Battery management system and vehicle

Abstract

Provided is a system enabling high-accuracy estimation by acquiring highly accurately data pertaining to the internal states of a battery, such as the SOC-OCV property and FCC, even in cases of repeated charging and discharging over a long term. This battery management system includes a vehicle provided with a means enabling transmission and receipt of data, wherein: the vehicle comprises a battery, a balance circuit electrically connected to the battery, and a vehicle control unit having the function of controlling the balance circuit; the battery comprises a battery pack that includes a plurality of power cells; the vehicle control unit has a function of selecting an estimated value close also to the state of the power cells included in the battery pack; and the balance circuit has a function of being controlled on the basis of the selected estimated value.

Description

[Technical Field]

[0001] One aspect of the present invention relates to a storage battery management system. Another aspect of the present invention relates to a server device or a computer program used in the storage battery management system. Another aspect of the present invention relates to a storage battery management system using a neural network.

[0002] Another embodiment of the present invention relates to a vehicle equipped with a storage battery management system. Another embodiment of the present invention relates to an electronic device equipped with the storage battery management system. Furthermore, the present invention is not limited to vehicles and electronic devices, and one embodiment of the present invention relates to a power storage device for storing power obtained from a power generation facility such as a solar power generation panel.

[0003] One embodiment of the present invention is not limited to the above technical fields, but relates to a semiconductor device, a display device, a light-emitting device, a recording device, a driving method thereof, or a manufacturing method thereof. That is, the technical field of one embodiment of the invention disclosed in this specification and the like relates to an object, a method, or a manufacturing method. [Background technology]

[0004] Storage batteries, such as lithium-ion secondary batteries, have become indispensable in modern society as reusable energy sources. While lithium-ion secondary batteries offer high output and high energy density, they are known to pose high safety risks due to overcharging and overdischarging. Therefore, when using lithium-ion secondary batteries, it is necessary to understand and manage the internal state of the battery, such as the charge rate and internal resistance.

[0005] Known estimation methods for grasping the internal state include the coulomb counting method, the open circuit voltage (OCV) method, and the Kalman filter (see, for example, Patent Document 1). In estimation methods such as the Kalman filter, it is important to obtain data related to the internal state of the storage battery, such as the state of charge (SOC)-OCV characteristics and the full charge capacity (FCC), with high accuracy. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] WO2019 / 193471 Brochure Summary of the Invention [Problem to be solved by the invention]

[0007] Although not taken into consideration in Patent Document 1, repeated charging and discharging over a long period of time can cause deterioration of a storage battery. Furthermore, errors can accumulate in the measured values ​​of a storage battery. As a result, there is a risk of a decrease in the accuracy of data related to the internal state, such as SOC-OCV characteristics and FCC. Furthermore, managing a storage battery with inaccurate data related to the internal state also reduces the accuracy of estimation, which could result in accelerated deterioration of the storage battery or put the storage battery in a dangerous state.

[0008] For example, in order to obtain highly accurate SOC-OCV characteristic data, it is desirable to acquire a large amount of data. Acquiring a large amount of data includes collecting a large amount of data over time. However, if the amount of data is large, the amount of data used by the control unit or memory unit of the storage battery or the vehicle equipped with the storage battery may exceed the processing capacity, raising concerns about insufficient computing power. In such a situation, estimation processing, etc., takes time, and there is also concern about a decrease in estimation accuracy.

[0009] In view of the above, an object of one embodiment of the present invention is to provide a battery management system, a vehicle, or a server device that enables highly accurate estimation of internal states of a battery, such as SOC-OCV characteristics and FCC, even when charging and discharging are repeated for a long period of time.

[0010] Another object of one embodiment of the present invention is to provide a system or a method that enables highly accurate estimation of the storage battery in a short time.

[0011] Note that the description of these problems does not preclude the existence of other problems. Note that one embodiment of the present invention does not necessarily solve all of these problems. Note that it is possible to extract problems other than these from the description of the specification, drawings, and claims (hereinafter referred to as the specification, etc.). [Means for solving the problem]

[0012] One aspect of the present invention is a battery management system having a vehicle equipped with means for transmitting and receiving data, wherein the vehicle has a battery, a balancing circuit electrically connected to the battery, and a vehicle control unit having a function of controlling the balancing circuit, the battery has a battery pack having a plurality of battery cells, the vehicle control unit has a function of selecting an estimated value that is closest to the state of the battery cells in the battery pack, and the balancing circuit has a function of being controlled based on the selected estimated value.

[0013] Another aspect of the present invention is a battery management system having a server device and a vehicle equipped with means for transmitting and receiving data to and from the server device, wherein the vehicle has a storage battery, a balancing circuit electrically connected to the storage battery, and a vehicle control unit having a function of controlling the balancing circuit, and the storage battery has a battery pack having a plurality of battery cells, the server device has a function of calculating at least two or more estimated values ​​based on first data regarding the internal state of the battery pack transmitted from the vehicle and a function of transmitting the two or more estimated values ​​to the vehicle, the vehicle control unit has a function of selecting, from the two or more estimated values, an estimated value that is closest to the state of the battery cells of the battery pack, and the balancing circuit has a function of being controlled based on the selected estimated value.

[0014] In any one of the above battery management systems, the first data preferably includes sequential data relating to an internal state of the battery pack.

[0015] In any one of the above battery management systems, the sequential data preferably includes an SOC-OCV characteristic.

[0016] In any one of the above storage battery management systems, the sequential data preferably includes an internal resistance.

[0017] In any one of the above battery management systems, the internal resistance preferably includes a fast-response resistance component R1 and a slow-response resistance component R2.

[0018] In any one of the above storage battery management systems, the server device preferably has a function of predicting changes in the fast-response resistance component R1 and the slow-response resistance component R2 using LSTM (Long Short-Term Memory).

[0019] Another embodiment of the present invention is a vehicle including a storage battery, a balancing circuit electrically connected to the storage battery, and a vehicle control unit having a function of controlling the balancing circuit, wherein the storage battery includes a battery pack having a plurality of battery cells, the vehicle control unit having a function of selecting an estimated value that is closest to the state of each battery cell of the battery pack from two or more estimated values ​​transmitted from a server device, and the balancing circuit having a function of being controlled based on the selected estimated value.

[0020] In any one of the above-described vehicles, the server device preferably has sequential data relating to the internal state of the battery pack transmitted from the vehicle.

[0021] In any one of the above-described vehicles, the sequential data preferably includes SOC-OCV characteristics.

[0022] In any one of the above-described vehicles, the sequential data preferably includes an internal resistance.

[0023] In any one of the above-described vehicles, the internal resistance preferably includes a fast-response resistance component R1 and a slow-response resistance component R2.

[0024] In any one of the above-described vehicles, the internal resistance preferably includes a measured value for each of the plurality of battery cells.

[0025] In any one of the above-described vehicles, it is preferable that the vehicle has a function of measuring the internal resistance by a current-rest method.

[0026] Another embodiment of the present invention is a server device that has a function of receiving first data regarding an internal state of a battery cell in a battery pack transmitted from a vehicle having the battery pack, a function of calculating at least two or more estimated values ​​using the first data and a first algorithm, and a function of transmitting the two or more estimated values ​​to the vehicle.

[0027] In any one of the above server devices, the first data preferably includes sequential data relating to an internal state of the battery pack.

[0028] In any one of the above server devices, the sequential data preferably includes SOC-OCV characteristics.

[0029] In any one of the above server devices, the sequential data preferably includes an internal resistance.

[0030] In any one of the above server devices, the internal resistance preferably includes a fast-response resistance component R1 and a slow-response resistance component R2.

[0031] In any one of the above server devices, it is preferable that the server device has a function of predicting changes in the fast-response resistance component R1 and the slow-response resistance component R2 by using LSTM. [Effects of the Invention]

[0032] According to the present invention, it is possible to perform estimation processing regarding the internal state of a storage battery with high accuracy and in a short time. Even when the storage battery has a battery pack, it is possible to perform estimation processing regarding the internal state of the storage battery with high accuracy and in a short time.

[0033] Note that the description of these effects does not preclude the existence of other effects. Note that one embodiment of the present invention does not necessarily have all of these effects. Note that effects other than these will become apparent from the description in the specification, drawings, claims, etc., and it is possible to extract other effects from the description in the specification, drawings, claims, etc. [Brief explanation of the drawings]

[0034] 1A and 1B are conceptual diagrams of a battery management system according to one embodiment of the present invention. FIG. 2 is a conceptual diagram of a vehicle according to one embodiment of the present invention. FIG. 3 is a diagram illustrating a balancing process or a balance circuit according to one embodiment of the present invention. FIG. 4 is a diagram illustrating a processing method for SOC-OCV characteristic data according to one embodiment of the present invention. FIG. 5 is a diagram illustrating a description method of SOC-OCV characteristic data according to one embodiment of the present invention. FIG. 6 is a diagram illustrating a processing method relating to FCC and internal resistance, which is one embodiment of the present invention. FIG. 7 is a diagram illustrating a method for estimating internal resistance according to one aspect of the present invention. FIG. 8 shows a method for analyzing current resting method measurements. 9A and 9B are examples of analysis results of current rest method measurements. 10A to 10C illustrate a positive electrode that is one embodiment of the present invention. 11A and 11B are diagrams illustrating an all-solid-state secondary battery according to one embodiment of the present invention. FIG. 12 illustrates a method for manufacturing a positive electrode active material according to one embodiment of the present invention. FIG. 13 illustrates a method for manufacturing a positive electrode active material according to one embodiment of the present invention. 14A to 14C illustrate a method for manufacturing a secondary battery according to one embodiment of the present invention. 15A and 15B are diagrams illustrating the appearance of a secondary battery according to one embodiment of the present invention. 16A to 16C are diagrams illustrating the appearance of a secondary battery according to one embodiment of the present invention. 17A to 17C are diagrams illustrating the appearance of a secondary battery according to one embodiment of the present invention. 18A to 18D are diagrams illustrating the appearance of a secondary battery according to one embodiment of the present invention. 19A to 19D are diagrams illustrating a vehicle according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0035] Hereinafter, examples of embodiments of the present invention will be described with reference to the drawings, etc. However, the present invention should not be construed as being limited to the following examples. The embodiments of the present invention can be modified within the scope of the spirit of the present invention.

[0036] In this specification, crystal planes and crystal directions are expressed using Miller indices. Individual planes indicating crystal planes are expressed using ( ). In crystallography, crystal planes, crystal directions, and space groups are expressed with a bar above the number, but in this specification, due to formatting restrictions, they may be expressed with a - (minus sign) before the number instead of a bar above the number.

[0037] In this specification, the theoretical capacity of a positive electrode active material refers to the amount of electricity when all of the intercalable lithium contained in the positive electrode active material is deintercalated. For example, the theoretical capacity of LiCoO2 is 274 mAh / g, that of LiNiO2 is 275 mAh / g, and that of LiMn2O4 is 148 mAh / g.

[0038] In this specification, the term "storage battery" refers to all elements and devices that have a power storage function, including, for example, secondary batteries such as lithium ion secondary batteries, lithium ion capacitors, and electric double layer capacitors.

[0039] In this specification and the like, the term "electricity storage device" includes a device for storing electric power obtained from a power generation facility such as a solar power generation panel.

[0040] In this specification and the like, electronic equipment refers to all devices that have a storage battery, and electro-optical devices that have a storage battery, information terminal devices that have a storage battery, and the like are all electronic equipment.

[0041] In this specification and the like, a semiconductor device refers to an element, circuit, device, or the like that can function by utilizing semiconductor characteristics. As one example, a semiconductor element such as a transistor or a diode is a semiconductor device. As another example, a circuit having a semiconductor element is a semiconductor device. As yet another example, a device including a circuit having a semiconductor element is a semiconductor device.

[0042] (Embodiment 1) In this embodiment, a battery management system according to one embodiment of the present invention will be described.

[0043] 1A and 1B are conceptual diagrams of a battery management system. The battery management system includes a server device 1 and a vehicle 3 equipped with a battery pack (also referred to as a battery pack) 4 having multiple battery cells and a means for transmitting and receiving data to and from the server device 1. In this battery management system, the server device 1 can estimate the internal states of the battery cells, and the vehicle 3 can receive the results of the estimation. That is, the server device 1 can estimate the internal states of the battery cells, which was previously performed by the vehicle 3. To have the server device 1 estimate the internal states of the battery cells, data (including measured data or estimated data) related to the internal states of the battery cells can be sequentially transmitted from the vehicle 3 to the server device 1. Sequentially transmitted data is sometimes referred to as sequential data. Although the sequential data has a large number of data items, they are recorded, i.e., stored, by the server device 1, and do not impose a burden on the storage unit of the vehicle 3. Furthermore, it is desirable that the server device 1 estimates, based on the sequential data, two or more pieces of data (sometimes referred to as estimated values) for each battery cell. Because the server device 1 executes the estimation process, it is possible to perform the estimation process even while the vehicle is moving, allowing for time to be spent on the estimation process. Furthermore, even taking into account the computing power of the server device 1, it is possible to calculate two or more estimated values. The server device 1 then transmits two or more estimated values ​​to the vehicle 3, and the vehicle 3 can select the most appropriate one from the two or more estimated values. The vehicle 3 selects the received estimated value without performing the estimation process. Note that the estimated value not selected may contain an error, which is the reason why the vehicle 3 made that decision. The vehicle 3 can return multiple pieces of information regarding the selected estimated value, the unselected estimated value, and the error to the server device 1. This system enables highly accurate and quick estimation of the internal state of the storage battery. Furthermore, the accuracy of the estimated value increases as the transmission and reception of estimated values ​​between the server device 1 and the vehicle 3 is repeated multiple times, which is preferable.

[0044] The current, voltage, and temperature of the battery cell can be measured using sensors and the like installed in the vehicle 3. For example, the current of the battery cell can be measured as an integrated value using coulomb counting. These measured values ​​can be used to estimate the internal state of the battery cell. Estimating the internal state includes estimating the SOC-OCV characteristics, estimating the FCC, or estimating the internal resistance (R). When estimating the SOC-OCV characteristics, the battery management system can be described as a battery SOC estimation system.

[0045] The server device 1 can execute one or more of the above-described internal state estimations. Any estimation not executed by the server device 1 may be executed by the vehicle 3. For example, the estimation of internal resistance (R), which requires a small data volume, may be executed by the vehicle 3.

[0046] 1B is a conceptual diagram of a battery management system used in a plurality of vehicles, which may be the same model or different models.

[0047] The server device 1 preferably functions as a cloud server, an AI (Artificial Intelligence) server, or a GPU (Graphics Processing Unit) server. The server device 1 preferably has an algorithm with a neural network, and the battery management system can be said to be a battery management system with artificial intelligence. In addition to the GPU, it is preferable that the server device 1 has a CPU (Central Processing Unit). Having a GPU or CPU enables high-speed calculation processing.

[0048] The storage battery pack 4 has multiple battery cells (so-called assembled battery). Because the battery pack 4 has multiple battery cells, the amount of data relating to the internal state is enormous. However, in one aspect of the present invention, the data can be recorded, i.e., saved, in the server device 1. Furthermore, the server device 1 can perform estimation processing based on the data, which is preferable because it does not place a burden on the control unit or memory unit of the vehicle 3.

[0049] The server device 1 and the vehicle 3 can transmit and receive data to and from each other via the communication network 7. That is, the server device 1 and the vehicle 3 each have communication means compatible with the communication network 7. Data can be transmitted and received at any time, but it is preferable to transmit and receive data while the vehicle 3 is being charged. During the charging period, the server device 1 should execute an estimation process and transmit and receive estimated values.

