This application claims the benefit of priority to Japanese Patent Application No. 2023-058822 filed on Mar. 31, 2023. The entire contents of this application are hereby incorporated herein by reference.
The present disclosure relates to a power storage module including a plurality of power storage devices and a manufacturing method for the same.
A power storage module in which a plurality of power storage devices (unit cells) are electrically connected to each other has been widely used conventionally in a power source for driving a vehicle and the like. Conventional technical literatures related to this include Japanese Patent Application Publication No. 2021-44212.
For example, Japanese Patent Application Publication No. 2021-44212 discloses a power storage module including a plurality of submodules and a housing that accommodates the plurality of submodules at predetermined positions. In Japanese Patent Application Publication No. 2021-44212, each of the plurality of submodules includes a cell group in which the plurality of power storage devices (unit cells) are arranged, and a restriction member that restricts the cell group by operating a restriction pressure in an arrangement direction. Inside the housing, a region where temperature tends to become relatively low exists. The submodule disposed in the region where temperature tends to become relatively low is configured so that the restriction pressure of the restriction member becomes relatively lower than the other submodules. According to Japanese Patent Application Publication No. 2021-44212, making the restriction pressure on the power storage device low in the region where high-rate durability tends to decrease (the temperature tends to become low) can equalize the high-rate durability of the plurality of power storage devices (increase in resistance when high-rate charging and discharging are repeated).
In the art according to Japanese Patent Application Publication No. 2021-44212, the restriction pressure cannot be made different among the plurality of power storage devices included in one cell group. Therefore, according to the present inventors' examination, if a temperature distribution occurs inside the cell group, it may be difficult to equalize the high-rate durability among the plurality of power storage devices. In addition, since the restriction member is necessary for each cell group, the restriction members become bulky, which may result in the decrease in volume energy density of the entire power storage module, and in a case of mounting the power storage module on a moving body such as a vehicle, for example, the weight increases, which may result in the deterioration in fuel efficiency.
The present disclosure has been made in view of the above circumstances, and a main object thereof is to provide a power storage module with a novel structure that can equalize the high-rate durability among a plurality of power storage devices and a manufacturing method for the same.
The present disclosure provides a power storage module including a plurality of power storage devices, in which each of the plurality of power storage devices includes an electrode body and a nonaqueous electrolyte solution, the nonaqueous electrolyte solution contains a nonaqueous solvent and an electrolyte salt, a low-temperature region with relatively low temperature and a high-temperature region with relatively high temperature exist in the power storage module when the plurality of power storage devices are charged and discharged, and in a first power storage device disposed in the low-temperature region among the plurality of power storage devices, a concentration of the electrolyte salt is closer to 1.1 mol/L than in a second power storage device disposed in the high-temperature region.
The present disclosure also provides a manufacturing method for a power storage module including a plurality of power storage devices, in which each of the plurality of power storage devices includes an electrode body and a nonaqueous electrolyte solution and the nonaqueous electrolyte solution includes a nonaqueous solvent and an electrolyte salt. This manufacturing method includes: a preparing step of preparing, as the plurality of power storage devices, a first power storage device in which a concentration of the electrolyte salt is relatively close to 1.1 mol/L and a second power storage device in which the concentration of the electrolyte salt is relatively far from 1.1 mol/L; a temperature distribution predicting step of predicting a temperature distribution inside the power storage module when the plurality of power storage devices are charged and discharged; and a constructing step of constructing the power storage module by disposing the first power storage device in a low-temperature region with relatively low temperature and disposing the second power storage device in a high-temperature region with relatively high temperature, based on the temperature distribution.
The present inventors' various examinations indicate that the power storage device in which the concentration of the electrolyte salt is close to 1.1 mol/L (first concentration) is superior relatively to the power storage device in which the concentration of the electrolyte salt is far from the first concentration, in terms of the high-rate durability. In view of this, in the present disclosure, the power storage device in which the concentration is relatively close to the first concentration (the high-rate durability is high) is disposed in the low-temperature region in which the high-rate durability tends to decrease. Thus, the high-rate durability of the plurality of power storage devices can be equalized. Furthermore, the high-rate durability of the entire power storage module can be improved. Since it is unnecessary to consider the concept of “cell group” that is given in the art disclosed in Japanese Patent Application Publication No. 2021-44212, the high-rate durability of the individual power storage device can be adjusted flexibly. Additionally, since the number of restriction members can be reduced compared to the art disclosed in Japanese Patent Application Publication No. 2021-44212, the volume energy density or fuel efficiency can also be improved.
Although there is no particular relation with the art disclosed herein, Japanese Patent Application Publication No. H9-245830 describes the concentration range of the electrolyte salt (specifically, LiPF6) that is suitable for the power storage device.
The above and other elements, features, steps, characteristics and advantages of the present disclosure will become more apparent from the following detailed description of the preferred embodiments with reference to the attached drawings.
