Electrode assembly, secondary battery and manufacturing method

Abstract

Disclosed is a secondary battery for cycling between a charged state and a discharged state. A secondary battery may include an electrode layer including a set of spacer structures including a material different from an electrode active material, where (a) a total volume occupied by the set of spacers within the electrode layer is in a range of about 0.1% to about 35% of a volume VE of the electrode layer, and (b) a total volume occupied by the set of spacers within the electrode layer is in a range of about 0.1% to about 35% of a volume VE of the electrode layer. And (b) the members of the set of spacers are located within each sub-volume of the electrode layer, the sub-volume comprising (i) at least 25% of the volume VE of the electrode layer, and (ii) on all sides is delimited by (a) a unit cell portion of an electrode current collector, (bb) a separator layer, (cc) a top surface of the electrode layer, (dd) a bottom surface of the electrode layer, (ee) a first end surface of the electrode layer, and (ff a second end surface of the electrode layer.

Description

[0001] This application is a divisional application of a patent application with an application date of May 15, 2020, application number 202080051036.6, and name "Electrode Assembly, Secondary Battery and Manufacturing Method". Technical Field

[0002] The present disclosure generally relates to methods of making electrode assemblies for energy storage devices, and to energy storage devices having electrode assemblies made according to the methods herein. Background Art

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

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

[0005] As carrier ions move between electrodes, an ongoing challenge is that the electrodes tend to expand and contract as the battery is repeatedly charged and discharged. Expansion and contraction during cycling often creates problems for battery reliability and cycle life because electrical shorts and battery failure can occur when the electrodes expand. Another problem that can occur is that mismatches in electrode alignment caused by physical or mechanical stress on the battery during manufacturing, use, or transportation, for example, can lead to battery shorts and failures.

[0006] Therefore, there is still a need to control the expansion and contraction of electrodes during battery cycling to improve the reliability and cycle life of the battery. In addition, there is still a need for reliable and efficient methods of manufacturing such batteries. That is, there is a need for an efficient manufacturing method for providing a battery with an electrode assembly whose expansion is controlled during battery cycling. Summary of the invention

[0007] Therefore, in short, one aspect of the present disclosure relates to a secondary battery for cycling between a charge state and a discharge state, the secondary battery comprising a battery housing, an electrode assembly within the battery housing, carrier ions, a non-aqueous liquid electrolyte, wherein the electrode assembly comprises a group of unit cells, each unit cell comprising a unit cell portion of an electrode current collector layer, an electrode layer comprising an electrode active material, a separator layer, a counter electrode layer, and a unit cell portion of a counter electrode current collector layer in a stacking sequence, the unit cell having a width W measured from the unit cell portion of the electrode current collector to the unit cell portion of the counter electrode current collector along a stacking direction of the stacking sequence. uc The electrode layer has a width W measured along the stacking direction of the stacking sequence from the unit cell portion of the electrode current collector adjacent to the electrode layer to the separator layer adjacent to the electrode layer. E , a height H measured from the top surface to the bottom surface of the electrode layer along a second direction orthogonal to the stacking direction E , and a length L measured from the first surface to the second surface along a third direction orthogonal to the stacking direction and the height direction E , and a volume V defined by the unit cell portion of the electrode current collector, the separator layer, the top surface of the electrode layer, the bottom surface of the electrode layer, the first end surface of the electrode layer, and the second end surface of the electrode layer E The electrode layer includes a set of spacer structures, the set of spacer structures includes a material different from the electrode active material, wherein (a) the total volume occupied by the spacer group in the electrode layer is within the volume V of the electrode layer E and (b) a member of the spacer set is located within each subvolume of the electrode layer, the subvolume comprising (i) the volume V of the electrode layer E at least 25% of the electrode layer, and (ii) is bounded on all sides by (aa) the unit cell portion of the electrode current collector, (bb) the separator layer, (cc) the top surface of the electrode layer, (dd) the bottom surface of the electrode layer, (ee) the first end surface of the electrode layer, and (ff) the second end surface of the electrode layer.

[0008] Another aspect of the present disclosure relates to an electrode assembly of a secondary battery for cycling between a charging state and a discharging state, wherein the electrode assembly includes a group of unit cells, each unit cell including a unit cell portion of an electrode current collector layer, an electrode layer including an electrode active material, a separator layer, a counter electrode layer, and a unit cell portion of a counter electrode current collector layer in a stacking sequence, the unit cell having a width W measured from the unit cell portion of the electrode current collector to the unit cell portion of the counter electrode current collector along a stacking direction of the stacking sequence. uc , the electrode layer has a width W measured along the stacking direction from the unit cell portion of the electrode current collector adjacent to the electrode layer to the separator layer adjacent to the electrode layer e , a height He measured from the top surface to the bottom surface of the electrode layer along a second direction orthogonal to the stacking direction, and a length Le measured from the first surface to the second surface along a third direction orthogonal to the stacking direction and the height direction, and a volume V defined by the unit cell portion of the electrode current collector, the separator layer, the top surface of the electrode layer, the bottom surface of the electrode layer, the first end surface of the electrode layer, and the second end surface of the electrode layer E The electrode layer includes a set of spacer structures, wherein (a) the total volume occupied by the spacer group in the electrode layer is within the volume V of the electrode layer. E and (b) a member of the spacer set is located within each subvolume of the electrode layer, the subvolume comprising (i) the volume V of the electrode layer E at least 25% of the electrode layer, and (ii) is bounded on all sides by (aa) the unit cell portion of the electrode current collector, (bb) the separator layer, (cc) the top surface of the electrode layer, (dd) the bottom surface of the electrode layer, (ee) the first end surface of the electrode layer, and (ff) the second end surface of the electrode layer.

[0009] Yet another aspect of the present disclosure relates to a method for forming a secondary battery for cycling between a charged state and a discharged state, the method comprising providing an electrode assembly, carrier ions, and a non-aqueous liquid electrolyte within a battery housing, wherein the electrode assembly comprises a group of unit cells, each unit cell comprising a unit cell portion of an electrode current collector layer, an electrode layer comprising an electrode active material, a separator layer, a counter electrode layer, and a unit cell portion of a counter electrode current collector layer in a stacking sequence, the unit cell having a width W measured from the unit cell portion of the electrode current collector to the unit cell portion of the counter electrode current collector along a stacking direction of the stacking sequence. uc, the electrode layer has a width W measured along the stacking direction from the unit cell portion of the electrode current collector adjacent to the electrode layer to the separator layer adjacent to the electrode layer e , a height H measured from the top surface to the bottom surface of the electrode layer in a direction orthogonal to the stacking direction E , and a length Le measured from the first surface to the second surface along a direction orthogonal to the stacking direction and the height direction, and a volume Ve defined by the unit cell portion of the electrode current collector, the separator layer, the top surface of the electrode layer, the bottom surface of the electrode layer, the first end surface of the electrode layer, and the second end surface of the electrode layer. The electrode layer includes a set of spacer structures, wherein (a) the total volume occupied by the spacer set within the electrode layer is in the range of about 0.1% to about 35% of the volume Ve of the electrode layer, and (b) members of the spacer set are located within each subvolume of the electrode layer, the subvolume including (i) at least 25% of the volume Ve of the electrode layer, and (ii) defined on all sides by (aa) the unit cell portion of the electrode current collector, (bb) the separator layer, (cc) the top surface of the electrode layer, (dd) the bottom surface of the electrode layer, (ee) the first end surface of the electrode layer, and (ff) the second end surface of the electrode layer. The method also includes performing a formation process involving charging the secondary battery from a discharged state to a charged state.

[0010] Other aspects, features, and embodiments of the present disclosure will be discussed in part and in part apparent from the following description and accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1A is a perspective view of one embodiment of a secondary battery including an electrode assembly;

[0012] Figure 1B is a perspective view of another embodiment of a secondary battery including an electrode assembly;

[0013] FIG. 2A to FIG. 2B are perspective views and cross-sectional views of other embodiments of secondary batteries including electrode assemblies;

[0014] Figure 3A is an exploded plan view of an embodiment of a structure of an electrode assembly including an electrode structure, a counter electrode structure, and a separator layer;

[0015] Figure 3B yes Figure 3A An exploded cross-sectional view of an embodiment of the structure of an electrode assembly;

[0016] Figure 3C Is in a stacked structure Figure 3A and Figure 3B A cross-sectional view of an embodiment of the structure of an electrode assembly and further comprising a set of restraints;

[0017] Figure 4A is a cross-sectional view of an embodiment of a structure of an electrode assembly including an electrode current collector, an electrode layer, a separator layer, and a counter electrode current collector as viewed in the YX plane;

[0018] Figure 4B is as observed in the YZ plane Figure 4A A cross-sectional view of an embodiment of the structure of an electrode assembly;

[0019] Figure 4C is a cross-sectional view of another embodiment of a structure of an electrode assembly including an electrode current collector, an electrode layer, a separator layer, and a counter electrode current collector and including a set of spacer structures in the electrode layer as viewed in the YZ plane;

[0020] Figure 5A is a cross-sectional view of another embodiment of a structure of an electrode assembly including an electrode current collector, an electrode layer, a separator layer, and a counter electrode current collector and including a set of spacer structures in the electrode layer as viewed in the YX plane;

[0021] Figure 5B is the post-formation stage after the formation process that increases the volume of the electrode active material in the electrode layer as viewed in the YX plane Figure 5A A cross-sectional view of an embodiment of the structure of an electrode assembly;

[0022] Figure 5C is as observed in the YZ plane Figure 5A A cross-sectional view of an embodiment of the structure of an electrode assembly;

[0023] Figure 5D is a cross-sectional view of another embodiment of a structure of an electrode assembly including an electrode current collector, an electrode layer, a separator layer, and a counter electrode current collector and including a set of spacer structures in the electrode layer as viewed in the YX plane;

[0024] Figure 6 is a cross-sectional view of another embodiment of a structure of an electrode assembly including an electrode current collector, an electrode layer, a separator layer, and a counter electrode current collector and including a set of spacer structures in the electrode layer as viewed in the YX plane;

[0025] Fig. 7Ais a cross-sectional view of another embodiment of a structure of a portion of an electrode assembly including first and second unit cells and including a plurality of sets of spacer structures in first and second electrode layers thereof as viewed in a YX plane;

[0026] Figure 7B is a cross-sectional view of another embodiment of a structure of a portion of an electrode assembly including first and second unit cells and including a plurality of sets of spacer structures in first and second electrode layers thereof as viewed in a YX plane;

[0027] Figure 7C is a cross-sectional view of another embodiment of a structure of a portion of an electrode assembly including first and second unit cells and including a plurality of sets of spacer structures in first and second electrode layers thereof and passing through a common electrode current collector as viewed in a YX plane;

[0028] FIG. 8A to FIG. 8H are plan views of various embodiments of spacer structures formed on electrode structures and / or spacer layers of an electrode assembly;

[0029] Figures 9 and 10 shows a schematic diagram of an embodiment of an electrode layer 116 including representative dimensions and subvolumes thereof;

[0030] FIG. 11A to FIG. 11B is a cross-sectional view of an embodiment of a wound electrode assembly ( Fig.11A ),as well as Fig.11A A close-up section of a wound electrode assembly showing a first unit cell and a second unit cell of the wound electrode assembly; and

[0031] Fig.12 is a cross-sectional view of another embodiment of a wound electrode assembly.

[0032] definition

[0033] As used herein, "a", "an", and "the" (ie, singular) refer to plural referents unless the context clearly indicates otherwise. For example, in one example, reference to an "electrode" includes a single electrode and multiple similar electrodes.

[0034] As used herein, "about" and "approximately" refer to the value plus or minus 10%, 5% or 1%. For example, in one example, about 250 μm will include 225 μm to 275 μm. As another example, in one example, about 1,000 μm will include 900 μm to 1,100 μm. Unless otherwise indicated, all numerical values ​​used in the specification and claims to represent quantities (e.g., measurements, etc.) should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise indicated, the numerical parameters set forth in the following specification and the attached claims are approximate values. Each numerical parameter should be interpreted at least according to the numerical value of the reported significant figures and by applying ordinary rounding techniques.

[0035] As used herein in the context of a secondary battery, "anode" refers to the negative electrode in the secondary battery.

[0036] As used herein, "anode active material" refers to a material suitable for use in an anode of a secondary battery.

[0037] As used herein in the context of a secondary battery, "cathode" refers to the positive electrode in the secondary battery.

[0038] As used herein, "cathode active material" refers to a material suitable for use in a cathode of a secondary battery.

[0039] As used herein in the context of the state of a secondary battery, "charged state" refers to a state in which the secondary battery is charged to at least 75% of its rated capacity. For example, the 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.

[0040] As used herein, "C-rate" refers to a measure of the rate at which a secondary battery is charged or discharged, and is defined as the discharge current divided by the theoretical current draw at which the battery will deliver its nominal rated capacity in one hour. For example, a C-rate of 1C represents a discharge current that discharges the battery in one hour, a rate of 2C represents a discharge current that discharges the battery in 1 / 2 hour, a rate of C / 2 represents a discharge current that discharges the battery in 2 hours, and so on.

[0041] As used herein in the context of the state of a secondary battery, "discharge state" refers to a state in which the secondary battery is discharged to less than 25% of its rated capacity. For example, the 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.

[0042] As used herein in the context of cycling of a secondary battery between a charged state and a discharged state, "cycling" refers to charging and / or discharging a battery to transition the battery from a first state that is a charged state or a discharged state to a second state opposite the first state (i.e., a charged state if the first state is discharged, or a discharged state if the first state is charged) in the cycle, and then transitioning the battery back to the first state to complete the cycle. For example, a single cycle of a secondary battery between a charged state and a discharged state may include, as in a charging cycle, charging the battery from a discharged state to a charged state, and then discharging it back to a discharged state to complete the cycle. A single cycle may also include, as in a discharging cycle, discharging the battery from a charged state to a discharged state, and then charging it back to a charged state to complete the cycle.

[0043] As used herein, "Y-axis," "X-axis," and "Z-axis" refer to axes that are perpendicular to each other (i.e., each is orthogonal to the other). For example, as used herein, "Y-axis," "X-axis," and "Z-axis" are analogous to a Cartesian coordinate system for defining a three-dimensional aspect or orientation. Thus, the description of elements of the inventive subject matter herein is not limited to one or more specific axes for describing the three-dimensional orientation of the elements. In other words, the axes may be interchangeable when referring to the three-dimensional aspects of the inventive subject matter.

[0044] As used herein, "Y direction", "X direction" and "Z direction" refer to mutually perpendicular directions (i.e., each is orthogonal to each other). For example, as used herein, "Y direction", "X direction" and "Z direction" may generally be parallel to the Y axis, X axis and Z axis of a Cartesian coordinate system for defining a three-dimensional aspect or orientation, respectively.

[0045] As used herein in the context of the cycle of a secondary battery between a charged state and a discharged state, "repeated cycling" refers to more than one cycle from a discharged state to a charged state or from a charged state to a discharged state. For example, the repeated cycling between the charged state and the discharged state may include at least 2 cycles from the discharged state to the charged state, such as charging from the discharged state to the charged state, discharging back to the discharged state, charging again to the charged state and finally discharging back to the discharged state. As another example, at least 2 repeated cycles between the charged state and the discharged state may include discharging from the charged state to the discharged state, charging back to the charged state, discharging again to the discharged state and finally charging back to the charged state. As another example, the repeated cycling between the charged state and the discharged state may include at least 5 cycles and even at least 10 cycles from the discharged state to the charged state. As another example, the repeated cycling between the charged state and the discharged state may include at least 25, 50, 100, 300, 500 and even 1000 cycles from the discharged state to the charged state.

[0046] As used herein in the context of a secondary battery, "rated capacity" refers to the capacity of a secondary battery measured under standard temperature conditions (25°C) to deliver a specified current over a period of time. For example, the rated capacity can be measured in ampere hours by determining the current output for a specified time, or by determining the time that the current can be output for a specified current, and taking the product of the current and time. For example, for a battery rated at 20 ampere hours, if the current is specified as 2 amperes, the battery can be understood as a battery that will provide a current output for 10 hours, and conversely, if the time is specified as 10 hours, the battery can be understood as a battery that will output 2 amperes during 10 hours. In particular, the rated capacity of a secondary battery can be given as a rated capacity at a specified discharge current, such as a C rate, where the C rate is a measure of the rate at which a battery is discharged relative to its capacity. For example, a C rate of 1C represents a discharge current that discharges the battery in one hour, 2C represents a discharge current that discharges the battery in 1 / 2 hour, C / 2 represents a discharge current that discharges the battery in 2 hours, and the like. So, for example, a 20 amp·hour battery rated at a C-rate of 1C will give a discharge current of 20 amps in 1 hour, while a 20 amp·hour battery rated at a C-rate of 2C will give a discharge current of 40 amps in 1 / 2 hour, and a 20 amp·hour battery rated at a C-rate of C / 2 will give a discharge current of 10 amps in 2 hours.

[0047] As used herein in the context of an electrode assembly of a secondary battery, "stacking direction" refers to the direction in which structures in the electrode assembly are stacked relative to each other. According to certain embodiments, the stacking direction may be substantially parallel to the shortest distance between structures in unit cells of the electrode assembly.

[0048] As used herein in the context of an electrode assembly of a secondary battery, "stacking sequence" refers to those structures within a unit cell (e.g., a unit cell portion of an electrode current collector, an electrode layer, a separator layer, a counter electrode layer, and a unit cell portion of a counter electrode layer), and / or segments of these structures encountered when traversing the electrode assembly in the stacking direction. According to one embodiment, for a prismatic electrode assembly, the stacking sequence of unit cells includes a unit cell structure defined by a first end of the unit cell and a second end of the unit cell in the stacking direction. According to another embodiment, for a wound electrode assembly, the stacking sequence of unit cells corresponds to those segments of the unit cell defined by a first end of the unit cell and a second end of the unit cell in the stacking direction, the segments being located in the same winding (wind) of the electrode assembly.

[0049] As used herein, "wound electrode assembly" refers to an electrode assembly in which an electrode structure and a counter electrode structure are wound around an inner region of the electrode assembly such that the electrode assembly includes a plurality of windings, and the diameter of each winding increases as the radius from the inner region of the electrode assembly increases. According to certain embodiments, the wound electrode assembly includes a stacking direction parallel to a direction parallel to the radius R from the inner region to the outer region of the wound electrode assembly, and one or more electrode layers in the wound electrode assembly include a width dimension W measured from the inner region to the outer region of the electrode assembly along a first direction parallel to the stacking direction. E , a height dimension H measured along a second direction orthogonal to the stacking direction E , and a length dimension L measured along a third direction orthogonal to the stacking direction and the second direction E According to one embodiment, the stacking direction is generally parallel to the radius R, the second direction is generally parallel to the Z direction (height direction), and the third direction is measured along the angular direction A for the total number of windings in the electrode assembly, as measured in cylindrical coordinates with mutually orthogonal coordinates R (radius), Z (height), and A (azimuth).

[0050] As used herein, "cylindrical coordinates" refers to a coordinate system that specifies positions in space by height (Z) from a selected origin (used as a reference axis), distance R (radius) from a reference axis (Z axis), and angular position or azimuth A, where R, Z, and A are mutually orthogonal coordinates.

[0051] As used herein, "orthogonal directions" refer to directions that are perpendicular to one another in a selected coordinate system. For example, for a Cartesian coordinate system, orthogonal directions are directions parallel to the X, Y, and Z axes in the coordinate system. As another example, for a cylindrical coordinate system, orthogonal directions are directions defined along mutually perpendicular R (radius), Z (altitude), and azimuth (A) coordinates.

