

[0230] Embodiment 130: The method, electrode assembly, or secondary battery according to any one of embodiments 129, 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 (having carbon, silver, or alloys thereof).

[0231] Embodiment 131: A method, electrode assembly, or secondary battery according to any one of the preceding embodiments, comprising a constraint system having first and second secondary growth constraints comprising any of stainless steel, titanium, or glass fiber composite materials.

[0232] Embodiment 132: The method, electrode assembly, or secondary battery of embodiment 131, comprising a constraint system having first and second secondary growth constraints comprising stainless steel.

[0233] Embodiment 133: A method, electrode assembly, or secondary battery according to any one of the preceding embodiments, comprising a constraint system having first and second secondary growth constraints, the first and second secondary growth constraints including a coating of insulating material on inner and outer surfaces of the first and second secondary growth constraints.

[0234] Embodiment 134: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrode assembly comprises at least five electrode structures and at least five counter electrode structures.

[0235] Embodiment 135: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrode assembly comprises at least 10 electrode structures and at least 10 counter electrode structures.

[0236] Embodiment 136: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrode assembly comprises at least 50 electrode structures and at least 50 counter electrode structures.

[0237] Embodiment 137: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrode assembly comprises at least 100 electrode structures and at least 100 counter electrode structures.

[0238] Embodiment 138: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the electrode assembly comprises at least 500 electrode structures and at least 500 counter electrode structures.

[0239] Embodiment 139: The method, electrode assembly, or secondary battery of any one of the preceding embodiments, wherein the counter electrode structure comprises a counter electrode current collector comprising aluminum.

[0240] Embodiment 140: A method for producing an electrode assembly or a secondary battery according to any one of embodiments 2 to 6 and 14 to 139, comprising: (1) stacking a group of unit cells stacked consecutively in a stacking direction, (i) each unit cell comprising an electrode structure, a counter electrode structure, and an electrically insulating separator between the electrode structure and the counter electrode structure, (ii) the electrode structure, the counter electrode structure, and the electrically insulating separator in each unit cell have opposing upper and lower end faces separated in a vertical direction, and (iii) the vertical direction is perpendicular to the stacking direction; (2) covering the upper or lower end surfaces of the electrodes or counter electrode structures of the individual cells with a porous electrically insulating material.

[0241] Embodiment 141: A manufacturing method described in embodiment 140, in which the porous electrically insulating material is provided by coating the upper end surface or the lower end surface with a slurry or paste comprising a particulate material binder material in a solvent, and evaporating the solvent to leave the particulate material dispersed in the binder material on the upper end surface and / or the lower end surface.

[0242]

[0081] Embodiment 142: The method of embodiment 141, wherein the binder material is soluble in a solvent, and the solvent is evaporated by heating and / or drying the solvent with a gas flow.

[0243] Embodiment 143: The process of any one of embodiments 141-142, wherein the solvent comprises any of N-methyl-2-pyrrolidone (NMP), heptane, octane, toluene, xylene, or mixed hydrocarbon solvents.

[0244] Embodiment 144: The method of any one of embodiments 141 to 143, wherein the slurry and / or paste comprises at least 50% by weight of particulate material.

[0245] Embodiment 145: The method of any one of embodiments 141 to 144, wherein the slurry and / or paste comprises at least 55% by weight of particulate material.

[0246] Embodiment 146: The method of any one of embodiments 141 to 145, wherein the slurry and / or paste comprises at least 60% by weight of particulate material.

[0247] Embodiment 147: The method of any one of embodiments 141 to 146, wherein the slurry and / or paste comprises at least 65% by weight of particulate material.

[0248] Embodiment 148: The method of any one of embodiments 141 to 147, wherein the slurry and / or paste comprises at least 70% by weight of particulate material.

[0249] Embodiment 149: The method of any one of embodiments 141 to 148, wherein the slurry and / or paste comprises at least 75% by weight of particulate material.