[0050] The data communication between the server device 1 and the vehicle 3 is not limited to one-to-one direct data communication, but may also be via the charger 2, electronic devices (including battery devices owned by the passenger), an internet line, a communication relay device, a communication base station, etc. The data communication method for the communication network 7 may be wired communication or wireless communication. When wireless communication is used, wireless communication conforming to communication standards such as the fourth generation mobile communication system (4G) and the fifth generation mobile communication system (5G) may be used. The signal frequency of the wireless communication may be any of the following frequencies: submillimeter waves (300 GHz to 3 THz), millimeter waves (30 GHz to 300 GHz), microwaves (3 GHz to 30 GHz), ultra-high frequency waves (300 MHz to 3 GHz), ultra-high frequency waves (30 MHz to 300 MHz), short waves (3 MHz to 30 MHz), medium waves (300 kHz to 3 MHz), long waves (30 kHz to 300 kHz), and ultra-high frequency waves (3 kHz to 30 kHz).

[0051] The charger 2 may have the above-mentioned communication means compatible with the communication network 7 for data transmission and reception.

[0052] As shown in FIGS. 1A and 1B, the data includes first data 11 sent from the vehicle 3 to the server device 1 and second data 12 sent from the server device 1 to the vehicle 3.

[0053] The first data 11 relates to the battery cells of the storage battery pack 4 and includes data measured by sensors in the vehicle 3 or data estimated based on the measurement data. Types of data related to the storage battery pack 4 include FCC, internal resistance (R), and SOC-OCV characteristic data. The data may further include an integrated charge amount. The integrated charge amount of the storage battery pack 4 is either or both of the integrated charge amount since it was installed in the vehicle 3 and the integrated charge amount since the previous data transmission. If both are true, there will be two pieces of data indicating the integrated charge amount of the storage battery pack 4. The first data 11 may also include error data.

[0054] The second data 12 is related to the storage battery pack 4 and includes estimated data (estimated values). The types of estimated values ​​related to the storage battery pack 4 include FCC, an internal resistance (R) value, SOC-OCV characteristic data, and data related to the integrated charge amount.

[0055] The estimated second data 12 preferably has two or more estimated values, such as estimated SOC-OCV characteristic data A and estimated SOC-OCV characteristic data B. In such a case, the vehicle 3 can select either data A or data B to be used as an estimated value of the SOC-OCV of the storage battery pack 4, and the estimated value is used to perform balancing processing as needed.

[0056] The first data 11 and the second data 12 can also be transmitted and received between the server device 1 and the vehicle 3 without going through the charger 2, and the vehicle 3 may preferably have a communication means.

[0057] 1B, there are multiple first data (first data 11a and second data 11b) sent from multiple chargers (first charger 2a and second charger 2b) and multiple vehicles (first vehicle 3a and second vehicle 3b) to server device 1, and multiple second data (second data 12a and second data 12b) sent from server device 1 to the multiple chargers and multiple vehicles, respectively. The multiple first data and the multiple second data can be exchanged with server device 1 simultaneously.

[0058] Although multiple chargers are shown in FIG. 1B, the battery management system of the present invention can also be used when multiple vehicles charge at one charger.

[0059] The battery management system of the present invention may be used after a passenger is registered. When registering a passenger, vehicle information can also be registered, allowing the vehicle information to be known in advance. The vehicle information includes initial value data, and the types of initial value data related to the battery pack 4 include the internal resistance (R) value, SOC-OCV characteristic data, FCC, etc. The initial values ​​can be known, for example, during aging before shipping the battery pack or vehicle.

[0060] FIG. 2 shows a detailed configuration example of vehicle 3. Vehicle 3 has a power receiving connector 5, and can be charged by plugging the power receiving connector 5 into charger 2. Charger 2 may also be equipped with a power receiving connector. Charger 2 is installed at home, at a charging station, in a public parking lot, or the like. Vehicle 3 is configured as a plug-in hybrid vehicle, an EV vehicle, or an industrial vehicle such as an electric forklift, which can charge storage battery pack 4 using power from charger 2.

[0061] As shown in FIG. 2, the storage battery pack 4 includes a storage battery (secondary battery) 41. The secondary battery 41 includes a battery pack having a plurality of battery cells. When the carrier ions of the secondary battery 41 are lithium ions, the secondary battery is referred to as a lithium-ion secondary battery. A nickel-metal hydride battery may also be used as the secondary battery 41. The storage battery pack 4 may also be referred to as a battery.

[0062] The secondary battery 41 is electrically connected to the power receiving connector 5 via at least a first switch SW11 and a second switch SW12. The first switch SW11 is electrically connected to the negative terminal of the secondary battery 41, and the second switch SW12 is electrically connected to the positive terminal of the secondary battery 41.

[0063] A power control unit 42 is electrically connected to the secondary battery 41, and a drive motor 43 is electrically connected to the power control unit 42. The power control unit 42 has a function of converting DC power supplied from the secondary battery 41 into AC power and outputting it to the drive motor 43. The power control unit 42 has, for example, an inverter circuit capable of the above conversion.

[0064] Furthermore, when the vehicle 3 decelerates or stops, the power control unit 42 may have a function of converting the AC power generated by the drive motor 43 into DC power and outputting the DC power to the secondary battery 41. In other words, the secondary battery 41 may store the regenerative power generated by the drive motor 43.

[0065] The secondary battery 41 has an assembled battery that includes multiple battery cells 44(1) to 44(n) (where n is a natural number equal to or greater than 2), which are connected in series. The assembled battery determines the cell balance state during charging, and if cell balancing is not possible, a balancing process is performed. The balancing process is preferably completed during charging using an estimated SOC of each battery cell.

[0066] Estimation of the SOC-OCV characteristics is important in the balancing process. The estimated values ​​of the SOC-OCV characteristics sent from the server device 1 are preferably in the form of a table, and the vehicle 3 can select the SOC-OCV characteristics that are optimal for the actual battery pack from the table, create a table for the vehicle 3, and complete the estimation of the SOC-OCV characteristics. The table for the vehicle 3 may be created by selecting the optimal SOC-OCV characteristics (table) from multiple SOC-OCV characteristics (tables) sent from the server device 1.

[0067] Furthermore, the server device 1 may transmit stored information on the health of the battery cells (FCC / FCC0, where FCC0 is the initial value of the full charge capacity) to the vehicle 3. The accuracy of the table for the vehicle 3 can be improved by using the health of the battery cells.

[0068] A balancing circuit 45 is electrically connected to the secondary battery 41 shown in FIG. 2 for balancing purposes. Balancing circuits 45 are available in active and passive types. An active type is a balancing circuit that distributes and balances the capacity among multiple battery cells connected in series. A passive type is a balancing circuit that balances the capacity by consuming the capacity of some of the battery cells in the assembled battery. Although FIG. 2 shows an example in which a passive type balancing circuit is used as the balancing circuit 45, an active type balancing circuit may also be used.

[0069] The balancing circuit 45 has at least a plurality of resistors 46(1) to 46(n) (where n is a natural number of 2 or greater) corresponding to a plurality of battery cells 44(1) to 44(n).

[0070] The balancing circuit 45 also has at least a plurality of switches SW21(1) to SW21(n) (where n is a natural number greater than or equal to 2) corresponding to a plurality of battery cells 44(1) to 44(n) and a plurality of resistors 46(1) to 46(n).

[0071] In the balancing circuit 45, a group including resistor 46(1) and switch SW21(1) is enclosed by a dotted line and is referred to as circuit 47(1). The balancing circuit 45 has multiple circuits 47(1) to 47(n) (where n is a natural number greater than or equal to 2) corresponding to the battery cells. The configuration of circuit 47 often differs between active and passive types, but the configuration including resistors and switches is often common. In other words, circuit 47 can be applied to either active or passive balancing circuits.

[0072] It is preferable that the number n of the above-mentioned multiple battery cells and multiple circuits is the same, that is, that the same number is arranged, but it is also possible to share a circuit with, for example, 2 to 15 battery cells. Sharing a circuit can reduce costs.

[0073] The balancing circuit 45 has a function of matching the SOC of the multiple battery cells 44(1) to 44(n). This function can also be said to be a function of managing all battery cells so that they operate within a safe operating area. Here, we will explain the function of matching the SOC and the importance of matching the SOC using the four battery cells (first battery cell 44(1) to fourth battery cell 44(4)) shown in Figure 3.

[0074] As shown in Figure 3, the SOC of the first battery cell 44(1) to the fourth battery cell 44(4) at a certain time is different from one another. This is equivalent to the SOC-OCV characteristics shown in Figure 3 being different for each battery cell. In this state, the SOC of the first battery cell 44(1) to the fourth battery cell 44(4) is said to vary from one another. Figure 3 shows a case where the SOC is greatest in the following order: fourth battery cell 44(4) > first battery cell 44(1) > third battery cell 44(3) > second battery cell 44(2).

[0075] The first to fourth battery cells 44(1) to 44(4) are electrically connected to the first to fourth circuits 47(1) to 47(4), respectively. Again, the first to fourth battery cells 44(1) to 44(4) are included in the secondary battery 41 shown in FIG. 2. The first to fourth circuits 47(1) to 47(4) are included in the balancing circuit 45 shown in FIG. 2.

[0076] 3, when charging of the secondary battery 41 is started, charging of the fourth battery cell 44(4) is completed first. If charging of the secondary battery 41 continues while the fourth battery cell 44(4) is fully charged, the fourth battery cell 44(4) will be overcharged. On the other hand, if charging of the secondary battery 41 is terminated while the fourth battery cell 44(4) is fully charged, the battery cells other than the fourth battery cell 44(4) will not be fully charged, and the dischargeable capacity of the secondary battery 41 will decrease.

[0077] 3, when the secondary battery 41 is used, the capacity of the second battery cell 44(2) is depleted the fastest. If the secondary battery 41 continues to be used while the capacity of the second battery cell 44(2) is depleted, the second battery cell 44(2) will enter an over-discharged state. On the other hand, if the use of the secondary battery 41 is stopped while the capacity of the second battery cell 44(2) is depleted, the battery cells other than the second battery cell 44(2) will still have capacity, and the dischargeable capacity of the secondary battery 41 will decrease.

[0078] To prevent this decrease in dischargeable capacity, it is desirable to align the SOC of each battery cell. Aligning the SOC of each battery cell is called balancing. Depending on the situation shown in Figure 3, the storage battery pack 4 may determine that balancing is necessary during charging, etc.

[0079] To align the SOC of each battery cell, it is necessary to estimate the current SOC of each battery cell with high accuracy. Because it is difficult to measure the SOC of each battery cell, it is preferable to estimate it using measurable values ​​(current and voltage) for each battery cell in the server device 1. When voltage is used as a measurable value, the SOC can be estimated using the SOC-OCV characteristic shown in Figure 3. The measured voltage can be correlated with the OCV in the SOC-OCV characteristic. The timing for performing SOC estimation using the OCV is preferably the early and late stages of charging, circled by dotted lines in Figure 3. The early and late stages of charging are periods in which the OCV changes significantly but the SOC changes only slightly in the SOC-OCV characteristic. These periods are preferable as estimation timing because they reduce the impact of OCV errors on SOC estimation.

[0080] The timing for estimating the SOC may be during the middle stage of charging, which is between the early and late stages of charging shown in Figure 3. The middle stage of charging is the period in which changes in OCV have a significant impact on changes in SOC in the SOC-OCV characteristics. During this period, it is advisable to use current integration (such as coulomb counting) in the SOC-OCV characteristics. Current integration requires knowing the amount of current flowing through each battery cell. By measuring this amount of current, obtaining the FCC of each battery cell, and combining this with methods such as a Kalman filter, it becomes possible to estimate the SOC.

[0081] When estimating the SOC using current integration, the following calculation should be performed for each battery cell:

[0082]

number

[0083] In the above formula, FCC is the full charge capacity, and when the state of health (SOH) of each battery cell is sent from the server device 1, it is preferable to calculate the FCC by multiplying it by FCC0, which is the initial value of FCC held by the vehicle 3. Note that SOH=FCC / FCC0.

[0084] On the vehicle 3 side, machine learning may be performed, and an optimal table may be determined by machine learning, or the internal resistance at each SOC may be estimated.

[0085] The internal resistance at each SOC can be estimated, for example, from the current and voltage measured in a battery cell of the vehicle 3. As described in the internal resistance estimation method of the second embodiment, the internal resistance may be estimated by separating it into a fast-response resistance component and a slow-response resistance component. The fast-response resistance component is thought to be related to electron transfer resistance, while the slow-response resistance component is thought to be related to ion diffusion resistance within the solid active material. Battery cells deteriorate due to repeated charging and discharging. However, the state of deterioration varies depending on the type of battery cell and the installation environment, so the fast-response resistance component and the slow-response resistance component may change differently. Therefore, estimating the fast-response resistance component and the slow-response resistance component separately as described above can be considered one means of indirectly determining the state of deterioration inside the battery. Therefore, when data on the internal resistance is used for estimating the SOC-OCV characteristics, SOC, and FCC, increasing the amount of information reflecting the internal state of the battery improves the accuracy of various estimations, which is preferable. When the internal resistance is estimated in the vehicle 3, it is preferable to include the estimated data as sequential data to be transmitted to the server device 1. The estimated data on the internal resistance reflects the deterioration state of each battery, and is therefore particularly useful for estimating the FCC in the server device 1. Here, the server device 1 can accumulate the estimated data for multiple vehicles 3.

[0086] In one aspect of the present invention, SOC estimation can be performed based on OCV when performed at the beginning and end of charging, and can be performed using current integration when performed at the middle of charging. Since SOC estimation is preferably performed at an early stage for balancing processing of each battery cell, SOC estimation is preferably performed at the beginning or middle of charging. While SOC estimation is preferably performed by a server device, SOC estimation may also be performed by a vehicle control unit or the like.

[0087] However, the SOC-OCV characteristics change over time due to degradation caused by repeated charging and discharging, etc. Therefore, to obtain the current, i.e., latest, SOC-OCV characteristics with high accuracy, estimation based on a large amount of data is required, which may require a long calculation time.

[0088] Degradation occurs unevenly, resulting in variations in the SOC-OCV characteristics of each battery cell. Other variations include variations in the degradation rate, impedance, and self-discharge rate. Variations in degradation rates, for example, can be temperature-dependent (the higher the temperature, the more rapid the degradation), voltage-dependent (the higher the charging voltage, the more rapid the degradation), or depth-of-discharge-dependent (the deeper the depth of discharge, the more rapid the degradation). These complex intertwining factors make it difficult to estimate the SOC of each battery cell, and when the above dependencies are added, estimating the SOC requires a massive amount of calculation.

[0089] Therefore, in one aspect of the present invention, it is preferable to have the server device 1 execute calculation processing related to estimation of the latest SOC-OCV characteristics.

[0090] 3, after the vehicle 3 acquires the latest SOC-OCV characteristics, to align the SOC of the other battery cells to the SOC of the second battery cell 44(2), the switches of the first circuit 47(1), the third circuit 47(3), and the fourth circuit 47(4) corresponding to the battery cells other than the second circuit 47(2) are turned on. Then, the battery cells other than the second battery cell 44(2) are discharged, and the SOC of the battery cells other than the second battery cell 44(2) can be aligned to the SOC of the second battery cell 44(2). Discharge using the resistance of the circuit 47 is referred to as resistive discharge.

[0091] Balancing the SOC in this way can typically be achieved with a balancing circuit 45 that has a simple circuit configuration of switches and resistors, but this wastes energy. Furthermore, the energy consumption generates heat. When energy consumption is involved, this is referred to as a passive balancing circuit or passive balancing process.

[0092] It is also possible to align the SOCs in other ways. For example, in Fig. 3, to align the SOCs of the other battery cells with the SOC of the fourth battery cell 44(4), the switches in the first circuit 47(1) to the third circuit 47(3) corresponding to the battery cells other than the fourth battery cell 44(4) are turned off, the switch (not shown) between the negative terminal of the battery cell 44(3) and the positive terminal of the battery cell 44(4) is turned off, and the switch in the fourth circuit 47(4) connected to the negative terminal of the battery cell 44(3) is turned on to start charging. This allows charging to bypass the fourth battery cell 44(4), and the SOCs of the battery cells other than the fourth battery cell 44(4) can be increased and aligned with the SOC of the fourth battery cell 44(4).