Hereinafter, preferred embodiments of the art disclosed herein will be described with reference to the drawings as appropriate. Matters that are other than matters particularly mentioned in the present specification and that are necessary for the implementation of the present disclosure (for example, the general configuration and manufacturing process of a power storage module and a power storage device that do not characterize the present disclosure) can be grasped as design matters of those skilled in the art based on the prior art in the relevant field. A power storage module disclosed herein can be implemented on the basis of the disclosure of the present specification and common technical knowledge in the relevant field.
Note that in the drawings below, the members and parts with the same operation are denoted by the same reference sign and the overlapping description may be omitted or simplified. Moreover, in the present specification, the notation “A to B” for a range signifies a value more than or equal to A and less than or equal to B, and is meant to encompass also the meaning of being “preferably more than A” and “preferably less than B”.
In the following description, reference signs L, R, F, Rr, U, and D in the drawings respectively denote left, right, front, rear, up, and down, and reference signs X, Y, and Z in the drawings respectively denote a short side direction of the power storage device 100, a long side direction that is orthogonal to the short side direction, and an up-down direction. The short side direction X also corresponds to an arrangement direction of the power storage devices 100. These directions are defined however for convenience of explanation, and do not limit the manner in which the power storage module 500 is disposed.
The restriction mechanism 300 is a member that restricts the plurality of power storage devices 100. Here, the number of restriction mechanism 300 is one. The restriction mechanism 300 here is configured to apply uniform restriction pressure on all of the power storage devices 100 and the spacers 200 from the arrangement direction X. The restriction mechanism 300 includes a pair of end plates 310, a pair of side plates 320, and a plurality of screws 330. The pair of end plates 310 and the pair of side plates 320 can be grasped as a housing that accommodates the plurality of power storage devices 100. The pair of end plates 310 and the pair of side plates 320 are preferably made of a metal.
The pair of end plates 310 are disposed at both ends of the power storage module 500 in the arrangement direction X. The pair of end plates 310 hold the plurality of power storage devices 100 and the plurality of spacers 200 therebetween in the arrangement direction X. The pair of side plates 320 link between the pair of end plates 310. The pair of side plates 320 are fixed to the end plates 310 by the plurality of screws 330 so that a restriction load is generally 10 to 15 kN, for example. Thus, the uniform restriction load is applied on the plurality of power storage devices 100 from the arrangement direction X and accordingly, the plurality of power storage devices 100 are held integrally. The structure of the restriction mechanism is, however, not limited to this example. In another example, the restriction mechanism 300 may alternatively include a plurality of restriction bands, bind bars, or the like instead of the side plates 320.
The spacers 200 are each disposed between the plurality of power storage devices 100 in the arrangement direction X here. That is to say, in the arrangement direction X, the power storage devices 100 and the spacers 200 are arranged alternately. However, in a case where the power storage module 500 does not include the spacer 200, the power storage devices 100 that are adjacent in the arrangement direction X may be in contact (direct contact) with each other. The spacer 200 preferably includes a part with a porous structure through which a fluid (typically, gas such as air) can pass.
The power storage device 100 is a device capable of being repeatedly charged and discharged. Note that in the present specification, the term “power storage device” refers to a concept encompassing secondary batteries such as lithium ion secondary batteries and nickel-hydrogen batteries and capacitors such as lithium ion capacitors and electrical double-layer capacitors. Here, the plurality of power storage devices 100 are arranged along the arrangement direction X (in other words, a thickness direction X of the power storage device 100) between the pair of end plates 310. The plurality of power storage devices 100 are preferably restricted by the restriction mechanism 300. The shape, the size, the number, and the like of the plurality of power storage devices 100 are not limited to the aspect disclosed in
Although not illustrated here, when the power storage module 500 is used, the plurality of power storage devices 100 are electrically connected to each other by a conductive member such as a busbar. The connection method is not limited in particular and may be, for example, series connection, parallel connection, multiple series-multiple parallel connection, or the like. In a preferred aspect, the plurality of power storage devices 100 are connected to each other in series. Thus, the output characteristic can be suitably improved to the level suitable for the use in a moving body such as a vehicle. In the case of series connection, the performance deterioration of some power storage devices 100 tends to lead to the performance deterioration of the entire power storage module 500. Thus, it is particularly effective to apply the art disclosed herein.
The battery case 10 is a container that accommodates the electrode body 20 and the nonaqueous electrolyte solution. As illustrated in
The sealing plate 14 is a plate-shaped member. The sealing plate 14 is substantially rectangular in shape. As illustrated in
The positive electrode terminal 30 is disposed on one end part of the sealing plate 14 in the long side direction Y (left end part in
As illustrated in
As illustrated in
The structure of the positive electrode 22 may be similar to the conventional one. Here, the positive electrode 22 includes a positive electrode current collector 22c, and a positive electrode active material layer 22a and a positive electrode protection layer 22p that are fixed on at least one surface of the positive electrode current collector 22c. However, the positive electrode protection layer 22p is not essential, and can be omitted in another embodiment. The positive electrode current collector 22c has a band shape. The positive electrode current collector 22c is preferably made of a metal, and more preferably made of a metal foil. Here, the positive electrode current collector 22c is an aluminum foil.