[0052] As used herein, "prismatic electrode assembly" refers to an electrode assembly having an electrode structure and a counter electrode structure, wherein the electrode structure and the counter electrode structure include a series of layers stacked alternately along a stacking direction. According to certain embodiments, the prismatic electrode assembly includes a stacking direction parallel to the Y axis, and one or more electrode layers in the wound electrode assembly include a width dimension W measured along a first direction parallel to the stacking direction. E , the height dimension H measured along the second direction parallel to the Z axis E , and the length dimension L measured along the third direction parallel to the X axis E , where X, Y and Z form mutually orthogonal axes in Cartesian coordinates.

[0053] As used herein with respect to a wound electrode assembly, a "wound turn" includes a unit cell segment extending from a start point to an end point that is rotated 360° in an azimuthal direction A from the start point in cylindrical coordinates. DETAILED DESCRIPTION

[0054] Generally speaking, aspects of the present disclosure relate to an energy storage device 100 (such as a secondary battery 102, such as, for example, Figure 1A The secondary battery 102 includes a battery housing 104, an electrode assembly 106, and carrier ions, and may also include an electrolyte such as a non-aqueous liquid electrolyte within the battery housing.

[0055] In addition, in certain embodiments, aspects of the present disclosure provide an electrode assembly 106 that can provide particular advantages when incorporated into an energy storage device 100 (such as a battery, a capacitor, a fuel cell, etc.). In one embodiment, the electrode assembly 106 and the secondary battery 102 including the electrode assembly 106 have a configuration and / or structure that is selected to accommodate at least one of the growth, expansion, and / or expansion of the electrode that may occur during the charging and / or discharging of the secondary battery having the electrode assembly 106. For example, when the secondary battery 102 is first charged from a discharged state to a charged state, the electrode assembly 106 can accommodate the growth, expansion, and / or expansion of the electrode that may occur during the initialization phase. The electrode assembly 106 can also be configured to accommodate growth, expansion, and / or expansion that may occur during the cycling of the secondary battery 102.

[0056] According to certain embodiments, in the process of changing from the discharge state to the charged state, carrier ions (such as one or more of lithium, sodium, potassium, calcium and magnesium) move between the positive and negative electrodes of the battery. After reaching the electrode, the carrier ions can then be embedded or alloyed into the electrode material, thereby increasing the size and volume of the electrode. On the contrary, the reverse transition from the charged state to the discharged state can cause ion deintercalation or dealloying, thereby shrinking the electrode. This alloying and / or embedding and dealloying and / or deintercalation can cause significant volume changes in the electrode. In another embodiment, the migration of carrier ions from the electrode can increase the size of the electrode, for example, by increasing the electrostatic repulsion of the remaining material layer (for example, with LCO and some other materials). Other mechanisms that can cause the expansion of the secondary battery 102 may include, for example, the formation of SEI on the electrode, the decomposition of electrolytes and other components, and even the formation of gas. In one embodiment, the electrode may include an electrode active material layer having a capacity to accept more than one mole of carriers per mole of electrode active material when the secondary battery is charged from a discharged state to a charged state, wherein the charged state is at least 75% of the rated capacity of the secondary battery and the discharged state is less than 25% of the rated capacity of the secondary battery, thereby causing expansion of the electrode and / or electrode assembly 106. Therefore, repeated expansion and contraction of the electrode during charging and discharging and other expansion mechanisms may generate strain in the electrode assembly 106, which may lead to reduced performance and eventually even failure of the secondary battery.

[0057] In addition, in the initialization formation process performed by an initial charging process of charging the secondary battery from a discharged state to a charged state in order to initialize the secondary battery, a similar mechanism causes the electrode assembly to expand, which can produce strain in the electrode assembly and is attributed to, for example, the growth and / or expansion of the electrode active material during the formation process. That is, in the manufacture of the secondary battery 102 having the electrode assembly 106, an initialization formation process including at least one initial charging cycle of the secondary battery 102 can be performed, and the at least one initial charging cycle can be performed under carefully controlled conditions including one or more of current, temperature, and duration to promote the formation of the desired structure and contact between the components of the secondary battery 102. Depending on the specific battery structure and composition, the initialization formation process may include only a single initial charging cycle, or may include multiple charging cycles (e.g., charging and discharging of the secondary battery in one or more cycles). In one embodiment, depending on the characteristics of the secondary battery to be formed, the initial formation process may include a series of partial charge and / or discharge cycles, such as a charging process that at least partially charges the secondary battery (e.g., charges to 10% of full capacity), followed by a subsequent discharge process that at least partially discharges the secondary battery (e.g., discharges to 5% of full capacity), followed by a further charging process that at least partially and even completely charges the secondary battery, and / or further charging and / or discharging processes. According to one embodiment, the initial formation process may be performed as the last stage in manufacturing to bring the secondary battery 102 to its full power and / or capacity.

[0058] refer to FIG. 3A to FIG. 3C According to certain embodiments, a set of spacer structures 400 may be provided as part of the electrode assembly 106 to at least partially accommodate electrode growth that may occur during the formation process. According to certain embodiments, the set of spacer structures 400 may be positioned relative to the expanded electrode active material in the electrode layer 116, such as within and / or around the electrode active material layer 125, to define a void and / or space between the electrode active material and an adjacent structure, such as an adjacent separator layer 130. In one embodiment, the void and / or space may provide a volume into which the electrode active material may grow, such as during the formation stage, thereby allowing the electrode active material to expand without overstraining the electrode assembly 106. Therefore, in certain embodiments, by providing a set of spacer structures 400 within the electrode assembly 106, a secondary battery 102 may be formed that exhibits less strain and / or less deformation of the structure therein due to the expansion of the electrode active material that may occur during the formation process and / or during repeated cycling of the secondary battery 102 between a charged state and a discharged state.

[0059] Reference again Figure 1A , Figure 1B and Figure 3B In one embodiment, the electrode assembly 106 includes a set of electrode structures 110, a set of counter electrode structures 112, and an electrically insulating separator 130 that electrically insulates the electrode structures 110 from the counter electrode structures 112. As shown in these figures, the electrode structures 110, the counter electrode structures 112, and the electrically insulating separator 130 may include a series of stacked layers arranged alternately. In one embodiment, the set of electrode structures 110 may include a set of electrode current collectors 114 and a set of electrode layers 116, which may include electrode active materials. The set of electrode layers 116 may include, for example, a first electrode layer 116a and a second electrode layer 116b disposed on opposite sides of the electrode current collector 114. The set of counter electrode structures 112 may include a set of counter electrode current collectors 118 and a set of counter electrode layers 120, which may include counter electrode active materials. The set of counter electrode layers 120 may include, for example, a first counter electrode electrode layer 120a and a second counter electrode electrode layer 120b disposed on opposite sides of the counter electrode current collector 118.

[0060] According to certain embodiments, the electrode assembly 106 may include a variety of different sizes, shapes, and configurations. Figure 1A and Figure 1B In one embodiment, the electrode assembly includes a series of electrode structures 110 and counter electrode structures 112, which include a series of stacked sheets stacked along a stacking direction in a first direction (e.g., parallel to the Y axis). Figure 1A In the illustrated embodiment, the electrode structure 110 including the electrode layer 116 has a height dimension H measured along a second direction orthogonal to the stacking direction (eg, parallel to the Z axis). E , and a length dimension L measured along a third direction orthogonal to the stacking direction and the second direction (e.g., parallel to the X-axis) E , and a width dimension W measured along the stacking direction (eg, parallel to the Y axis) E (See e.g. Figure 3B ). Figure 1B In the embodiment shown, the height dimension H of the electrode structure 110 including the electrode layer 116 is E yes Figure 1A half of the height.

[0061] refer to Figure 2A , Figure 2B and FIG. 11A to FIG. 11B, shows an embodiment of an electrode assembly 106, wherein the electrode structure 110 and the counter electrode structure 112 are configured as a wound electrode assembly 106 having a plurality of windings or turns 205, wherein the electrode sheet 110 and the counter electrode sheet 112 are wound in a spiral shape from an inner region 200 of the electrode assembly 106 to an outer region 202 of the electrode assembly 106. Each winding 205 of the wound electrode assembly includes a unit cell segment extending from a starting point 207a to an end point 207b, which is rotated 360° from the starting point along an azimuthal direction A (e.g., in cylindrical coordinates). According to this embodiment, the electrode structure 110 includes an electrode layer 116 having a height dimension H measured parallel to the Z axis. E and the width dimension W measured along the stacking direction E , for a wound configuration, the width dimension corresponds to a direction generally parallel to a radius R from the inner region 200 of the electrode assembly 106 to the outer region 202 of the electrode assembly 106, along which a series of windings 205a, 205b are encountered. In addition, in the illustrated embodiment, the stacking direction along R of the electrode assembly is in a direction orthogonal to the Z axis. That is, according to one embodiment, the stacking sequence 800 is stacked along the stacking direction R, and the height He of the electrode layer 116 is measured along a second direction orthogonal to the stacking direction R (e.g., along the Z direction). According to one embodiment, the length dimension L of the wound electrode layer 116 E The length L of the wound electrode layer is measured along a third direction orthogonal to the stacking direction and the second direction, wherein the third direction is measured from the inner region of the electrode assembly to the outer region of the electrode assembly along an angular direction and / or an azimuthal direction A (e.g., in cylindrical coordinates) for all the windings in the electrode assembly. E is the total length of the electrode layer 116 from the inner region 200 to the outer region 202 along the spiral path 208 of the wound electrode, wherein the direction T of the spiral path is orthogonal to the Z axis and the stacking direction R at each point along the spiral path 208. Figure 2A In the illustrated embodiment, the electrode assembly 106 includes a cross-section having an elliptical shape when viewed along the Z-axis. Figure 2B In the illustrated embodiment, the electrode assembly 106 includes a cross-section having a circular shape as viewed along the Z-axis.

[0062] refer to Figure 1A to Figure 1B and FIG. 3A to FIG. 3B According to one embodiment, the electrode assembly 106 includes a group of unit cells 500, each unit cell 500 including a unit cell portion of an electrode current collector layer 114, an electrode layer 116, a separator layer 130, a counter electrode layer 120, and a unit cell portion of a counter electrode current collector layer 118 in a stacking sequence 800. FIG. 3A to FIG. 3CIn one embodiment, the unit cell 500 includes a unit cell portion of an electrode current collector layer 114 and a unit cell portion of a counter electrode current collector layer 118, a first electrode layer 116a of the electrode structure 110 disposed on one side of the electrode current collector layer 114, and a first counter electrode layer 120a of the counter electrode structure 112 disposed on a side of the counter electrode current collector layer 118 facing the electrode current collector layer 114. The electrode layer and the counter electrode layer in the unit cell may be disposed such that the electrode layer is adjacent to a first side 133a of the separator 130, and the first counter electrode material layer is adjacent to an opposite second side 133b of the separator 130. According to certain embodiments, the separator 130 may electrically isolate the electrode layer 116 from the counter electrode layer 120 in the unit cell 500, and in the case where the electrode assembly including the unit cell is used as a part of a secondary battery during battery cycling between a charging state and a discharging state, carrier ions may be exchanged between the electrode layer 116 and the counter electrode layer 120 mainly via the separator 130 in the unit cell.

[0063] Furthermore, according to certain embodiments, the unit cell portion of the electrode current collector layer and / or the counter electrode current collector layer is a portion that participates in the electrochemical reaction in the unit cell, such as participating in passing current between them to facilitate the transfer of electrons between the unit cell portions of the electrode current collector layer and / or the counter electrode current collector layer. Figure 1A , the first unit cell 500a includes the unit cell portion of the electrode current collector 114 participating in the electrochemical reaction in the unit cell 500a, and the adjacent second unit cell 500b includes the unit cell portion of the common electrode current collector 114 participating in the electrochemical reaction in the second unit cell 500b. Figure 4A In the embodiment shown, the unit cell portion of the current collector may be half of the current collector split along the XZ plane in the Y direction, or may include a different configuration depending on the configuration and other characteristics of the electrode assembly 106 .

[0064] The stacking sequence 800 within the unit cell 500 includes those structures within the unit cell 500 (e.g., the unit cell portion of the electrode current collector, the electrode layer, the separator layer, the counter electrode layer, and the unit cell portion of the counter electrode layer), and / or segments of these structures encountered when traversing the electrode assembly along the stacking direction. The stacking direction is the direction in which the structures in the electrode assembly are stacked relative to each other. According to certain embodiments, the stacking direction can be approximately parallel to the shortest distance between the structures in the unit cells of the electrode assembly. For example, for Figure 1A and Figure 1BThe stacking direction of the prismatic electrode assembly in the embodiment is parallel to the axis Y, which is the direction in which the electrode layers 116 are stacked relative to each other, and the stacking sequence 800 includes those components of the unit cell encountered when traveling along the axis Y, namely, the unit cell portion of the electrode collector 114, the electrode layer 116, the separator layer 130, the counter electrode layer 120, and the unit cell portion of the counter electrode collector 118. Therefore, the stacking sequence 800 of unit cells 500 in this embodiment is defined in the Y direction by the unit cell portion of the electrode collector 114 and the unit cell portion of the counter electrode collector. Figure 2A and Figure 2B In the embodiment of the wound electrode assembly, and also as FIG. 11A to FIG. 11B As shown, the stacking direction is parallel to the direction R from the inner region 200 of the electrode assembly 106 to the outer region 202 of the electrode assembly 106, which is the direction in which each outer winding 205b is stacked on the inner winding 205. Therefore, the stacking sequence 800 of the electrode assembly 106 in the present embodiment includes those components of the unit cell encountered when traveling along the direction R, namely, the unit cell portion of the electrode collector 114, the electrode layer 116, the separator layer 130, the counter electrode layer 120, and the unit cell portion of the counter electrode collector 118. Therefore, the stacking sequence 800 of each individual unit cell 500 in the present embodiment is defined by the segment of the unit cell portion of the electrode collector 114 and the segment of the unit cell portion of the counter electrode collector in the same winding 205 of the electrode assembly along the direction R.

[0065] According to one embodiment, the unit cell 500 includes a width W measured from the unit cell portion of the electrode current collector 114 to the unit cell portion of the counter electrode current collector 118 along the stacking direction of the stacking sequence 800. UC , such as Figure 3B As well as Figures 4 to Figure 6 As shown, these figures show an embodiment of a unit cell 500 in a prismatic electrode assembly. In addition, in the case of a spirally wound battery, as shown in FIG. FIG. 11A to FIG. 11B As shown, the width W measured in any winding turn 205 of the unit cell 500 along the winding path 208 of the electrode assembly is UC Corresponds to the width along the stacking direction R from the unit cell portion of the electrode collector 114 to the unit cell portion of the counter electrode collector 118, as measured for a stacking sequence in a unit cell including adjacent segments 502 of the electrode collector and the counter electrode collector that are closest along the stacking direction (e.g., those segments 502 that are in the same winding turn 205 along the stacking direction R of the winding path 208).

[0066] According to yet another embodiment, the electrode layer 116 includes a width W measured in the stacking direction from a unit cell portion of the electrode current collector 114 adjacent to the electrode layer 116 to a separator layer 130 adjacent to the electrode layer 116. e . References Figure 3B Figure 4 to Figure 6 For the embodiment shown in FIG. 1 for a prismatic electrode assembly, the width W E is measured between the first surface 115a of the electrode current collector layer 114 and the opposite first surface 131a of the separator layer 130 along the stacking direction. Similarly, in the case of a spirally wound battery, as FIG. 11A to FIG. 11B As shown, for any winding turn 205 along the winding path 208 of the electrode assembly, the width W is measured E Corresponds to the width along the stacking direction R from the unit cell portion of the electrode collector 114 to the separator layer 130 adjacent to the electrode layer 116, as measured for the stacking sequence including the nearest adjacent segments of the electrode collector and separator along the stacking direction (for example, those segments 502 in the same winding turn 205 of the winding path 208 of the electrode assembly).

[0067] According to the embodiment, the electrode layer 116 further includes a height He measured from the top surface 119a to the bottom surface 119b of the electrode layer 116 in a direction orthogonal to the stacking direction. Figure 1A and Figure 1B , which depicts an embodiment of a prismatic electrode assembly, with a height H E It can be a dimension measured from the top surface 119a to the bottom surface of the electrode layer 116 parallel to the Z direction, and the Z direction is orthogonal to the stacking direction along Y. Figure 1A and Figure 1B As shown, the height H E Also related to the length L measured along the X direction E Orthogonal, where Figure 1B In the embodiment shown, the length L E Measured along the longest dimension of electrode layer 116. FIG. 2A to FIG. 2B The embodiment of the spirally wound electrode assembly shown has a height H E It can be a dimension measured parallel to the Z direction, which is orthogonal to the stacking direction along R.

[0068] According to some embodiments, the top surface 119a and the bottom surface 119b of the electrode layer 116 are substantially parallel to the width W of the electrode structure. E The surfaces of any physical structure in the electrode layer 116 along the direction orthogonal to the stacking direction at the ends of the electrode layer are coextensive. For example, in one embodiment of the post-formation electrode assembly, the top surface 119a and the bottom surface 119b may include the end surfaces of the electrode active material layer 125 in the electrode layer 116, such as Figure 1A and Figure 1B As another example, in one embodiment, the top surface 119a and the bottom surface 119b may include the top surface and the bottom surface of the spacer structure disposed at the respective top and bottom ends of the electrode layer 116, such as when the spacer structure is disposed around the periphery of the electrode layer 116 and the electrode active material layer 125 is disposed inside the peripheral spacer structure (e.g., as Figure 5C As yet another example, in the pre-formation electrode assembly, a void space 126 may exist between the electrode active material layer 125 and the separator, such as Figure 4B As shown, the top surface 119a and the bottom surface 119b are coextensive with the end surface of the electrode active material layer 125 in the electrode layer 116. Therefore, the height H E is the dimension measured between these top surface 119a and bottom surface 119b (e.g., Figure 4B Similarly, in one embodiment, top surface 119a and bottom surface 119b are coextensive with the top surface and bottom surface of spacer structure 400 disposed at the respective top and bottom ends of electrode layer 116, such as where the spacer structure is disposed around the periphery of electrode layer 116 and electrode active material layer 125 and void space 126 are disposed within the peripheral spacer structure (e.g., as shown in FIG. Figure 5A and Figure 5C shown).

[0069] According to the embodiments of this invention, the electrode layer 116 further includes a length Le measured from the first end surface 121a to the second end surface 121b in a direction orthogonal to the stacking direction and the height direction. Figure 1A , which depicts an embodiment of a prismatic electrode assembly having a length L E It may be a dimension measured from the first end surface 121a to the second end surface 121b of the electrode layer 116 parallel to the X direction, which is orthogonal to the stacking direction along Y and the height direction Z. Figure 1B , which depicts another embodiment of a prismatic electrode assembly having a length L E It can be a dimension measured from the first end surface 121a to the second end surface 121b of the electrode layer 116 parallel to the Z direction as shown in the figure, and the Z direction is orthogonal to the stacking direction along the Y direction and the X direction. FIG. 2A to FIG. 2B The embodiment of the wound electrode assembly shown has a length L E The length L of the electrode layer 116 may be measured along the spiral path 208 of the wound electrode from the first end surface 121a at the inner region 200 of the electrode assembly 106 to the second end surface 121b at the outer region 202, wherein the direction T of the spiral path is orthogonal to the Z axis and the stacking direction R at each point along the spiral path. That is, the length L of the wound electrode layer 116 according to certain embodiments isE It may be the total extent of the electrode layer 116 measured along each point in the winding path along a direction T orthogonal to the Z-axis and the stacking direction.

