WO2013069346A1 - 蓄電池状態監視システム - Google Patents
蓄電池状態監視システム Download PDFInfo
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- WO2013069346A1 WO2013069346A1 PCT/JP2012/069622 JP2012069622W WO2013069346A1 WO 2013069346 A1 WO2013069346 A1 WO 2013069346A1 JP 2012069622 W JP2012069622 W JP 2012069622W WO 2013069346 A1 WO2013069346 A1 WO 2013069346A1
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- storage battery
- monitoring system
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- state
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/382—Arrangements for monitoring battery or accumulator variables, e.g. SoC
- G01R31/3842—Arrangements for monitoring battery or accumulator variables, e.g. SoC combining voltage and current measurements
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/382—Arrangements for monitoring battery or accumulator variables, e.g. SoC
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/389—Measuring internal impedance, internal conductance or related variables
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/392—Determining battery ageing or deterioration, e.g. state of health
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/371—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC] with remote indication, e.g. on external chargers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/396—Acquisition or processing of data for testing or for monitoring individual cells or groups of cells within a battery
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E70/00—Other energy conversion or management systems reducing GHG emissions
- Y02E70/30—Systems combining energy storage with energy generation of non-fossil origin
Definitions
- the present invention relates to a technique for monitoring the state of a storage battery, and in particular, a storage battery which is used in combination with a power generation facility using natural energy and which monitors and estimates the state of a storage battery in a state of being constantly connected to equipment
- the present invention relates to an effective technology applied to a state monitoring system.
- a power supply system configured by combining a solar cell and a storage battery, for example, has been used as a self-supporting power source and as a mechanism of power leveling.
- this power supply system supplies the power generated by the solar cells to the load and charges the storage battery during the large amount of sunshine during the daytime, and needs the load due to the discharge from the storage battery during the daytime or the night when the amount of sunshine is small Power supply.
- the storage battery may be overcharged, and the deterioration of the storage battery proceeds.
- the storage battery may continue to be supplied with power from the storage battery, and the storage battery may be in an overdischarged state, and deterioration of the storage battery proceeds similarly.
- Patent Document 1 Japanese Unexamined Patent Publication No. 2010-063359
- the charge control device opens the charge circuit when the storage battery voltage during charging rises to the first set voltage, and closes the charge circuit again when the storage battery voltage decreases to the second set voltage lower than the first set voltage. Charge function.
- the charge circuit continues to be opened without opening the charge circuit even if the storage battery voltage rises above the first set voltage, and the illuminance measured by the light sensor is the set value
- power is supplied from the lead storage battery to the load to suppress a decrease in storage battery capacity caused by insufficient charging of the storage battery or overcharging.
- Patent Document 2 in a charge management system for charging a storage battery, a discharge capacity acquisition unit for acquiring a discharge capacity of the storage battery and a discharge capacity acquisition unit are acquired.
- a power supply system combining and using a solar cell and a storage battery must be in a battery state that can always perform normal charging and discharging, and a partial charge state called PSOC (Partial State Of Charge) (for example, It is desirable to use at a capacity of 40% to 80% of SOC (State Of Charge).
- PSOC Partial State Of Charge
- an object of the present invention is to efficiently estimate the state and life of each storage battery with high accuracy for a plurality of storage batteries charged with electric power generated using natural energy and always connected to the device
- To provide a storage battery state monitoring system that can Another object of the present invention is to provide a storage battery state monitoring system capable of controlling each storage battery to operate in a predetermined partial charge state.
- a storage battery state monitoring system monitors the state of each storage battery with respect to an apparatus provided with an assembled battery in which a plurality of storage batteries are connected in series and a power generation facility using natural energy. It is a storage battery state monitoring system, and has the following features.
- the storage battery state monitoring system includes a current detection unit that detects the current of each of the storage batteries, a state measurement unit that measures the temperature and voltage of each of the storage batteries, and internal resistance at at least two types of frequencies, and each of the storage batteries And a higher-level monitoring unit that issues measurement commands to the control unit and the state measurement unit while acquiring measurement data from the state measurement unit corresponding to the upper-level monitoring unit. From the ratio of the temperature, the voltage, the internal resistance, and the change in the value of the current detected by the current detection unit during charging and discharging of each storage battery and the change in the value of the voltage measured by the state measurement unit. Deterioration of each storage battery is estimated based on at least one or more values among the obtained direct current resistances of each storage battery.
- each storage battery can be controlled to operate in a predetermined partial charge state, and each storage battery can be prevented from being overdischarged or overcharged. It becomes.