[0093] This method requires charging by bypassing the fourth battery cell 44(4). Therefore, compared to when only the second battery cell 44(2) is used, the circuit configuration becomes more complex, requiring an increased number of switches in the secondary battery 41 and balancing circuit 45. Furthermore, heat is generated as energy is consumed. In other words, this method corresponds to a passive balancing circuit or balancing process.

[0094] When the balancing circuit 45 is operated in this manner, the current SOC value of each battery cell is used as the basis, and therefore a highly accurate SOC can be obtained by having the SOC estimated by the server device 1. Furthermore, when operating the balancing circuit 45, it is preferable that the SOC estimation by the server device 1 be started early in the charging period.

[0095] In addition, just as there is a demand for a shorter charging time, such as in a quick charge mode, it is also desirable to complete the balancing process in a short time. In this respect, it is also preferable for the server device 1 to start SOC estimation early in the charging period.

[0096] The estimation in the server device 1 can be performed using AI via an algorithm.

[0097] The estimation in vehicle 3 can utilize AI via algorithms.

[0098] In one aspect of the present invention, as a new balancing process, the storage battery pack 4 periodically acquires data on the internal states of the battery cells 44, and the data is transmitted from the storage battery pack 4 to the server device 1 using the communication network 7 or the like. The server device 1 then executes an estimation process on the internal states, creating and saving multiple execution results, and the storage battery pack 4 selects the internal state that is closest to the current state of the battery cells 44, i.e., the most recent internal state, from the data saved in the server device 1 or the memory unit 52. Communication between the storage battery pack 4 and the server device 1 can be performed via the vehicle control unit 50, but the storage battery pack 4 may also have a communication function.

[0099] According to this aspect of the present invention, data related to the SOC and the like can be obtained with high accuracy in a short time. The calculation process related to the SOC estimation executed by the server device 1 can be completed in a short time, and the frequency of the calculation process can also be increased by the server device 1. Furthermore, the calculation process by the server device 1 can be executed in parallel while the vehicle 3 is being charged, so that the balancing process can be completed in a short time.

[0100] Furthermore, the data and estimation results related to SOC, etc. stored in the server device 1 are versatile, so they can be provided to multiple battery packs 4. This system allows the battery packs 4 to acquire highly accurate estimated SOC, eliminating the need for a new control unit or the like in the battery packs 4 and enabling the most efficient balancing of SOC. This reduces unnecessary energy consumption during balancing processing, allowing the battery packs 4 to maximize their capabilities.

[0101] 1A and 1B, data is transmitted and received between the vehicle 3 and the server device 1. Data transmission and reception is preferably performed while the vehicle 3 is stopped and connected to the charger 2. When the vehicle 3 is connected to the charger 2, charging of the battery pack 4 of the vehicle 3 begins. The charging period while the power receiving connector 5 is connected to the charger 2 can be divided into an initial and middle CC (constant current) charging period, and a final CV (constant voltage) charging period.

[0102] While the power receiving connector 5 is connected to the charger 2, communication is possible between the server device 1 and the vehicle 3. During the initial and middle stages of charging, that is, the period corresponding to CC charging, the optimal SOC-OCV characteristics can be determined in the vehicle 3 using communication.

[0103] At the end of charging, i.e., during the CV charging period, the remaining capacity until full charge is calculated for each battery cell, and the battery cell that will take the longest time to be fully charged may be identified. For the other battery cells, the timing at which discharge in the circuit 47 starts, or the so-called discharge order in the circuit 47, may be determined.

[0104] During the CC charging period, the SOC-OCV characteristic table is created by the server device 1, but after charging is completed, the table can be corrected by the GPU installed in the vehicle if necessary.

[0105] The vehicle 3 may integrate the SOC data of each battery cell 44 to create a fuel gauge table for the passenger (user).

[0106] The first data 11 and the second data 12 can be transmitted and received by a vehicle control unit 50 shown in Fig. 2. The vehicle control unit 50 has at least a CPU 51, a storage unit 52, and a communication unit 53, and operates by receiving power from the secondary battery 41 or a separately provided storage battery.

[0107] The vehicle control unit 50 is sometimes called a vehicle control unit. The vehicle control unit 50 is a control device that determines the state of the vehicle and maintains the optimum state, and can control the entire vehicle using CAN (Controller Area Network) communication, CAN FD (CAN with Flexible Data rate), automotive Ethernet (registered trademark), etc.

[0108] The vehicle control unit 50 can select data related to the SOC and the like stored in the server device 1. For example, the vehicle control unit 50 has at least a CPU 51, and the CPU 51 can execute arithmetic processing to select data related to the optimal SOC and the like that is closest to the current state of the battery cell from the data stored in the server device 1 or the storage unit 52. In addition to the CPU 51, the vehicle control unit 50 can also have a CPU and a GPU that are capable of arithmetic processing.

[0109] The vehicle control unit 50 has a memory unit 52, which includes RAM, ROM, etc. The memory unit 52 can record SOC-OCV characteristic data of the multiple battery cells 44. The memory unit 52 can also record data related to the SOC, etc. selected from the server device 1. The memory unit 52 can also record programs, etc. for controlling the storage battery pack 4. By executing one of the programs, the CPU 51 can select data related to the SOC, etc. that is closest to the current state for each of the multiple battery cells 44 from the data stored in the server device 1 or the memory unit 52.

[0110] The vehicle control unit 50 has a communication section 53 and is capable of sending and receiving data to and from the server device 1 .

[0111] The storage battery pack 4 has a protection circuit 60. The current monitoring circuit 61 included in the protection circuit 60 may have a sensor function for measuring charge / discharge current as a measurement value obtained from the secondary battery 41. By measuring the charge / discharge current using the current monitoring circuit 61, it is possible to perform coulomb counting of the battery cell and obtain data related to the SOC, etc.

[0112] The voltage monitoring circuit 62 included in the protection circuit 60 may have a sensor function capable of measuring the terminal voltage of each battery cell 44 as a measurement value obtained from the secondary battery 41, etc. The temperature monitoring circuit 63 included in the protection circuit 60 may have a sensor function capable of measuring the temperature of each battery cell 44 as a measurement value obtained from the secondary battery 41, etc. The path blocking circuit 64 included in the protection circuit 60 can block the path of charge / discharge current for the secondary battery 41, etc.

[0113] The vehicle control unit 50 can acquire the measurement values ​​obtained from the protection circuit 60 as parameters. Based on the acquired measurement values, it can forcibly stop discharging or charging a battery cell that is determined to be in an over-discharged or over-charged state. The vehicle control unit 50 can determine whether to forcibly stop the discharge or charging.

[0114] The vehicle control unit 50 can control the balancing circuit 45 in accordance with the selected data related to the SOC, etc. Specifically, the vehicle control unit 50 can control the on / off of the switches SW21(1) to SW21(n) of the balancing circuit 45.

[0115] A start switch 71 is electrically connected to the vehicle control unit 50. The vehicle control unit 50 can switch the vehicle 3 between a running state and a stopped state in response to the operation of the start switch 71 by the passenger. The vehicle control unit 50 can also switch the vehicle 3 between a running state and a stopped state in response to the charge state of the secondary battery 41, thereby enabling the start switch 71 to be operated.

[0116] In this embodiment, data on the SOC and the like of each battery cell is acquired as sequential data at regular intervals from the storage battery pack 4, and the acquired data is stored in the server device 1 using the communication network 7 or the like, and further, calculations related to SOC estimation are performed by the server device 1 to calculate the estimation result. The storage battery pack 4 can select data on the SOC and the like that is closest to the current state of the battery cell 44 from the data stored in the server device 1 or the memory unit 52, so that the data on the SOC and the like can be acquired with high accuracy in a short time.

[0117] The data and estimation results relating to the SOC and the like stored in the server device are versatile and can be provided to the battery packs 4 of multiple vehicles 3 .

[0118] Such a system allows the storage battery pack 4 to acquire a highly accurate estimated SOC, etc., and allows the most efficient SOC balancing process using a balancing circuit or the like. The storage battery pack 4 that has undergone balancing processing is configured to utilize the optimal FCC. This configuration is sometimes referred to as battery utilization at its limit, as it allows the battery to be utilized to the maximum extent possible. The storage battery management system according to one embodiment of the present invention allows the multiple battery cells 44 in the storage battery pack 4 to be utilized at their limit.

[0119] This embodiment mode can be implemented in appropriate combination with other embodiment modes.

[0120] (Embodiment 2) In this embodiment, a processing method for SOC-OCV characteristic data will be described.

[0121] [Processing method for SOC-OCV characteristic data] FIG. 4 is a diagram illustrating the creation of SOC-OCV characteristic data in the server device 1 and the selection of SOC-OCV characteristic data in the vehicle 3, for example, in the vehicle control unit 50, with respect to the SOC-OCV characteristic data contained in the first data 11 and the second data 12.

[0122] The server device 1 has a first algorithm 121. The first algorithm 121 has a function of creating first SOC-OCV characteristic data 162 using at least a portion of the first data 11 as input data. The first SOC-OCV characteristic data 162 has an estimated value. The first algorithm 121 preferably has a first neural network 131. The server device 1 also has a function of transmitting the first SOC-OCV characteristic data 162 to the vehicle 3 as part of the second data 12. The transmitted first SOC-OCV characteristic data 162 is added as part of the SOC-OCV characteristic data list 161 of the vehicle 3.

[0123] The vehicle 3 has a second algorithm 122. The second algorithm 122 may be stored in the storage unit 52 of the vehicle control unit 50 or the like. The second algorithm 122 has a function of selecting second SOC-OCV characteristic data 163 from the SOC-OCV characteristic data lists 161 using input values ​​such as SOC-OCV characteristic data lists 161 and voltage values, current values, battery cell temperatures, and capacity values ​​related to the storage battery pack 4, which are aggregated in the vehicle control unit 50. The second SOC-OCV characteristic data 163 selected is the data that most closely matches the state of the battery cells 44 of the vehicle 3 at the time of selection. "Closest" means that the data has the smallest difference from the entire range of the SOC-OCV characteristics of the battery cells. Because it is difficult to actually measure the entire range of the SOC-OCV characteristics of the battery cells, the second algorithm 122 must select the second SOC-OCV characteristic data 163 based on limited input data. Therefore, it is preferable that the second algorithm 122 includes a second neural network 132. By including the second neural network 132, the second algorithm 122 can select the second SOC-OCV characteristic data 163 that most closely matches the state of the battery cell using limited input data. The vehicle 3 also has a function of transmitting the second SOC-OCV characteristic data 163 to the server device 1 as part of the first data 11. The second algorithm 122 may be installed in an electronic device such as a smartphone owned by a passenger of the vehicle 3.

[0124] The first neural network 131 may be, for example, any one of a FFNN (Feedforward Neural Network), a CNN (Convolutional Neural Network), an RNN (Recurrent Neural Network), and an LSTM (Long Short-Term Memory).

[0125] For example, any one of FFNN, CNN, RNN, and LSTM can be used as the second neural network 132. In addition, the second neural network 132 may select the second SOC-OCV characteristic data 163 from the SOC-OCV characteristic data list 161 as a classification problem using a decision tree.

[0126] Next, a data description method for the first SOC-OCV characteristic data 162 will be described using FIG. 5 . A battery management system according to one embodiment of the present invention may employ a data description method in which SOC data and OCV data for acquiring the first SOC-OCV characteristic data 162 are assigned to specific bits, as shown in FIG. 5 . FIG. 5 illustrates the description method for SOC data, showing the relationship between bit data and the corresponding SOC [%]. Also, as a description method for OCV data, it shows the relationship between bit data and the corresponding voltage [V]. For example, when the specific bit data in the SOC data is 0011, the corresponding SOC is 40%, and the corresponding voltage in the OCV data is 3,300 V. Under normal usage conditions, a battery cell is used so that its SOC is between 0% and 100%. However, if the battery cell is not used for an extended period of time, it may be in an over-discharged state below 0%. Furthermore, when charging, overcharging beyond 100% is a potential risk that must be addressed. Therefore, it is desirable that the SOC data also correspond to an SOC range smaller than 0% and an SOC range larger than 100%, as shown in Figure 5. In addition, the OCV data is data that pairs with the SOC data, and is assigned as OCV data to correspond to each SOC data.

[0127] 5 shows an example of a data description method for the first SOC-OCV characteristic data 162, in which data intervals are narrower in the range where the SOC is close to 100%. In a battery cell, an overcharged state where the SOC exceeds 100% can lead to a decrease in the safety of the battery cell and a decrease in battery life, so it is desirable to allocate more bit data in the SOC range where the SOC is close to 100%. The allocation of bit data can be performed by the server device 1. The SOC range where the SOC is close to 100% is preferably between 90% and 110%, and more preferably between 95% and 105%, and it is desirable to allocate more bit data in this range than in other ranges.

[0128] 5, more bit data is allocated in the SOC range close to 100%, but it is also advisable to allocate data at finer intervals in the SOC range closer to 0%. Allocating more bit data in the SOC range close to 0% makes it easier to prevent sudden shutdowns in the vehicle 3 having battery cells, leading to improved safety.

[0129] As shown in Figure 5, by allocating a large amount of bit data to a portion of the SOC range, it becomes possible to form sufficient SOC-OCV characteristic data even with a small number of bits, thereby enabling a reduction in the amount of data communication between the server device 1 and the vehicle 3, and a reduction in the amount of data within the vehicle 3.

[0130] While FIG. 5 shows an example using 4 bits for the sake of explanation, the data may be described using a number of bits greater than 4, such as 8 bits, 16 bits, 32 bits, or 64 bits. When using a larger number of bits, it may not be necessary to allocate more bit data to the partial range of SOC shown above. This is because when a large number of bits are allocated to the SOC-OCV characteristic data, the entire range of SOC can be described in detail, not just a partial range of SOC.

[0131] 5 shows an example of a data description format for the first SOC-OCV characteristic data 162 in which, in addition to the allocation of SOC data and OCV data, State A to State D, which represent the states of the battery cells, are allocated to surplus bit data. State A to State D, which represent the states of the battery cells, can be allocated as data indicating a dangerous state such as an internal short circuit, for example.

[0132] As described above, the data processing function for SOC-OCV characteristic data possessed by the battery management system according to one embodiment of the present invention makes it possible to improve the estimation accuracy of the battery cell. Furthermore, the reduction in the amount of data (data volume) of the SOC-OCV characteristic data performed by the server device 1 and the optimization for neural network processing make it possible to reduce the power consumption of the control unit of the vehicle 3.

[0133] [FCC, internal resistance processing function] 6 shows an example in which, with respect to the FCC included in the first data 11 and the internal resistance (R) included in the second data, the server device 1 estimates the FCC, and the vehicle 3 estimates the internal resistance. In this way, in addition to the estimation in the server device 1, estimation may also be performed in the vehicle 3. The functional configuration of the battery management system related to the estimation of the FCC and internal resistance will be described with reference to FIG. 6.

[0134] The server device 1 has a third algorithm 123. The third algorithm 123 uses an internal resistance 171a calculated based on the battery cell (R data from a certain previous cycle estimated by the battery cell, R n-1 The third algorithm 123 preferably includes a third neural network 133. The server device 1 also has a function of transmitting the FCC 172 to the vehicle 3 as part of the second data 12.

[0135] The vehicle 3 has a fourth algorithm 124. The fourth algorithm 124 receives the FCC 172, the second SOC-OCV characteristic data 163, and the voltage value, current value, and capacity value of the battery cell as input data, and calculates the internal resistance 171b of the battery cell (R data estimated at the battery cell, R n The fourth algorithm 124 preferably includes a fourth neural network 134. The vehicle 3 also includes an internal resistance 171b (R n ) to the server device 1 as part of the first data 11.

[0136] The third neural network 133 may be, for example, any one of FFNN, CNN, RNN, and LSTM.

[0137] The fourth neural network 134 may be, for example, any one of FFNN, CNN, RNN (and LSTM).