[0070] According to one embodiment, the length L E It may correspond to the longest dimension of the electrode layer 116, for example, parallel to Figure 1B The X-axis dimension L E , as depicted, which has a larger size than W E or H E The larger dimension is therefore the "longest" dimension. In another embodiment, for example Figure 1A As shown, where the two dimensions of the electrode layer are equal, the length L E Can be selected as the dimension along the X direction, height H E Measured along the Z direction, but from Figure 1A It can be seen that the X direction and the Z direction in this embodiment can be interchanged when the lateral dimensions of the electrode layer 116 are equal. FIG. 2A to FIG. 2B In the winding embodiment shown, the longest dimension will be equal to the dimension wound along the spiral path in direction T. For example, if FIG. 2A to FIG. 2B The electrode coil 116 is shown unrolled into a flattened embodiment such as Figure 1A to Figure 1B As shown, the dimension along the spiral path in direction T will be greater than the height dimension H measured in the direction parallel to the X dimension. E , or the width dimension W of the electrode layer measured along a direction parallel to the Y axis (e.g., along the direction R when in a wound configuration) E Therefore, in some embodiments, the length L of the coiled electrode 116 is E The longest dimension of the electrode may be included, corresponding to the dimension of the electrode layers wound to form the wound electrode assembly 106 .

[0071] According to one embodiment, the length L of the electrode layer 116 may be defined as E The first end surface 121a and the second end surface 121b of the electrode layer 116 are connected to the width W of the electrode structure. E 116. The surfaces of any physical structure in the electrode layer 116 along the length direction Le located at the ends of the electrode layer extend together. For example, in the post-formation electrode assembly, the first end surface 121a and the second end surface 121b may include the end surfaces of the electrode active material layer 125 in the electrode layer 116. As another example, in one embodiment, the first end surface 121a and the second end surface 121b may include the end surfaces of the spacer structure disposed at the respective first and second ends of the electrode layer 116, such as when the spacer structure is disposed around the periphery of the electrode layer 116 and the electrode active material layer 125 is disposed inside the peripheral spacer structure (e.g., as Figure 5BAs yet another example, in the pre-formation electrode assembly, a void space 126 may exist between the electrode active material layer 125 and the separator, such as Figure 4A As shown, the first end surface 121a and the second end surface 121b are coextensive with the end surface of the electrode active material layer 125 in the electrode layer 116. Similarly, in one embodiment, the first end surface 121a and the second end surface 121b are coextensive with the end surface of the spacer structure disposed at the respective first and second ends of the electrode layer 116, such as when the spacer structure is disposed around the periphery of the electrode layer 116 and the electrode active material layer 125 and the void space 126 are disposed inside the peripheral spacer structure (e.g., as Figure 5A shown).

[0072] According to yet another embodiment, for an electrode layer 116 having an irregular or jagged interface between the electrode current collector 114 and / or the separator layer 130, the width W of the electrode layer 116 may be determined to be E Such irregular interfaces may exist, for example, where portions of separator material and / or electrode current collector material extend into electrode layer 116, such as when portions of separator material and / or electrode current collector material are used as, for example Figure 4C In such embodiments where a jagged or irregular interface is present, a width W may be measured between a unit cell portion of the electrode current collector 114 adjacent to the electrode layer 116 and a separator layer adjacent to the electrode layer 116 on a side of the electrode layer opposite to the unit cell portion of the electrode current collector by setting one or more of a first boundary plane 123a and a second boundary plane 123b identifying one or more of the electrode current collector and / or separator surfaces 115a, 131a. E That is, one or more of the first surface 115a of the electrode current collector 114 and the first surface 131a of the separator layer 130 may be defined according to the boundary planes 123a, 123b identifying the interface between the electrode current collector layer 114 and / or the separator layer 113 and the electrode layer 116 (e.g., Figure 3BFor example, according to one embodiment, the first boundary plane 123a of the first surface 115a of the unit cell portion, which is set as the electrode current collector layer 114, can be defined as a plane in which (i) at least 80% of the area in the first boundary plane and any other plane parallel to the first boundary plane and on the second side of the first boundary plane in the direction away from the separator layer 130 in the stacking sequence of the unit cells includes electrode current collector material, and (ii) the area of ​​any other plane parallel to the first boundary plane on the first side of the first boundary plane toward the separator in the stacking sequence of the unit cells includes less than 80% of the electrode current collector material. That is, the boundary plane (first surface) of the electrode current collector can be set to correspond to a position in the unit cell along the stacking direction when traveling from the separator to the electrode current collector, wherein at least 80% of the material encountered in the plane at the position along the direction orthogonal to the stacking direction is the current collector material. As can be appreciated, in further embodiments, the boundary plane (first surface) can be set as one in which it is required that (i) at least 90% of the area is current collector material, and / or at least 95% of the area is current collector material, and / or at least 98% of the area is current collector material. Therefore, in the case where the interface between the current collector layer 114 and the electrode layer 116 is relatively flat and / or smooth, the first surface 115a can be identified as equivalent to a boundary plane, wherein 100% of the material in the plane is the electrode current collector, and any plane on the first side of the boundary plane facing the separator layer includes little or no electrode current collector in the boundary plane. That is, according to the embodiments of the present invention, the boundary plane defined in the present invention can be set for structures in which the interface between the electrode current collector and the electrode layer 116 is relatively jagged and / or uneven, and for structures in which the interface is more clearly defined.

[0073] Similarly, the second boundary plane 123b set as the first surface 131a of the separator 130 may be a plane where (i) at least 80% of the area in the second boundary plane and any other plane parallel to the second boundary plane and on the first side of the second boundary plane in the direction away from the electrode current collector 114 in the unit cell in the stacking sequence of the unit cells includes separator material, and (ii) the area of ​​any other plane parallel to the second boundary plane on the second side of the second boundary plane toward the electrode current collector 114 in the stacking sequence of the unit cells includes less than 80% of the separator material. That is, the boundary plane (first surface) of the separator layer may be set to correspond to a position in the unit cell along the stacking direction when traveling from the electrode current collector to the separator, where at least 80% of the material encountered in the plane at the position along the direction orthogonal to the stacking direction is separator material. As can be appreciated, in further embodiments, the boundary plane (first surface) can be set as one in which it is required that (i) at least 90% of the area is separator material, and / or at least 95% of the area is current separator material, and / or at least 98% of the area is separator material. Therefore, in the case where the interface between the separator layer 130 and the electrode layer 116 is relatively flat and / or smooth, the first surface 131a can be identified as equivalent to a boundary plane, in which 100% of the material in the plane is separator material, and any plane on the second side of the boundary plane facing the electrode current collector layer includes little or no separator material in the boundary plane. That is, according to the embodiments of the present invention, the boundary plane defined in the present invention can be set for structures in which the interface between the separator layer 130 and the electrode layer 116 is relatively jagged and / or uneven, and for structures in which the interface is more clearly defined.

[0074] Furthermore, according to certain embodiments, although Figure 3B The first boundary plane 123a and the second boundary plane 123b depicted in FIG. 1 are planes having dimensions along Cartesian coordinates (X, Y, and Z), but it is understood that the boundary planes 123a, 123b showing the interface between the surfaces in the unit cells along the stacking direction may also include curved boundary planes or boundary planes having other shapes. For example, referring to Figure 2A and Figure 2B as well as Fig.11A and Fig. 11B The first boundary plane and the second boundary plane may have a curved shape substantially corresponding to the spiral winding of the electrode layer 116. According to some embodiments, the width W of the electrode layer 116 is EIt can be measured as the distance between the first boundary plane 123a and the second boundary plane 123b of the unit cell portion of the electrode current collector and the separator layer 130 in the stacking sequence. According to yet another embodiment, when the first surface 115a and the second surface 131a of the electrode current collector 114 and the separator are relatively smooth and / or easily identifiable, the width W E It may simply be equal to the distance between surfaces 115a, 131a. According to yet another embodiment, the width W E It can be the width between one or more of the first boundary plane and / or the second boundary plane set for the electrode collector and / or separator having a relatively irregular shape and the surface of the other one of the electrode collector and / or separator that is relatively smooth and / or easily identifiable. That is, the width W E It can be understood as a size range between the surfaces of the electrode current collector and the separator, wherein the surface is defined as the surface of an easily identifiable interface between structures and / or as a boundary plane corresponding to the surface and meeting the above criteria.

[0075] According to one embodiment, the electrode layer 116 includes a volume Ve defined by a unit cell portion of the electrode current collector 114, a separator layer 130, a top surface 119a of the electrode layer 116, a bottom surface 119b of the electrode layer 116, a first end surface 121a of the electrode layer 116, and a second surface 121a of the electrode layer 121a. For example, referring to Figure 3A and Figure 3B , the volume Ve is calculated as the length L of the electrode layer measured between the first end surface 121a and the second end surface 121b E Multiply the height H of the electrode layer 116 measured between the top surface 119a and the bottom surface 119b by E Multiply by the width W measured between the first surface 115a of the unit cell portion of the electrode current collector layer 114 and the first surface 131a of the separator layer 130 E Width W E It can also be measured by determining the distance between a first boundary plane 123a and a second boundary plane 123b, which are set as the first surface 115a of the unit cell portion of the electrode collector layer 1124 and the first surface 131a of the separator layer, as discussed herein.

[0076] refer to Fig. 9 According to one embodiment, the volume Ve of the electrode layer 116 can be calculated even for an electrode layer having an irregular or non-uniform shape in a dimension orthogonal to the width dimension We. Fig. 9 As shown, as viewed along the stacking direction Y, the electrode layer 116 is viewed in the XZ plane, and it can be seen that the dimension H EThe length L along the electrode layer 116 E Similarly, in other embodiments, dimension L E The height H of the electrode layer 116 may be E Changes, and the other two sizes L E and / or H E and can vary as a function of each other and / or as a function of the width We. Therefore, in some embodiments, to determine the volume, the volume integral of the electrode layer 116 can be calculated to determine the volume Ve. The volume integral of the electrode layer 116 can be calculated according to suitable mathematical methods understood by those of ordinary skill in the art. As an example of calculating such a volume integral, the width W E The distance (length L) between the first end surface and the second end surface can be set by determining the first boundary plane 123a and the second boundary plane 123b of the unit cell portion of the electrode current collector and the separator in the unit cell (for example, at the surfaces of these structures), and E ) and the distance between the top and bottom surfaces (height H E ) can be used to calculate the volume of the electrode layer according to the following formula:

[0077] Volume = ∫H E (l)×W E (l) × dl (for L = 0 to L = L E integral)

[0078] Other ways of determining the volume of the electrode layer 116, which is defined by the unit cell portion of the electrode current collector, the separator layer, the top surface of the electrode layer, the bottom surface of the electrode layer, the first surface of the electrode layer, and the second surface of the electrode layer, may also be used. For example, in one embodiment, a computing technique may be used to take multiple cross sections at various points along the X, Y, and Z planes (which may be used to construct a three-dimensional model that closely approximates the 3D structure of the electrode layer) to calculate the total volume V of the electrode layer. E .

[0079] In the implementation scheme, FIG. 3A to FIG. 3C Figure 4 to Figure 6 As shown, the electrode layer 116 includes a set of spacer structures 400 disposed therein. In one embodiment, the set of spacer structures 400 can be disposed as part of the electrode layer 116 to physically separate the electrode material from the separator layer 130 before performing a formation process for forming a secondary battery. Thus, the set of spacers 400 can allow for void space to exist between the electrode material in the layer 116 and the separator 130 to reduce any stress that may be induced during the formation process that may cause expansion of components of the electrode assembly 106 (such as the electrode material). For example, Figure 5AIn the depicted embodiment, the electrode layer 116 may include at least partially along the width W of the electrode layer 116. E The electrode active material layer 125 is extended, and the void space 126 fills the remaining portion of the electrode layer 116. For example, in the case where the electrode assembly 106 is in the pre-formation stage, the void space 126 can be provided before performing a formation process to charge and / or form a secondary battery including the electrode assembly 106. In another embodiment, as Figure 5B As shown, the electrode assembly 106 in the post-formation stage after the formation process is performed includes an electrode active material layer 125 that has expanded during the formation stage to extend along the width W of the electrode layer 116. E The liner further extends and may even extend to the interface with the separator layer 130 .

[0080] In one embodiment, the set of spacer structures includes a plurality of spacer structures disposed within the electrode layer 116 and disposed along a direction of the electrode layer orthogonal to the stacking direction. Figure 3C In the illustrated embodiment, the plurality of spacer structures are arranged along a length L corresponding to the electrode layer 116. E The length of the electrode layer 116 may be arranged in a direction (e.g., X direction), and in some embodiments, the length may be the longest dimension of the electrode layer 116. As another example, Fig.11A As shown in the embodiment depicted in , the set of spacer structures 400 can be arranged at various points along the direction T of the spiral path of the wound electrode 116, which direction can correspond to the longest dimension of the electrode layer in some embodiments. According to yet another embodiment, the set of spacer structures 400 in the electrode layer 116 can include only a single spacer structure 400, such as a single spacer structure that extends at least partially along the periphery 404 of the electrode layer, such as, for example Figure 8B The set of spacer structures can be disposed along the electrode layer 116 at and / or near the interface between the electrode layer 116 and the separator layer 130, such as at and / or near the surface 131a of the separator layer 130, as shown in the embodiment depicted. Figure 6 As shown in the embodiment depicted. Figure 6 In the embodiment shown, the members of the set of spacer structures 400 extend only partially across the width W of the electrode layer. E , reaching the electrode active material layer 125. According to yet another embodiment, the set of spacer structures may be disposed along the electrode layer 116 at and / or near the interface between the electrode layer 116 and the unit cell portion of the electrode current collector 114, such as at and / or near the surface 115a of the unit cell portion of the electrode current collector 114, and / or may be disposed between the interface between the electrode layer 116 and the unit cell portion of the electrode current collector 114 and the separator layer 130 along the width W of the electrode layer 116. EExtension, such as Figure 5A The depicted embodiment is shown.

[0081] According to yet another embodiment, the member of the set of spacer structures 400 may include a member having a first portion 410a thereof extending from the surface 131a of the separator layer 130 to the surface 115a of the unit cell portion of the electrode current collector (e.g., substantially across the width W of the electrode layer 116) and a second portion 410b thereof. E ), the second portion only partially spans the width W of the electrode layer 116 E The electrode current collector 114 extends to a position flush with the surface 127 of the electrode active material layer 126, which is disposed adjacent to the unit cell portion of the electrode current collector 114 (see, e.g. Figure 5D ). That is, the same spacer structural member may have a width W along the electrode layer 116. E Different portions 410a, 410b terminate at different points of the spacer structure, such as different portions along the X direction or the Z direction. According to yet another embodiment, one or more members in the set of spacer structures may include a first segment 410c and a second segment 410d, which may optionally include a first spacer material and a second spacer material. For example, again referring to Figure 5D In one embodiment, one or more spacer structures 400 may include a first segment 410c and a second segment 410d in a portion of the structure, the first segment extending from the current collector surface 115a to the W along the electrode layer. E The second section is flush with the surface 127 of the electrode active material layer, and the second section is from W along the electrode layer. E The position flush with the electrode active material layer surface 127 extends to the surface 131a of the separator layer 130. The first segment 410c and the second segment 410d can be, for example, different segments of the spacer structure 400 that are manufactured separately but include the same spacer material, and / or can include the first segment and the second segment that each include a first spacer material and a second spacer material that are different from each other. According to further embodiments, the spacer structure 400 can include a combination of the first portion 410a and the second portion 410b and the first segment 410c and the second segment 410d.

[0082] In certain embodiments, the electrode active material layer 125 may expand during the formation stage to substantially completely fill the void space 126 left in the pre-formation stage. In other embodiments, the electrode active material layer 125 expands during the formation process to only partially fill the void space, so that at least some of the remaining void space 126 remains in the electrode layer 116 after formation. This partial filling may be advantageous, for example, to accommodate any further expansion of the electrode active material or other materials that may occur during the cycling of the secondary battery having the electrode assembly. According to certain embodiments, the electrode active material layer 125 may further include a porous layer before and / or after formation, so that the electrode active material layer 125 itself may include void space, regardless of any void space imparted by the presence of the spacer 400 before and / or after the secondary battery 102 is formed. For example, in one embodiment, the electrode active material layer 125 (at the pre-formation or post-formation stage) may include at least 10%, at least 25%, and / or at least 50% void space, measured as a void volume percentage per volume of the electrode active material layer 125, and the electrode active material layer may generally include less than 70% void space, such as less than 60% void space, less than 50% void space, and / or less than 25% void space, such as void space in the range of about 10% to 70% of the volume of the electrode active material layer. Thus, including any void space contained in the electrode active material layer 125 itself, in one embodiment, the electrode layer 116 at the post-formation stage includes less than 10% of the total volume V of the electrode layer. E The void space is less than 60% in percentage, such as the total volume V of the electrode layer 116. E In another embodiment, the electrode layer in the pre-formation stage includes at least 40% void space as a percentage of the total volume of the electrode layer, such as at least 50% void space, at least 60% void space, at least 75% void space, and / or at least 90% void space as a percentage of the total volume of the electrode layer. That is, the void space can be as high as or equal to 90% in the electrode layer in the pre-formation stage and can be reduced to as little as 10% in the post-formation stage.

[0083] In one embodiment, the group of spacer structures 400 includes a material different from the electrode active material in the electrode active material layer 125. For example, in one embodiment, the group of spacer structures 400 may include a material that does not substantially increase in volume during the formation process for forming a secondary battery and / or during the charging cycle of the secondary battery. As another example, the group of spacer structures may include a spacer material that increases in volume during the formation and / or charging cycle, but the amount of volume increase per mole of spacer material that occurs during the formation process and / or during the cycle of the secondary battery is less than any increase in volume per mole of electrode active material. For example, in one embodiment, the group of spacer structures may include a spacer material that has a capacity of accepting less than one mole of carrier ions per mole of spacer material when the secondary battery 102 including the electrode assembly 106 is charged from a discharged state to a charged state. Therefore, for example, in the case where the electrode active material layer has a capacity of accepting more than one mole of carriers per mole of electrode active material when the secondary battery is charged from a discharged state to a charged state, the spacer material may exhibit less expansion than the electrode active material used in the electrode layer. The state of charge of the secondary battery is at least 75% of the rated capacity of the secondary battery, and the state of discharge is less than 25% of the rated capacity of the secondary battery. In one embodiment, the group of spacer structures 400 includes any one or more materials suitable for use in the separator layer, and / or materials suitable for use as electrode materials and / or counter electrode materials, such as any materials described elsewhere herein. According to another embodiment, the group of spacer structures 400 may include electrode active materials, such as any electrode active materials described elsewhere herein. According to one embodiment, the group of spacer structures includes materials that are relatively inert and / or non-reactive in operation and storage in a battery environment, such as materials that are inert and / or non-reactive in electrochemical reactions occurring in the secondary battery 102. For example, in one embodiment, the group of spacer structures may include a polymer material, such as any polymer material described elsewhere herein that will be suitable for use in the separator layer 130. In one embodiment, the group of spacer structures 400 may include a non-porous spacer material. In another embodiment, the set of spacer structures 400 may include a porous spacer material, for example, the set of spacer structures 400 may include a porous spacer material that imparts a porosity of at least 10%, at least 25%, at least 50%, at least 75%, and even at least 90% to the structure. In one embodiment, the set of spacer structures 400 includes such a spacer material that can provide sufficient mechanical strength to withstand the pressure that may be applied during the formation process and / or during repeated cycling of the secondary battery, such as during the formation process and / or during repeated cycling of the secondary battery 102 to substantially maintain a predetermined size and shape.