[0250] Embodiment 150: The method of any one of embodiments 141 to 149, wherein the slurry and / or paste comprises at least 80% by weight of particulate material.

[0251] Embodiment 151: The method of any one of embodiments 141 to 150, wherein the slurry and / or paste comprises 90% or less by weight of particulate material.

[0252] Embodiment 152: The method of any one of embodiments 141 to 151, wherein the slurry and / or paste comprises 85% or less by weight of particulate material.

[0253] Embodiment 153: The method of any one of embodiments 141 to 152, wherein the slurry and / or paste comprises 80% or less by weight of particulate material.

[0254] Embodiment 154: The method of any one of embodiments 141 to 153, wherein the slurry and / or paste comprises 75% or less by weight of particulate material.

[0255] EMBODIMENT 155: The method of any one of embodiments 140 to 154, further comprising connecting vertically separated first and second secondary growth constraints to a constituent electrode current collector of the electrode structure, the first and second secondary growth constraints having openings formed through their respective vertical thicknesses, and the secondary growth constraint system at least partially inhibiting growth of the electrode assembly in the vertical direction upon cycling of the electrode assembly.

[0256] EMBODIMENT 156: (1) positioning an auxiliary electrode including a source of carrier ions outside the porous electrically insulating material; (2) applying a bias voltage between the auxiliary electrode and the constituent units of the electrode group or the constituent units of the counter electrode group to provide a flow of carrier ions through the openings in the first and second secondary growth constraints and through the porous electrically insulating material to the electrode group and / or counter electrode structure of the constituent units of the unit cell group.

[0257] Embodiment 157: A manufacturing method described in any one of embodiments 140 to 156, comprising carrying out a method for transferring carrier ions from an auxiliary electrode including a carrier ion source to an electrode assembly during an initial or subsequent charging cycle of a secondary battery described in any one of embodiments 1 and 7 to 13.

[0258] Embodiment 158: The method, electrode assembly, or secondary battery according to any one of embodiments 1 to 18 and 31 to 157, wherein the porous electrically insulating material has a porosity in the range of 20% to 60%.

[0259] 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.

[0260] 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.

[0261] 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. A transfer device for transferring carrier ions to an energy storage device, comprising: The transfer device comprises: A carrier ion source; An electrolyte; and a housing. the carrier ion source is configured to electrochemically interact with a unit cell including an electrode separated from a counter electrode by a separator; the unit cell is configured to be at least partially charged and / or discharged by using the carrier ions; the carrier ion source is configured to at least partially form a solid electrolyte interface within the unit cell by using the carrier ions; the carrier ion source is configured to be operatively coupled to a constraint system coupled to the unit cell such that the carrier ions travel from the carrier ion source through the constraint system to the unit cell; the constraint system is configured to constrain growth of the unit cells during operation; the electrolyte is configured to fluidly transport the carrier ions from the carrier ion source to the unit cell; The housing is configured to surround the carrier ion source and the electrolyte. Transport device.

2. the electrolyte is configured to fluidly transport the carrier ions from the carrier ion source to the unit cell via a porous material configured to provide a path for the carrier ions to propagate from the carrier ion source to the unit cell; the porous material is operatively coupled to the unit cell and the constraint system. The transfer device of claim 1 .

3. The transfer device is configured for initial formation and / or replenishment of the energy storage device; The replenishment is at least partially due to loss of carrier ions during use of the energy storage device. The transfer device of claim 1 .

4. The carrier ion source is configured to be coupled to a constraint system including a plurality of openings such that the carrier ions are transported through the constraint system by being at least partially transported through the plurality of openings. The transfer device of claim 1 .

5. The carrier ion source is coupled to a constraining system including apertures that (a) include curvature, (b) are equidistant from one another, (c) are aligned, or (d) any combination thereof, thereby the transport device is configured such that the carrier ions are transported at least in part through the constraining system by being transported through an opening that includes a curvature. The transfer device of claim 1 .