[0138] Next, a method for estimating the internal resistance 171 (denoted as R) will be described with reference to Fig. 7. Fig. 7 shows the function of the fourth algorithm 124 of the vehicle 3, and the internal resistance 171 is estimated by inputting the first SOC-OCV characteristic data 162, the FCC 172, and the internal measurement values ​​of the battery cell 44 into the fourth algorithm 124. The internal resistance may be estimated by the server device 1.

[0139] The first SOC-OCV characteristic data 162 is preferably in the data format explained in Fig. 5. The internal measurement values ​​of each battery cell can be calculated based on the voltage value (V) 31 and current value (I) 32 measured from the battery cell, and the capacity value (Q) 33 and temperature (T) 34 measured by a coulomb counter or the like.

[0140] As described above, the function of estimating the FCC and internal resistance of the battery management system according to one embodiment of the present invention makes it possible to improve the accuracy of estimating the FCC and internal resistance of the battery cell. Furthermore, by using lighter SOC-OCV characteristic data (reduced data volume) for estimating the internal resistance, it becomes suitable for neural network processing, and it becomes possible to reduce the power consumption of the control unit of the vehicle 3.

[0141] [Method for measuring internal resistance] Instead of the method of estimating the internal resistance 171 shown in Fig. 7, the internal resistance 171 may be estimated from the measurement results by the current rest method described in Fig. 8 and Fig. 9. In this case, the fourth algorithm 124 may have a function of estimating the internal resistance by the current rest method described below.

[0142] The current rest method is a method of estimating internal resistance by setting a rest period during CC charging where no charging is performed for a certain period of time and analyzing the change in battery cell voltage during this rest period. Alternatively, it is a method of estimating internal resistance by setting a rest period during CC discharging where no discharging is performed for a certain period of time and analyzing the change in battery cell voltage during this rest period. The rest period is preferably from 1 second to 10 minutes, more preferably from 5 seconds to 5 minutes, and even more preferably from 10 seconds to 3 minutes.

[0143] FIG. 8 is a diagram illustrating an analysis method for the current pause method. While FIG. 8 shows an example of the current pause method for CC discharge, the current pause method may also be used for CC charging. The difference between the battery voltage immediately before the pause period and the battery voltage 0.1 seconds after the pause period begins is defined as ΔV(0.1s). The difference between the battery voltage 0.1 seconds after the pause period begins and the battery voltage 120 seconds after the pause period begins (the battery voltage at the end of the pause period) is defined as ΔV(0.1s-120s). Next, the value obtained by dividing ΔV(0.1s) by the current value of constant current discharge is defined as the fast-response resistance component R(0.1s), and the value obtained by dividing ΔV(0.1s-120s) by the current value of constant current discharge is defined as the slow-response resistance component R(0.1s-120s). The fast-response resistance component R (0.1 s) is thought to be mainly due to electrical resistance (electronic conduction resistance), while the slow-response resistance component R (0.1 s to 120 s) is thought to be mainly due to Li diffusion resistance within the active material particles.

[0144] Next, examples of analysis results using the current rest method are shown below. For battery samples (sample 1 and sample 2) using different positive electrode active materials, the analysis method described in FIG. 8 was used to analyze the fast-response resistance component R (0.1 s) and the slow-response resistance component R (0.1 s to 120 s). As an example, FIG. 9A shows the transition of the fast-response resistance component R (0.1 s). FIG. 9B shows the transition of the fast-response resistance component R (0.1 s) and the slow-response resistance component R (0.1 s to 120 s) for sample 1.

[0145] As shown in Figure 9A, the fast-response resistance component R(0.1s) of Sample 1 tends to decrease and then increase, while the fast-response resistance component R(0.1s) of Sample 2 only increases. Thus, the change in the fast-response resistance component R(0.1s) is not uniform and may vary depending on the battery.

[0146] As shown in Figure 9B, the slow-response resistance component R (0.1s to 120s) changes more significantly than the fast-response resistance component R (0.1s). The slow-response resistance component R (0.1s to 120s) increases sharply from around the 20th cycle and remains almost constant from the 27th cycle onwards. In this way, the fast-response resistance component R (0.1s) and the slow-response resistance component R (0.1s to 120s) may have different change trends.

[0147] Therefore, it is preferable that the fourth algorithm 124 has a function of predicting future changes in internal resistance for each resistance component, that is, for the fast-response resistance component R (0.1 s) and the slow-response resistance component R (0.1 s to 120 s), using a neural network such as LSTM to estimate time series data.

[0148] The above-mentioned prediction function may be possessed by the server device 1. If the server device 1 has a function to predict future changes in internal resistance for each resistance component, that is, the fast-response resistance component R (0.1 s) and the slow-response resistance component R (0.1 s to 120 s), by using a neural network such as LSTM to estimate time-series data, it is possible to accumulate data corresponding to the secondary batteries 41 of multiple vehicles 3 and improve the prediction accuracy of the neural network, which is preferable.

[0149] When a vehicle has multiple battery cells 44, as in the vehicle 3 shown in the examples above, it is preferable to measure, estimate, and predict the internal resistance for each battery cell. The multiple battery cells 44 have manufacturing characteristic variations, and the ambient temperature may also change depending on the mounting position of the battery cells 44 in the secondary battery 41. Therefore, by measuring, estimating, and predicting the internal resistance for each of the multiple battery cells 44, a storage battery control system that allows for more accurate control can be achieved.

[0150] In estimating the internal resistance, in order to accurately analyze the fast-response resistance component R (0.1 s) and the slow-response resistance component R (0.1 s to 120 s), it is important to synchronize the measurement values ​​of the voltage values ​​(V) 31 and the current values ​​(I) 32 measured from the battery cells 44. Therefore, in the current monitoring circuit 61 and the voltage monitoring circuit 62, it is preferable to measure the voltage values ​​(V) 31 and the current values ​​(I) 32 of the multiple battery cells 44 using an A / D conversion unit of the scanning type, but to provide an A / D conversion unit for each of the voltage values ​​(V) 31 and the current values ​​(I) 32 of the multiple battery cells 44. In this case, the voltage values ​​(V) 31 of the multiple battery cells 44 may be acquired using a change in the current value (I) 32 as a trigger.

[0151] Furthermore, the vehicle 3 may have third SOC-OCV characteristic data in addition to the SOC-OCV characteristic data list 161 and the second SOC-OCV characteristic data 163. The third SOC-OCV characteristic data can be created based on the second SOC-OCV characteristic data 163 and an estimated load of the vehicle 3. The average current consumption value of the battery cell can be used as the estimated load. Compared to the second SOC-OCV characteristic data 163, the third SOC-OCV characteristic data has a voltage corresponding to a low SOC range set higher in the OCV data in accordance with the estimated load of the vehicle 3. As a simplified example, for example, an SOC of 10% in the second SOC-OCV characteristic data 163 is recorded as an SOC of 0% in the third SOC-OCV characteristic data. In this example, the OCV at which the SOC is 0% in the third SOC-OCV characteristic data is higher than the OCV at which the SOC is 0% in the second SOC-OCV characteristic data 163. The third SOC-OCV characteristic data can also be displayed to the passengers of the vehicle 3, which is preferable because it can prevent unexpected shutdown of the vehicle 3.

[0152] This embodiment mode can be implemented in appropriate combination with other embodiment modes.

[0153] (Embodiment 3) In this embodiment, a positive electrode used in a battery cell of the present invention will be described.

[0154] [Positive electrode] 10A shows an example of a cross-sectional view of a positive electrode. The positive electrode has a positive electrode active material layer 571 on a positive electrode current collector 550. The positive electrode active material layer 571 includes a positive electrode active material 561, a positive electrode active material 562, a binder (binding agent) 555, a conductive additive 553, a conductive additive 554, and an electrolyte 556. The positive electrode active material 561 has an average particle size larger than that of the positive electrode active material 562.

[0155] [Cathode active material] Positive electrode active material 561 and / or positive electrode active material 562 may be called positive electrode active material particles, but may take various shapes other than particulates. Positive electrode active material 561 and / or positive electrode active material 562 may be primary particles having multiple crystallites, or secondary particles formed by aggregation of primary particles.

[0156] A material capable of inserting and extracting carrier ions can be used for positive electrode active material 561 and / or positive electrode active material 562. The carrier ions can be lithium ions, sodium ions, potassium ions, calcium ions, strontium ions, barium ions, beryllium ions, or magnesium ions.

[0157] Materials capable of intercalating and deintercalating lithium ions include lithium composite oxides with an olivine-type crystal structure, a layered rock-salt-type crystal structure, or a spinel-type crystal structure. For example, a lithium composite oxide with an olivine-type crystal structure is represented by LiMPO4 (where M = Fe, Mn, Ni, or Co). Because Fe and Mn have excellent thermal stability, they are expected to be next-generation cathode materials. For example, a lithium composite oxide with a layered rock-salt-type crystal structure is represented by LiMO2 (where M = Fe, Mn, Ni, or Co). When M is Co, LiMO2 is represented by LiCoO2, which is sometimes written as LCO or referred to as lithium cobalt oxide. In a lithium composite oxide with a layered rock-salt-type crystal structure, M may contain one or more elements selected from Fe, Mn, Ni, and Co.

[0158] LiNi as a composite oxide containing Ni, Mn and Co x Co y Mn zThere is a NiCoMn system (also referred to as NCM) represented by O2(x>0, y>0, 0.8<x + y + z<1.2). Specifically, for example, it is preferable to satisfy 0.1x<y<8x and 0.1x<z<8x. As an example, x, y, and z preferably satisfy x:y:z = 1:1:1 or values in the vicinity thereof. Or as an example, x, y, and z preferably satisfy x:y:z = 5:2:3 or values in the vicinity thereof. Or as an example, x, y, and z preferably satisfy x:y:z = 8:1:1 or values in the vicinity thereof. Or as an example, x, y, and z preferably satisfy x:y:z = 9:0.5:0.5 or values in the vicinity thereof. Or as an example, x, y, and z preferably satisfy x:y:z = 6:2:2 or values in the vicinity thereof. Or as an example, x, y, and z preferably satisfy x:y:z = 1:4:1 or values in the vicinity thereof.

[0159] Also, in the NiCoMn system shown above, it is preferable to have any one or more selected from aluminum, magnesium, titanium, and boron in an amount of 0.1 mol% or more and 3 mol% or less.

[0160] In addition to this, oxides such as V2O5 and Nb2O5 are being studied as cathode materials. For example, spinel-type crystal structure lithium composite oxides include lithium manganese spinel (LiMn2O4) and the like.

[0161] The lithium composite oxide may contain at least one or more elements selected from the group consisting of nickel, chromium, aluminum, iron, magnesium, molybdenum, zinc, zirconium, indium, gallium, copper, titanium, niobium, silicon, fluorine, and phosphorus. A lithium composite oxide containing aluminum and having Ni, Mn, and Co may be denoted as NCMA. A lithium composite oxide containing aluminum and having Ni and Co may be denoted as NCA.

[0162] The average particle size of the positive electrode active material 561 is 1 μm or more and 50 μm or less, preferably 5 μm or more and 20 μm or less. In the case of a ternary composite oxide such as NCM, the positive electrode active material 561 can be considered as secondary particles, and the average particle size of the secondary particles is 1 μm or more and 50 μm or less, preferably 5 μm or more and 20 μm or less.

[0163] To increase the packing density of the active material, a positive electrode active material 562 having a different particle size may be further added. Different particle sizes refer to different maximum values ​​of the average particle size. For example, the maximum value of the average particle size of the positive electrode active material 562 is smaller than that of the positive electrode active material 561. The maximum value of the average particle size of the positive electrode active material 562 is preferably 1 / 6 to 1 / 10 of the maximum value of the average particle size of the positive electrode active material 561. By mixing active materials having different particle sizes, the packing density of the active material in the positive electrode active material layer 571 can be increased.

[0164] The charge density can be increased without the positive electrode active material 562. When the positive electrode active material 562 is not used, the number of manufacturing steps can be reduced, leading to further cost reduction.

[0165] Positive electrode active material 561 and / or positive electrode active material 562 may have grain boundaries. The grain boundaries may be located between crystallites.

[0166] Positive electrode active material 561 and / or positive electrode active material 562 may have an additive element in the surface layer portion. Fig. 10A shows surface layer portion 572 of positive electrode active material 561. Surface layer portion 572 exists within 50 nm, more preferably within 35 nm, even more preferably within 20 nm, and most preferably within 10 nm from the surface of positive electrode active material 561 toward the inside in a cross-sectional view.

[0167] The additive element may be unevenly distributed in the surface layer. "Uneven distribution" refers to the state in which the additive element is unevenly or unevenly distributed, with the concentration of the additive element being higher in one region than in another. Uneven distribution may also be expressed as segregation or precipitation.

[0168] Depending on the type, some additive elements may not contribute to the capacity of the positive electrode active material. It is preferable that such additive elements are unevenly distributed in the surface layer of the positive electrode active material. The uneven distribution of the additive elements can be confirmed by the presence of a higher concentration of the additive elements in the surface layer than in the interior of the positive electrode active material. The presence of the additive elements at least in the surface layer can prevent structural deterioration during charge and discharge, resulting in a positive electrode active material that is less susceptible to deterioration.

[0169] The structure in which the surface layer 572 is provided inside the active material is sometimes referred to as a core-shell structure. The core-shell structure can also be applied to the positive electrode active material 562.

[0170] [Binder] Binder 555 is provided to prevent positive electrode active material 561 or conductive additive 553 from sliding off positive electrode current collector 550. Binder 555 also plays a role in binding positive electrode active material 561 and conductive additive 553 together. For this reason, binder 555 may be positioned so as to be in contact with positive electrode current collector 550, positioned between positive electrode active material 561 and conductive additive 553, or positioned so as to be entangled with conductive additive 553.

[0171] The binder 555 contains a resin, which is a polymer material. If a large amount of binder is contained, the proportion of the positive electrode active material 561 in the positive electrode active material layer 571 may decrease. A decrease in the proportion of the positive electrode active material 561 leads to a decrease in the discharge capacity of the secondary battery, so the amount of the binder 555 mixed is minimized.

[0172] [Conductive additive] Because the positive electrode active material 561 is a composite oxide, it may have high resistance. This makes it difficult to collect current from the positive electrode active material 561 to the positive electrode current collector 550. Therefore, the conductive additive 553 and / or the conductive additive 554 functions to assist the current path between the positive electrode active material 561 and the positive electrode current collector 550, the current path between the plurality of positive electrode active materials 561, the current path between the plurality of positive electrode active materials and the positive electrode current collector 550, etc. To fulfill such a function, the conductive additive 553 and / or the conductive additive 554 is made of a material having lower resistance than the positive electrode active material 561, and the conductive additive 553 and / or the conductive additive 554 may be positioned so as to be in contact with the positive electrode current collector 550 or may be positioned in the gaps in the positive electrode active material 561.

[0173] The conductive additive 553 is also called a conductivity imparting agent or conductive material due to its role, and is made of a carbon material or a metal material. Carbon black (furnace black, acetylene black, graphite, etc.) is an example of a carbon material used for the conductive additive 553. Carbon black has a smaller particle size than the positive electrode active material 561. Carbon nanotubes (CNTs) and VGCF (registered trademark) are examples of fibrous carbon materials used for the conductive additive 554. Multilayer graphene is an example of a sheet-like carbon material used for the conductive additive 554. Figure 10A shows a cross section of the positive electrode, and the sheet-like carbon material may appear thread-like.

[0174] The particulate conductive additive 553 can penetrate into the gaps between the positive electrode active materials 561 and is prone to agglomeration. Therefore, the particulate conductive additive 553 can assist the conductive path between nearby positive electrode active materials (between adjacent positive electrode active materials). The fibrous or sheet-like conductive additive 554 has a folded region, but is larger than the positive electrode active material 561. Therefore, the fibrous or sheet-like conductive additive 554 can assist the conductive path between adjacent positive electrode active materials as well as between positive electrode active materials that are spaced apart. It is preferable to mix particulate, fibrous, and sheet-like conductive additives.

[0175] When graphene is used as a sheet-like conductive additive and is mixed with carbon black as a particulate conductive additive, the weight of the carbon black in the slurry is preferably 1.5 to 20 times, and more preferably 2 to 9.5 times, the weight of the graphene.