[0084] According to yet another embodiment, the set of spacer structures 400 may include a spacer material having a relatively low conductivity, such that the total conductance of all spacer structures 400 in the electrode layer is less than the conductance of either and / or both of the electrode current collector layer and the counter electrode current collector, and may even be less than the total conductance of the electrode active materials in the electrode layer 116. For example, according to one embodiment, the ratio of the conductance of the electrode active materials in the electrode layer to the total conductance of all members of the spacer set in the electrode layer is at least 2:1, at least 5:1, and / or at least 50:1.

[0085] In one embodiment, the set of spacer structures may include the same spacer material as the spacer layer 130. For example, in one embodiment, a spacer structure may be provided that extends from the spacer layer 130 (such as from the second boundary plane 123b defined for the spacer layer) at least partially along the width W defined for the electrode layer. E In yet another embodiment, the set of spacer structures may include the same spacer material as the electrode current collector layer. For example, in one embodiment, a spacer structure may be provided that is at least partially along the width defined by the electrode layer 116. E A spacer structure extending from a unit cell portion of the current collector layer 114 (such as from a first boundary plane 123a defined for a unit cell portion of the current collector layer). In one embodiment, the spacer structure including the separator material can be manufactured as an integral piece with the separator layer, or the spacer structure can be formed separately from the separator layer and disposed in the electrode layer 116. In yet another embodiment, the group of spacer structures can include the same spacer material as the electrode active material. According to yet another embodiment, the group of spacer structures can include such a spacer material having the ability to act as an electrode active material (e.g., the ability to accept carrier ions), even if it is different from the electrode active material of the electrode active material layer 125. In one embodiment, the spacer material can include any electrode active material described elsewhere herein, including a lithium spacer structure (e.g., for a lithium secondary battery including a lithium sheet electrode), lithium titanium oxide, graphene, tin, germanium, and transition metal oxides and one or more of their sulfides, phosphides, and nitrides.

[0086] According to some embodiments, the set of spacer structures 400 is disposed in the electrode layer 116 and is configured and distributed such that the total volume occupied by the set of spacer structures in the electrode layer 116 is within the volume V of the electrode layer 116. EIn other words, according to certain embodiments, the set of spacer structures 400 includes a total volume in the electrode layer 116 sufficient to provide void space 126 in the electrode assembly before formation. In addition, according to certain embodiments, the total volume of the set of spacer structures 400 in the electrode layer 116 is small enough so that the presence of any spacer structure after formation does not significantly adversely affect the cycle of the secondary battery between the charging state and the discharging state. Therefore, in one embodiment, the total volume occupied by the set of spacer structures in the electrode layer is the volume V of the electrode layer. E In another embodiment, the total volume occupied by the set of spacer structures within the electrode layer 116 is less than the volume V of the electrode layer. E 35%, such as less than 25%, less than 10%, less than 5% and / or less than 2%. For example, the total volume occupied by the set of spacer structures within the electrode layer 116 may be less than the volume V of the electrode layer. E In the range of 0.25% to 25%, such as the volume V of the electrode layer E The range is from 0.5% to 10%.

[0087] According to another embodiment, the volume of the solid electrode active material layer 125 is 1 / 4 of the total volume V of the electrode layer 116. E The percentage increases after the formation process due to the growth and / or expansion of the electrode active material layer. According to one embodiment, the electrode layer 116 includes a first volume of solid electrode active material before the formation process, and includes a second volume of solid electrode active material greater than the first volume after the formation process. That is, according to certain embodiments, the formation process can be performed to increase the volume of the solid electrode active material in the electrode layer to a second volume that is at least 3%, at least 5%, at least 10%, at least 25%, at least 50%, at least 75% and / or at least 100% greater than the first volume of the solid electrode active material in the electrode layer. In addition, the increase in the volume of the solid electrode active material can occur while being proportional to the unit cell width W before formation. UC In comparison, the width W of the unit cell after formation is UC The variation of W in some embodiments may be less than 1%, less than 0.5%, less than 0.25%, and / or less than 0.1%, and / or the unit cell width W before and after formation. UC Both may be substantially the same so that the width of the unit cell 500 does not substantially change during the formation process.

[0088] According to yet another embodiment, the set of spacer structures 400 is distributed and / or arranged within the electrode layer 116 such that at least one member of the set is located within each subvolume of the electrode layer 116, the subvolumes comprising (i) the volume V of the electrode layer 116; E 14, and (ii) is bounded on all sides by (aa) a unit cell portion of current collector 114, (bb) separator layer 130, (cc) a top surface of an electrode layer, (dd) a bottom surface of an electrode layer, (ee) a first end surface of an electrode layer, and (ff) a second end surface of an electrode layer. As will be appreciated by one of ordinary skill in the art, the total volume V of electrode layer 116 is E The subvolume SV in E This can be calculated using appropriate mathematical methods. Fig.10 According to one example, along the length L of the electrode layer 116 E The subvolume SV between any two points E It can be calculated according to the following formula:

[0089] Subvolume SV E =∫H E (l)×W E (l) × dl (integrated from L = L1 to L = L2)

[0090] Therefore, for the total volume V of the electrode layer 116 defined above, E The spacer structures are distributed in the electrode layer 116 so that at least one member of the group is located in the subvolume. According to one embodiment, the spacer structures are arranged in a stacking direction (width direction W) with the spacer structure ... E ) are distributed in the electrode layer 116 to provide sufficient support for the unit cell structure in the electrode assembly so that the integrity of the unit cell structure in the electrode assembly can be maintained. According to one embodiment, the spacer structure is distributed to provide sufficient structural support so as to avoid excessive gaps or void spaces that may cause collapse or failure of the unit cells in the stacking sequence of the electrode assembly. In one embodiment, the set of spacer structures is distributed so that at least one member is located in the volume V of the electrode assembly including the electrode layer. E at least 20% of each subvolume, and even within the volume V of the electrode assembly including the electrode layer E At least 10% of each subvolume, such as the volume V of the electrode assembly including the electrode layer, is located within E at least 5% of each subvolume.

[0091] refer to 4A to 7C , various embodiments of unit cells 500 of electrode assemblies including multiple sets of spacer layers are shown. Figure 4A , showing that along such FIG. 3B to FIG. 3C A cross section of a unit cell 500 of an electrode assembly of an embodiment shown in FIG. 1 is taken along the XY plane of the unit cell 500 of the electrode assembly. In this embodiment, the unit cell has a width W measured between the unit cell portion of the electrode current collector 114 and the unit cell portion of the counter electrode current collector 118 along the stacking direction (parallel to the Y axis). UC The electrode layer 116 includes an electrode active material layer 125 disposed adjacent to the electrode current collector, and a void space 126 between the electrode active material layer 125 and the surface of the separator, wherein the width W of the electrode layer E Defined between the electrode current collector 114 and the separator, as shown and described elsewhere herein, wherein both the electrode active material layer 125 and the void space 126 are contained within the width W of the electrode layer 116 E According to one embodiment, before performing a formation process to fully form a secondary battery including the unit cell 500, the unit cell 500 may be in a pre-formation stage, and the same unit cell 500 in a post-formation stage may include a significantly larger portion and even substantially all of the electrode active material layer 125 filling the void space 126. In addition, as shown in the figure, a cross-section of the XY plane is taken at a position where no spacer exists along Z, but all unit cells in three dimensions will include spacer structures in other planes along Z. The electrode layer 116 includes a first end surface 121a and a second end surface 121b, which include ends of the electrode active material layer 125.

[0092] refer to Figure 4B , showing that along such FIG. 3B to FIG. 3C A cross section of a unit cell 500 taken along the YZ plane of the unit cell 500 of the electrode assembly 106 of the illustrated embodiment. In this embodiment, the unit cell has a width W measured between the unit cell portion of the electrode current collector 114 and the unit cell portion of the counter electrode current collector 118 along the stacking direction (parallel to the Y axis). UC The electrode layer 116 includes an electrode active material layer 125 disposed adjacent to the electrode current collector, and a void space 126 between the electrode active material layer 125 and the surface of the separator, wherein the width W of the electrode layer E Defined between the electrode current collector 114 and the separator, as shown and described elsewhere herein, wherein both the electrode active material layer 125 and the void space 126 are contained within the width W of the electrode layer 116 EAccording to one embodiment, before performing a formation process to fully form a secondary battery including the unit cell 500, the unit cell 500 may be in a pre-formation stage, and the same unit cell 500 in a post-formation stage may include an electrode active material layer 125 that fills a significantly larger portion of the void space 126 and even substantially all of the void space 126. In addition, as shown in the figure, a cross-section of the YZ plane is taken at a position where no spacer exists along X, but all unit cells in three dimensions may include a spacer structure in other planes along Z. The electrode layer 116 includes a top surface 119a and a bottom surface 119b, which include ends of the electrode active material layer 125.

[0093] refer to Figure 5A , shows a cross section of another embodiment of a unit cell 500 taken along the YZ plane at a position along the Z where the spacer structure 400 can be seen. In this embodiment, the unit cell has a width W measured between the unit cell portion of the electrode current collector 114 and the unit cell portion of the counter electrode current collector 118 along the stacking direction (parallel to the Y axis). UC The cross-section of the electrode layer 116 includes an electrode active material layer 125 disposed adjacent to the electrode current collector, a spacer structure 400 on either side of the electrode active material layer 125, and a void space 126 between the electrode active material layer 125 and the surface 131a of the separator 130. The width W of the electrode layer E can be defined between the electrode current collector 114 and the separator 130, as shown and described elsewhere herein, wherein the electrode active material layer 125, the spacer structure 400, and the void space 126 are contained within the width W of the electrode layer 116. E According to one embodiment, before performing a formation process to fully form a secondary battery including the unit cell 500, the unit cell 500 may be in a pre-formation stage, and the same unit cell 500 in a post-formation stage may include an electrode active material layer 125 that fills a significantly larger portion of the void space 126 and even substantially the entire void space 126. Two spacer structures 400 are disposed at both ends of the electrode active material layer 125 and extend from the unit cell portion of the electrode current collector along the width W E 130. In addition, as shown, a cross section of the YX plane is taken at a location where a spacer exists along Z, and all of the unit cells in three dimensions may include additional spacer structures in other planes along Z, depending on the desired spacing characteristics. The electrode layer 116 includes a first end surface 121a and a second end surface 121b, which in the embodiment shown include the ends of each of the individual spacer structures along the length dimension and define the length dimension L of the electrode layer 116. E . Figure 5BIt is depicted in the post-chemical stage after the chemical process. Figure 5A Embodiments of a unit cell in which the electrode active material layer 125 has expanded to at least partially and even substantially completely fill the void space 126.

[0094] Figure 5C The cross section taken along the YZ plane and at a location along X where the spacer structure 400 can be seen is depicted. Figure 5A In this embodiment, the unit cell has a width W measured between the unit cell portion of the electrode current collector 114 and the unit cell portion of the counter electrode current collector 118 along the stacking direction (parallel to the Y axis). UC The cross-section of the electrode layer 116 includes the spacer structure 400, wherein the width W of the electrode layer E Defined between the electrode current collector 114 and the separator, as shown and described elsewhere herein, wherein the spacer structure 400 comprises a width W of the electrode layer 116 E The electrode layer 116 includes a top surface 119a and a bottom surface 119b, which in the embodiment shown include the top and bottom ends of each of the spacer structures 400 along the height dimension (parallel to the Z axis) and define the height H of the electrode layer 116. E According to other embodiments, the set of spacer structures 400 may include a plurality of spacers along the length L. E and / or height H E A plurality of structures 400 are provided, such as in Fig. 8A , Figure 8C and FIG. 8E to FIG. 8H , and / or may include a length L that substantially spans the electrode layer 116. E and / or height H E One or more spacer structures 400 are extended.

[0095] Figure 6 Yet another embodiment of a unit cell having a spacer structure 400 is depicted in a cross section taken along the YX plane and at a location along Z where the spacer structure 400 is seen, the spacer structure being located at the periphery of the electrode layer 116 along the length direction and extending from the inner surface 127 of the electrode active material layer 125. In this embodiment, the unit cell has a width W measured along the stacking direction (parallel to the Y axis) between the unit cell portion of the electrode current collector 114 and the unit cell portion of the counter electrode current collector 118. UC The cross-section of the electrode layer 116 includes the spacer structure 400 on either side of the electrode active material layer 125, wherein the width W of the electrode layer EDefined between the electrode current collector 114 and the separator, as shown and described elsewhere herein, wherein the electrode active material layer 125, the void space 126 and the spacer structure 400 are contained within the width W of the electrode layer 116 E The electrode layer 116 includes a first end surface 121a and a second end surface 121b, which in the embodiment shown include end surfaces of the electrode active material layer 125 and are adjacent to the spacer structure 400 along the length dimension (along the X axis) and define a length L of the electrode layer 116 including the spacer structure 400 and the electrode active material layer 116. E . Figure 5A Compared with the embodiment shown in Figure 6 The depicted spacer structure 400 extends only the width W of the electrode layer from the interface with the separator. E According to one embodiment, in the pre-formation stage, the spacer structure 400 extends from the surface 127 of the electrode active material layer 125 to the surface 131 of the separator layer 130. In the post-formation stage, in embodiments where the electrode active material expands to at least partially fill the pre-formation void space 126, the spacer structure may be formed along the width dimension W. E The separator structure 400 may extend at least partially from the surface 131a of the separator layer 130 through the electrode active material layer. E The spacer structure extends at least partially through the electrode active material layer from the surface 115a of the electrode current collector 114. According to one embodiment, the components of the set of spacer structures span the entire width dimension W of the electrode layer between the opposing surfaces of the electrode current collector and the separator layer. E (Width W E 100% of the electrode layer) or even across the width W of the electrode layer E According to another embodiment, the intermediate extent to which the spacer structure 400 enters the electrode layer 116 may be the width W of the electrode layer 116. E less than 60%, less than 50%, less than 40%, less than 25% and / or less than 15% of the width of the electrode layer, for example, measured from the separator layer 130 toward the electrode current collector 114, or vice versa. In one embodiment, the median extent of the members of the set of spacer structures in the electrode layer 116 can be the width W of the electrode layer E 2%, at least 3%, and / or at least 5%, for example as measured from separator layer 130 toward electrode current collector 114, or vice versa. According to another embodiment, the set of spacer structures may include a plurality of spacers extending completely along the width dimension W. E The extended spacer structure is only partially along the width dimension W of the electrode layer 116. E A combination of extended spacer structures (e.g., Figure 5A and Figure 6 Other suitable spacer structure configurations and arrangements may also be provided.

[0096] 7A to 7C Other embodiments of spacer structures 400 suitable for use with the electrode assembly 106 of the secondary battery 102 are depicted. Fig. 7A In the illustrated embodiment, portions of two adjacent unit cells 500a, 500b are shown, which share a common electrode current collector 114. In the illustrated embodiment, the electrode current collector 114 includes a first electrode layer 116a disposed on a first side of the electrode current collector (in the first unit cell 500a), and a second electrode layer 116b disposed on a second opposite side of the electrode current collector (in the second unit cell 500b). For the first unit cell 500a, the first electrode layer 116 includes a first layer of electrode active material layer 125a and a first void space 126a between the first layer of electrode active material 125a and the separator 130, wherein the spacer structure 400 extends from the first unit cell portion of the electrode current collector 114 toward the separator in the stacking direction and surrounds the periphery of the first electrode active material layer 125a. For the second unit cell 500b, the second electrode layer 116b includes a second layer of electrode active material layer 125b and a second void space 126b between the second layer of electrode active material 125b and the separator 130, wherein the spacer structure 400 extends from the second unit cell portion of the electrode current collector 114 toward the separator in the stacking direction and surrounds the periphery of the second electrode active material layer 125b. Although the embodiment shown depicts the pre-formation electrode assembly 106 having void spaces 126a, 126b, in the embodiment of the post-formation electrode assembly, the electrode active material can expand toward the separator and can substantially fill the void space.

[0097] Figure 7BSimilarly depicted is an embodiment in which adjacent unit cells 500a, 500b share a common electrode current collector 114, wherein the spacer structure 400 is disposed in the first electrode layer 116a and the second electrode layer 116b of the adjacent unit cells 500a, 500b. For the first unit cell 500a, the first electrode layer 116a includes a first layer of electrode active material layer 125a and a first void space 126a between the first layer of electrode active material 125a and the separator 130. The spacer structure 400 extends from the first inner surface 127a of the first electrode active material layer 125 toward the separator in the stacking direction and is located at the peripheral edge of the first inner surface. For the second unit cell 500b, the second electrode layer 116b includes a second layer of electrode active material layer 125b and a second void space 126b between the second layer of electrode active material 125b and the separator 130. The spacer structure 400 extends from the second inner surface 127b of the second electrode active material layer 125b toward the separator 130 in the stacking direction and is located at the peripheral edge of the second inner surface 127b. According to the embodiment shown in the figure, the spacer structure 400 is only partially along the width W of the electrode layer 116. E A unit cell portion extending from the separator 130 to the electrode current collector 114 .

[0098] According to Fig. 7A and Figure 7B In the embodiment shown, adjacent first unit cells 500a and second unit cells 500b may include a spacer structure 400 disposed in the first electrode layer 116a and the second electrode layer 116b thereof, such as adjacent unit cells sharing a common electrode current collector 114. Figure 2A and Figure 2B In the winding structure shown, the spacer structure 400 can be arranged in adjacent windings of the electrode structure along the stacking direction R. However, in other embodiments, the spacer structure 400 can be arranged in alternating unit cells (e.g., every other unit cell), or only in certain unit cells and / or certain unit cell stacking sequences along the stacking direction of the electrode assembly. In yet another embodiment, the spacer structure 400 can be arranged so that they are aligned with each other along the stacking direction. For example, in Fig. 7A In the illustrated embodiment, the spacer structure 400 is aligned so that the spacer in the first electrode layer 116a of the first unit cell 500a is aligned with the spacer in the second electrode layer 116b of the second unit cell 500b along the stacking direction (Y direction). Such spacing can be advantageous, for example, to provide substantially uniform void spaces in the unit cells along the stacking direction. Similarly, referring to Fig.11A , the positions of the spacers may be arranged so that at least some of the spacers are aligned with each other along the stacking direction R. In addition, although the spacers 400 are Fig. 7A and Figure 7B 116 , the spacers are shown as being positioned toward the periphery of the electrode layer 116 , but the spacers may also be disposed more centrally in the electrode layer 116 , and / or may be located at the periphery and along an interior region of the electrode layer 116 .

[0099] Figure 7C Another embodiment of adjacent first and second unit cells 500 a and 500 b having the spacer structure 400 disposed in the electrode layers 116 thereof is shown. Figure 7C An implementation similar to Fig. 7A , wherein the first electrode layer 116a and the second electrode layer 116b each include an electrode active material layer 125a, 125b having a peripherally positioned spacer structure 400, and the adjacent first unit cell and the second unit cell 500 share an electrode current collector 400. However, in the case of Figure 7C In the illustrated embodiment, the spacer structures 400 extend through holes formed in the electrode current collector 114 shared by two unit cells 500a, 500b, so that the same set of spacer structures 400 extends into both the first unit cell 500a, 500b.

[0100] According to yet another embodiment, the set of spacer structures 400 may be provided as part of both the electrode structure 110 and the counter electrode structure 112 in the electrode assembly 106, such as by providing a set of spacer structures 400 in one or more electrode layers 116 and in one or more counter electrode layers 118. For example, a first set of spacer structures 400 may be provided in the electrode layer 116 in the electrode assembly, and a second set of spacer structures 400 may be provided in the counter electrode layer 120 of the electrode assembly, such layers being in the same unit cell and / or different unit cells in the electrode assembly. According to certain embodiments, the set of spacer structures 400 provided in one or more counter electrode layers 120 may be provided in a configuration and / or arrangement corresponding to any configuration and / or arrangement described elsewhere herein with respect to the electrode layer 116, such as in FIG. 3A to FIG. 3C , FIG. 4A to FIG. 4C , FIG. 5A to FIG. 5D , Figure 6 , 7A to 7C , FIG. 8A to FIG. 8H , Figures 9 and 10 and FIG. 11A to FIG. 11BThat is, in certain embodiments, the arrangement and / or construction described elsewhere herein for the set of spacer structures 400 in the electrode layer 116 can be applied to a set of spacer structures in the counter electrode layer, wherein the counter electrode layer 120, the counter electrode active material, and / or the counter electrode current collector 118 replace the electrode layer 116, the electrode active material, and / or the electrode current collector 114 described elsewhere herein.