- ⁇ Overview> For example, it may be difficult or inefficient to use a commercial power source for outdoor devices that require power, such as park lights and clocks, street lights and traffic lights in areas with few people.
- a stand-alone power source using natural energy such as a solar cell may be used.
- this power supply system is configured by combining storage batteries for power leveling, and according to the amount of solar radiation (generation amount of solar cells), the load by charging the storage batteries with surplus power and discharging from the storage batteries Control the power supply to (outdoor equipment).
- this storage battery degrades with age even when it is not operating, and generally, the higher the ambient temperature, the more the degradation progresses. Therefore, for example, in a device equipped with a storage battery such as UPS (Uninterruptible Power Supply: Uninterruptible Power Supply), for example, it usually occurs that the storage battery does not operate normally due to the life or failure at the time of operation (discharge). In order to avoid, the condition of the storage battery is monitored. In addition, when the life of the storage battery is actually abnormal by predicting the time of the life due to deterioration such as ambient temperature and years of use, it is of course new before the predicted life of the normal state comes. Methods have been taken to replace the UPS (Uninterruptible Power Supply: Uninterruptible Power Supply), for example, it usually occurs that the storage battery does not operate normally due to the life or failure at the time of operation (discharge). In order to avoid, the condition of the storage battery is monitored. In addition, when the life of the storage battery is actually abnormal by predicting the time of the life due to deteriorati
- the internal resistance is measured not at a single frequency as in existing devices or systems, but at multiple frequencies, it is possible to estimate a more accurate life corresponding to various deterioration modes of the storage battery. It is.
- a device that measures the internal resistance at multiple frequencies by varying the measurement frequency for each storage battery, it is practically difficult to measure multiple storage batteries of outdoor equipment as with portable measuring instruments. It is. In order to monitor the status of a large number of storage batteries in parallel, it is necessary to automate to some extent at least the process of measuring each parameter and recording data.
- a storage battery state monitoring system is configured to automatically charge various storage battery parameters for a plurality of storage batteries which are charged with electric power generated using natural energy such as a solar battery and are constantly connected to devices. Measure or acquire at This makes it possible to efficiently estimate the state and life of each storage battery with high accuracy, and to control the storage battery to operate properly in a predetermined partial charge state.
- each storage battery is provided with a measuring device for measuring various parameters and acquiring and holding data, and the data measured by the measuring device is wirelessly communicated to the monitoring device according to the request.
- Sent by The monitoring device centrally performs processing to estimate the state and life of the storage battery based on the measurement data collected from each measurement device, for example, if there is a storage battery that needs replacement, the relevant information and so on It has an interface such as notifying a user.
- the monitoring is performed in consideration of the reduction of communication load due to the monitoring device having a communication session with a large number of measuring devices, the ease of installation of the measuring device by using wireless communication, flexibility, and the like.
- a hierarchical configuration is provided having relay devices for performing communication load distribution and / or communication protocol conversion between devices and measurement devices.
- the voltage and internal resistance mainly AC impedance, reactance of battery is also included in measurement
- the deterioration is determined multilaterally on the basis of a plurality of parameters such as “internal resistance”) and DC resistance at the time of discharge and charge.
- the value of the temperature or voltage of the storage battery acquired at a fixed interval exceeds a predetermined threshold It is determined that the Specifically, for example, when the temperature of the storage battery exceeds room temperature + 10 ° C., it is determined as a minor abnormality, and when it exceeds room temperature + 20 ° C., it is determined that the replacement is necessary immediately.
- the timing of the life may be determined from a table or an equation showing the correlation between the temperature and the life.
- internal resistance is measured at regular timing such as once a day, for example, or at timing when an instruction from the user is received, as the trend management of normal time, and the initial value of internal resistance value (for example, The deterioration rate of the storage battery is estimated from the rate of change from the value initially measured at the time of installation. For example, when the internal resistance value is increased by 20% or more from the initial value, it is determined as slight deterioration, and when it is increased by 50% or more from the initial value, it is determined that replacement is necessary (for example, within one year). If it increases by 100% or more from the initial value, it is immediately determined that replacement is necessary. Since the absolute value of the internal resistance is different depending on the type of the storage battery, etc., the determination based on the relative value is performed in this manner.
- the internal resistance is measured at a plurality of frequencies so that the life can be more accurately estimated corresponding to various deterioration modes of the storage battery, and the above-described values are obtained for each internal resistance at each frequency. It is assumed that the determination is made based on the relative value to the initial value. It is known that, in a conventional measuring device for internal resistance, a frequency of about 1 kHz is generally used, and the situation in which the storage battery is gradually deteriorated can be determined to some extent by the internal resistance measured at the frequency . Further, regarding the frequency, there is also a large amount of accumulation of data serving as a reference because of the background that has been widely used in the past, one frequency is about 1 kHz (for example, 350 Hz or more and less than 2000 Hz) in this embodiment.