[0176] Furthermore, when the mixture ratio of graphene and carbon black is within the above range, the carbon black is easily dispersed without aggregation. Furthermore, when the mixture ratio of graphene and carbon black is within the above range, the electrode density can be increased compared to when only carbon black is used as the conductive additive. Increasing the electrode density can increase the capacity per unit weight. Specifically, the density of the positive electrode active material layer can be increased to more than 3.5 g / cc.

[0177] A positive electrode using a mixture of graphene and carbon black as a conductive additive can handle faster charging than a positive electrode using only graphene as a conductive additive. Furthermore, it is preferable that the mixture ratio of graphene and carbon black be within the above range.

[0178] Laminated secondary batteries are used in vehicles. Increasing the number of laminated secondary batteries to achieve high capacity increases the vehicle's mileage. However, this increases the vehicle's weight due to the laminated batteries, which increases the energy required to move the vehicle. However, it is possible to extend the mileage without increasing the number of laminated secondary batteries, with little change in the vehicle's total weight.

[0179] Furthermore, when the capacity of a secondary battery mounted on a vehicle increases, it is desirable to complete charging in a short time because it requires more power to charge. Furthermore, when the capacity of a secondary battery mounted on a vehicle increases, it is desirable to enable rapid charging in so-called regenerative charging, in which temporary power is generated when the vehicle brakes are applied and the generated power is charged.

[0180] [Electrolyte] The electrolyte 556 preferably includes a solvent and a metal salt that serves as a carrier ion. The electrolyte solvent is preferably an aprotic organic solvent, such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, chloroethylene carbonate, vinylene carbonate, γ-butyrolactone, γ-valerolactone, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, 1,3-dioxane, 1,4-dioxane, dimethoxyethane (DME), dimethyl sulfoxide, diethyl ether, methyl diglyme, acetonitrile, benzonitrile, tetrahydrofuran, sulfolane, or sultone, or any combination and ratio of two or more of these.

[0181] Furthermore, by using one or more flame-retardant and non-volatile ionic liquids (room-temperature molten salts) as the electrolyte solvent, it is possible to prevent the secondary battery from exploding or catching fire even if the internal temperature of the secondary battery rises due to an internal short circuit, overcharging, or the like. Ionic liquids are composed of cations and anions, including organic cations and anions. Examples of organic cations used in the electrolyte include aliphatic onium cations such as quaternary ammonium cations, tertiary sulfonium cations, and quaternary phosphonium cations, and aromatic cations such as imidazolium cations and pyridinium cations. Examples of anions used in the electrolyte include monovalent amide anions, monovalent methide anions, fluorosulfonate anions, perfluoroalkylsulfonate anions, tetrafluoroborate anions, perfluoroalkylborate anions, hexafluorophosphate anions, and perfluoroalkylphosphate anions.

[0182] Examples of salts that can be dissolved in the solvent include LiPF6, LiClO4, LiAsF6, LiBF4, LiAlCl4, LiSCN, LiBr, LiI, Li2SO4, and Li2B 10 Cl10 , Li2B 12 Cl 12 Lithium salts such as LiCF3SO3, LiC4F9SO3, LiC(CF3SO2)3, LiC(C2F5SO2)3, LiN(CF3SO2)2, LiN(C4F9SO2)(CF3SO2), LiN(C2F5SO2)2 can be used alone or in any combination and ratio of two or more of these.

[0183] The electrolyte used in the secondary battery is preferably a highly purified electrolytic solution with a low content of granular dust and elements other than the constituent elements of the electrolyte (hereinafter simply referred to as "impurities"). Specifically, the weight ratio of impurities to the electrolyte is preferably 1% or less, preferably 0.1% or less, and more preferably 0.01% or less.

[0184] The electrolyte may also contain additives such as vinylene carbonate, propane sultone (PS), tert-butylbenzene (TBB), fluoroethylene carbonate (FEC), lithium bis(oxalato)borate (LiBOB), or dinitrile compounds such as succinonitrile and adiponitrile. The concentration of the additive may be, for example, 0.1 wt% to 5 wt% of the total solvent. VC or LiBOB are particularly preferred because they easily form a good coating.

[0185] A solution containing a solvent and a salt that serves as carrier ions may be called an electrolyte.

[0186] A polymer gel electrolyte in which a polymer is swollen with an electrolytic solution may also be used.

[0187] The use of a polymer gel electrolyte improves safety against leakage, etc. It also enables the secondary battery to be made thinner and lighter.

[0188] Examples of polymers that can be gelled include silicone gel, acrylic gel, acrylonitrile gel, polyethylene oxide gel, polypropylene oxide gel, and fluorine-based polymer gel.

[0189] Examples of polymers that can be used include polymers having a polyalkylene oxide structure such as polyethylene oxide (PEO), PVDF, polyacrylonitrile, and copolymers containing these. For example, PVDF-HFP, a copolymer of PVDF and hexafluoropropylene (HFP), can be used. The polymer formed may also have a porous shape.

[0190] In addition, a solid electrolyte containing an inorganic material can be used as the electrolyte. For example, a sulfide-based solid electrolyte, an oxide-based solid electrolyte, a halide-based solid electrolyte, etc. can be used. A solid electrolyte containing a polymer material such as PEO (polyethylene oxide) can also be used. When a solid electrolyte is used, the installation of a separator and spacer is unnecessary. Furthermore, since the entire battery can be solidified, the risk of leakage is eliminated, dramatically improving safety.

[0191] Sulfide-based solid electrolytes include thiolithium-based (Li 10 GeP2S 12 , Li 3.25 Ge 0.25 P 0.75 S4, etc.), sulfide glasses (70Li2S·30P2S5, 30Li2S·26B2S3·44LiI, 63Li2S·36SiS2·1Li3PO4, 57Li2S·38SiS2·5Li4SiO4, 50Li2S·50GeS2, etc.), sulfide crystallized glasses (Li7P3S 11 , Li 3.25 P 0.95 Sulfide-based solid electrolytes have the advantages of being highly conductive, being able to be synthesized at low temperatures, and being relatively soft, which makes it easy to maintain conductive paths even after charging and discharging.

[0192] Oxide-based solid electrolytes include materials with a perovskite crystal structure (La 2 / 3-x Li 3x TiO3, etc.), materials with NASICON-type crystal structure (Li 1-X Al XTi 2-X (PO4)3, etc.), materials having a garnet-type crystal structure (Li7La3Zr2O 12 etc.), materials having a LISICON-type crystal structure (Li 14 ZnGe4O 16 etc.), LLZO (Li7La3Zr2O 12 ), oxide glasses (Li3PO4-Li4SiO4, 50Li4SiO4·50Li3BO3, etc.), oxide crystallized glasses (Li 1.07 Al 0.69 Ti 1.46 (PO4)3, Li 1.5 Al 0.5 Ge 1.5 (PO4)3, etc.) are included. Oxide-based solid electrolytes have the advantage of being stable in the atmosphere.

[0193] Halide-based solid electrolytes include LiAlCl4, Li3InBr6, LiF, LiCl, LiBr, LiI, etc. Also, composite materials in which these halide-based solid electrolytes are filled in the pores of porous aluminum oxide or porous silica can be used as solid electrolytes. [[ID=​​​​​​​​​​​​​​​​​A metal foil containing aluminum, titanium, copper, nickel, or the like can be used for the positive electrode current collector 550. A slurry containing a positive electrode active material layer 571 is applied to the metal foil and dried to complete the positive electrode. A carbon material may be coated on the metal foil.

[0197] The slurry contains at least positive electrode active material 561, binder 555, and a solvent, and preferably further contains conductive additive 553 and / or conductive additive 554. The slurry is sometimes called an electrode slurry or an active material slurry, and is sometimes called a positive electrode slurry when a positive electrode active material layer is formed, and sometimes called a negative electrode slurry when a negative electrode active material layer is formed.

[0198] Although the positive electrode active material 561 is shown as particulate in Fig. 10A, it is not limited to being particulate. As shown in Fig. 10B, the cross-sectional shape of the positive electrode active material 561 may be elliptical, rectangular, trapezoidal, conical, square with rounded corners, or asymmetrical. Note that the particulate positive electrode active material may be deformed into a shape such as that shown in Fig. 10B by pressing during the positive electrode fabrication process.

[0199] Figure 10C shows an example of a positive electrode in which carbon nanotubes are used instead of the graphene shown in Figure 10B. The use of carbon nanotubes can prevent the aggregation of carbon black such as acetylene black and improve dispersibility.

[0200] In Figure 10C, the areas not filled with the positive electrode active material 561 or carbon nanotubes are hollow, and some areas are impregnated with electrolyte 556. The positive electrode active material 561 has gaps that allow the electrolyte 556 to penetrate easily, creating voids. The volume of the positive electrode active material 561 may change during charging and discharging. However, by placing an electrolyte 556 containing an organic solvent containing fluorine, such as a fluorinated carbonate ester, and an ionic liquid between multiple positive electrode active materials 561, the active materials can slide easily even when volume changes occur during charging and discharging, suppressing cracking and improving cycle performance. It is important that a fluorine-containing organic compound is present between the multiple active materials that make up the positive electrode.

[0201] A secondary battery can be fabricated using any one of the positive electrodes shown in Figures 10A to 10C. A separator is placed on the positive electrode, and a negative electrode is placed on the separator. This laminate is placed in a container (such as an outer casing or a metal can), and the container is filled with an electrolyte.

[0202] [Negative electrode] The negative electrode includes a negative electrode active material layer and a negative electrode current collector. The negative electrode active material layer may also include a conductive additive and a binder.

[0203] <Negative electrode active material> The negative electrode active material may be, for example, an alloy-based material, a carbon-based material, or the like. The negative electrode active material used in the secondary battery of one embodiment of the present invention preferably contains fluorine as a halogen. Fluorine has a high electronegativity, and the presence of fluorine in the surface layer of the negative electrode active material may have the effect of facilitating the desorption of a solvated solvent from the surface of the negative electrode active material.

[0204] As the negative electrode active material, an element capable of undergoing a charge-discharge reaction by alloying and dealloying with lithium can be used. For example, a material containing at least one of silicon, tin, gallium, aluminum, germanium, lead, antimony, bismuth, silver, zinc, cadmium, indium, etc. can be used. These elements have a larger capacity than carbon, and silicon in particular has a high theoretical capacity of 4200 mAh / g. For this reason, it is preferable to use silicon as the negative electrode active material. Alternatively, a compound containing these elements may be used. For example, SiO (silicon monoxide, SiO X where x is preferably 0.2 or more and 1.5 or less), Mg2Si, Mg2Ge, SnO, SnO2, Mg2Sn, SnS2, V2Sn3, FeSn2, CoSn2, Ni3Sn2, Cu6Sn5, Ag3Sn, Ag3Sb, Ni2MnSb, CeSb3, LaSn3, La3Co2Sn7, CoSb3, InSb, SbSn, etc. Here, elements that can undergo charge-discharge reactions through alloying and dealloying reactions with lithium, and compounds containing such elements, are sometimes referred to as alloy-based materials.

[0205] Silicon nanoparticles can be used as the silicon-containing negative electrode active material. The median diameter (D50) of the silicon nanoparticles is 5 nm or more and less than 1 μm, preferably 10 nm or more and 300 nm or less, and more preferably 10 nm or more and 100 nm or less. The silicon nanoparticles may be crystalline. Furthermore, the silicon nanoparticles may have a crystalline region and an amorphous region.

[0206] The silicon-containing negative electrode active material may be in the form of silicon monoxide particles containing one or more silicon crystal grains. The silicon monoxide may be amorphous. The silicon monoxide particles may be carbon-coated. The carbon-coated particles may be mixed with graphite to form the negative electrode active material.

[0207] Examples of carbon-based materials that can be used include graphite, graphitizable carbon (soft carbon), non-graphitizable carbon (hard carbon), carbon nanotubes, graphene, and carbon black. It is preferable to incorporate fluorine into these carbon-based materials. A carbon-based material containing fluorine can also be called a particulate or fibrous fluorinated carbon material. When measuring a carbon-based material by X-ray photoelectron spectroscopy, the fluorine concentration is preferably 1 atomic % or more relative to the total concentration of fluorine, oxygen, lithium, and carbon.

[0208] Furthermore, although negative electrode active materials may undergo volume changes during charge and discharge, disposing an organic compound containing fluorine, such as a fluorinated carbonate, between the negative electrode active materials makes the active materials more slippery and suppresses cracking, even when volume changes occur during charge and discharge, thereby improving cycle characteristics. It is important that an organic compound containing fluorine is present between multiple negative electrode active materials.

[0209] Examples of graphite include artificial graphite and natural graphite. Examples of artificial graphite include mesocarbon microbeads (MCMB), coke-based artificial graphite, and pitch-based artificial graphite. Here, spherical graphite having a spherical shape can be used as the artificial graphite. For example, MCMB may have a spherical shape and is preferred. Furthermore, it is relatively easy to reduce the surface area of ​​MCMB, and this may be preferred. Examples of natural graphite include flake graphite and spherical natural graphite.

[0210] When lithium ions are inserted into graphite (when lithium-graphite intercalation compounds are formed), graphite exhibits a low potential similar to that of metallic lithium (0.05 V to 0.3 V vs. Li / Li + ) This allows lithium-ion secondary batteries to exhibit high operating voltages. Furthermore, graphite is preferred because it has advantages such as a relatively high capacity per unit volume, a relatively small volume expansion, low cost, and a higher level of safety compared to lithium metal.

[0211] In addition, titanium dioxide (TiO2), lithium titanium oxide (Li4Ti5O 12 ), lithium-graphite intercalation compound (Li x C6), niobium pentoxide (Nb2O5), tungsten oxide (WO2), molybdenum oxide (MoO2), and other oxides can be used.

[0212] In addition, the negative electrode active material is a composite nitride of lithium and transition metals, Li3N-type 3-x M x N (M=Co, Ni, Cu) can be used. For example, Li 2.6 Co 0.4 N3 has a large charge / discharge capacity (900mAh / g, 1890mAh / cm 3 ) and is preferred.

[0213] When a composite nitride of lithium and a transition metal is used, lithium ions are contained in the negative electrode active material, and therefore it can be preferably combined with a material that does not contain lithium ions, such as V2O5 or Cr3O8, as the positive electrode active material. Even when a material containing lithium ions is used as the positive electrode active material, the composite nitride of lithium and a transition metal can be used as the negative electrode active material by first desorbing the lithium ions contained in the positive electrode active material.

[0214] Materials that undergo a conversion reaction can also be used as the negative electrode active material. For example, transition metal oxides that do not form alloys with lithium, such as cobalt oxide (CoO), nickel oxide (NiO), and iron oxide (FeO), can be used as the negative electrode active material. The conversion reaction can also occur in oxides such as Fe2O3, CuO, Cu2O, RuO2, and Cr2O3, and CoS 0.89 It also occurs with sulfides such as NiS and CuS, nitrides such as Zn3N2, Cu3N and Ge3N4, phosphides such as NiP2, FeP2 and CoP3, and fluorides such as FeF3 and BiF3.

[0215] Lithium can also be used as the negative electrode active material. When lithium is used as the negative electrode active material, foil-shaped lithium can be provided on the negative electrode current collector. Lithium can also be provided on the negative electrode current collector by a gas phase method such as vapor deposition or sputtering. Lithium can also be electrochemically deposited on the negative electrode current collector in a solution containing lithium ions.

[0216] The conductive additive and binder that can be contained in the negative electrode active material layer can be the same materials as the conductive additive and binder that can be contained in the positive electrode active material layer.

[0217] In addition to the same materials as the positive electrode current collector, copper etc. can also be used as the current collector. It is preferable to use a material that does not alloy with carrier ions such as lithium for the negative electrode current collector.