At one end part of the positive electrode current collector 22c in the long side direction Y (left end part in
The positive electrode active material layer 22a is provided to have a band shape along a longitudinal direction of the positive electrode current collector 22c. The positive electrode active material layer 22a includes a positive electrode active material that is capable of reversibly storing and releasing charge carriers. Examples of the positive electrode active material include a lithium transition metal complex oxide. The positive electrode active material layer 22a may contain an optional component other than the positive electrode active material, for example, various additive components such as a binder or a conductive material.
The positive electrode protection layer 22p is provided at a border part between the positive electrode current collector 22c and the positive electrode active material layer 22a in the long side direction Y. The positive electrode protection layer 22p is provided to have a band shape along the positive electrode active material layer 22a. The positive electrode protection layer 22p contains inorganic filler (for example, alumina). The positive electrode protection layer 22p may contain an optional component other than the inorganic filler, such as a conductive material, a binder, or various additive components.
The structure of the negative electrode 24 may be similar to the conventional one. The negative electrode 24 here includes a negative electrode current collector 24c, and a negative electrode active material layer 24a that is fixed on at least one surface of the negative electrode current collector 24c. The negative electrode current collector 24c has a band shape. The negative electrode current collector 24c is preferably made of a metal, and more preferably made of a metal foil. Here, the negative electrode current collector 24c is a copper foil.
At one end part of the negative electrode current collector 24c in the long side direction Y (right end part in
The negative electrode active material layer 24a is provided to have a band shape along a longitudinal direction of the negative electrode current collector 24c. A length Ln of the negative electrode active material layer 24a in the long side direction Y is preferably more than or equal to a length Lp of the positive electrode active material layer 22a in the long side direction Y. The negative electrode active material layer 24a includes a negative electrode active material that is capable of reversibly storing and releasing the charge carriers. Examples of the negative electrode active material include a carbon material such as graphite. The negative electrode active material layer 24a may contain an optional component other than the negative electrode active material, for example, various additive components such as a binder, a thickener, or a dispersing agent.
The separator 26 is disposed between the positive electrode 22 and the negative electrode 24. The separator 26 is a member that insulates the positive electrode 22 and the negative electrode 24. The structure of the separator 26 may be similar to the conventional one. A length Ls of the separator 26 in the long side direction Y is preferably more than or equal to the length Ln of the negative electrode active material layer 24a in the long side direction Y. The separator 26 is suitably a porous sheet (microporous film) made of resin including polyolefin resin such as polyethylene (PE) or polypropylene (PP), for example. The separator 26 may include a functional layer (for example, adhesive layer, heat resistance layer (HRL), or the like) on a surface of the porous sheet made of resin.
The nonaqueous electrolyte solution contains a nonaqueous solvent and an electrolyte salt (supporting salt). Examples of the nonaqueous solvent include various organic solvents used for the electrolyte solution of the general lithium ion secondary batteries, such as carbonates, esters, ethers, nitriles, sulfones, and lactones. Any of these can be used alone or two or more kinds thereof can be used in combination. In particular, the nonaqueous solvent preferably includes carbonates or esters, more preferably includes carbonates, and is particularly preferably formed of carbonates (the nonaqueous solvent is carbonates). Note that in the present specification, the term “carbonates” refers to general compounds including at least one carbonate structure (—O—CO—O—) in a molecule.
Specific examples of the carbonates include: cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC), and fluoroethylene carbonate; and chain carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), monofluoroethylene carbonate (MFEC), and difluoroethylene carbonate (DFEC). In particular, from the viewpoints of improving the ion conductivity, decreasing the viscosity of the nonaqueous electrolyte solution, and the like, the nonaqueous solvent preferably includes both the cyclic carbonate (for example, EC) and the chain carbonate (for example, DMC and/or EMC). The ratio of the cyclic solvent (for example, cyclic carbonate) in the entire nonaqueous solvent is preferably 50 vol % or less, and may be, for example, 10 to 50 vol % or 20 to 30 vol %.
Specific examples of the esters include methyl acetate (MA), ethyl acetate, n-propyl acetate, n-butyl acetate, and other chain esters. Specific examples of the ethers include chain ethers such as diethyl ether.