- the frequency is high in order to obtain information related to a power generation element such as an electrode reaction, and only information that can determine the life of the storage battery can be obtained. Therefore, in order to obtain more detailed information, it is desirable to measure also the internal resistance at low frequency close to direct current or near direct current.
- the direct current resistance component when the storage battery is discharged or charged, the voltage value and the current value measured successively from the measuring device installed in each storage battery (when measuring internal resistance with alternating current) And the ratio between the change (slope) of the current value during discharge and the change value for the voltage value. By comparing this with the initial value in the same manner as described above, the deterioration of the storage battery can be determined more accurately.
- the timing at which DC resistance can be measured is limited as described above . Therefore, during standby (when the storage battery is not discharged or charged), the internal resistance at low frequency is also measured. For example, a frequency of less than about 100 Hz can be used which can constitute the apparatus practically without any problem and does not interfere with the commercial power supply (not an integral multiple of 50 Hz or 60 Hz). In order to further improve the accuracy of the deterioration determination, it is desirable to measure the internal resistance with a plurality of different frequencies.
- the measurement frequency of the internal resistance includes a high frequency of at least about 1 kHz (for example, 350 Hz or more and less than 2000 Hz) and a low frequency of less than 100 Hz (a frequency that does not interfere with commercial power).
- the internal resistance is to be measured by three kinds of frequencies to which an intermediate frequency (for example, 100 Hz or more and less than 350 Hz) is added as a frequency different from these.
- the accuracy of the deterioration determination can be determined by measuring the internal resistance with a plurality of frequencies selected at least one each from, for example, a low frequency region of less than 200 Hz and a high frequency region of 200 Hz or more and less than 2000 Hz. It is possible to improve. Furthermore, it can be said that it is possible to further improve the accuracy by adding and measuring other different frequencies in the above-mentioned frequency domain.
- the state and life of the storage battery can be determined by determining deterioration in multiple aspects based on one or more of a plurality of parameters including temperature, voltage, internal resistance, direct current resistance in discharging and charging, and the like. It is possible to estimate with high accuracy.
- FIG. 1 is a diagram showing an outline of a configuration example of a storage battery state monitoring system according to an embodiment of the present invention.
- the storage battery state monitoring system 1 is, for example, a device having a battery assembly including a plurality of storage batteries 41 connected in series, such as the power supply device 40, and automatically measuring or acquiring various parameters for each storage battery 41 to obtain each storage battery. It is a system that estimates the state and life of 41.
- the storage battery state monitoring system 1 is fixedly installed one by one for each storage battery 41 of one or more power supply devices 40, and a state measurement device 30 for measuring various parameters of the storage battery 41, and a state measurement device
- the upper monitoring apparatus 10 collectively performs processing for collecting data measured at 30 and estimating the state and life of the storage battery 41.
- a data relay device 20 that relays measurement data transmitted from each state measuring device 30 and transmits the data to the upper monitoring device 10 is provided between the upper level monitoring device 10 and each state measuring device 30.
- M data relay devices 20 (hereinafter sometimes referred to as “master device”) are communicably connected to one upper monitoring device 10, and each data relay device 20 is connected.
- the host monitoring device 10 and the parent device 20 are connected by wired communication via a network 60 such as a LAN (Local Area Network), and the parent device 20 and the child device 30 are connected by wireless communication.
- the standard or protocol of the wired / wireless communication is not particularly limited, and known techniques can be appropriately used.
- the slave unit 30 can be installed on the storage battery 41 without the need for wiring to the outside, etc., and the ease of installation and flexibility As well as improving the efficiency of installation, it is possible to reduce the risk of failure based on wiring errors and aged deterioration of wiring.
- parent device 20 at least has a function of converting the communication protocol between wireless communication with child device 30 and wired communication with higher-level monitoring apparatus 10. , Need not have other functions.
- the master unit 20 may perform wireless communication with each slave unit 30 in parallel or sequentially.
- the configuration is a two-tier configuration in which handset 30 directly communicates with upper monitoring device 10 without parent device 20.
- the communication between the child device 30 and the parent device 20 (or the upper monitoring device 10) may be wired communication as well as wireless communication.
- a control / power supply device 50 for controlling the operation of the power supply device 40 is connected to each power supply device 40.