[0218] As another embodiment of the negative electrode of the present invention, a negative electrode having no negative electrode active material can be used. In a secondary battery using a negative electrode having no negative electrode active material, lithium is deposited on the negative electrode current collector during charging, and the lithium on the negative electrode current collector can be eluted during discharging. Therefore, except in a fully discharged state, lithium is present on the negative electrode current collector.

[0219] When a negative electrode having no negative electrode active material is used, a film for uniformly depositing lithium may be provided on the negative electrode current collector. For example, a solid electrolyte having lithium ion conductivity can be used as the film for uniformly depositing lithium. Examples of solid electrolytes that can be used include sulfide-based solid electrolytes, oxide-based solid electrolytes, and polymer-based solid electrolytes. Among these, polymer-based solid electrolytes are suitable as a film for uniformly depositing lithium because they can be formed uniformly on the negative electrode current collector with relative ease.

[0220] Furthermore, when a negative electrode that does not have a negative electrode active material is used, a negative electrode current collector having projections and recesses can be used. When a negative electrode current collector having projections and recesses is used, the recesses of the negative electrode current collector become cavities into which lithium contained in the negative electrode current collector can be easily deposited, and therefore, when lithium is deposited, it is possible to prevent it from forming a dendritic shape.

[0221] [Fluorine-modified conductive additive] The conductive additive contained in the negative electrode can be the same as the conductive additive contained in the positive electrode.

[0222] The conductive additive in the negative electrode is preferably modified with fluorine. For example, the conductive additive may be any of the above-mentioned conductive additives modified with fluorine.

[0223] The fluorine modification of the conductive additive can be carried out by, for example, treatment with a fluorine-containing gas, heat treatment, plasma treatment in a fluorine-containing gas atmosphere, etc. Examples of the fluorine-containing gas that can be used include fluorine gas, fluoromethane (CF4), etc.

[0224] Alternatively, the conductive additive may be immersed in a solution containing hydrofluoric acid, tetrafluoroboric acid, hexafluorophosphoric acid, or the like, or a solution containing a fluorine-containing ether compound, for example, to modify the conductive additive with fluorine.

[0225] Fluorine modification of the conductive additive is expected to stabilize the structure of the conductive additive and suppress side reactions during the charge / discharge process of the secondary battery. Suppression of side reactions can improve charge / discharge efficiency. Furthermore, capacity reduction due to repeated charge / discharge can be suppressed. Therefore, by using a fluorine-modified conductive additive in the negative electrode of one embodiment of the present invention, an excellent secondary battery can be realized.

[0226] By stabilizing the structure of the conductive additive, the conductive properties are stabilized, and high output properties can be achieved in some cases.

[0227] [Separator] A separator is placed between the positive electrode and the negative electrode. The separator provides insulation between the positive electrode and the negative electrode. It is preferable that the separator is made of a material that is stable against the electrolyte and has excellent liquid retention properties. The separator can be made of, for example, cellulose-containing fibers such as paper, nonwoven fabric, glass fiber, ceramics, or synthetic fibers such as nylon (polyamide), vinylon (polyvinyl alcohol-based fiber), polyester, polyimide, acrylic, polyolefin, or polyurethane.

[0228] The separator preferably has a porosity of 30% to 85%, preferably 45% to 65%. A high porosity is preferable because it facilitates electrolyte impregnation. The porosity of the separator may be different between the positive electrode side and the negative electrode side, and it is preferable that the porosity on the positive electrode side is higher than the porosity on the negative electrode side. To achieve different porosities, the same material may be used but with different porosities, or different materials with different porosities may be used. When different materials are used, the porosity of the separator can be made different by stacking them.

[0229] The thickness of the separator is 5 μm or more and 200 μm or less, preferably 5 μm or more and 100 μm or less.

[0230] The separator preferably has an average pore size of 40 nm to 3 μm, preferably 70 nm to 1 μm. A larger average pore size is preferable because carrier ions can easily pass through the separator. The average pore size of the separator may be different between the positive electrode side and the negative electrode side, and it is preferable that the average pore size on the positive electrode side is larger than the average pore size on the negative electrode side. To make the average pore size different, the same material may be used but with different average pore sizes, or different materials with different average pore sizes may be used. When different materials are used, the average pore size of the separator can be made different by stacking them.

[0231] The separator preferably has a heat resistance of 200°C or higher.

[0232] It is preferable to use a separator made of polyimide, which has a thickness of 10 μm or more and 50 μm or less and a porosity of 75% or more and 85% or less, since this improves the output characteristics of the secondary battery.

[0233] The separator may be processed into a bag shape, and the bag-shaped separator may be disposed so as to wrap or sandwich either the positive electrode or the negative electrode.

[0234] The overall thickness of the separator is preferably 1 μm or more and 100 μm or less, and as long as it is within this thickness range, the separator may have either a single-layer structure or a multilayer structure. In the case of a multilayer structure, an organic material film such as polypropylene or polyethylene may be coated with a ceramic material, a fluorine-based material, a polyamide-based material, or a mixture of these. Examples of ceramic materials that can be used include aluminum oxide particles or silicon oxide particles. Examples of fluorine-based materials that can be used include PVDF or polytetrafluoroethylene. Examples of polyamide-based materials that can be used include nylon or aramid (meta-aramid, para-aramid).

[0235] Coating the separator surface with a ceramic material improves oxidation resistance, suppressing separator degradation during high-voltage charging and discharging and improving the reliability of the secondary battery. Coating the separator surface with a fluorine-based material also improves adhesion between the separator and electrodes, improving output characteristics. Coating the separator surface with a polyamide-based material, especially aramid, improves heat resistance, improving the safety of the secondary battery.

[0236] For example, both sides of a polypropylene film may be coated with a mixed material of aluminum oxide and aramid, or the surface of the polypropylene film that comes into contact with the positive electrode may be coated with a mixed material of aluminum oxide and aramid, and the surface that comes into contact with the negative electrode may be coated with a fluorine-based material.

[0237] The use of such a multilayer separator allows the functions of each material to be imparted to the separator, so that even if the separator as a whole is thin, insulation between the positive and negative electrodes can be ensured and the safety of the secondary battery can be maintained, which is preferable because it allows the capacity per volume of the secondary battery to be increased.

[0238] This embodiment mode can be implemented in appropriate combination with other embodiment modes.

[0239] (Fourth embodiment) In this embodiment, an example of manufacturing an all-solid-state battery using the positive electrode active material obtained in the above-described embodiment will be described.

[0240] As shown in FIG. 11A, a secondary battery 400 according to one embodiment of the present invention includes a positive electrode 410, a solid electrolyte layer 420, and a negative electrode 430.

[0241] Positive electrode 410 has positive electrode current collector 413 and positive electrode active material layer 414. Positive electrode active material layer 414 has positive electrode active material 411 and solid electrolyte 421. Positive electrode active material layer 414 may also have a conductive additive and a binder.

[0242] Solid electrolyte layer 420 has solid electrolyte 421. Solid electrolyte layer 420 is located between positive electrode 410 and negative electrode 430, and is a region that has neither positive electrode active material 411 nor negative electrode active material 431.

[0243] The negative electrode 430 includes a negative electrode current collector 433 and a negative electrode active material layer 434. The negative electrode active material layer 434 includes a negative electrode active material 431 and a solid electrolyte 421. The negative electrode active material layer 434 may also include a conductive additive and a binder. When metallic lithium is used as the negative electrode active material 431, it is not necessary to form the material into particles, and therefore, as shown in FIG. 11B , the negative electrode 430 can be one that does not include a solid electrolyte 421. Using metallic lithium for the negative electrode 430 is preferable because it can improve the energy density of the secondary battery 400.

[0244] As solid electrolyte 421 included in solid electrolyte layer 420, for example, a sulfide-based solid electrolyte, an oxide-based solid electrolyte, a halide-based solid electrolyte, or the like can be used.

[0245] Again, sulfide-based solid electrolytes include thiolithium-based (Li 10 GeP2S 12 , Li 3.25 Ge 0.25 P 0.75 S4, etc.), sulfide glasses (70Li2S·30P2S5, 30Li2S·26B2S3·44LiI, 63Li2S·36SiS2·1Li3PO4, 57Li2S·38SiS2·5Li4SiO4, 50Li2S·50GeS2, etc.), sulfide crystallized glasses (Li7P3S 11 , Li 3.25 P 0.95 Sulfide-based solid electrolytes have the advantages of being highly conductive, being able to be synthesized at low temperatures, and being relatively soft, which makes it easy to maintain conductive paths even after charging and discharging.

[0246] To reiterate, oxide-based solid electrolytes include materials with a perovskite crystal structure (La 2 / 3-x Li 3x TiO3, etc.), materials with NASICON-type crystal structure (Li 1-Y Al Y Ti 2-Y (PO4)3, etc.), materials with garnet-type crystal structure (Li7La3Zr2O 12 etc.), materials with LISICON-type crystal structure (Li 14 ZnGeO 16 etc.), LLZO(Li7La3Zr2O 12 ), oxide glass (Li3PO4-Li4SiO4, 50Li4SiO4·50Li3BO3, etc.), oxide glass-ceramics (Li 1.07 Al 0.69 Ti 1.46 (PO4)3, Li 1.5 Al 0.5 Ge 1.5 Oxide-based solid electrolytes have the advantage of being stable in the atmosphere.

[0247] As previously mentioned, halide-based solid electrolytes include LiAlCl4, Li3InBr6, LiF, LiCl, LiBr, LiI, etc. In addition, composite materials in which these halide-based solid electrolytes are filled in the pores of porous alumina or porous silica can also be used as solid electrolytes.

[0248] Also, different solid electrolytes may be mixed and used.

[0249] As previously mentioned, Li 1+x Al x Ti 2-x (PO4)3 (0 < x < 1) (hereinafter referred to as LATP) contains aluminum and titanium, which are elements that the positive electrode active material used in the secondary battery 400 of one embodiment of the present invention may have. Therefore, a synergistic effect can be expected for improving cycle characteristics, which is preferable. In addition, an improvement in productivity due to reduction of processes can also be expected. In this specification and the like, the NASICON-type crystal structure refers to a compound represented by M2(XO4)3 (M: transition metal, X: S, P, As, Mo, W, etc.), which has a structure in which MO6 octahedra and XO4 tetrahedra share vertices and are three-dimensionally arranged.

[0250] This embodiment can be used in appropriate combination with other embodiments.

[0251] (Embodiment 5) In this embodiment, a method for producing a positive electrode active material, which is one embodiment of the present invention, by a coprecipitation method will be described using the flowcharts and the like described in FIGS. 12 and 13. Note that FIG. 13 is a flowchart that details some of the procedures in FIG. 12, but the detailed procedures are not necessarily required.

[0252] The transition metal M source 81 (denoted as the M source in the drawing) shown in FIGS. 12 and 13 will be described.

[0253] <Transition metal M source> For example, at least one of nickel, cobalt, and manganese can be used as the transition metal M. For example, as the transition metal M, there are cases where only nickel is used, cases where two types of metals, cobalt and manganese, nickel and cobalt, or three types of metals, nickel, cobalt, and manganese, are used.

[0254] When at least one of nickel, cobalt, and manganese is used, it is preferable to set the mixing ratio of nickel, cobalt, and manganese within a range that allows a layered rock salt type crystal structure to be formed.

[0255] In particular, containing a large amount of nickel as the transition metal M is preferable because the raw material may be cheaper than when it contains a large amount of cobalt, and the charge / discharge capacity per weight may increase. For example, nickel preferably accounts for more than 25 atomic % of the transition metal M, more preferably 60 atomic % or more, and even more preferably 80 atomic % or more. However, if the proportion of nickel is too high, chemical stability and heat resistance may decrease. Therefore, it is preferable that nickel accounts for 95 atomic % or less of the transition metal M.

[0256] Cobalt is preferable as the transition metal M because it provides a high average discharge voltage and contributes to stabilizing the layered rock-salt structure, resulting in a highly reliable secondary battery. However, cobalt is more expensive than nickel and manganese and is unstable, so if the proportion of cobalt is too high, the cost of manufacturing the secondary battery may increase. Therefore, for example, it is preferable that the cobalt content of the transition metal M be 2.5 atomic % or more and 34 atomic % or less.

[0257] The transition metal M does not necessarily have to contain cobalt.

[0258] The inclusion of manganese as the transition metal M is preferable because it improves heat resistance and chemical stability. However, if the proportion of manganese is too high, the discharge voltage and discharge capacity tend to decrease. Therefore, for example, it is preferable that manganese be present in the transition metal M in an amount of 2.5 atomic % or more and 34 atomic % or less.

[0259] The transition metal M does not necessarily have to contain manganese.

[0260] The transition metal M source 81 is prepared as an aqueous solution containing the transition metal M. As the nickel source, a nickel salt such as nickel sulfate, nickel chloride, or nickel nitrate, or an aqueous solution of a hydrate thereof, can be used. Alternatively, an organic acid salt of nickel, such as nickel acetate, or an aqueous solution of a hydrate thereof can be used. Alternatively, an aqueous solution of nickel alkoxide or an organic nickel complex can be used. In this specification and the like, organic acid salt refers to a compound of a metal with an organic acid, such as acetic acid, citric acid, oxalic acid, formic acid, or butyric acid.

[0261] Similarly, the cobalt source can be a cobalt salt such as cobalt sulfate, cobalt chloride, cobalt nitrate, or an aqueous solution of a hydrate thereof. It can also be an aqueous solution of an organic acid salt of cobalt, such as cobalt acetate, or an aqueous solution of a hydrate thereof. It can also be an aqueous solution of a cobalt alkoxide or an organic cobalt complex.

[0262] Similarly, as the manganese source, a manganese salt such as manganese sulfate, manganese chloride, manganese nitrate, or an aqueous solution of a hydrate thereof can be used. Alternatively, an organic acid salt of manganese, such as manganese acetate, or an aqueous solution of a hydrate thereof can be used. Alternatively, an aqueous solution of a manganese alkoxide or an organic manganese complex can be used.

[0263] In this embodiment, an aqueous solution in which nickel sulfate, cobalt sulfate, and manganese sulfate are dissolved in pure water is prepared as the transition metal M source 81. The atomic ratio of nickel, cobalt, and manganese is Ni:Co:Mn=8:1:1 or approximately this. The aqueous solution is acidic.

[0264] A first additive element may be added to the transition metal M source 81. Specific examples of the first additive element include one or more selected from the group consisting of gallium, aluminum, boron, and indium.

[0265] When the first additive element is gallium, it can be referred to as a gallium source. A gallium-containing compound is used as the gallium source. Examples of the gallium-containing compound include gallium sulfate, gallium chloride, and gallium nitrate, as well as hydrates thereof. Gallium alkoxides or organic gallium complexes may also be used as gallium-containing compounds. Furthermore, organic acids of gallium, such as gallium acetate, or hydrates thereof may also be used as gallium-containing compounds.

[0266] When the first additive element is aluminum, it can be referred to as an aluminum source. An aluminum-containing compound is used as the aluminum source. Examples of the aluminum-containing compound include aluminum sulfate, aluminum chloride, and aluminum nitrate, as well as hydrates thereof. Aluminum alkoxides or organic aluminum complexes may also be used as aluminum-containing compounds. Organic aluminum acids, such as aluminum acetate, or hydrates thereof may also be used as aluminum-containing compounds.

[0267] When the first additive element is boron, it can be referred to as a boron source. A compound containing boron is used as the boron source. The compound containing boron can be, for example, boric acid or a borate.

[0268] When the first additive element is indium, it can be referred to as an indium source. A compound containing indium is used as the indium source. Examples of the indium-containing compound include indium sulfate, indium chloride, and indium nitrate, as well as hydrates thereof. Indium alkoxides or organic indium complexes may also be used as indium-containing compounds. Furthermore, organic acids of indium, such as indium acetate, or hydrates thereof may also be used as indium-containing compounds.

[0269] When a solution is used as the first additive element, an aqueous solution containing the above compound is prepared.

[0270] Here, the chelating agent 83 shown in FIGS. 12 and 13 will be described.