[0101] In one embodiment, for example, in the case where both the electrode active material and the counter electrode active material are subject to expansion and / or contraction, such as during the formation process and / or during the cycling of a secondary battery including the electrode active material and the counter electrode active material between a charging state and a discharging state, it may be advantageous to provide a first group of spacer structures and a second group of spacer structures in the electrode layer and the counter electrode layer. According to one embodiment, the group of spacer structures may be provided for a construction including an electrode active material that expands during charging of a secondary battery and a counter electrode active material that expands during discharging of a secondary battery, and / or both the electrode active material and the counter electrode active material may expand when the secondary battery is charged, and / or both may expand when the secondary battery is discharged. According to yet another embodiment, one or more of the electrode active material and / or the counter electrode active material may also shrink when the secondary battery is charged and / or discharged. In one embodiment, both the electrode active material and the counter electrode active material may expand and shrink together (with the same or different degrees of expansion) during the charging process and / or the discharging process. In one embodiment, in the same unit cell and / or in different unit cells, one set of spacer structures may be disposed at the interface between the electrode layer and the separator layer, and another set of spacer structures may be disposed at the interface between the counter electrode layer and the separator layer to accommodate expansion (and possible contraction) that may occur in the electrode active material and the counter electrode active material during the formation process and / or during cycling of the secondary battery between a charge state and a discharge state.

[0102] FIG. 8A to FIG. 8H A further embodiment of multiple sets of spacer structures 400 disposed in the electrode layer 116 is depicted. As shown, the spacer structure 400 may include a protrusion 402, which may be formed on a surface of the electrode structure (such as the surface of the electrode current collector 114 and / or the electrode active material layer 125), and may take a variety of shapes and forms. According to yet another embodiment, the spacer structure 400 may be formed on the surface of one or more of the separator layer 130 and the electrode current collector layer 114, such as on FIG. 8A to FIG. 8H and then joined during assembly of the electrode assembly to form a unit cell 500 having an electrode layer. In one embodiment, as Fig. 8AAs shown, the spacer structure includes a series of raised bumps positioned around the periphery 404 of the electrode layer 116. By providing the protrusions and / or bumps around the periphery 400, in certain embodiments, the structure can stabilize the layers around the void space so that the spacer layer and the electrode layer 116 remain spaced apart from each other, e.g., without substantially bending or deforming the layers into the void space. Figure 8B In the embodiment shown, the set of spacer structures includes a single raised ridge around the periphery 400 of the electrode layer 116 .

[0103] In another embodiment, Figure 8C As shown in , the set of spacer structures 400 may include a plurality of posts or other raised features distributed at different points on the surface of the electrode layer 116. By distributing the protrusions on the surface, bending and / or deformation of the layer 116 having the protrusions may be inhibited because the protrusions may contact an adjacent layer (i.e., the separator layer 130) to maintain separation between the layers, even under the stacking pressure of the electrode layers when placed in a stacking sequence.

[0104] Fig.8D and Fig. 8E A further embodiment is shown in , which shows a set of spacer structures comprising a series of ridges ( Fig.8D ), and a series of cross-shaped protrusions formed around the periphery 404 of the electrode layer 116. Fig.8F An embodiment is further depicted in which the set of spacer structures 400 includes a series of protrusions distributed around a periphery 404 of the electrode layer 116 and specifically located at the edge of the electrode layer in the height direction (Z dimension). Figure 8G and Figure 8H Depicting additional embodiments of the distribution and configuration of multiple spacer structures, in one embodiment, the spacing between the spacer structures decreases along the height direction (Z dimension) of the electrode layer 116 ( Figure 8H ), and in one embodiment, the spacing between the spacer structures is uniform along the height direction (Z dimension) ( Figure 8G ).

[0105] According to certain embodiments, the distance between the spacer structures can increase and / or decrease along one or more dimensions of the electrode layer 116 and / or can increase and / or decrease between unit cells and / or windings in a wound electrode. Fig.11A and Fig. 11B The spiral wound cell embodiment depicted, in one embodiment, the spacing between the spacer structures is along the length L of the electrode. EThe spacing increases from the inner region to the outer region of the electrode assembly so that the spacer structures in adjacent windings of the electrode assembly can be aligned with each other along the stacking direction R. That is, the spacing between the spacing structures can increase as R increases to provide the spacer structures aligned with each other along the stacking direction R. In one embodiment, the members of the set of spacer structures 400 are aligned so that the spacer structure 40 disposed in the inner winding 205a of the unit cell is aligned with the spacer structure 400 in the outer winding 205b of the unit cell along the stacking direction.

[0106] According to one embodiment, the electrode assembly 106 having the group of spacers 400 in the electrode layer 116 is an electrode assembly suitable for a secondary battery to circulate between a charged state and a discharged state. According to certain embodiments, the electrode assembly having the group of spacers can be in a pre-formation stage before performing a formation process, as described elsewhere herein. That is, the electrode assembly 106 can be an electrode assembly suitable for being incorporated into a storage device (such as a secondary battery) and undergoing a formation process. The embodiments herein may also consider the electrode assembly 106 in the post-formation stage, such as when the electrode assembly forms a part of a secondary battery or other storage device that has undergone a formation process.

[0107] According to one embodiment, a method for forming a secondary battery that cycles between a charged state and a discharged state includes: providing an electrode assembly, carrier ions, and a non-aqueous liquid electrolyte within a battery housing; and performing a formation process involving charging the secondary battery from a discharged state to a charged state. In one embodiment, the formation process can be performed to increase the volume of the solid electrode active material in the electrode layer so that the volume after formation is at least 3%, at least 5%, at least 10%, at least 25%, at least 50%, at least 75%, and / or at least 100% greater than the first volume of the solid electrode active material in the electrode layer. In addition, the increase in the volume of the solid electrode active material can occur while being proportional to the unit cell width W before formation. UC In comparison, the width W of the unit cell after formation is UC The variation of W in some embodiments may be less than 1%, less than 0.5%, less than 0.25%, and / or less than 0.1%, and / or the unit cell width W before and after formation. UC Both may be substantially the same so that the width of the unit cell 500 does not substantially change during the formation process.

[0108] According to certain embodiments, the formation process may include at least one initial charging cycle of the secondary battery 102, which may be performed under carefully controlled conditions including one or more of current, temperature, and duration to facilitate the formation of the desired structure and the contact between the components of the secondary battery 102, such as the contact between the desired structure and the structure in the unit cell 500. In general, the formation process may involve one or more initial charging steps, which are performed under conditions of rearranging and / or optimizing the internal structure and morphology so that the secondary battery can be charged to its rated capacity. Depending on the specific battery structure and composition, the formation process may include only a single initial charging cycle, or may include multiple charging cycles, as described elsewhere herein, and may be performed as the final stage in the manufacture of the secondary battery to allow the secondary battery 102 to reach its full power and / or capacity.

[0109] In one embodiment, reference Figure 3C A set of electrode constraints 602 is provided to constrain the growth of the electrode assembly along the stacking direction during the formation process and / or maintain the alignment of the group of unit cells in the electrode assembly. For example, the set of electrode constraints 602 may include a first constraint member 600a and a second constraint member 600b, the first constraint member and the second constraint member are aligned along the stacking direction ( Figure 3C The electrode restraints 602 are spaced apart from each other in the Y direction in the electrode assembly and are capable of maintaining the alignment of the structures in the electrode assembly during the formation process and optionally after formation in the stacking direction. In one embodiment, the growth and / or expansion of the electrode active material in the electrode layer 116 may apply pressure in the stacking direction and / or may cause the unit cells 500 to be misaligned with each other. Therefore, by providing the set of electrode restraints 602, the alignment of the structures in each unit cell may be maintained, so that the void space 126 in the unit cell may be effectively utilized to allow the electrode active material to expand therein.

[0110] In one embodiment, the set of electrode constraints 602 includes a first constraint member 600a and a second constraint member 600b spaced apart from each other along the stacking direction, such as Figure 3C As shown. In another embodiment, the set of electrode restraints includes a first restraint member 600a and a second restraint member 600b, which are spaced apart from each other along another direction orthogonal to the stacking direction (such as along one or more of the X direction or the Z direction) to restrain in one or more of the X direction and the Z direction, and / or a combination of restraints that restrain along the stacking direction and one or more restraints that restrain along a direction orthogonal to the stacking direction may also be provided. According to one embodiment of the prismatic electrode assembly, the first restraint member and the second restraint member may be spaced apart along the Y direction corresponding to the stacking direction, such as Figure 3CAccording to another embodiment of the wound electrode assembly, the set of restraints 602 can be configured to restrain along the stacking direction R, such as by providing a cylindrical restraining member and / or one or more segments of a cylindrical restraining member extending around the outer circumference of the wound electrode assembly. For example, the set of restraints for the wound electrode assembly can be a shell or other housing 104 for the electrode assembly.

[0111] In one embodiment, the set of electrode constraints is disposed within the battery housing 104 (not shown). In another embodiment, the set of electrode constraints 602 is disposed outside the battery housing (e.g., Figure 3C ). The battery housing 104 may be a sealed housing that seals the electrolyte used in the secondary battery therein. In another embodiment, the set of electrode constraints 602 is provided before and / or during the formation process and may be removed from the electrode assembly 106 after formation. According to yet another embodiment, the set of electrode constraints 602 may be provided before and / or during the formation process and remain as part of the secondary battery after formation, for example to resist the growth and / or expansion of the electrode active material during normal cycling of the secondary battery. Without limitation thereto, embodiments of suitable electrode constraints that may be provided before, during, and / or after the formation process for constraining the electrode assembly 106 are described, for example, in U.S. Patent No. 10,283,807 to Busacca et al., issued on May 7, 2019, and U.S. Patent No. 10,177,400 to Busacca et al., issued on January 8, 2019, both of which are incorporated herein by reference in their entirety.

[0112] According to one embodiment, after the formation process, at least a portion and even all of the group of spacer structures 400 may no longer exist, for example, because the spacer structure 400 can be mixed into the electrode active material in the post-formation stage. In addition, according to certain embodiments, the group of spacer structures can be incorporated into the electrode active material layer 125 in the post-formation stage, for example, so that the electrode active material layer 125 substantially occupies the entire volume of the electrode layer after formation. For example, for a secondary battery including a lithium electrode, in the case of using a spacer structure including a lithium spacer structure in the pre-formation stage, the formation process causes the growth of the lithium-containing electrode active material, so that the interface between the lithium spacer structure and the remaining portion of the electrode layer in the post-formation stage may not be discernible. According to another embodiment, after the electrolyte is filled into the electrode assembly before formation, the group of spacers can undergo a chemical reaction so that at least a portion and / or all of the group of spacers are no longer discernible after formation. According to yet another embodiment, at least a portion and / or all of the set of spacers can be removed after assembly of the electrode assembly 106 (e.g., after stacking the unit cells 500) and before, during, or after the formation process (e.g., where another method of maintaining the void spaces 126 in the unit cells 500 is provided).

[0113] According to various embodiments, the spacer structure 400 can be formed by a variety of different methods. For example, in one embodiment, the spacer structure 400 can be formed by printing the spacer material onto the electrode structure 110 (e.g., electrode current collector and / or electrode active material layer) and / or separator layer, such as by screen printing, stencil printing, inkjet printing, gravity printing and other methods. According to another embodiment, the spacer structure can be manufactured by a vapor deposition method using a shadow mask. According to another embodiment, the spacer structure can be manufactured by mechanically interfering a pin including a spacer material into the electrode structure 110 and / or the separator layer 130. According to another embodiment, the spacer structure can be manufactured by co-molding with one or more parts of the separator layer 130 and / or the electrode structure 110. According to another embodiment, the spacer structure can be manufactured by laying an open mesh between the electrode structure 110 and the separator 130 during the assembly of the unit cell 500. According to yet another embodiment, the spacer structure can be manufactured by laying the wire on the top of the electrode structure 110 with glue and pressing it to the desired height above the electrode structure. According to certain embodiments, the group of spacer structures 400 can be deposited or otherwise formed simultaneously with the electrode active material of the electrode active material layer 125. For example, in the case where the electrode active material is deposited or otherwise formed on the surface of the electrode current collector 114, the group of spacer materials can be similarly deposited or otherwise formed as part of the electrode active material layer formation process. According to yet another embodiment, the group of spacer structures can be deposited before and / or after the electrode active material has been deposited or otherwise formed on the electrode current collector 114. According to yet another embodiment, the group of spacer structures can be at least partially deposited and / or formed during the electrode active material layer deposition / formation process, and can be completed after the electrode active material layer is formed. According to another embodiment, the group of spacer structures can be formed as an addition or subtraction process before and / or after the electrode active material layer is formed. Other methods and / or combinations of manufacturing methods for manufacturing spacer structures can also be provided.

[0114] In addition, as used herein, for each embodiment in which the term "electrode" (such as "electrode structure" or "electrode active material") is used to describe a material or structure, it should be understood that such structure and / or material may correspond to the structure and / or material of the "negative electrode" (such as "negative electrode structure" or "negative electrode active material") in certain embodiments. Similarly, as used herein, for each embodiment in which the term "counter electrode" (such as "counter electrode structure" or "counter electrode active material") is used to describe a material or structure, it should be understood that such structure and / or material may correspond to the structure and / or material of the "positive electrode" (such as "positive electrode structure" or "positive electrode active material") in certain embodiments. That is, where appropriate, any embodiment described for an electrode and / or counter electrode may correspond to the same embodiment in which the electrode and / or counter electrode is specifically a negative electrode and / or a positive electrode, including their corresponding structures and materials, respectively.

[0115] Other battery components

[0116] The components of the electrode 110 and the counter electrode 112 group 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 components of the electrode structure 110 group include an anode-active electroactive material (sometimes referred to as a negative electrode), while the components of the counter electrode structure 112 group include a cathode-active electroactive material (sometimes referred to as a positive electrode). In other embodiments, the components of the electrode structure 110 group include a cathode-active electroactive material, while the components of the counter electrode structure 112 group include an anode-active electroactive material. For example, the negative electrode active material can be, for example, a particle agglomerated electrode, an electrode active material formed from a particle material, for example, by forming a slurry of the particle material and casting it into a layer, or a monolithic electrode.

[0117] Exemplary anode active electroactive materials include carbon materials, such as graphite and soft or hard carbon, or any of the range of metals, semimetals, alloys, oxides, and compounds that can form alloys with lithium. Specific examples of metals or semimetals that can constitute anode materials 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 an 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.

[0118] In yet another embodiment, the anode active material may include lithium metal, lithium alloy, carbon, petroleum coke, activated carbon, graphite, silicon compounds, tin compounds, and alloys thereof. In one embodiment, the anode active material includes: carbon, such as non-graphitizable carbon, graphite-based carbon, etc.; metal composite oxides, such as 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 in Group 1, Group 2 and Group 3 of the periodic table, halogens; 0 < x ≦ 1; 1 ≦ y ≦ 3; 1 ≦ z ≦ 8), etc.; lithium metal; lithium alloy; silicon-based alloy; tin-based alloy; metal oxides, such as SnO, SnO2, PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O4, Sb2O5, GeO, GeO2, Bi2O3, Bi2O4, Bi2O5, etc.; conductive polymers, such as polyacetylene, etc.; Li—Co—Ni-based materials, etc. In one embodiment, the anode active material may include a carbon-based active material, which includes crystalline graphite (such as natural graphite, synthetic graphite, etc.) and amorphous carbon (such as soft carbon, hard carbon, etc.). Other examples of carbon materials suitable for the anode active material may include graphite, kish graphite, pyrolytic carbon, mesophase pitch-based carbon fiber, mesophase carbon microspheres, mesophase pitch, graphitized carbon fiber, and high-temperature sintered carbon such as coke derived from petroleum or coal tar pitch. In one embodiment, the negative electrode active material may include tin oxide, titanium nitrate, and silicon. In another embodiment, the negative electrode may 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 may include: metal compounds capable of alloying with lithium and / or intercalating 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 alloys, Sn alloys, Al alloys, etc.; metal oxides capable of doping and de-doping lithium ions, such as SiO v(0 < v < 2), SnO2, vanadium oxides or lithium vanadium oxides; and composites including metal compounds and carbon materials, such as Si—C composites or Sn—C composites. For example, in one embodiment, the material capable of alloying / inserting lithium can be a metal, such as lithium, indium, tin, aluminum or silicon or their alloys; transition metal oxides, such as Li4 / 3Ti5 / 3O4 or SnO; and carbonaceous materials, such as artificial graphite, graphite carbon fiber, resin calcined carbon, pyrolytic vapor grown carbon, cork, mesocarbon microbeads (“MCMB”), furfuryl alcohol resin calcined carbon, polyacene, pitch-based carbon fiber, vapor grown carbon fiber or natural graphite. In yet 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 can include a layered carbonaceous material; and a composition of the formula Na x Sn y-z M z provided between the layers of the layered carbonaceous material, where M is Ti, K, Ge, P or a combination thereof, and 0 < x ≤ 15, 1 ≤ y ≤ 5, and 0 ≤ z ≤ 1.

[0119] In one embodiment, the negative electrode active material can also include a conductive material and / or a conductive aid, such as a carbon-based material, carbon black, graphite, graphene, activated carbon, carbon fiber, carbon black such as acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal carbon black, etc.; conductive fibers, such as carbon fiber, metal fiber, etc.; conductive tubes, such as carbon nanotubes, etc.; metal powders, such as carbon fluoride powder, aluminum powder, nickel powder, etc.; conductive whiskers, such as zinc oxide, potassium titanate, etc.; conductive metal oxides, such as titanium oxide, etc.; or conductive materials, such as polyphenylene derivatives, etc. Additionally, metal fibers, such as metal mesh, can also be used; metal powders, such as copper, silver, nickel and aluminum; or organic conductive materials, such as polyphenylene derivatives. In yet another embodiment, a binder can be provided. For example, one or more of polyethylene, poly(ethylene oxide), polypropylene, polytetrafluoroethylene (PTFE), poly(vinylidene fluoride) (PVDF), styrene-butadiene rubber, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, vinylidene fluoride-pentafluoropropylene copolymer, propylene-tetrafluoroethylene copolymer, ethylene-trifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene copolymer, ethylene-acrylic acid copolymer, etc. can be used alone or as a mixture.