- the control / power supply device 50 is a control device configured to include, for example, a power conditioning device (PCS), a power supply device such as an uninterruptible power supply (UPS) or a direct current power supply, etc. 40.
- PCS power conditioning device
- UPS uninterruptible power supply
- a direct current power supply etc. 40.
- the control / power supply device 50 is connected to, for example, the network 60, and the higher-level monitoring device 10 receives the current value of the storage battery 41 from the control / power supply device 50 and the presence or absence of charging and discharging via the network 60. It is possible to obtain information related to the quantity.
- the control / power supply device 50 detects the current value of each storage battery 41, and the higher-level monitoring device 10 can obtain the information from the control / power supply device 50, but the present invention is not limited thereto.
- the child device 30, which will be described later may be configured to measure the current value of each storage battery 41 and transmit it to the upper monitoring device 10 as in the case of other parameters such as temperature and voltage.
- the host monitoring device 10 is configured on the network 60 so that a plurality of power supply devices 40 (child devices 30) can be centrally monitored.
- the function of the upper-level monitoring device 10 may be integrated with the control / power supply device 50 corresponding to each power supply device 40, and each control / power supply device 50 may monitor the power supply device 40 individually.
- the power generation facility 70 is a power generation facility that includes, for example, a power generation device using natural energy, such as a solar power generation device (solar battery) or a wind power generation device, and can generate power autonomously without artificially supplying energy. .
- a power generation device using natural energy such as a solar power generation device (solar battery) or a wind power generation device, and can generate power autonomously without artificially supplying energy.
- FIG. 2 is a diagram showing an outline of a configuration example of the upper layer monitoring device 10.
- the upper-level monitoring device 10 collects information on various parameters measured for each storage battery 41 from each child device 30 via the parent device 20, and estimates the state and the life of each storage battery 41 based on the collected data. Monitor the presence or absence of abnormal conditions or the end of life.
- the upper monitoring device 10 is configured by an information processing device such as a PC (Personal Computer) or a server device, and is implemented as a software program that operates on middleware such as an OS (Operating System) or a DBMS (Data Base Management System) not shown. Interface unit 11, the monitoring control unit 12, and the deterioration determination unit 13 and the like. Further, it has a measurement history 14 which is a database for accumulating measurement data collected from the child device 30, and setting information 15 including a file, a registry, and the like for holding various settings related to the operation of the storage battery state monitoring system 1.
- an information processing device such as a PC (Personal Computer) or a server device
- middleware such as an OS (Operating System) or a DBMS (Data Base Management System) not shown.
- Interface unit 11 the monitoring control unit 12, and the deterioration determination unit 13 and the like.
- a measurement history 14 which is a database for accumulating measurement data collected from the child device 30, and setting information 15 including a file,
- the interface unit 11 has a function of a user interface that provides the user with a screen for the user to input various instructions and a screen for displaying the result of status monitoring of the storage battery 41.
- a screen may be displayed by accessing from a web browser on the user's client terminal by a web server program (not shown).
- various instructions input by the user for example, designation of operation conditions of the upper monitoring device 10 and the handset 30 set in the setting information 15, and instructions of measurement and collection of data to the handset 30 based on user's request and so on.
- the monitoring control unit 12 is configured to measure various parameters with respect to the slave unit 30 (via the master unit 20) according to the setting content registered in the setting information 15 or an instruction from the user via the interface unit 11. Request the specification of and the execution of measurement. Further, it has a function of requesting the slave unit 30 to transmit measurement data of various parameters, collecting measurement data, and recording and storing the measurement data in the measurement history 14 for each storage battery 41.
- the plurality of handsets 30 simultaneously measure the storage batteries 41. Will do.
- the slave unit 30 supplies power to the storage battery 41 even though it is minute at the time of parameter measurement, and a voltage drop occurs. Therefore, if a large number of slave units 30 measure at the same time, the power supply device 40 is adversely affected. It is also conceivable.
- the slaves 30 transmit measurement data to the upper-level monitoring device 10 via the master 20 at the same time, resulting in large communication with these devices. It is also conceivable that a load is applied.
- the appropriate number of child devices 30 For example, grouping is made about every 30% of the whole, and instructions are given by providing a sufficient time difference for each group either automatically or manually so that the processing timing by the belonging child device 30 does not overlap between each group .
- the monitoring control unit 12 controls the discharge of the storage battery 41 and the charging from the power generation facility 70 so that the storage battery 41 operates in a predetermined partial charge state based on the voltage data in the collected measurement data.
- the control / power supply device 50 is instructed in accordance with the procedure described later.