[0271] <Chelating agent> Examples of compounds that constitute chelating agents include glycine, oxine, 1-nitroso-2-naphthol, 2-mercaptobenzothiazole, and EDTA (ethylenediaminetetraacetic acid). It is also possible to use a plurality of compounds selected from glycine, oxine, 1-nitroso-2-naphthol, and 2-mercaptobenzothiazole. At least one of these compounds is dissolved in water (e.g., pure water) to prepare a chelating aqueous solution. Chelating agents are preferable to general complexing agents because they are complexing agents that form chelate compounds. Of course, general complexing agents may also be used; for example, ammonia water or the like may be used instead of a chelating agent.

[0272] The use of the above-described chelate aqueous solution is preferable because it can suppress the generation of unnecessary crystal nuclei and promote crystal growth. Suppressing the generation of unnecessary nuclei suppresses the generation of fine particles, allowing a cobalt compound with a good particle size distribution to be obtained. Furthermore, the use of the chelate aqueous solution can delay the acid-base reaction, allowing the reaction to proceed gradually, resulting in a cobalt compound with a nearly spherical shape.

[0273] Glycine, which is exemplified as a compound contained in the aqueous chelate solution, has the effect of maintaining a constant pH value at or near a pH of 9 to 10. Therefore, using an aqueous glycine solution as the aqueous chelate solution is preferable because it makes it easier to control the pH in the reaction vessel when obtaining the cobalt compound.

[0274] <Pure water> The water used in the chelate aqueous solution is preferably pure water. Pure water is water with a resistivity of 1 MΩ cm or more, more preferably 10 MΩ cm or more, and even more preferably 15 MΩ cm or more. Water that satisfies this resistivity range has high purity and contains very few impurities.

[0275] <Step S14> Next, a description will be given of step S14 shown in Figures 12 and 13. In step S14, a transition metal M source 81 and a chelating agent 83 are mixed together. Then, an acid solution 91 is obtained.

[0276] Next, the alkaline solution 84 shown in FIGS. 12 and 13 will be described.

[0277] <Alkaline solution> The alkaline solution may be, for example, an aqueous solution containing sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia, but is not limited to these aqueous solutions as long as it functions as a pH adjuster. For example, it may be an aqueous solution in which multiple types selected from sodium hydroxide, potassium hydroxide, and lithium hydroxide are dissolved in water. The water used may be the above-mentioned pure water.

[0278] Here, we will explain the water 85 shown in Figure 13. Water 85 may be referred to as the charging solution or the adjusting solution, and refers to the aqueous solution in the initial reaction state. It is recommended to use the above-mentioned pure water or an aqueous solution obtained by dissolving the above-mentioned chelating agent in the above-mentioned pure water. Using a chelating agent can suppress the generation of unwanted crystal nuclei and promote growth, as described above. Suppressing the generation of unwanted nuclei suppresses the generation of fine particles, which has the effect of producing a cobalt compound with a good particle size distribution, or slowing the acid-base reaction, allowing the reaction to proceed gradually and resulting in a cobalt compound with a nearly spherical shape. However, it is not necessary to use water 85 as shown in Figure 12.

[0279] <Step S31> 12 and 13, step S31 is described below. In step S31, the acid solution 91 and the alkaline solution 84 are mixed. By mixing, the acid solution 91 and the alkaline solution 84 react with each other, and a coprecipitate 95 is produced.

[0280] The reaction in step 31 may be referred to as a neutralization reaction, an acid-base reaction, or a co-precipitation reaction. The resulting coprecipitate 95 may be referred to as a precursor of the positive electrode active material.

[0281] <Reaction conditions> When reacting the acid solution 91 and the alkaline solution 84 according to the coprecipitation reaction, the pH of the reaction tank is adjusted to 9 or more and 11 or less, preferably 9.8 or more and 10.5 or less. This range is preferable because it allows for a large particle size of the secondary particles of the resulting coprecipitate. If the pH is outside this range, productivity will be low and the resulting coprecipitate will be more likely to contain impurities.

[0282] When the acid solution 91 is placed in a reaction tank and the alkaline solution 84 is added dropwise to the reaction tank, it is advisable to maintain the pH of the aqueous solution in the reaction tank within the range of the above conditions. Also, when the alkaline solution 84 is placed in a reaction tank and the acid solution 91 is added dropwise to the reaction tank, it is advisable to maintain the pH within the range of the above conditions.

[0283] To further promote the coprecipitation reaction efficiently, it is recommended to place water 85 shown in Fig. 13 in the reaction tank and then dropwise add acid solution 91. If the pH of the reaction tank deviates from the predetermined value due to the dropwise addition of acid solution 91, it is recommended to control the pH of the reaction tank by dropping alkaline solution 84.

[0284] The solution in the reaction vessel may be stirred using a stirring means, such as a stirrer or stirring blades. Two to six stirring blades may be provided.

[0285] The temperature of the solution in the reaction tank is adjusted to be between 50° C. and 90° C. Dropping should begin after the temperature reaches the desired level. The above range is preferable because it allows the particle size of the secondary particles of the resulting coprecipitate 95 to be large.

[0286] The reactor may also be equipped with a reflux condenser, which allows nitrogen gas to escape from the reactor and water to return to the reactor.

[0287] After the above reaction, a coprecipitate 95 is deposited in the reaction tank as a reaction product.

[0288] <Steps S32 and S33> Here, the precipitate 92 shown in FIG. 13, the filtration in step S32, and the drying in step S33 will be described. The precipitate 92 contains the above-mentioned coprecipitate 95. The precipitate 92 also contains impurities other than the coprecipitate 95. Therefore, in order to recover the coprecipitate 95, the filtration in step S32 is preferably performed. The filtration can be performed by suction filtration or vacuum filtration. Centrifugation may also be used instead of filtration. When suction filtration is used, it is preferable to wash the reaction product precipitated in the reaction tank with pure water and then add an organic solvent with a low boiling point (e.g., acetone) before performing the suction filtration.

[0289] After filtration, the mixture may be further dried in step S33. For example, the mixture may be dried under vacuum at a temperature of 60° C. to 90° C. for 0.5 to 3 hours. In this manner, a coprecipitate 95 can be obtained.

[0290] The coprecipitate 95 contains a precursor of the positive electrode active material. The precursor of the positive electrode active material is obtained as secondary particles formed by aggregation of primary particles. In this specification and the like, a primary particle refers to a particle (agglomerate) of the smallest unit that does not have a grain boundary when observed at, for example, 5000 times magnification using a scanning electron microscope (SEM). In other words, a primary particle refers to a particle of the smallest unit that is surrounded by a grain boundary. A secondary particle refers to a particle (particle independent from other particles) in which the primary particles aggregate to share a part of the grain boundary (such as the outer periphery of the primary particle) and are not easily separated. In other words, the secondary particle may have a grain boundary.

[0291] Next, a lithium compound is prepared as the lithium source 88 (referred to as Li source in the drawings) shown in FIGS.

[0292] <Lithium compounds> As the lithium compound, lithium hydroxide, lithium carbonate, lithium oxide, or lithium nitrate is prepared. For example, when cobalt hydroxide is obtained as coprecipitate 95, lithium hydroxide can be used as the lithium compound.

[0293] It is advisable to pulverize the lithium compound beforehand. The container used for pulverization, such as a mortar, is preferably made of a material that does not easily release impurities. Specifically, it is advisable to use an alumina mortar with a purity of 90% or more, preferably 99% or more. Wet pulverization using a ball mill may also be used. In wet pulverization, acetone can be used as the solvent.

[0294] <Step S51> Next, step S51 shown in Figures 12 and 13 will be described. In step S51, the coprecipitate 95 and the lithium source 88 are mixed. Thereafter, a mixed mixture 97 is obtained. A revolutionary agitator may be used as a means for mixing the coprecipitate 95 and the lithium source 88. Because revolutionary agitators do not use media, pulverization is often not performed.

[0295] When mixing and pulverizing the coprecipitate 95 and the lithium source 88 simultaneously, a ball mill or a bead mill may be used. Alumina balls or zirconia balls may be used as media for the ball mill or bead mill. In a ball mill or bead mill, centrifugal force is applied to the media, making it possible to micronize the material. However, if there is a concern about contamination from the media, it is preferable to use the zirconia balls.

[0296] When pulverization is performed simultaneously, there are dry pulverization and wet pulverization. Dry pulverization is performed in an inert gas or air, and can pulverize particles to a diameter of 3.5 μm or less, preferably 3 μm or less. Wet pulverization is performed in a liquid, and can pulverize particles to nano-sized sizes. In other words, wet pulverization is recommended when small particle diameters are desired.

[0297] In this way, mixture 97 is obtained.

[0298] Here, the heating step will be explained in more detail using S52 and S53 shown in FIG.

[0299] <Step S52> Next, step S52 shown in FIG. 13 will be described. The heating step may be performed multiple times, or, as in step S52, heating may be performed at a temperature of 400°C to 700°C before step S54, which will be described later. The heating in step S52 is sometimes referred to as pre-baking because it is performed at a lower temperature than step S54. Step S52 may release gas components contained in the coprecipitate 95 or lithium source 88. By using a material from which gas components have been released, a composite oxide with few impurities can be obtained. However, as shown in FIG. 12, a positive electrode active material can be obtained without performing pre-baking in step S52.

[0300] <Step S53> Next, step S53 shown in Fig. 13 will be described. In step S53, a crushing step is performed. For example, classification may be performed using a sieve with a mesh size of 40 µm or more and 60 µm or less. However, as shown in Fig. 12, the positive electrode active material can be obtained without performing the crushing step of step S53.

[0301] <Step S54> Next, step S54 shown in FIGS. 12 and 13 will be described. In step S54, the mixture is heated. By heating, a composite oxide, NCM, is obtained. This is the positive electrode active material 100. Step S54 is sometimes referred to as main calcination. There are many heating steps, including step S52, but to distinguish between them, they are sometimes referred to as first heating, second heating, etc., with appropriate ordinal numbers.

[0302] <Heating conditions> The heating temperature is preferably 700° C. or higher but lower than 1100° C., more preferably 800° C. or higher but lower than 1000° C., and even more preferably 800° C. or higher but lower than 950° C. When producing cobalt oxide through this heat treatment, heating is performed at a temperature at which at least the coprecipitate 95 and the lithium source 88 diffuse into each other. This temperature is the reason why this temperature is called the main calcination temperature.

[0303] The heating time can be, for example, from 1 hour to 100 hours, and is preferably from 2 hours to 20 hours.

[0304] The heating atmosphere is preferably an oxygen-containing atmosphere or a so-called dry air atmosphere containing little water (for example, a dew point of -50°C or less, more preferably a dew point of -80°C or less).

[0305] For example, when heating at 750°C for 10 hours, the temperature rise rate should be 150°C / hour or more and 250°C / hour or less. The flow rate of dry air that can constitute the drying atmosphere is preferably 3 L / min or more and 10 L / min or less. The temperature drop time is preferably 10 hours or more and 50 hours or less until the temperature drops from the specified temperature to room temperature, and the temperature drop rate can be calculated from the temperature drop time, etc.

[0306] It is preferable that the crucible, sheath, setter, or container used during heating be made of a material that does not easily release impurities. For example, it is recommended to use a crucible made of alumina with a purity of 99.9%. For mass production, it is recommended to use a sheath made of mullite or cordierite (Al2O3, SiO2, MgO).

[0307] Furthermore, when recovering the material after heating, it is preferable to transfer it from the crucible to a mortar and then recover it, as this prevents impurities from being mixed into the material. The mortar is also preferably made of a material that does not easily release impurities, specifically, an alumina or zirconia mortar with a purity of 90% or more, preferably 99% or more.

[0308] As described above, the positive electrode active material 100 such as NCM can be manufactured. The positive electrode active material 100 can reflect the shape of the coprecipitate 95, which is the precursor.

[0309] Furthermore, cathode active materials 100 such as NCM are preferred because they have few impurities. However, if sulfide is used as the starting material, sulfur may be detected. The sulfur concentration can be measured by performing elemental analysis of the entire particle of the cathode active material using GD-MS, ICP-MS, or the like.

[0310] (Embodiment 6) In this embodiment, a process for producing a positive or negative electrode coating will be described.

[0311] A coated electrode refers to a positive electrode mixture (containing at least a positive electrode active material) formed on a positive electrode current collector, or a negative electrode mixture (containing at least a negative electrode active material) formed on a negative electrode current collector. Each mixture may contain a conductive material or a binder.

[0312] For example, the positive electrode active material, conductive material, and binder shown in the above embodiment are mixed, and a dispersion medium is added to the mixture. After the dispersion medium is added, the mixture is further mixed to form a slurry. The viscosity of the slurry is preferably 80 Pa·s or more and 130 Pa·s or less.

[0313] The slurry is applied to a positive electrode current collector and dried. At least the dispersion medium is evaporated. The slurry may then be pressed and rolled. Pressurization may be performed multiple times at different pressures, and the second pressurization may be performed at a higher pressure than the first pressurization. In this way, a coated electrode is completed. The thickness of the coated electrode is preferably 1 μm or more and 10 μm or less. The electrode density of the coated electrode is 3.0 g / cm. 3 More than 5.0g / cm 3 The following would be appropriate.

[0314] Although the positive electrode has been described, the negative electrode can also be produced in the same manner.

[0315] This embodiment can be used in combination with other embodiments.

[0316] (Embodiment 7) In this embodiment, a manufacturing process of a secondary battery will be described.

[0317] 14 shows an example of a process for producing a secondary battery. In step S110, a positive electrode coating and a negative electrode coating are prepared. Each of the coating electrodes can be produced, for example, according to the above-described embodiment.

[0318] In step S120 of FIG. 14, each coated electrode is punched out into a desired shape. The tab region is provided at a position protruding from the rectangular positive or negative electrode, and the length of one side of the tab region is between 1 / 3 and 1 / 5 of the length of one side of the positive or negative electrode. During the punching process, the region to which the tab is bonded (tab region) is made conductive. For example, insulating films and the like are removed from the tab region punched out in the predetermined position using a chemical solution. The chemical solution can be acetone, ethanol, or N-methyl-2-pyrrolidone (NMP). In this way, the positive and negative electrodes to be mounted in the secondary battery can be obtained in step S130.

[0319] Next, a separator is prepared as shown in step S135 of Figure 14, and the separator is processed in step S140. For example, the cut-out separator can be folded in half and processed into a bag-shaped separator by welding two sides. The width of the welded area should be 3 nm or more and 10 nm or less. Heat of 120 °C or more and 170 °C or less, preferably 130 °C or more and 150 °C or less, may be applied for welding. In this case, placing metal foil in areas that should not be welded (areas that will become bags) can prevent welding in unnecessary areas.

[0320] Next, as shown in step S150 of FIG. 14, positive and negative electrodes and separators are assembled. For example, one of the positive and negative electrodes is placed in a pouch-shaped separator, and the separator is then stacked on the other positive or negative electrode. Ten single-sidedly coated positive and negative electrodes are prepared, and five separators are prepared. When placing positive electrodes in the separators, two positive electrodes are placed with their positive electrode current collectors facing each other. Positive electrodes are placed in the remaining separators in the same manner. Two negative electrodes are placed between the separators with their negative electrode current collectors facing each other. There are two pairs of outermost separators, but only one negative electrode is placed on each of them, and the negative electrode active material is arranged toward the separator. In this way, structure X can be assembled as shown in step S160. It is preferable to bond the tab regions in structure X. For example, the tab regions for the positive and negative electrodes are bonded using an ultrasonic metal bonding tool.

[0321] Next, as shown in step S170 of Fig. 14, a positive electrode tab and a negative electrode tab are prepared. As shown in step S180, a chemical treatment is performed to remove insulating films and the like from the positive electrode tab and the negative electrode tab. Acetone, ethanol, or NMP can be used as the chemical.

[0322] 14, a positive electrode tab and a negative electrode tab are bonded to the structure X. The positive electrode tab and the negative electrode tab are bonded to the tab regions bonded in step S160 using an ultrasonic metal bonder.