Examples of the electrolyte salt include various lithium salts used as the electrolyte salt for the electrolyte solution of the general lithium ion secondary batteries, and specifically include: lithium hexafluorophosphate (LiPF6); lithium tetrafluoroborate (LiBF4); perfluoroalkyl sulfonyl imide compounds such as lithium bis (fluorosulfonyl) imide (LiFSI, LiN (SO2F)2), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI, LiN (SO2CF3)2), and lithium bis (pentafluoroethanesulfonyl) imide; and the like. Any of these can be used alone or two or more kinds thereof can be used in combination. In particular, the electrolyte salt preferably contains LiPF6, and is more preferably formed of LiPF6 (the electrolyte salt is LiPF6).
The nonaqueous electrolyte solution may additionally contain an additive as necessary. Examples of the additive include a gas generating agent such as biphenyl (BP) or cyclohexyl benzene (CHB), and a film forming agent such as an oxalato complex compound containing a boron atom and/or a phosphorus atom. Note that the nonaqueous electrolyte solution is typically a liquid type, and may be a gel type.
In this embodiment, the intake port IP is provided on one side (front F side) of the power storage module 500 in the arrangement direction X. The exhaust port OP is provided on the other side (rear Rr side) in the arrangement direction X. The air-cooling fan 410 is attached to the intake port IP. The air-cooling fan 410 is configured to supply wind (air) to the intake port IP. The structure of the air-cooling fan 410 is not limited and, for example, includes an electric motor (not illustrated). The temperature sensor 420 is disposed at a central part of an XY plane of the power storage module 500 here. The temperature sensor 420 is, for example, a thermocouple, a thermistor, or the like.
The control device 430 is electrically connected to the temperature sensor 420 and the electric motor of the air-cooling fan 410. When the temperature sensor 420 detects that the temperature inside the power storage module 500 becomes a predetermined first temperature or more, for example, the control device 430 operates the air-cooling fan 410. Thus, air with low temperature outside the power storage module 500 is supplied into the power storage module 500 through the intake port IP, so that an air flow AF is generated inside the power storage module 500. The supplied air passes inside the power storage module 500 while cooling the power storage devices 100, and is discharged through the exhaust port OP. When the temperature sensor 420 detects that the temperature in the power storage module 500 becomes a predetermined second temperature or less, for example, the control device 430 stops the air-cooling fan 410. With the air-cooling type cooling device 400 described above, the power storage device 100 can be cooled at low cost.
Incidentally, according to the present inventors' examination, a temperature distribution can occur inside the power storage module 500 having a cooling mechanism, for example the cooling device 400, when the plurality of power storage devices 100 are charged and discharged, and accordingly, a low-temperature region A1 where the temperature is relatively low and a high-temperature region A2 where the temperature is relatively high can be generated. Specifically, as the power storage device 100 generates heat along with the charging and discharging, the adjacent power storage devices 100 generate heat mutually. Thus, at a central part in the arrangement direction X, heat is generated from the power storage devices 100 successively and the temperature tends to become high relatively. On the other hand, at both end parts in the arrangement direction X (front F part and rear Rr part in
In particular, in this embodiment, the intake port IP through which the coolant (air) is supplied and the air-cooling fan 410 are disposed on the front F side in the arrangement direction X and the exhaust port OP is disposed on the rear Rr side in the arrangement direction X. Accordingly, the temperature tends to become low at the both end parts in the arrangement direction X. Thus, the central part in the arrangement direction X tends to become the high-temperature region A2 where the temperature is relatively high and the both end parts in the arrangement direction X (front F part and rear Rr part in
For example, as also described in Japanese Patent Application Publication No. 2021-44212 and the like, if the temperature distribution occurs inside the power storage module 500, variation may occur in high-rate durability of the power storage devices 100. Specifically, the high-rate durability of the power storage devices 100 may decrease in the low-temperature region A1. In this case, if charging and discharging of the entire power storage module 500 are controlled based on the high-rate durability of the power storage devices 100 in the low-temperature region A1, the high high-rate durability of the power storage devices 100 in the high-temperature region A2 cannot be utilized sufficiently. On the other hand, if based on the high-rate durability of the power storage devices 100 in the high-temperature region A2, high voltage is applied to the power storage devices 100 in the low-temperature region A1 and high-rate deterioration tends to accelerate. In this manner, if the temperature distribution occurs inside the power storage module 500, the high-rate durability of the entire power storage module 500 may decrease following the high-rate durability of the power storage devices 100 in the low-temperature region A1. In a case where the power storage module is mounted on the moving body such as a vehicle, the fuel efficiency may deteriorate.