6. The carrier ion source configured to couple to the constraint system including an elongated aperture such that carrier ions are transported at least in part through the constraint system by being transported through the aperture; each of the openings having a longitudinal axis; the unit cell has a length measured in a transverse direction, the major axis being perpendicular to the length; The transfer device of claim 1 .

7. The constraint system includes a first constraint opposed to a second constraint; the unit cell is disposed between the first constraint and the second constraint; the carrier ion source is configured to contact the first constraint and the second constraint to facilitate movement of the carrier ions; 13. The transfer device of claim 1.

8. The constraining system comprising: (a) a ceramic; and (b) a metal, a composite, or a metal and a composite. The transfer device of claim 1 .

9. The carrier ion includes any one of a lithium ion, a sodium ion, a potassium ion, a calcium ion, a magnesium ion, and an aluminum ion. The transfer device of claim 1 .

10. The electrode comprising silicon, a particulate silicon material, a silicon oxide, a silicon carbon composite, a silicon alloy, a silicon compound, or any combination thereof. The transfer device of claim 1 .

11. The unit cell is a wound type unit cell. The transfer device of claim 1 .

12. The unit cell is stacked on other unit cells similar to the unit cell to form a stack; The stack comprises at least 2, 5, 10, 25, 50, or 100 members of the unit cell; The transfer device of claim 1 .

13. The electrolyte is a non-aqueous electrolyte. The transfer device of claim 1 .

14. The method of claim 13, wherein the carrier ion source is configured to electrochemically interact with a stack of unit cells that constitute the unit cell; the carrier ion source is configured to be operatively coupled to the constraining system coupled to the stack of unit cells such that the carrier ions travel from the carrier ion source through the constraining system to the stack of unit cells. The transfer device of claim 1 .

15. The stack of unit cells is stacked along an axis, the carrier ion source is configured to be operably coupled to the stack of unit cells such that the carrier ion source is axis-parallel; 15. The transfer device of claim 14.

16. The stack of electrodes and counter electrodes is stacked along an axis; the constraint system is configured to be operably coupled to the unit cell such that the constraint system is parallel to the axis.

15. The transfer device of claim 14.

17. The unit cell is an electrode assembly having a maximum length to maximum height ratio of at least 2:1 and a maximum width to maximum height ratio of at least 2:

1.

15. The transfer device of claim 14.

18. The housing is a sealed housing configured to seal the electrolyte within the housing and seal the electrolyte from an environment external to the housing. The transfer device of claim 1 .

19. The housing is configured to enclose the constraint system and the unit cell. The transfer device of claim 1 .

20. A transport device as described in claim 19, wherein the housing and the constraint system occupy up to 75% of the volume enclosed by the outer surface of the housing.

21. The housing, wherein the housing is a sealed housing configured to seal the electrolyte within the housing and seal the electrolyte from an environment external to the housing.

20. The transfer device of claim 19.

22. The electrode and the counter electrode are stacked along an axis within the unit cell, the carrier ion source is configured to couple to the unit cell such that the carrier ion source is disposed parallel to the axis; The transfer device of claim 1 .

23. The method of claim 22, wherein the carrier ion source is configured to couple to the unit cell such that the carrier ion source is disposed parallel to the axis on opposing sides of the unit cell.

23. The transfer device of claim 22.

24. A method for transporting carrier ions to an energy storage device, comprising: (a) providing any of the transfer devices according to any of claims 1 to 23 and using the transfer device to transfer the carrier ions to the unit cell; The method includes:

25. An apparatus for transporting carrier ions to an energy storage device, comprising: The apparatus includes a control unit electrically coupled to a unit cell and a transport device according to any one of claims 1 to 23, the control unit is configured to at least partially control the transfer of the carrier ions to the unit cell. Device.

26. The electrically coupling includes a plurality of wires.

26. The apparatus of claim 25.

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