[0120] 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 may be selectively used. The transition metal elements of these transition metal oxides, transition metal sulfides, and transition metal nitrides may include metal elements with d-shells or f-shells. 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. Other cathode active materials include LiCoO2, LiNi 0.5 Mn 1.5 O4、Li(Ni x Co y Al z )O2, LiFePO4, Li2MnO4, V2O5, molybdenum oxysulfide, phosphate, silicate, vanadate, sulfur, sulfur compounds, oxygen (air), Li(Ni x Mn y Co z )O2 and combinations thereof. In addition, the compound used for the cathode active material layer may include a lithium-containing compound, which also includes a metal oxide or a metal phosphate, such as a compound including lithium, cobalt and oxygen (e.g., LiCoO2), a compound including lithium, manganese and oxygen (e.g., LiMn2O4), and a compound 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 a composite oxide formed by a combination of the above oxides. In another embodiment, the cathode active material may include one or more of the following: lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2), etc., or a substituted compound with one or more transition metals; lithium manganese oxide, such as Li 1+x Mn 2-x O4 (where x is 0 to 0.33), LiMnO3, LiMn2O3, LiMnO2, etc.; lithium copper oxide (Li2CuO2); vanadium oxides such as LiV3O8, LiFe3O4, V2O5, Cu2V2O7, etc.; 1-x M x Ni-type lithium nickel oxide represented by O2 (wherein M = Co, Mn, Al, Cu, Fe, Mg, B or Ga, and x = 0.01 to 0.3); represented by the chemical formula LiMn 2-x M xA lithium manganese composite oxide represented by O2 (where M = Co, Ni, Fe, Cr, Zn or Ta, and x = 0.01 to 0.1) or Li2Mn3MO8 (where M = Fe, Co, Ni, Cu or Zn); LiMn2O4, in which a part of Li is replaced by an alkaline earth metal ion; a disulfide compound; Fe2(MoO4)3, etc. In one embodiment, the cathode active material may include a lithium metal phosphate having an olivine crystal structure of Formula 2:

[0121] 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, such as at least one of LiFePO4, Li(Fe,Mn)PO4, Li(Fe,Co)PO4, Li(Fe,Ni)PO4, etc. In one embodiment, the cathode active material includes at least one of 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 a mixture of two or more of them.

[0122] In yet another embodiment, the cathode active material may include elemental sulfur (S8), a chalcogenide compound, or a mixture thereof. The chalcogenide compound may specifically be Li2S n (n ≥ 1), an organic sulfur compound, a carbon-sulfur polymer ((C2S x ) n : x = 2.5 to 50, n ≥ 2), etc. In yet another embodiment, the cathode active material may include an oxide of lithium and zirconium.

[0123] In yet another embodiment, the cathode active material may include at least one composite oxide of lithium and a metal such as cobalt, manganese, nickel, or a combination thereof, which may be used, and 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 (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 X2 (where 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 (where 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 (where 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 cO 2-a X2 (where 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 (where 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 (where 0.90≤a≤1, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, and 0.001≤e≤0.1); Li a NeG b O2 (where 0.90≤a≤1, and 0.001≤b≤0.1); Li a CoG b O2 (where 0.90≤a≤1, and 0.001≤b≤0.1); Li a MnG b O2 (where 0.90≤a≤1, and 0.001≤b≤0.1); Li a Mn b O4 (where 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 yO2 (0≤x≤0.5, 0≤y≤0.5) or FePO4. In one embodiment, the cathode active material includes at least one of the following: a lithium compound such as lithium cobalt oxide, lithium nickel oxide, lithium nickel cobalt oxide, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, lithium manganese oxide or lithium iron phosphate; nickel sulfide; copper sulfide; sulfur; iron oxide; or vanadium oxide.

[0124] In one embodiment, the cathode active material may include a sodium-containing material such as a material of the formula NaM 1 a At least one of the oxides of O2, such as NaFeO2, NaMnO2, NaNiO2 or NaCoO2; or an oxide of the formula NaMn 1-a M 1 a O2 represents an oxide, where M 1 is at least one transition metal element, and 0≤a<1. Representative positive electrode active materials include Na[Ni 1 / 2 Mn 1 / 2 ]O2、Na 2 / 3 [Fe 1 / 2 Mn 1 / 2 ]O2, etc.; by Na 0.44 Mn 1-a M 1 a Oxide represented by O2; composed of Na 0.7 Mn 1-a M 1 a O 2.05 The oxide represented by 1 is at least one transition metal element, and 0≤a<1); Na b M 2 c Si 12 O 30 Represents oxides, such as Na6Fe2Si 12 O 30 or 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 Represents an oxide such as Na2Fe2Si6O 18 or Na2MnFeSi6O 18 (where M 3 is at least one transition metal element, 3≤d≤6, and 1≤e≤2); Na f M 4g Oxides represented by Si2O6, such as Na2FeSiO6 (where M 4 is at least one element selected from transition metal elements, magnesium (Mg) and aluminum (Al), 1≤f≤2, and 1≤g≤2); phosphates such as NaFePO4, Na3Fe2(PO4)3, Na3V2(PO4)3, Na4Co3(PO4)2P2O7, etc.; borates such as NaFeBO4 or Na3Fe2(BO4)3; h M 5 F6 represents a fluoride, such as Na3FeF6 or Na2MnF6 (where M 5 is at least one transition metal element, and 2≤h≤3); fluorophosphates such as Na3V2(PO4)2F3, Na3V2(PO4)2FO2, etc. The positive electrode active material is not limited to the aforementioned ones, and any suitable positive electrode active material used in the art can be used. In one embodiment, the positive electrode active material preferably includes a layered oxide cathode material such as NaMnO2, Na[Ni 1 / 2 Mn 1 / 2 ]O2 and Na 2 / 3 [Fe 1 / 2 Mns 1 / 2 ]O2; a phosphate cathode such as Na3V2(PO4)3 and Na4Co3(PO4)2P2O7; or a fluorophosphate cathode such as Na3V2(PO4)2F3 and Na3V2(PO4)2FO2.

[0125] In yet another embodiment, the cathode active material may further include one or more conductive aids and / or binders, which may be, for example, any conductive aid and / or binder described herein for the anode active material.

[0126] In one embodiment, the electrode current collector 114 may include a suitable conductive material, such as a metallic material. According to the embodiments herein, the electrode current collector 114 may be a negative electrode current collector, and / or may be a positive electrode current collector. According to one embodiment, the electrode current collector is a negative electrode current collector. In one embodiment, the 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, lithium, copper or stainless steel and carbon, nickel, titanium, silver, aluminum-cadmium alloy and / or their other alloys of surface treatment materials. As another example, in one embodiment, the electrode current collector includes at least one of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel and carbon, nickel, titanium, silver, aluminum-cadmium alloy and / or their other alloys of surface treatment materials. In one embodiment, the electrode current collector includes at least one of copper and stainless steel.

[0127] In one embodiment, the electrode current collector 118 may include a suitable conductive material, such as a metallic material. According to the embodiments herein, the electrode current collector 114 may be a negative electrode current collector, and / or may be a positive electrode current collector. According to one embodiment, the electrode current collector is a positive electrode current collector. In one embodiment, the electrode current collector includes at least one of stainless steel, aluminum, nickel, titanium, calcined carbon, sintered carbon, aluminum or stainless steel and carbon, nickel, titanium, silver and / or their alloys. In one embodiment, the electrode current collector includes aluminum.

[0128] In one embodiment, the anode active material is microstructured to provide a significant void volume fraction to accommodate volume expansion and contraction when lithium ions (or other carrier ions) are introduced into or leave the anode active material during the charging and discharging processes. Generally speaking, the void volume fraction of the anode active material is at least 0.1. However, typically, the void volume fraction of the anode active material is not greater than 0.8. For example, in one embodiment, the void volume fraction of the negative electrode active material is about 0.15 to about 0.75. As another example, in one embodiment, the void volume fraction of the anode active material is about 0.2 to about 0.7. As another example, in one embodiment, the void volume fraction of the anode active material is about 0.25 to about 0.6.

[0129] In one embodiment, the anode active material comprises porous aluminum, tin or silicon or their alloys, for example in the form of an electrode active layer 125 comprising a porous anode active material. The porous silicon layer can be formed, for example, by anodization, by etching (e.g., by depositing a noble metal such as gold, platinum, silver or gold / palladium on the surface of single crystal silicon and etching the surface with a mixture of hydrofluoric acid and hydrogen peroxide) or by other methods known in the art (such as patterned chemical etching). In addition, the porous anode active material will generally have a porosity fraction of at least about 0.1 but less than 0.8, and have a thickness of about 1 micron to about 100 microns. For example, in one embodiment, the electrode active material layer 125 comprises an anode active material comprising porous silicon, having a thickness (W of about 5 microns to about 100 microns) of about 5 microns to about 100 microns. E ), and having a porosity fraction of about 0.15 to about 0.75. As another example, in one embodiment, the electrode active material layer 125 includes an anode active material including porous silicon, having a thickness (W of about 10 microns to about 80 microns) E ), and having a porosity fraction of about 0.15 to about 0.7. As another example, in one such embodiment, the electrode active material layer 125 includes porous silicon having a thickness (W of about 20 microns to about 50 microns). E), and has a porosity fraction of about 0.25 to about 0.6. As another example, in one embodiment, the electrode active material layer 125 includes a porous silicon alloy (such as nickel silicide) having a thickness (W of about 5 microns to about 100 microns). E ), and having a porosity fraction of about 0.15 to about 0.75.

[0130] The length (L E ) will vary depending on the energy storage device and its intended use. However, in one embodiment, the members of the set may have a length (L) in the range of about 5 mm to about 500 mm. E For example, in one such embodiment, the members of the set of electrode layers have a length (L) of about 10 mm to about 250 mm. E As another example, in one such embodiment, the members of the set have a length (L) of about 25 mm to about 100 mm. E As another example, in one embodiment corresponding to a wound electrode assembly, the member of the group has a length (L) of at least 50 cm (such as at least 75 cm and even at least 90 cm). E ), and may even have a length of at least about 10 meters and even at least 100 meters. Thus, for example, in one embodiment of the wound electrode assembly, the members of the group may have a length L in the range of about 50 cm to about 800 m. E , such as 75 cm to about 500 m, and even about 75 cm to about 1 m.

[0131] The width (W E ) will also vary depending on the energy storage device and its intended use. In one embodiment, each member of the set of electrode layers 116 may have a width (W) in the range of about 0.01 mm to 2.5 mm. E For example, in one embodiment, the width (W) of each member of the group E ) will be in the range of about 0.025 mm to about 2 mm. As another example, in one embodiment, the width (W) of each member of the group E ) will be in the range of about 0.05 mm to about 1 mm.

[0132] The height (H E ) will also vary depending on the energy storage device and its intended use. However, in one embodiment, the members of the set of electrode layers 116 may have a height (H) in the range of about 0.05 mm to about 10 mm. E For example, in one embodiment, the height (H) of each member of the group E) will be in the range of about 0.05 mm to about 5 mm. As another example, in one embodiment, the height (H) of each member of the group E ) will be in the range of about 0.1 mm to about 1 mm. As another example, in one embodiment of the wound electrode assembly, the height (HE) of each member of the group will be in the range of about 10 mm to about 500 mm, such as in the range of about 25 mm to about 100 mm, including the range of 30 mm to 90 mm, and even in the range of 50 mm to 500 mm, such as in the range of 100 mm to 400 mm.

[0133] In one embodiment, the members of the set of electrode layers 116 have a width substantially greater than their width (W E ) and its height (H E ) of each of the lengths (L E ). For example, in one embodiment, for each member of the set of electrode layers 116, L E With W E and H E The ratio of each of them is at least 5:1 (i.e., L E With W E The ratio of L E With H E As another example, in one embodiment, L E With W E and H E The ratio of each of is at least 10:1. As another example, in one embodiment, L E With W E and H E The ratio of each of is at least 15:1. As another example, in one embodiment, for each member of the group, L E With W E and H E The ratio of each is at least 20:1.

[0134] In one embodiment, the height (H) of the components of the set of electrode layers 116 is E ) and width (W E ) are at least 0.4:1, respectively. For example, in one embodiment, for each member of the group, H E With W E The ratio of H to NH will be at least 2:1 respectively. As another example, in one embodiment, H E With W E The ratio of H to NH will be at least 10:1 respectively. As another example, in one embodiment, H E With WE The ratio of H to NH will be at least 20:1, respectively. E With W E The ratio of H to NH will generally be less than 1,000:1, respectively. For example, in one embodiment, H E With W E As another example, in one embodiment, H E With W E As another example, in one embodiment, H E With W E As another example, in one embodiment, for each member of the group, H E With W E The ratios will be in the range of about 2:1 to about 100:1, respectively.

[0135] The width (W) of the components of the set of counter electrode layers 120 is CE ) will also vary depending on the energy storage device and its intended use. In one embodiment, the set of members of the electrode layer may have a width (W) in the range of about 0.01 mm to 2.5 mm. CE For example, in one embodiment, the width (W) of each member of the group CE ) will be in the range of about 0.025 mm to about 2 mm. As another example, in one embodiment, the width (W) of each member of the group CE ) will be in the range of about 0.05 mm to about 1 mm.

[0136] The height (H) of the components of the group of counter electrode layers 120 is CE ) will also vary depending on the energy storage device and its intended use. In one embodiment, the members of the set of counter electrode layers 120 may have a height (H) in the range of about 0.05 mm to about 10 mm. CE For example, in one embodiment, the height (H) of each member of the group CE ) will be in the range of about 0.05 mm to about 5 mm. As another example, in one embodiment, the height (H) of each member of the group CE ) will be in the range of about 0.1 mm to about 1 mm.

[0137] In one embodiment, each member of the set of counter electrode layers 120 has a length (L CE ), which is substantially greater than the width (W CE ) and is substantially greater than its height (H CE ). For example, in one embodiment, for each member of the group, LCE With W CE and H CE The ratio of each of them is at least 5:1 (i.e., L CE With W CE The ratio of L CE With H CE As another example, in one embodiment, for each member of the group, L CE With W CE and H CE The ratio of each of is at least 10:1. As another example, in one embodiment, for each member of the group, L CE With W CE and H CE The ratio of each of is at least 15:1. As another example, in one embodiment, for each member of the group, L CE With W CE and H CE The ratio of each is at least 20:1.

[0138] In one embodiment, the height (H) of the components of the set of counter electrode layers 120 is CE ) and width (W CE ) are at least 0.4:1. For example, in one embodiment, for each member of the set of counter electrode layers 120, H CE With W CE The ratio of H will be at least 2:1 respectively. As another example, in one embodiment, for each member of the group, H CE With W CE The ratio of H will be at least 10:1 respectively. As another example, in one embodiment, for each member of the group, H CE With W CE The ratio of H to H will be at least 20:1 respectively. In one embodiment, for each member of the group, H CE With W CE The ratio of H will generally be less than 1,000:1, respectively. For example, in one embodiment, for each member of the set, H CE With W CE As another example, in one embodiment, H CE With W CE As another example, in one embodiment, H CE With W CE As another example, in one embodiment, for each member of the group, HCE With W CE The ratios will be in the range of about 2:1 to about 100:1, respectively.

[0139] According to one embodiment, one or more of the electrode current collector and the counter electrode current collector may include a metal such as aluminum, carbon, copper chromium, gold, nickel, NiP, palladium, platinum, rhodium, ruthenium, an alloy of silicon and nickel, titanium, or a combination thereof (see AH Whitehead and M. Schreiber, "Current collectors for positive electrodes of lithium-based batteries", Journal of the Electrochemical Society, 152 (11) A2105-A2113 (2005)). As another example, in one embodiment, the electrode current collector includes gold aluminum. As another example, in one embodiment, the counter electrode current collector includes copper or its alloy.

[0140] The electrically insulating separator layer 130 can electrically isolate each member of the electrode structure 110 group from each member of the counter electrode structure 112 group. The electrically insulating separator layer 130 can include a microporous separator material that can be permeated by the non-aqueous electrolyte; for example, in one embodiment, the microporous separator material includes at least More usually , and a porosity in the range of about 25% to about 75%, more typically in the range of about 35% to 55%. In addition, the microporous separator material can be permeated with a non-aqueous electrolyte to allow carrier ions to be conducted between the electrode and adjacent members of the counter electrode group. In certain embodiments, for example, and ignoring the porosity of the microporous separator material, at least 70% by volume of the electrically insulating separator material between the members of the electrode structure 110 group for ion exchange and the nearest members of the counter electrode structure 112 group (i.e., the "adjacent pairs" and / or members of the same unit cell 500) during the charge or discharge cycle is microporous separator material; in other words, in one embodiment, the microporous separator material constitutes at least 70% by volume, at least 80% by volume, at least 85% by volume, at least 90% by volume, at least 95% by volume, and / or at least 99% by volume of the electrically insulating material between the members of the electrode structure 110 group and the nearest members of the counter electrode structure 112 group.

[0141] In one embodiment, the microporous separator material comprises a particulate material and a binder and has a porosity (void fraction) of at least about 20% by volume. The pores of the microporous separator material will have at least and will usually fall around to The microporous separator material will typically have a porosity of less than about 75%. In one embodiment, the microporous separator material has a porosity (void fraction) of at least about 25 volume %. In one embodiment, the microporous separator material will have a porosity of about 35% to 55%.

[0142] The binder for microporous separator material can be selected from a variety of inorganic or polymer materials. For example, in one embodiment, the binder is an organic material selected from the group consisting of silicate, phosphate, aluminate, aluminosilicate and hydroxide (such as magnesium hydroxide, calcium hydroxide, etc.). For example, in one embodiment, the binder is a fluorine-containing polymer derived from a monomer containing vinylidene fluoride, hexafluoropropylene, tetrafluoropropylene, etc. In another embodiment, the binder is a polyolefin, such as polyethylene, polypropylene or polybutene, which has a molecular weight and density of any range of changes. In another embodiment, the binder is selected from the group consisting of ethylene-diene-propylene terpolymer, polystyrene, polymethyl methacrylate, polyethylene glycol, polyvinyl acetate, polyvinyl butyral, polyacetal and polyethylene glycol diacrylate. In another embodiment, the binder is selected from the group consisting of methylcellulose, carboxymethyl cellulose, 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 resin and silicone. Other suitable binders can be selected from polyvinylidene fluoride-to-hexafluoropropylene, polyvinylidene fluoride-to-trichloroethylene, polymethyl methacrylate, polyacrylonitrile, polyvinyl pyrrolidone, polyvinyl acetate, polyethylene-to-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 a mixture thereof. In yet another embodiment, the binder can be selected from polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trichloroethylene, polymethyl methacrylate, polyacrylonitrile, polyvinyl pyrrolidone, polyvinyl acetate, ethylene vinyl acetate copolymer, polyethylene oxide, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cyanoethyl amylopectin, cyanoethyl polyvinyl alcohol, cyanoethyl cellulose, cyanoethyl sucrose, amylopectin, carboxymethyl 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 one of their combinations. In another embodiment, the binder is a copolymer or blend of two or more of the above-mentioned polymers.

[0143] The particulate material included in the microporous separator material can also be selected from a variety of materials. Generally speaking, such materials have relatively low electronic and ionic conductivity at operating temperatures and do not corrode at the operating voltage of the battery electrode or current collector that contacts the microporous separator material. For example, in one embodiment, the conductivity of the particulate material to carrier ions (such as lithium) is less than 1×10 -4 As another example, in one embodiment, the conductivity of the particle material to carrier ions is less than 1×10 -5 As another example, in one embodiment, the conductivity of the particle material to carrier ions is less than 1×10 -6 S / cm. 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, titanium dioxide, magnesium oxide, kaolin, talc, diatomaceous earth, calcium silicate, aluminum silicate, calcium carbonate, magnesium carbonate, or a combination 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. (See, e.g., P. Arora and J. Zhang, "Battery Separators" Chemical Reviews 2004, 104, 4419-4462). Other suitable particles may include BaTiO3, Pb(Zr,Ti)O3 (PZT), Pb 1-x La x Zr 1-y Ti y O3(PLZT), PB(Mg3Nb 2 / 3 )O3-PbTiO3 (PMN-PT), hafnium dioxide (HfO2), SrTiO3, SnO2, CeO2, MgO, NiO, CaO, ZnO, ZrO2, Y2O3, Al2O3, TiO2, SiC or mixtures thereof. In one embodiment, the particulate material will have an average particle size of about 20nm to 2 microns, more typically 200nm to 1.5 microns. In one embodiment, the particulate material will have an average particle size of about 500nm to 1 micron.