In view of this, first power storage devices 110 and second power storage devices 120 that are different from each other in terms of the concentration of the electrolyte salt are used as the plurality of power storage devices 100 in the art disclosed herein. In the first power storage device 110, the concentration of the electrolyte salt is closer to 1.1 mol/L (first concentration) than in the second power storage device 120. The present inventors' examination indicates that as the concentration of the electrolyte salt is closer to the first concentration, the high-rate durability becomes higher, which will be described in detail below. That is to say, the high-rate durability is the highest at the first concentration. Therefore, in this embodiment, the first power storage devices 110 in which the concentration of the electrolyte salt is relatively close to the first concentration (high-rate durability is high) are disposed in the low-temperature regions A1 with the relatively low temperature, which are the both end parts in the arrangement direction X (front F part and rear Rr part in
With such a structure, the high-rate durability of the plurality of power storage devices 100 can be equalized at a high level. Additionally, the acceleration of deterioration can be suppressed and the high-rate durability of the entire power storage module 500 can be improved. Since it is unnecessary to consider the concept of “cell group” that is given in the art disclosed in Japanese Patent Application Publication No. 2021-44212, the high-rate durability of the plurality of power storage devices 100 can be flexibly adjusted in accordance with the temperature distribution inside the power storage module 500. Therefore, the high-rate durability of the plurality of power storage devices 100 may be equalized with high accuracy compared to the art disclosed in Japanese Patent Application Publication No. 2021-44212. Moreover, the number of restriction mechanisms 300 can be reduced compared to the art disclosed in Japanese Patent Application Publication No. 2021-44212; thus, the volume energy density or the fuel efficiency can also be improved. Additionally, by reducing the number of components, the manufacturing cost can be reduced.
In the case where the plurality of first power storage devices 110 and the plurality of second power storage devices 120 exist as described in this embodiment, it is preferable that the concentration of the electrolyte salt be closer to the first concentration in each of the plurality of first power storage devices 110 than in the plurality of second power storage devices 120. Although not limited in particular, the concentration of the electrolyte salt is preferably in the range of about 0.5 to 2.0 mol/L and more preferably in the range of 0.8 to 1.5 mol/L in both the first power storage devices 110 and the second power storage devices 120 from the viewpoint of making the energy density and the high-rate durability balanced at a high level. In particular, when the concentration is a predetermined value or less, the high-rate charging characteristic of the power storage module 500 can be improved.
The specific value of the concentration of the electrolyte salt is a design matter that is adjusted as appropriate based on the temperature distribution inside the power storage module 500 or the like, for example. Therefore, although not limited in particular, in the case where the temperature distribution is largely different between the first power storage devices 110 and the second power storage devices 120, for example, the concentration of the electrolyte salt in the first power storage device 110 is preferably in a first range of about 1.1±0.2 mol/L (that is, 0.9 to 1.3 mol/L) and more preferably in the first range of 1.1±0.1 mol/L (that is, 1.0 to 1.2 mol/L). The concentration of the electrolyte salt in the second power storage device 120 is preferably in a second range that is out of the first range. That is to say, the concentration of the electrolyte salt is preferably less than 0.9 mol/L and more than 1.3 mol/L, and more preferably less than 1.0 mol/L and more than 1.2 mol/L. The concentration of the electrolyte salt in the second power storage device 120 is preferably 0.5 mol/L or more, and more preferably 0.8 mol/L or more, and is preferably 2.0 mol/L or less, and more preferably 1.5 mol/L or less. Thus, the effect of the art disclosed herein can be achieved more remarkably.
In one embodiment, the first power storage device 110 and the second power storage device 120 preferably include the same electrolyte salt in terms of the kind and composition. The first power storage device 110 and the second power storage device 120 may include the electrolyte salt that is formed of LiPF6. In this case, the electrolyte salt can be rephrased as LiPF6, that is, the concentration of LiPF6 in the first power storage device 110 is closer to 1.1 mol/L than in the second power storage device 120.
In one embodiment, the first power storage device 110 and the second power storage device 120 more preferably include the same nonaqueous solvent in terms of the kind and composition. Thus, the battery performance other than the high-rate durability can be easily equalized between the first power storage devices 110 and the second power storage devices 120. The first power storage device 110 and the second power storage device 120 may include the nonaqueous solvent that is formed of carbonates. In particular, a mixed solvent including the cyclic carbonate and the chain carbonate is preferable.
In one embodiment, the first power storage device 110 and the second power storage device 120 preferably have the same structure other than the nonaqueous electrolyte solution; in particular, the structure of the electrode body 20 is preferably the same (error in manufacture or the like is allowable). Thus, the energy density can be equalized between the first power storage devices 110 and the second power storage devices 120 and the high energy density as the entire power storage module 500 can be achieved.
Next, the manufacturing method for the power storage module 500 including the plurality of power storage devices 100 is described. For example, the power storage module 500 can be manufactured by the manufacturing method including the following steps: (step A) a preparing step of preparing the first power storage devices 110 and the second power storage devices 120; (step B) a temperature distribution predicting step of predicting the temperature distribution inside the power storage module 500; and (step C) a constructing step of constructing the power storage module 500 by combining the first power storage devices 110 and the second power storage devices 120. Note that the order of (step A) the preparing step and (step B) the temperature distribution predicting step is not limited in particular and for example, (step B) the temperature distribution predicting step may be performed after (step A) the preparing step, (step A) the preparing step may be performed after (step B) the temperature distribution predicting step, or both steps may be performed at the same time. The manufacturing method disclosed herein may further include another step at an optional stage.