[0323] Next, as shown in step S200 of Fig. 14, a laminate film is prepared, and the laminate film is processed as shown in step S210. For example, as part of the processing, a recess having a depth of 1 mm to 10 mm, preferably 1.5 mm to 3 mm, is formed in a part of the laminate film.

[0324] Assembly is performed as shown in step S220 of Figure 14. For example, the structure X with the tab joined to the recess is placed in the recess, the laminate film is folded, and at least two opposing sides are welded. Heat is applied at 150°C to 190°C, preferably 170°C to 180°C. Furthermore, it is preferable to perform the welding in a dry atmosphere.

[0325] Next, as shown in step S230 of Fig. 14, an electrolyte is poured. The electrolyte is preferably poured in an inert atmosphere (an atmosphere containing an inert gas). The remaining sides of the laminate film are welded. The remaining sides are preferably welded in a reduced pressure atmosphere.

[0326] Then, as shown in step S240 of FIG. 14, a laminated secondary battery is completed.

[0327] <Laminated secondary battery> 15A and 15B show examples of external views of a laminated secondary battery. Each of the batteries shown in Fig. 15A and 15B includes a positive electrode 503, a negative electrode 506, a separator 507, an outer casing 509, a positive electrode lead electrode 510, and a negative electrode lead electrode 511. The positive electrode lead electrode 510 and the negative electrode lead electrode 511 may be provided on the same side as in Fig. 15A, or may be provided on opposing sides as in Fig. 15B.

[0328] This embodiment mode can be implemented in appropriate combination with other embodiment modes.

[0329] (Embodiment 8) In this embodiment, another configuration example of the secondary battery will be described with reference to FIGS.

[0330] [Other examples of secondary battery structures] 16A has a wound body 950 provided with terminals 951 and 952 inside a housing 930. The wound body 950 is immersed in an electrolyte inside the housing 930. The terminal 952 contacts the housing 930, and the terminal 951 is not in contact with the housing 930 by using an insulating material or the like. Note that in FIG. 16A, for convenience, the housing 930 is shown separated, but in reality, the wound body 950 is covered by the housing 930, and the terminals 951 and 952 extend outside the housing 930. The housing 930 can be made of a metal material (such as aluminum) or a resin material.

[0331] 16B, the housing 930 shown in Fig. 16A may be formed from a plurality of materials. For example, the secondary battery 913 shown in Fig. 16B has housings 930a and 930b bonded together, and a wound body 950 is provided in the area surrounded by housings 930a and 930b.

[0332] The housing 930a can be made of an insulating material such as organic resin. In particular, by using a material such as organic resin on the surface on which the antenna is formed, it is possible to prevent the secondary battery 913 from blocking the electric field. Note that if the electric field blocking effect of the housing 930a is small, the antenna may be provided inside the housing 930a. The housing 930b can be made of, for example, a metal material.

[0333] 16C shows the structure of wound body 950. Winding body 950 has a negative electrode 931, a positive electrode 932, and a separator 933. Winding body 950 is a wound body in which negative electrode 931 and positive electrode 932 are stacked on top of each other with separator 933 sandwiched therebetween, and the stacked sheet is wound. Note that multiple stacks of negative electrode 931, positive electrode 932, and separator 933 may be stacked.

[0334] 17A to 17C, a secondary battery 913 may be provided having a wound body 950a. The wound body 950a shown in Fig. 17A has a negative electrode 931, a positive electrode 932, and a separator 933. The negative electrode 931 has a negative electrode active material layer 931a. The positive electrode 932 has a positive electrode active material layer 932a.

[0335] By using the positive electrode active material obtained in the above embodiment for the positive electrode 932, the secondary battery 913 can have a large capacity, a high charge / discharge capacity, and excellent cycle characteristics.

[0336] The separator 933 has a width wider than the negative electrode active material layer 931a and the positive electrode active material layer 932a, and is wound so as to overlap the negative electrode active material layer 931a and the positive electrode active material layer 932a. From the standpoint of safety, it is preferable that the negative electrode active material layer 931a be wider than the positive electrode active material layer 932a. A wound body 950a having such a shape is preferable because of its high safety and productivity.

[0337] 17B, ​​negative electrode 931 is electrically connected to terminal 951. Terminal 951 is electrically connected to terminal 911a. Positive electrode 932 is electrically connected to terminal 952. Terminal 952 is electrically connected to terminal 911b.

[0338] 17C, wound body 950a and the electrolyte are covered by casing 930 to form secondary battery 913. It is preferable to provide casing 930 with a safety valve, an overcurrent protection element, etc. The safety valve is a valve that opens when the inside of casing 930 reaches a predetermined internal pressure to prevent the battery from exploding.

[0339] As shown in Fig. 17B, the secondary battery 913 may have multiple wound bodies 950a. Using multiple wound bodies 950a can result in a secondary battery 913 with a larger charge / discharge capacity. For other elements of the secondary battery 913 shown in Figs. 17A and 17B, the descriptions of the secondary battery 913 shown in Figs. 16A to 16C can be referred to.

[0340] <Cylindrical secondary battery> Next, an example of a cylindrical secondary battery will be described with reference to Fig. 18. Fig. 18A shows an external view of a cylindrical secondary battery 600. Fig. 18B is a schematic diagram showing a cross section of the cylindrical secondary battery 600. As shown in Fig. 18B, the cylindrical secondary battery 600 has a positive electrode cap (battery lid) 601 on the top surface, and a battery can (external can) 602 on the side and bottom surfaces. The positive electrode cap and the battery can (external can) 602 are insulated by a gasket (insulating packing) 610.

[0341] A battery element is provided inside a hollow cylindrical battery can 602, in which a strip-shaped positive electrode 604 and a negative electrode 606 are wound with a separator 605 sandwiched between them. Although not shown, the battery element is wound around a center pin. One end of the battery can 602 is closed and the other end is open. The battery can 602 can be made of a metal such as nickel, aluminum, or titanium that is corrosion-resistant to the electrolyte, or an alloy of these metals or alloys of these metals with other metals (e.g., stainless steel). To prevent corrosion by the electrolyte, the battery can 602 is preferably coated with nickel, aluminum, or the like. Inside the battery can 602, the wound battery element, in which the positive electrode, negative electrode, and separator are wound, is sandwiched between a pair of opposing insulating plates 608 and 609. A nonaqueous electrolyte (not shown) is poured into the battery can 602, in which the battery element is provided. The nonaqueous electrolyte may be the same as that used in coin-type secondary batteries.

[0342] Because the positive and negative electrodes used in cylindrical secondary batteries are wound, it is preferable to form active materials on both sides of the current collector. A positive electrode terminal (positive electrode current collector lead) 603 is connected to the positive electrode 604, and a negative electrode terminal (negative electrode current collector lead) 607 is connected to the negative electrode 606. Both the positive electrode terminal 603 and the negative electrode terminal 607 can be made of a metal material such as aluminum. The positive electrode terminal 603 is resistance-welded to a safety valve mechanism 612, and the negative electrode terminal 607 is resistance-welded to the bottom of the battery can 602. The safety valve mechanism 612 is electrically connected to the positive electrode cap 601 via a PTC (Positive Temperature Coefficient) element 611. The safety valve mechanism 612 cuts off the electrical connection between the positive electrode cap 601 and the positive electrode 604 when the internal pressure of the battery exceeds a predetermined threshold. The PTC element 611 is a thermosensitive resistor whose resistance increases as the temperature rises, and the increased resistance limits the amount of current to prevent abnormal heat generation. Barium titanate (BaTiO3) based semiconductor ceramics or the like can be used for the PTC element.

[0343] 18C , a module 615 may be configured by sandwiching a plurality of secondary batteries 600 between conductive plates 613 and 614. The plurality of secondary batteries 600 may be connected in parallel, in series, or in parallel and then in series. By configuring a module 615 having a plurality of secondary batteries 600, a large amount of power can be extracted.

[0344] FIG. 18D is a top view of module 615. For clarity, conductive plate 613 is shown with dotted lines. As shown in FIG. 18D, module 615 may have conductors 616 that electrically connect multiple secondary batteries 600. A conductive plate can be superimposed on the conductors 616. Furthermore, a temperature control device 617 may be provided between multiple secondary batteries 600. When a secondary battery 600 overheats, it can be cooled by the temperature control device 617, and when a secondary battery 600 is too cold, it can be heated by the temperature control device 617. This makes the performance of module 615 less susceptible to the influence of the outside air temperature. It is preferable that the heat medium in temperature control device 617 is insulating and non-flammable.

[0345] By using the positive electrode active material described in the above embodiment for the positive electrode 604, the cylindrical secondary battery 600 can have high charge / discharge capacity and excellent cycle characteristics.

[0346] (Embodiment 9) In this embodiment, an example in which a battery management system according to one embodiment of the present invention is installed in a moving object such as a vehicle will be described.

[0347] By installing a secondary battery in a vehicle, next-generation clean energy automobiles such as hybrid vehicles (HVs), electric vehicles (EVs), and plug-in hybrid vehicles (PHVs) can be realized. Secondary batteries can also be installed in agricultural machinery, motorized bicycles including electrically assisted bicycles, motorcycles, electric wheelchairs, electric carts, small or large ships, submarines, aircraft such as fixed-wing aircraft and rotary-wing aircraft, rockets, artificial satellites, space probes, planetary probes, spacecraft, and the like. The secondary battery of one embodiment of the present invention can be a high-capacity secondary battery. Therefore, the secondary battery of one embodiment of the present invention is suitable for miniaturization and weight reduction and can be suitably used in transportation vehicles.

[0348] FIG. 19 illustrates an example of a moving object such as a vehicle using a battery storage management system according to one embodiment of the present invention. The automobile 8400 illustrated in FIG. 19A is an electric automobile that uses an electric motor as a power source for traveling. Alternatively, it is a hybrid automobile that can appropriately select and use an electric motor or an engine as a power source for traveling. By using one embodiment of the present invention, it is possible to utilize the maximum capacity of a secondary battery installed therein, thereby achieving a vehicle with a long cruising range. The automobile 8400 also includes a secondary battery. The secondary battery not only drives the electric motor 8406 but also supplies power to light-emitting devices such as a headlight 8401 and an interior light (not shown).

[0349] The secondary battery can also supply power to display devices such as a speedometer and a tachometer included in the automobile 8400. The secondary battery can also supply power to semiconductor devices such as a navigation system included in the automobile 8400.

[0350] The automobile 8500 shown in FIG. 19B can charge its secondary battery by receiving power from an external charging facility using a plug-in system or a wireless power supply system. FIG. 19B shows a state in which a secondary battery 8024 mounted on the automobile 8500 is being charged via a cable 8022 from a ground-mounted charging device 8021. The charging method and connector specifications may be determined appropriately using a predetermined system such as CHAdeMO (registered trademark) or Combo. The charging device 8021 may be a charging station installed in a commercial facility or a household power source. For example, plug-in technology can be used to charge the secondary battery 8024 mounted on the automobile 8500 using external power supply. Charging can be performed by converting AC power to DC power using a conversion device such as an AC-DC converter.

[0351] Although not shown, a power receiving device can be mounted on a vehicle and power can be supplied contactlessly from a ground power transmitting device to charge the vehicle. In the case of this contactless power supply method, by incorporating a power transmitting device into a road or an exterior wall, charging can be performed not only while the vehicle is stopped but also while the vehicle is moving. This contactless power supply method can also be used to transmit and receive power between vehicles. Furthermore, a solar cell can be installed on the exterior of the vehicle to charge the secondary battery while the vehicle is stopped and while moving. For such contactless power supply, an electromagnetic induction method or a magnetic field resonance method can be used.

[0352] 19C shows an example of a motorcycle using the battery management system of one embodiment of the present invention. A scooter 8600 shown in FIG. 19C includes a secondary battery 8602, a side mirror 8601, and a turn signal light 8603. The secondary battery 8602 can supply electricity to the turn signal light 8603.

[0353] 19C can store a secondary battery 8602 in under-seat storage 8604. Even if under-seat storage 8604 is small, secondary battery 8602 can be stored in under-seat storage 8604. Secondary battery 8602 is removable, and when charging, secondary battery 8602 can be carried indoors, charged, and stored before riding.

[0354] 19D shows an example of a satellite using the battery management system of one embodiment of the present invention. A satellite 8800 shown in FIG. 19D includes a secondary battery 8801. Because the satellite 8800 is used in space at extremely low temperatures, the secondary battery 8801 is preferably mounted inside the satellite 8800 and covered with a heat-insulating material.

[0355] According to one aspect of the present invention, the cycle characteristics of the secondary battery are improved, and the charge / discharge capacity of the secondary battery can be increased. Therefore, the secondary battery itself can be made smaller and lighter. Reducing the size and weight of the secondary battery itself contributes to reducing the weight of the vehicle, thereby improving the cruising range. Furthermore, the secondary battery mounted on the vehicle can also be used as a power supply source for purposes other than the vehicle. In this case, for example, it is possible to avoid using a commercial power source during peak power demand periods. Avoiding the use of a commercial power source during peak power demand periods can contribute to energy conservation and the reduction of carbon dioxide emissions. Furthermore, good cycle characteristics allow the secondary battery to be used for a long period of time, thereby reducing the amount of rare metals used, such as cobalt.

[0356] This embodiment mode can be implemented in appropriate combination with other embodiment modes. [Explanation of symbols]

[0357] 1: Server device, 2: Charger, 3: Vehicle, 4: Battery pack, 5: Power receiving connector, 7: Communication network, 11: Data, 41: Secondary battery, 42: Power control unit, 43: Drive motor, 44: Battery cell, 45: Balancing circuit, 46: Resistor, 47: Circuit, 50: Vehicle control unit, 51: CPU, 52: Memory unit, 53: Communication unit, 60: Protection circuit, 61: Current monitoring circuit, 62: Voltage monitoring circuit, 63: Temperature monitoring circuit, 64: Path blocking circuit, 71: Start switch

Claims

1. A battery management system including a server device and a vehicle equipped with a means capable of transmitting and receiving data to and from the server device, The vehicle includes a storage battery and a balancing circuit electrically connected to the storage battery; a vehicle control unit having a function of controlling the balancing circuit, the storage battery includes a battery pack having a plurality of battery cells, the server device has a function of calculating sequential data including SOC-OCV characteristic data based on values ​​of voltage, current, temperature, or capacity of the battery cell transmitted from the vehicle, as at least two or more estimated values, and a function of transmitting the two or more estimated values ​​to the vehicle; the vehicle control unit has a memory unit, and the memory unit has a function of storing two or more estimated values; the vehicle control unit has a function of selecting, from the two or more estimated values, an estimated value that is optimal for the battery cells of the battery pack and does not include any error; The balancing circuit has a function that is controlled based on the selected estimated value.

2. The battery management system of claim 1 , wherein the sequential data includes an internal resistance.

3. 3. The battery management system according to claim 2, wherein the internal resistance includes a resistance component R1 having a fast response and a resistance component R2 having a slow response.

4. 4. The battery management system according to claim 3, wherein the server device has a function of predicting changes in the fast-response resistance component R1 and the slow-response resistance component R2 using a long short-term memory (LSTM).

5. A storage battery and a balancing circuit electrically connected to the storage battery; a vehicle control unit having a function of controlling the balancing circuit, the storage battery includes a battery pack having a plurality of battery cells, the vehicle control unit has a memory unit, and the memory unit has a function of storing two or more estimated values ​​related to sequential data including SOC-OCV characteristic data of the battery cell transmitted from a server device; the vehicle control unit has a function of selecting, from the two or more estimated values, an estimated value that is optimal for the battery cells of the battery pack and does not include any error; The balancing circuit has a function that is controlled based on the selected estimated value.

6. 6. The vehicle of claim 5, wherein the sequential data includes an internal resistance.

7. 7. The vehicle according to claim 6, wherein the internal resistance includes a resistance component R1 having a fast response and a resistance component R2 having a slow response.

8. 8. The vehicle according to claim 6, wherein the internal resistance includes a measured value for each of the plurality of battery cells.

9. 9. The vehicle according to claim 6, further comprising a function for measuring the internal resistance by a current-rest method.

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