[0144] In alternative embodiments, the microporous separator material comprises particulate material that can be bonded by techniques such as sintering, bonding, curing, etc., while maintaining the electrolyte in the desired void fraction to provide ionic conductivity for battery function.

[0145] The microporous separator material can be deposited, for example, by electrophoretic deposition of particulate separator material (where the particles coalesce by surface energy such as electrostatic attraction or van der Waals forces), slurry deposition of particulate separator material (including spin coating or spray coating), screen printing, dip coating, and electrostatic spray deposition. A binder can be included in the deposition process; for example, the particulate material can be slurry deposited with a dissolved binder that precipitates upon evaporation of the solvent, electrophoretically deposited in the presence of a dissolved binder material, or co-electrophoretically deposited with a binder and insulating particles, etc. Alternatively or additionally, the binder can be added after the particles are deposited into or onto the electrode structure; for example, the particulate material can be dispersed in an organic binder solution and dip coated or sprayed, and then the binder material can be dried, melted, or cross-linked to provide bonding strength.

[0146] In the assembled secondary battery 102, the microporous separator material can be infiltrated with a non-aqueous electrolyte suitable for use as a secondary battery electrolyte. Typically, the non-aqueous electrolyte includes a lithium salt and / or a mixture of salts dissolved in an organic solvent and / or a solvent mixture. Exemplary lithium salts include inorganic lithium salts such as LiClO4, LiBF4, LiPF6, LiAsF6, LiCl and LiBr; and organic lithium salts such as LiB(C6H5)4, LiN(SO2CF3)2, LiN(SO2CF3)3, LiNSO2CF3, LiNSO2CF5, LiNSO2C4F9, LiNSO2C5F 11 、LiNSO2C6F 13 and LiNSO2C7F 15 . As another example, the electrolyte may include sodium ions dissolved therein, such as any one or more of NaClO4, NaPF6, NaBF4, NaCF3SO3, NaN(CF3SO2)2, NaN(C2F5SO2)2, and NaC(CF3SO2)3. Magnesium salts and / or potassium salts may be similarly provided. For example, a magnesium salt such as magnesium chloride (MgCl2), magnesium bromide (MgBr2), or magnesium iodide (MgI2) may be provided, and / or the magnesium salt may be at least one selected from the group consisting of magnesium perchlorate (Mg(ClO4)2), magnesium nitrate (Mg(NO3)2), magnesium sulfate (MgSO4), magnesium tetrafluoroborate (Mg(BF4)2), magnesium tetraphenylborate (Mg(B(C6H5)4)2), magnesium hexafluorophosphate (Mg(PF6)2), magnesium hexafluoroarsenate (Mg(AsF6)2), magnesium perfluoroalkylsulfonate (Mg(R f1 SO3)2), where R f1 is a perfluoroalkyl group), perfluoroalkylsulfonyl imide magnesium (Mg((R f2 SO2)2N)2, where R f2is a perfluoroalkyl group) and magnesium hexaalkyldisilazide ((Mg(HRDS)2), wherein R is an alkyl group). Exemplary organic solvents for dissolving lithium salts include cyclic esters, chain esters, cyclic ethers, and chain 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, ethyl methyl 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, alkyltetrahydrofuran, dialkyltetrahydrofuran, alkoxytetrahydrofuran, dialkoxytetrahydrofuran, 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.

[0147] In yet another embodiment, the secondary battery 102 may include an electrolyte, which may be any of an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, an inorganic solid electrolyte, a molten inorganic electrolyte, etc. In yet another embodiment, when the electrolyte is a solid electrolyte, the solid electrolyte itself can provide insulation between the electrodes and carrier ions pass therethrough, so that a separate separator layer may not be required. That is, in certain embodiments, a solid electrolyte may replace the separator 130 described in the embodiments herein. In one embodiment, a solid polymer electrolyte may include any polymer formed by a polyethylene oxide (PEO) group, a polyvinyl acetate (PVA) group, a polyethyleneimine (PEI) group, a polyvinylidene fluoride (PVDF) group, a polyacrylonitrile (PAN) group, a LiPON group, and a polymethyl methacrylate (PMMA) group polymer or a copolymer thereof. In another embodiment, a sulfide-based solid electrolyte may be provided, such as a sulfide-based solid electrolyte including at least one of lithium and / or phosphorus (such as at least one of Li2S and P2S5) and / or other sulfides (such as SiS2, GeS2, Li3PS4, Li4P2S7, Li4SiS4, Li2S-P2S5, and 50Li4SiO4.50Li3BO3 and / or B2S3). Still other embodiments of the solid electrolyte may include nitrides, halides and sulfates of lithium (Li), such as Li3N, LiI, Li5NI2, Li3N-LiI-LiOH, LiSiO4, LiSiO4-LiI-LiOH, Li2SiS3, Li4SiO4, Li4SiO4-LiI-LiOH and Li3PO4-Li2S-SiS2.

[0148] The present disclosure also includes the embodiments listed below.

[0149] Embodiment 1. A secondary battery for cycling between a charging state and a discharging state, the secondary battery comprising a battery housing, an electrode assembly in the battery housing, carrier ions, and a non-aqueous liquid electrolyte, wherein

[0150] The electrode assembly includes a group of unit cells, each unit cell including a unit cell portion of an electrode current collector layer, an electrode layer including an electrode active material, a separator layer, a counter electrode layer, and a unit cell portion of a counter electrode current collector layer in a stacking sequence, the unit cell having a width W measured from the unit cell portion of the electrode current collector to the unit cell portion of the counter electrode current collector along a stacking direction of the stacking sequence. uc, the electrode layer has a width W measured along the stacking direction of the stacking sequence from the unit cell portion of the electrode current collector adjacent to the electrode layer to the separator layer adjacent to the electrode layer E , a height H measured from the top surface to the bottom surface of the electrode layer along a second direction orthogonal to the stacking direction E , and a length L measured from the first surface to the second surface along a third direction orthogonal to the stacking direction and the height direction E , and a volume V defined by the unit cell portion of the electrode current collector, the separator layer, the top surface of the electrode layer, the bottom surface of the electrode layer, the first end surface of the electrode layer, and the second end surface of the electrode layer E ,and

[0151] The electrode layer includes a set of spacer structures comprising a material different from the electrode active material, wherein the total volume occupied by the spacer set within the electrode layer is within the volume V of the electrode layer. E The range of about 0.1% to about 35%.

[0152] Embodiment 2. The secondary battery according to enumerated embodiment 1, wherein the member of the spacer group is located within each sub-volume of the electrode layer, the sub-volume comprising (i) the volume V of the electrode layer E at least 50% of the electrode layer, and (ii) is defined by (aa) the unit cell portion of the electrode current collector, (bb) the separator layer, (cc) the top surface of the electrode layer, (dd) the bottom surface of the electrode layer, (ee) the first end surface of the electrode layer and (ff) the second end surface of the electrode layer.

[0153] Embodiment 3. A secondary battery according to any of the aforementioned embodiments, wherein a member of the spacer group is located within each subvolume of the electrode layer, the subvolumes comprising (i) the volume V of the electrode layer E at least 40% of the electrode layer, and (ii) is defined by (aa) the unit cell portion of the electrode current collector, (bb) the separator layer, (cc) the top surface of the electrode layer, (dd) the bottom surface of the electrode layer, (ee) the first end surface of the electrode layer and (ff) the second end surface of the electrode layer.

[0154] Embodiment 4. A secondary battery according to any of the aforementioned embodiments, wherein a member of the spacer group is located within each subvolume of the electrode layer, the subvolumes comprising (i) the volume V of the electrode layer Eat least 30% of the electrode layer, and (ii) is defined by (aa) the unit cell portion of the electrode current collector, (bb) the separator layer, (cc) the top surface of the electrode layer, (dd) the bottom surface of the electrode layer, (ee) the first end surface of the electrode layer and (ff) the second end surface of the electrode layer.

[0155] Embodiment 5. A secondary battery according to any of the aforementioned enumerated embodiments, wherein a member of the spacer group is located within each subvolume of the electrode layer, the subvolumes comprising (i) the volume V of the electrode layer E at least 25% of the electrode layer, and (ii) is defined by (aa) the unit cell portion of the electrode current collector, (bb) the separator layer, (cc) the top surface of the electrode layer, (dd) the bottom surface of the electrode layer, (ee) the first end surface of the electrode layer, and (ff) the second end surface of the electrode layer.

[0156] Embodiment 6. A secondary battery according to any of the aforementioned embodiments, wherein the electrode layer includes an electrode active material layer, and when the secondary battery is charged from the discharge state to the charge state, the electrode active material layer has a capacity of accepting more than one mole of carriers per mole of electrode active material, wherein the charge state is at least 75% of the rated capacity of the secondary battery, and the discharge state is less than 25% of the rated capacity of the secondary battery.

[0157] Embodiment 7. A secondary battery according to any of the aforementioned embodiments, wherein the set of spacer structures includes a spacer material, and when the secondary battery is charged from the discharge state to the charge state, the spacer material has a capacity of accepting less than one mole of carrier ions per mole of spacer material, and the charge state is at least 75% of the rated capacity of the secondary battery, and the discharge state is less than 25% of the rated capacity of the secondary battery.

[0158] Embodiment 8. A secondary battery according to any of the aforementioned embodiments, wherein the set of spacer structures includes spacer materials, and the spacer materials include any one or more of polymer materials, electrode active materials, electrode current collector materials, counter electrode current collector materials and separator materials.

[0159] Embodiment 9. A secondary battery according to any of the aforementioned embodiments, wherein the set of spacer structures includes a spacer material, and the spacer material includes any one or more of a fluorine-containing polymer derived from a monomer containing the following substances: vinylidene fluoride, hexafluoropropylene, tetrafluoropropylene, a polyolefin such as polyethylene, polypropylene or polybutylene, an ethylene-diene-propylene terpolymer, polystyrene, polymethyl methacrylate, polyethylene glycol, polyvinyl acetate, polyvinyl butyral, polyacetal and polyethylene glycol diacrylate, methyl cellulose, carboxymethyl cellulose, styrene rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, polyacrylamide, polyethylene ether, polyacrylic acid, polymethacrylic acid, polyacrylonitrile, polyvinylidene fluoride polyacrylonitrile, polyethylene oxide, acrylate, styrene, epoxy resin, silicone, polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene, polymethyl methacrylate, polyacrylonitrile, polyvinyl pyrrole alkylone, 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, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trichloroethylene, polymethyl methacrylate, polyacrylonitrile, polyvinyl pyrrolidone, polyvinyl acetate, ethylene vinyl acetate copolymer, 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, polyethylene terephthalate, polybutylene terephthalate, polyester, polyacetal, polyamide, polyetheretherketone, polyethersulfone, polyphenylene ether, polyphenylene sulfide, polyethylene naphthalene and / or combinations and copolymers thereof.

[0160] Embodiment 10. A secondary battery according to any of the aforementioned embodiments, wherein the total volume occupied by the spacer group is at least 0.1%, at least 0.25%, at least 0.5% and / or at least 0.75% of the total volume Ve of the electrode layer and is less than 35%, less than 25%, less than 10% and / or less than 5%.

[0161] Embodiment 11. A secondary battery according to any of the preceding enumerated embodiments, wherein a member of the spacer group is located within each subvolume of the electrode layer, the subvolumes comprising (i) the volume V of the electrode layer Eat least 20%, at least 10% and / or at least 5% of the electrode layer, and (ii) is defined by (aa) the unit cell portion of the electrode current collector, (bb) the separator layer, (cc) the top surface of the electrode layer, (dd) the bottom surface of the electrode layer, (ee) the first end surface of the electrode layer and (ff) the second end surface of the electrode layer.

[0162] Embodiment 12. A secondary battery according to any of the aforementioned embodiments, wherein the secondary battery comprises a series of stacked sheets, the series of stacked sheets comprising the electrode layer and the counter electrode layer, wherein the stacking direction is along a first direction, and the height H of the electrode layer is E is measured along a second direction orthogonal to the stacking direction, and the length L of the electrode layer E It is measured along a third direction that is orthogonal to both the second direction and the stacking direction.

[0163] Embodiment 13. The secondary battery according to any of the preceding enumerated embodiments, wherein a member of the set of spacer structures in each unit cell of the stacking sequence is aligned with other members of the set of spacer structures along the stacking direction.

[0164] Embodiment 14. A secondary battery according to any of the aforementioned embodiments, wherein the secondary battery includes at least one unit cell continuously wound around an internal region, wherein the diameter of the inner winding circle of the unit cell is smaller than the diameter of the outer winding circle of the unit cell, and wherein the diameter of the unit cell increases as the radius from the internal region increases.

[0165] Embodiment 15. The secondary battery according to the aforementioned embodiment 14, wherein the stacking sequence is along the first direction, and the height H of the electrode layer is E is measured along a second direction orthogonal to the stacking direction, and the length L of the electrode layer E is measured along the longest dimension of the electrode layer, the longest dimension corresponding to a winding path of the electrode layer from a central region of the secondary battery to an outer section of the secondary battery.

[0166] Embodiment 16. A secondary battery according to the aforementioned embodiment 14, wherein the components of the group of spacer structures are aligned so that the spacer structures arranged in the inner winding circle of the unit battery are aligned with the spacer structures in the outer winding circle of the unit battery along the stacking direction.

[0167] Embodiment 17. A secondary battery according to the aforementioned embodiment 16, wherein the distance between the spacers arranged in the electrode layer along the longest dimension of the electrode layer increases as the radius increases from the inner region of the secondary battery to the outer region of the secondary battery.

[0168] Embodiment 18. A secondary battery according to any of the aforementioned enumerated embodiments, wherein the set of spacer structures includes a plurality of spacers along the length L of the electrode layer. E A plurality of spacer structures are disposed within the electrode layer.

[0169] Embodiment 19. The secondary battery according to any of the preceding enumerated embodiments, wherein the set of spacer structures includes a single spacer structure located at the periphery of the electrode layer.

[0170] Embodiment 20. A secondary battery according to any of the preceding enumerated embodiments, wherein the set of spacer structures comprises the width W of the set passing through the electrode layer. E One or more members extending from the electrode current collector to the separator layer.

[0171] Embodiment 21. A secondary battery according to any of the preceding enumerated embodiments, wherein the set of spacer structures is arranged along the width W of the electrode layer. E The median value of the extent from the first surface of the electrode current collector layer to the first surface of the separator layer opposite to the first surface of the electrode current collector layer is the width W of the electrode layer. E less than 60%, less than 50%, less than 40%, less than 25% and / or less than 25% of the width W of the electrode layer E at least 2%, at least 3% and / or at least 5%.

[0172] Embodiment 22. A secondary battery according to any of the aforementioned embodiments, comprising adjacent first unit cells and second unit cells, wherein the adjacent first unit cells and second unit cells comprise respective first electrode layers and second electrode layers, and a common electrode current collector, and wherein both the adjacent first unit cells and second unit cells comprise multiple groups of spacer structures in their respective first electrode layers and second electrode layers.

[0173] Embodiment 23. A secondary battery according to the aforementioned embodiment 22, wherein the adjacent first unit cell and second unit cell share the same set of spacer structures, and the same set of spacer structures extends through the common electrode current collector into each of the first electrode layer and the second electrode layer.

[0174] Embodiment 24. A secondary battery according to any of the aforementioned embodiments, comprising a first unit cell and a second unit cell, wherein the first unit cell and the second unit cell comprise respective first electrode layers and second electrode layers and comprise a first group of spacer structures and a second group of spacer structures in their respective first electrode layers and second electrode layers, and wherein the position of the first group of spacer structures in the first electrode layer is aligned with the position of the second group of spacer structures in the second electrode layer along the stacking direction.

[0175] Embodiment 25. The secondary battery according to any of the preceding enumerated embodiments, wherein the set of spacer structures is disposed at the interface between the electrode layer and the separator layer.

[0176] Embodiment 26. The secondary battery of any of the preceding enumerated embodiments, wherein the set of spacer structures is disposed at the interface between the electrode layer and the surface of the current collector layer.

[0177] Embodiment 27. A secondary battery according to any of the preceding enumerated embodiments, wherein the electrode layer comprises a total volume V of the electrode layer. E The percentage of void space is less than 70% void space, less than 60% void space, less than 25% void space, and / or less than or equal to 10% void space.

[0178] Embodiment 28. A secondary battery according to any of the aforementioned embodiments, wherein the ratio of the conductivity of the electrode active material in the electrode layer to the total conductivity of all components of the spacer group in the electrode layer is at least 2:1, at least 5:1 and / or at least 50:1.

[0179] Embodiment 29. An electrode assembly for a secondary battery that cycles between a charging state and a discharging state, wherein

[0180] The electrode assembly includes a group of unit cells, each unit cell including a unit cell portion of an electrode current collector layer, an electrode layer including an electrode active material, a separator layer, a counter electrode layer, and a unit cell portion of a counter electrode current collector layer in a stacking sequence, the unit cell having a width W measured from the unit cell portion of the electrode current collector to the unit cell portion of the counter electrode current collector along a stacking direction of the stacking sequence. uc , the electrode layer has a width W measured along the stacking direction from the unit cell portion of the electrode current collector adjacent to the electrode layer to the separator layer adjacent to the electrode layer e, a height He measured from the top surface to the bottom surface of the electrode layer along a second direction orthogonal to the stacking direction, and a length Le measured from the first surface to the second surface along a third direction orthogonal to the stacking direction and the height direction, and a volume V defined by the unit cell portion of the electrode current collector, the separator layer, the top surface of the electrode layer, the bottom surface of the electrode layer, the first end surface of the electrode layer, and the second end surface of the electrode layer E ,and

[0181] The electrode layer comprises a set of spacer structures, wherein the total volume occupied by the spacer set within the electrode layer is within the volume V of the electrode layer. E The range of about 0.1% to about 35%.

[0182] Embodiment 30. The electrode assembly of embodiment 29, wherein the members of the spacer group are located within each subvolume of the electrode layer, the subvolumes comprising (i) the volume V of the electrode layer E at least 50% of the electrode layer, and (ii) is defined by (aa) the unit cell portion of the electrode current collector, (bb) the separator layer, (cc) the top surface of the electrode layer, (dd) the bottom surface of the electrode layer, (ee) the first end surface of the electrode layer and (ff) the second end surface of the electrode layer.

[0183] Embodiment 31. An electrode assembly according to any of the aforementioned embodiments 29-30, wherein the members of the spacer group are located in each sub-volume of the electrode layer, and the sub-volumes include (i) the volume V of the electrode layer E at least 40% of the electrode layer, and (ii) is defined by (aa) the unit cell portion of the electrode current collector, (bb) the separator layer, (cc) the top surface of the electrode layer, (dd) the bottom surface of the electrode layer, (ee) the first end surface of the electrode layer and (ff) the second end surface of the electrode layer.

[0184] Embodiment 32. An electrode assembly according to any one of the aforementioned embodiments 29-31, wherein the members of the spacer group are located in each sub-volume of the electrode layer, and the sub-volumes include (i) the volume V of the electrode layer E at least 30% of the electrode layer, and (ii) is defined by (aa) the unit cell portion of the electrode current collector, (bb) the separator layer, (cc) the top surface of the electrode layer, (dd) the bottom surface of the electrode layer, (ee) the first end surface of the electrode layer and (ff) the second end surface of the electrode layer.

[0185] Embodiment 33. An electrode assembly according to any one of the aforementioned embodiments 29-32, wherein the members of the spacer group are located in each subvolume of the electrode layer, and the subvolumes include (i) the volume V of the electrode layer E at least 25% of the electrode layer, and (ii) is defined by (aa) the unit cell portion of the electrode current collector, (bb) the separator layer, (cc) the top surface of the electrode layer, (dd) the bottom surface of the electrode layer, (ee) the first end surface of the electrode layer, and (ff) the second end surface of the electrode layer.