In (step A) the preparing step, the first power storage devices 110 in which the concentration of the electrolyte salt is relatively close to 1.1 mol/L and the second power storage devices 120 in which the concentration of the electrolyte salt is relatively far from 1.1 mol/L are prepared as the plurality of power storage devices 100. In this embodiment, (step A) the preparing step includes (A-1) an electrolyte solution preparing step of preparing the nonaqueous electrolyte solution, (A-2) an accommodating step of accommodating the electrode body 20 and the prepared nonaqueous electrolyte solution in the battery case 10, and (A-3) a conditioning step in this order.
In (A-1) the electrolyte solution preparing step, at least two kinds of nonaqueous electrolyte solutions in which the concentration of the electrolyte salt is different are prepared. Specifically, a first electrolyte solution for the first power storage device 110, in which the concentration of the electrolyte salt is relatively close to 1.1 mol/L, and a second electrolyte solution for the second power storage device 120, in which the concentration of the electrolyte salt is relatively far from 1.1 mol/L, are prepared. The first electrolyte solution and the second electrolyte solution may be a commercial product that is purchased, or may be prepared by a conventionally known method. In a preferred embodiment, for example, the aforementioned electrolyte salt (for example, LiPF6) is added to a mixed solvent (nonaqueous solvent) including two or more kinds of organic solvents and the mixture is stirred and mixed until homogenized. Thus, the first electrolyte solution for the first power storage device 110 and the second electrolyte solution for the second power storage device 120 are prepared.
In (A-2) the accommodating step, the electrode body 20 prepared separately is accommodated in the battery case 10 together with the first electrolyte solution and the second electrolyte solution. In a preferred embodiment, first, the positive electrode tab group 23 of the electrode body 20 is joined to the positive electrode current collecting part 50 and the negative electrode tab group 25 of the electrode body 20 is joined to the negative electrode current collecting part 60. Thus, the sealing plate 14 and the electrode body 20 are integrated. Next, the opening 12h of the exterior body 12 is covered with the sealing plate 14 and the electrode body 20 is disposed inside the exterior body 12. Subsequently, the sealing plate 14 is welded to the periphery of the opening 12h of the exterior body 12 to integrate the exterior body 12 and the sealing plate 14. Then, the first electrolyte solution and the second electrolyte solution are injected into the battery case 10 through the liquid injection hole 15 of the sealing plate 14. Thus, a battery assembly for the first power storage device 110 and the battery assembly for the second power storage device 120 are manufactured.
In (A-3) the conditioning step, the manufactured battery assembly is charged at least once. The manufactured battery assembly is preferably charged and discharged at least once. The battery assembly can be charged and discharged similarly to the conventional charging and discharging. Typically, an external power source is connected between the positive electrode terminal 30 and the negative electrode terminal 40, and charging or discharging is performed until a predetermined state of charge (SOC) is achieved between the terminals. Then, the battery case 10 is hermetically sealed (closed). In this manner, the first power storage devices 110 and the second power storage devices 120 that are different from each other in terms of the concentration of the electrolyte salt can be prepared.
In (step B) the temperature distribution predicting step, the temperature distribution inside the power storage module 500 when the plurality of power storage devices 100 are charged and discharged is predicted. That is to say, in an aspect illustrated in
Additionally, the range of the low-temperature region A1 (the length in the arrangement direction X), for example, can also change depending on the number of power storage devices 100, the charging and discharging conditions, and the like. Accordingly, it is preferable to predict the temperature distribution inside the power storage module 500 at the charging and discharging by preliminary experiments, simulation using commercial analysis software, or the like. In particular, it is preferable to measure the temperature distribution actually by constructing the power storage module for preliminary tests for simulating the power storage module 500, and predict the temperature distribution inside the power storage module 500 on the basis of the actual measurements.
In a preferred embodiment, first, a plurality of power storage devices for the preliminary tests, which are different from the first power storage devices 110 and the second power storage devices 120 manufactured in the preparing step, are prepared and a temperature sensor is attached to each of the plurality of power storage devices. Next, using the plurality of power storage devices for the preliminary tests, the power storage module for the preliminary tests for simulating the power storage module 500 is assembled. Next, the plurality of power storage devices for the preliminary tests are actually charged and discharged (preferably charged and discharged at a high rate) and the temperature distributions at this time are acquired. The charging and discharging conditions are preferably the conditions in consideration of the mode of the actual use. Then, based on the acquired temperature distributions, the temperature distribution inside the power storage module 500 is predicted and the inside of the power storage module 500 is sectioned into, for example, the low-temperature region A1 and the high-temperature region A2 (for example, divided into two).
In (step C) the constructing step, the first power storage devices 110 and the second power storage devices 120 are disposed to construct the power storage module 500 on the basis of the temperature distribution predicted in the temperature distribution predicting step. Specifically, in a region sectioned as the low-temperature region A1, the first power storage devices 110 in which the concentration of the electrolyte salt is relatively close to 1.1 mol/L are disposed and in a region sectioned as the high-temperature region A2, the second power storage devices 120 in which the concentration of the electrolyte salt is relatively far from the 1.1 mol/L are disposed. Then, the first power storage devices 110 and the second power storage devices 120 are restricted by the restriction mechanism 300 together with the plurality of spacers 200, for example, and are held integrally. The power storage module 500 can be constructed as above.
The power storage module 500 can be used for various applications, but since the power storage module 500 has the excellent high-rate durability, the power storage module 500 can be suitably used in an application in which high output is needed, for example, as a motive power source for a motor (power source for driving) that is mounted on a vehicle such as a passenger car or a truck. The vehicle is not limited to a particular type, and may be, for example, a plug-in hybrid electric vehicle (PHEV), a hybrid electric vehicle (HEV), or a battery electric vehicle (BEV). By mounting the power storage module 500 on the moving body such as a vehicle, the fuel efficiency (electricity efficiency) of the moving body can be improved.
Several test examples relating to the present disclosure will be explained below, but the present disclosure is not meant to be limited to these test examples.
In these test examples, the power storage devices in which the concentration of the electrolyte salt was different were constructed and the high-rate durability was checked. Specifically, first, the nonaqueous electrolyte solutions using LiPF6 as the electrolyte salt and including the electrolyte salt (LiPF6) at the concentrations shown in Table 1 were prepared and the power storage devices (lithium ion secondary batteries, Examples 1 to 3) were manufactured using the nonaqueous electrolyte solutions. Note that the nonaqueous solvent was a mixed solvent in which the carbonates, specifically EC, DMC, and EMC were mixed at a volume ratio of EC:DMC:EMC=30:40:30 in all the power storage devices. The structure other than the nonaqueous electrolyte solution (electrode body and the like) is also common among all the power storage devices. Next, under an environment with a temperature of 25° C., the SOC of the power storage device was adjusted to 50% and constant-current discharging was performed at 150 A for 10 seconds; then, the discharging resistance was measured. Subsequently, a battery voltage ΔV dropped in 10 seconds was read and based on the battery voltage ΔV and the discharging current value (150 A), IV resistance (initial resistance) was calculated.
Next, under the environment with a temperature of 25° C., the SOC of the power storage device was adjusted to 50%, constant-current charging was performed at a charging rate of 150 A for 10 seconds, which was followed by 5-second rest, and then constant-current discharging was performed at a discharging rate of 10 A for 150 seconds, which was followed by 5-second rest. These charging and discharging are regarded as one cycle, and 1000 cycles were repeated to perform the high-rate durability test. After the high-rate durability test, the IV resistance was measured similarly to the initial resistance, and from the ratio of the IV resistance after the durability test to the initial resistance (IV resistance after the durability test/initial resistance), the resistance increase rate was calculated. The results are shown in Table 1. Note that Table 1 shows the relative values when the resistance increase rate in Example 1 is 1.00 (standard).
As shown in Table 1, in the power storage device in which the concentration of the electrolyte salt was 1.1 mol/L, the increase in resistance after the high-rate durability test was suppressed to be the smallest, that is, the high-rate durability was the highest, although the reason is not clear. In other words, it has been suggested that as the concentration of the electrolyte salt is far from 1.1 mol/L, the resistance after the high-rate durability test increased more, that is, the high-rate durability decreased. Accordingly, the experiment results have also proved that the power storage device in which the concentration of the electrolyte salt is close to 1.1 mol/L is relatively superior to the power storage device in which the concentration of the electrolyte salt is far from 1.1 mol/L, in terms of the high-rate durability.
Although the preferable embodiments of the present disclosure have been described above, they are merely examples. The present disclosure can be implemented in various other modes. The present disclosure can be implemented based on the contents disclosed in the present specification and the technical common sense in the relevant field. The techniques described in the scope of claims include those in which the embodiments exemplified above are variously modified and changed. For example, another modification can replace a part of the aforementioned embodiment or be added to the aforementioned embodiment. Additionally, the technical feature may be deleted as appropriate unless such a feature is described as an essential element.
(1) For example, in the aforementioned embodiment, in (step A) the preparing step, the power storage devices 100 in which the concentration of the electrolyte salt was varied on purpose were manufactured. However, the present disclosure is not limited to this. In another example, the first power storage devices 110 and the second power storage devices 120 can be selected and prepared in a predetermined range of good products from a number of power storage devices in which the concentration of the electrolyte salt varies.