[0186] Embodiment 34. An electrode assembly according to any one of the aforementioned embodiments 29-33, wherein the electrode layer includes an electrode active material layer, and when the secondary battery is charged from the discharge state to the charge state, the electrode active material layer has a capacity of accepting more than one mole of carriers per mole of electrode active material, wherein the charge state is at least 75% of the rated capacity of the secondary battery, and the discharge state is less than 25% of the rated capacity of the secondary battery.

[0187] Embodiment 35. An electrode assembly according to any one of the aforementioned embodiments 29-34, wherein the set of spacer structures includes a spacer material, and when the secondary battery is charged from the discharge state to the charge state, the spacer material has a capacity of accepting less than one mole of carrier ions per mole of spacer material, and the charge state is at least 75% of the rated capacity of the secondary battery, and the discharge state is less than 25% of the rated capacity of the secondary battery.

[0188] Embodiment 36. An electrode assembly according to any one of the aforementioned embodiments 29-35, wherein the set of spacer structures includes spacer materials, and the spacer materials include any one or more of polymer materials, electrode active materials, electrode current collector materials, counter electrode current collector materials and separator materials.

[0189] Embodiment 37. An electrode assembly according to the aforementioned embodiment 36, wherein the set of spacer structures includes a spacer material, and the spacer material includes any one or more of a fluorine-containing polymer derived from a monomer containing the following substances: vinylidene fluoride, hexafluoropropylene, tetrafluoropropylene, a polyolefin such as polyethylene, polypropylene or polybutylene, an ethylene-diene-propylene terpolymer, polystyrene, polymethyl methacrylate, polyethylene glycol, polyvinyl acetate, polyvinyl butyral, polyacetal and polyethylene glycol diacrylate, methyl cellulose, carboxymethyl cellulose, styrene rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, polyacrylamide, polyethylene ether, polyacrylic acid, polymethacrylic acid, polyacrylonitrile, polyvinylidene fluoride polyacrylonitrile, polyethylene oxide, acrylate, styrene, epoxy resin, silicone, polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene, polymethyl methacrylate, polyacrylonitrile, polyvinyl pyrrole alkylone, 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, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trichloroethylene, polymethyl methacrylate, polyacrylonitrile, polyvinyl pyrrolidone, polyvinyl acetate, ethylene vinyl acetate copolymer, 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, polyethylene terephthalate, polybutylene terephthalate, polyester, polyacetal, polyamide, polyetheretherketone, polyethersulfone, polyphenylene ether, polyphenylene sulfide, polyethylene naphthalene and / or combinations and copolymers thereof.

[0190] Embodiment 38. An electrode assembly according to any one of the aforementioned embodiments 29-37, wherein the total volume occupied by the spacer group is the total volume V of the electrode layer. E At least 0.1%, at least 0.25%, at least 0.5% and / or at least 0.75% and less than 35%, less than 25%, less than 10% and / or less than 5%.

[0191] Embodiment 39. An electrode assembly according to any one of the aforementioned embodiments 29-38, wherein the members of the spacer group are located in each subvolume of the electrode layer, and the subvolumes include (i) the volume V of the electrode layer Eat least 20%, at least 10% and / or at least 5% of the electrode layer, and (ii) is defined by (aa) the unit cell portion of the electrode current collector, (bb) the separator layer, (cc) the top surface of the electrode layer, (dd) the bottom surface of the electrode layer, (ee) the first end surface of the electrode layer and (ff) the second end surface of the electrode layer.

[0192] Embodiment 40. The electrode assembly according to any one of the aforementioned embodiments 29-39, wherein the electrode assembly comprises a series of stacked sheets, wherein the series of stacked sheets comprises the electrode layer and the counter electrode layer, wherein the stacking direction is along a first direction, and the height H of the electrode layer is E is measured along a second direction orthogonal to the stacking direction, and the length L of the electrode layer E It is measured along a third direction that is orthogonal to both the second direction and the stacking direction.

[0193] Embodiment 41. The electrode assembly according to the aforementioned enumerated embodiment 40, wherein a member of the set of spacer structures in each unit cell of the stacking sequence is aligned with other members of the set of spacer structures along the stacking direction.

[0194] Embodiment 42. An electrode assembly according to any one of the aforementioned embodiments 29-41, wherein the electrode assembly includes at least one unit cell continuously wound around an internal region, wherein the diameter of the inner winding circle of the unit cell is smaller than the diameter of the outer winding circle of the unit cell, and wherein the diameter of the unit cell increases as the radius from the internal region increases.

[0195] Embodiment 43. The electrode assembly according to the aforementioned embodiment 42, wherein the stacking sequence is along the first direction, and the height H of the electrode layer is E is measured along a second direction orthogonal to the stacking direction, and the length L of the electrode layer E is measured along the longest dimension of the electrode layer, the longest dimension corresponding to the winding path of the electrode layer from the central region of the electrode assembly to the outer sections of the electrode assembly.

[0196] Embodiment 44. An electrode assembly according to the aforementioned embodiment 43, wherein the components of the group of spacer structures are aligned so that the spacer structure arranged in the inner winding circle of the unit cell is aligned with the spacer structure in the outer winding circle of the unit cell along the stacking direction.

[0197] Embodiment 45. An electrode assembly according to the aforementioned embodiment 44, wherein the distance between the spacers arranged in the electrode layer along the longest dimension of the electrode layer increases as the radius from the inner region of the secondary battery to the outer region of the electrode assembly increases.

[0198] Embodiment 46. An electrode assembly according to any one of the aforementioned embodiments 29-45, wherein the set of spacer structures includes a length L along the electrode layer. E A plurality of spacer structures are disposed within the electrode layer.

[0199] Embodiment 47. An electrode assembly according to any of the aforementioned embodiments 29-46, wherein the set of spacer structures includes a single spacer structure located at the periphery of the electrode layer.

[0200] Embodiment 48. An electrode assembly according to any one of the aforementioned embodiments 29-47, wherein the set of spacer structures includes the width W of the set passing through the electrode layer. E One or more members extending from the electrode current collector to the separator layer.

[0201] Embodiment 49. An electrode assembly according to any one of the aforementioned embodiments 29-48, wherein the set of spacer structures is along the width W of the electrode layer. E The median value of the extent from the first surface of the electrode current collector layer to the first surface of the separator layer opposite to the first surface of the electrode current collector layer is the width W of the electrode layer. E less than 60%, less than 50%, less than 40%, less than 25% and / or less than 25% of the width W of the electrode layer E at least 2%, at least 3% and / or at least 5%.

[0202] Embodiment 50. An electrode assembly according to any one of the aforementioned embodiments 29-49, comprising adjacent first unit cells and second unit cells, wherein the adjacent first unit cells and second unit cells comprise respective first electrode layers and second electrode layers, and a common electrode current collector, and wherein both the adjacent first unit cells and second unit cells comprise multiple groups of spacer structures in their respective first electrode layers and second electrode layers.

[0203] Embodiment 51. An electrode assembly according to the aforementioned embodiment 50, wherein the adjacent first unit cells and second unit cells share the same set of spacer structures, and the same set of spacer structures extends through the common electrode current collector into each of the first electrode layer and the second electrode layer.

[0204] Embodiment 52. An electrode assembly according to any one of the aforementioned embodiments 29-51, comprising a first unit cell and a second unit cell, wherein the first unit cell and the second unit cell comprise respective first electrode layers and second electrode layers and comprise a first group of spacer structures and a second group of spacer structures in their respective first electrode layers and second electrode layers, and wherein the position of the first group of spacer structures in the first electrode layer is aligned with the position of the second group of spacer structures in the second electrode layer along the stacking direction.

[0205] Embodiment 53. An electrode assembly according to any one of the aforementioned embodiments 29-52, wherein the set of spacer structures is arranged at the interface between the electrode layer and the separator layer.

[0206] Embodiment 54. An electrode assembly according to any one of the aforementioned embodiments 29-53, wherein the set of spacer structures is arranged at the interface between the electrode layer and the surface of the current collector layer.

[0207] Embodiment 55. An electrode assembly according to any one of the aforementioned embodiments 29-54, wherein the electrode layer comprises a total volume V of the electrode layer. E The percentage of void space is at least 40% void space, at least 50% void space, at least 60% void space, at least 75% void space and / or at least 90% void space.

[0208] Embodiment 56. An electrode assembly according to any one of the aforementioned embodiments 29-55, wherein the ratio of the electrical conductivity of the electrode active material in the electrode layer to the total electrical conductivity of all components of the spacer group in the electrode layer is at least 2:1, at least 5:1 and / or at least 50:1.

[0209] Embodiment 57. A method for forming a secondary battery that cycles between a charged state and a discharged state, comprising:

[0210] An electrode assembly, carrier ions, and a non-aqueous liquid electrolyte are provided within a battery housing, wherein

[0211] The electrode assembly includes a group of unit cells, each unit cell including a unit cell portion of an electrode current collector layer, an electrode layer including an electrode active material, a separator layer, a counter electrode layer, and a unit cell portion of a counter electrode current collector layer in a stacking sequence, the unit cell having a width W measured from the unit cell portion of the electrode current collector to the unit cell portion of the counter electrode current collector along a stacking direction of the stacking sequence. uc , the electrode layer has a width W measured along the stacking direction from the unit cell portion of the electrode current collector adjacent to the electrode layer to the separator layer adjacent to the electrode layer e , a height H measured from the top surface to the bottom surface of the electrode layer in a direction orthogonal to the stacking direction E , and a length Le measured from a first surface to a second surface along a direction orthogonal to the stacking direction and the height direction, and a volume Ve defined by the unit cell portion of the electrode current collector, the separator layer, the top surface of the electrode layer, the bottom surface of the electrode layer, the first end surface of the electrode layer, and the second end surface of the electrode layer,

[0212] The electrode layer includes a set of spacer structures, wherein a total volume occupied by the spacer set within the electrode layer is in a range of about 0.1% to about 35% of the volume Ve of the electrode layer, and

[0213] A formation process is performed involving charging the secondary battery from a discharged state to a charged state.

[0214] Embodiment 58. A method according to the aforementioned embodiment 57, wherein the components of the spacer group are located within each subvolume of the electrode layer, the subvolume including (i) at least 50% of the volume Ve of the electrode layer, and (ii) defined by (aa) the unit cell portion of the electrode collector, (bb) the separator layer, (cc) the top surface of the electrode layer, (dd) the bottom surface of the electrode layer, (ee) the first end surface of the electrode layer and (ff) the second end surface of the electrode layer.

[0215] Embodiment 59. A method according to any one of the aforementioned embodiments 57-58, wherein the components of the spacer group are located within each subvolume of the electrode layer, the subvolume including (i) at least 40% of the volume Ve of the electrode layer, and (ii) defined by (aa) the unit cell portion of the electrode current collector, (bb) the separator layer, (cc) the top surface of the electrode layer, (dd) the bottom surface of the electrode layer, (ee) the first end surface of the electrode layer, and (ff) the second end surface of the electrode layer.

[0216] Embodiment 60. A method according to any one of the aforementioned embodiments 57-59, wherein the components of the spacer group are located within each subvolume of the electrode layer, the subvolume including (i) at least 30% of the volume Ve of the electrode layer, and (ii) defined by (aa) the unit cell portion of the electrode collector, (bb) the separator layer, (cc) the top surface of the electrode layer, (dd) the bottom surface of the electrode layer, (ee) the first end surface of the electrode layer, and (ff) the second end surface of the electrode layer.

[0217] Embodiment 61. A method according to any of the aforementioned embodiments 57-60, wherein the members of the spacer group are located in each subvolume of the electrode layer, and the subvolumes include (i) the volume V of the electrode layer E at least 25% of the electrode layer, and (ii) is defined by (aa) the unit cell portion of the electrode current collector, (bb) the separator layer, (cc) the top surface of the electrode layer, (dd) the bottom surface of the electrode layer, (ee) the first end surface of the electrode layer, and (ff) the second end surface of the electrode layer.

[0218] Embodiment 62. A method according to any one of the aforementioned embodiments 57-61, wherein the electrode layer comprises a first volume of solid electrode active material before the formation process, and comprises a second volume of solid electrode active material greater than the first volume after the formation process, and wherein the method comprises performing the formation process to increase the volume of the solid electrode active material in the electrode layer to a second volume that is at least 3%, at least 5%, at least 10%, at least 25%, at least 50%, at least 75% and / or at least 100% greater than the first volume of the solid electrode active material in the electrode layer, to achieve a W of the unit cell from before the formation process to after the formation process. UC The change is less than 1%, less than 0.5%, less than 0.25% and / or less than 0.1%.

[0219] Embodiment 63. A method according to any one of the aforementioned embodiments 57-62, which also includes providing a set of electrode restraints during the formation process to restrain the growth of the electrode assembly along the stacking direction and / or maintain the alignment of the set of unit cells in the electrode assembly.

[0220] Embodiment 64. A method according to the aforementioned embodiment 63, wherein the set of electrode constraints constrains growth along the stacking direction.

[0221] Embodiment 65. A method according to any of the aforementioned embodiments 63-64, comprising removing the set of electrode constraints after the formation process.

[0222] Embodiment 66. A method according to any of the aforementioned enumerated embodiments 63-65, comprising providing the set of electrode restraints within the housing of the secondary battery.

[0223] Embodiment 67. A method according to any of the aforementioned enumerated embodiments 63-66, comprising providing the set of electrode restraints outside the housing of the secondary battery.

[0224] Embodiment 68. A method according to any one of the aforementioned enumerated embodiments 63-67, wherein the electrode assembly comprises any one of the aforementioned enumerated embodiments 29-56, and wherein the secondary battery comprises any one of the enumerated embodiments 1-28.

[0225] Incorporated by Reference

[0226] All publications and patents mentioned herein (including those items listed below) are hereby incorporated by reference in their entirety for all purposes to the same extent as if each individual publication or patent was specifically and individually incorporated by reference. In the event of a conflict, the present application, including any definitions herein, will control.

[0227] Equivalent solutions

[0228] Although specific embodiments have been discussed, the above description is illustrative rather than restrictive. Many variations will be apparent to those skilled in the art upon reading this specification. The full scope of the embodiments should be determined by reference to the full scope of the claims and their equivalents, the specification, and these variations.

[0229] Unless otherwise indicated, all numerical values ​​expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained.

Claims

1. A secondary battery for cycling between a charging state and a discharging state, the secondary battery comprising a battery housing, an electrode assembly in the battery housing, carrier ions, and a non-aqueous liquid electrolyte, wherein The electrode assembly includes a group of unit cells, each unit cell including a unit cell portion of an electrode current collector layer, an electrode layer including an electrode active material, a separator layer, a counter electrode layer, and a unit cell portion of a counter electrode current collector layer in a stacking sequence, wherein the electrode active material includes silicon, and the unit cell has a width W measured from the unit cell portion of the electrode current collector to the unit cell portion of the counter electrode current collector along a stacking direction of the stacking sequence. uc , the electrode layer has a width W measured along the stacking direction of the stacking sequence from the unit cell portion of the electrode current collector adjacent to the electrode layer to the separator layer adjacent to the electrode layer E , a height H measured from the top surface to the bottom surface of the electrode layer along a second direction orthogonal to the stacking direction E , and a length L measured from the first surface to the second surface along a third direction orthogonal to the stacking direction and the height direction E , and a volume V defined by the unit cell portion of the electrode current collector, the separator layer, the top surface of the electrode layer, the bottom surface of the electrode layer, the first end surface of the electrode layer, and the second end surface of the electrode layer E ,and The electrode layer comprises a set of spacer structures, the set of spacer structures comprising a material different from the electrode active material, wherein the set of spacer structures is disposed at an interface between the electrode active material and the separator layer, and wherein the electrode layer comprises the electrode active material located between members of the set of spacer structures, the members of the set of spacer structures being disposed along a length L of the electrode layer. E The third direction is separated from each other, wherein the total volume occupied by the spacer structure in the electrode layer is within the volume V of the electrode layer E The range is from 0.1% to 10%. 2 . The secondary battery according to claim 1 , wherein the electrode layer comprises an electrode active material layer.

3. A secondary battery according to claim 1, wherein the set of spacer structures includes a spacer material, and when the secondary battery is charged from the discharge state to the charge state, the spacer material has a capacity of accepting less than one mole of carrier ions per mole of spacer material, and the charge state is at least 75% of the rated capacity of the secondary battery, and the discharge state is less than 25% of the rated capacity of the secondary battery.

4. The secondary battery according to claim 1, wherein the set of spacer structures comprises a spacer material, the spacer material comprising any one or more of a fluorine-containing polymer derived from a monomer containing the following substances: vinylidene fluoride, hexafluoropropylene, tetrafluoropropylene, polyolefin, ethylene-diene-propylene terpolymer, polystyrene, polymethyl methacrylate, polyethylene glycol, polyvinyl acetate, polyvinyl butyral, polyacetal and polyethylene glycol diacrylate, methyl cellulose, carboxymethyl cellulose, styrene rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, polyacrylamide, polyvinyl ether, polyacrylic acid, polymethacrylic acid, polyacrylonitrile, polyvinylidene fluoride polyacrylonitrile, polyethylene oxide, acrylate, styrene, Epoxy resin, silicone, polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene, polyvinyl pyrrolidone, polyethylene-co-vinyl acetate, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cyanoethyl pullulan, cyanoethyl polyvinyl alcohol, cyanoethyl cellulose, cyanoethyl sucrose, pullulan, acrylonitrile-styrene-butadiene copolymer, polyimide, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trichloroethylene, ethylene vinyl acetate copolymer, acrylonitrile styrene butadiene copolymer, polyethylene terephthalate, polybutylene terephthalate, polyester, polyacetal, polyamide, polyetheretherketone, polyethersulfone, polyphenylene ether, polyphenylene sulfide, polyethylene naphthalene and / or combinations and copolymers thereof.

5. The secondary battery according to claim 1, wherein the total volume occupied by the spacer group is the total volume V of the electrode layer. E of at least 0.25%.

6. The secondary battery of claim 1, wherein a member of the spacer group is located within each subvolume of the electrode layer, the subvolumes comprising (i) the volume V of the electrode layer E at least 5% and the volume V E (ii) is defined on all sides by (aa) the unit cell portion of the electrode current collector, (bb) the separator layer, (cc) the top surface of the electrode layer, (dd) the bottom surface of the electrode layer, (ee) the first end surface of the electrode layer and (ff) the second end surface of the electrode layer. 7 . The secondary battery according to claim 1 , wherein a member of the set of spacer structures in each unit battery cell of the stacking sequence is aligned with other members of the set of spacer structures in the stacking direction.

8. A secondary battery according to claim 1, wherein the secondary battery includes at least one unit cell continuously wound around an internal area, wherein a diameter of an inner winding circle of the unit cell is smaller than a diameter of an outer winding circle of the unit cell, and wherein the diameter of the unit cell increases as the radius from the internal area increases.

9. The secondary battery according to claim 8, wherein the stacking sequence is along a first direction, and the height H of the electrode layer is E is measured along a second direction orthogonal to the stacking direction, and the length L of the electrode layer E is measured along the longest dimension of the electrode layer, the longest dimension corresponding to a winding path of the electrode layer from a central region of the secondary battery to an outer section of the secondary battery.

10. The secondary battery according to claim 8, wherein members of the set of spacer structures are aligned so that spacer structures disposed in inner windings of the unit cells are aligned with spacer structures in outer windings of the unit cells in the stacking direction.

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