Specific examples include a case where used power storage devices (which may be in the state of the power storage module) are collected from the market and reused, that is, the power storage devices 100 are the reused products. In recent years, some power storage devices such as a lithium ion secondary battery may have identification information from the viewpoint of traceability or the like. In one example, an optical symbol that is readable by a reading device is given on a surface of the power storage module (for example, sealing plate 14). Alternatively, a small substrate including identification information is mounted inside the power storage device, for example. The identification information may include, for example, ID information such as a model number, the names of a manufacturer, a country of manufacture, and a factory of manufacture, and the date of manufacture and additionally, the material information such as the kind of positive electrode active material, the kind of negative electrode active material, or the kind or concentration of the electrolyte salt.
In this case, (step A) the preparing step may include (A-a) an acquiring step of reading out the identification information given to a number of collected power storage devices and acquiring information about the concentration of the electrolyte salt and (A-b) a selecting step of selecting the first power storage devices 110 in which the concentration of the electrolyte salt is relatively close to 1.1 mol/L and the second power storage devices 120 in which the concentration of the electrolyte salt is relatively far from 1.1 mol/L, based on the acquired information about the concentration. The manufacturing method for the power storage module as described above can be grasped as a method of reusing the power storage device. Note that in the present specification, the term “optical symbol” is a generic term of information media that store information by a combination of a part with high optical reflectivity and a part with low optical reflectivity, and is a concept encompassing two-dimensional symbols (also referred to as two-dimensional code, two-dimensional barcode, or the like) such as QR code (registered trademark), data matrix, and data tags.
(2) In the aforementioned embodiment in
In this case, for example, as illustrated in
In these cases, for example, as illustrated in
The allocation of the low-temperature region A1 and the high-temperature region A2 may vary depending on, for example, the number of power storage devices 100, the charging and discharging conditions, and the like. Therefore, the low-temperature region A1 and the high-temperature region A2 may be provided uniformly in the arrangement direction X as illustrated in
In this case, for example, as illustrated in
Note that although the inside of the power storage module 500 is sectioned into three temperature regions in
As described above, the following items are given as specific aspects of the art disclosed herein.
Item 1: The power storage module including the plurality of power storage devices, in which each of the plurality of power storage devices includes the electrode body and the nonaqueous electrolyte solution, the nonaqueous electrolyte solution contains the nonaqueous solvent and the electrolyte salt, the low-temperature region with relatively low temperature and the high-temperature region with relatively high temperature exist in the power storage module when the plurality of power storage devices are charged and discharged, and in the first power storage device disposed in the low-temperature region among the plurality of power storage devices, the concentration of the electrolyte salt is closer to 1.1 mol/L than in the second power storage device disposed in the high-temperature region.
Item 2: The power storage module according to Item 1, in which both the first power storage device and the second power storage device contain LiPF6 as the electrolyte salt.
Item 3: The power storage module according to Item 1 or 2, in which the concentration of the electrolyte salt in the first power storage device is in the first range of 1.1±0.2 mol/L (0.9 mol/L or more and 1.3 mol/L or less), and the concentration of the electrolyte salt in the second power storage device is in the second range that is out of the first range.
Item 4: The power storage module according to any one of Items 1 to 3, in which the middle-temperature region with the temperature higher than the temperature in the low-temperature region and lower than the temperature in the high-temperature region exists between the low-temperature region and the high-temperature region inside the power storage module, and the plurality of power storage devices are disposed so that the concentration of the electrolyte salt gradually becomes closer to 1.1 mol/L in the order of the high-temperature region, the middle-temperature region, and the low-temperature region.
Item 5: The power storage module according to any one of Items 1 to 4, in which in both the first power storage device and the second power storage device, the concentration of the electrolyte salt is in the range of 0.8 mol/L or more and 1.5 mol/L or less.
Item 6: The power storage module according to any one of Items 1 to 5, in which both the first power storage device and the second power storage device contain carbonates as the nonaqueous solvent.
Item 7: The manufacturing method for the power storage module including the plurality of power storage devices, in which each of the plurality of power storage devices includes the electrode body and the nonaqueous electrolyte solution and the nonaqueous electrolyte solution includes the nonaqueous solvent and the electrolyte salt, the manufacturing method including: the preparing step of preparing, as the plurality of power storage devices, the first power storage device in which the concentration of the electrolyte salt is relatively close to 1.1 mol/L and the second power storage device in which the concentration of the electrolyte salt is relatively far from 1.1 mol/L; the temperature distribution predicting step of predicting the temperature distribution inside the power storage module when the plurality of power storage devices are charged and discharged; and the constructing step of constructing the power storage module by disposing the first power storage device in the low-temperature region with relatively low temperature and disposing the second power storage device in the high-temperature region with relatively high temperature, based on the temperature distribution.
Number | Date | Country | Kind |
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2023-058822 | Mar 2023 | JP | national |