- the deterioration determination unit 13 collects the temperature from the slave unit 30 and records the temperature, voltage, internal resistance, etc., according to the setting contents registered in the setting information 15 or the instruction from the user via the interface unit 11. On the basis of the measured values of various parameters and the current value at the time of discharge and charge in the power supply device 40 obtained from the control and power supply device 50, etc. To estimate the state and the lifetime.
- degradation of the storage battery 41 is mainly estimated at two timings, as described later.
- the first is based on acquired data of temperature and voltage continuously measured at a fixed time interval (a short interval such as 5 minutes in the present embodiment or a long interval such as 1 day). Estimate the abnormalities and lifespan including sudden failure etc.
- the deterioration tendency of the storage battery 41 in a plurality of deterioration modes is estimated based on the measured values of the internal resistance measured at a plurality of frequencies.
- the DC resistance calculated from the measurement data of the voltage at the time of discharge or charge and the value of the DC current at the time of discharge or charge acquired from the control / power supply device 50 The deterioration tendency of the storage battery 41 may be estimated with higher accuracy based on The initial values of the internal resistance and the direct current resistance may be obtained from the first measurement data of the storage battery 41 of interest in the measurement history 14, or may be separately recorded for each storage battery 41.
- the setting information 15 includes, for example, measurement intervals (for example, every 5 minutes or once a day) of the temperature and voltage of the handset 30 and measurement intervals of the internal resistance as setting contents related to the operation of the storage battery state monitoring system 1. (For example, once a day) may be set or changed by the user or the administrator. Further, the conditions of the operation mode (normal mode or power saving mode) of the slave unit 30 may be set.
- FIG. 3 is a diagram showing an outline of a configuration example of the state measurement device (child unit) 30.
- the slave unit 30 is fixed to the lid of the storage battery 41 one by one, and measures and records various parameters of the storage battery 41, and from the upper-level monitoring device 10 via the master unit 20 In response to the instruction, the measurement data is transmitted to the upper monitoring device 10 via the parent device 20.
- the battery By fixing the battery to the storage battery 41, it is possible to stabilize the connection of the wiring between the terminals for measuring various parameters, the sensor, and the like, and to reduce the variation of the measurement data.
- one slave unit 30 is installed for one storage battery 41, but for a plurality of storage batteries 41 installed in series according to cost, voltage of storage battery 41, etc. It may be made to monitor collectively by one child machine.
- the slave unit 30 includes a measurement control unit 31 implemented as a software program or circuit executed by a CPU (Central Processing Unit), a temperature measurement unit 32, a voltage measurement unit 33, an internal resistance measurement unit 34, and a sine wave generation unit It has 35 parts. Further, it has a communication unit 36 which performs wireless communication with the parent device 20, and an internal memory 37 which is a storage device comprising a nonvolatile semiconductor memory or the like. Moreover, while the temperature sensor 39 wired from the temperature measurement unit 32 is disposed in the storage battery 41, the terminals wired from the voltage measurement unit 33, the internal resistance measurement unit 34, and the sine wave generation unit 35 are positive and negative of the storage battery 41. Are connected to the terminals of.
- a measurement control unit 31 implemented as a software program or circuit executed by a CPU (Central Processing Unit)
- a temperature measurement unit 32 a voltage measurement unit 33, an internal resistance measurement unit 34, and a sine wave generation unit It has 35 parts. Further, it has a communication unit 36 which performs wireless communication with the parent device 20,
- move shall be acquired from the storage battery 41.
- the measurement control unit 31 has a function of controlling the entire process in the child device 30, such as measurement processing of various parameters in the child device 30, recording of measurement data, and transmission.
- Each measuring unit constantly monitors the storage battery 41 (for example, at intervals of every 5 minutes, once a day, etc.) and sequentially records the measured data in a predetermined area of the internal memory 37. At this time, old measurement data is overwritten to cyclically use the area.
- the communication unit 36 communicates with the parent device 20 by wireless communication, and based on an instruction from the upper layer monitoring device 10 via the parent device 20, transmits measurement data to the upper layer monitoring device 10 via the parent device 20. Do.
- the measurement data recorded in the internal memory 37 can be copied, moved, etc. to the external memory 38 composed of a semiconductor memory or the like mounted on the slave 30. Further, the external memory 38 may be used as a storage area equivalent to the internal memory 37.
- the temperature measurement unit 32 measures the temperature of the storage battery 41 with the temperature sensor 39 according to an instruction (for example, every 5 minutes) from the measurement control unit 31, and outputs measurement data to the measurement control unit 31.
- voltage measurement unit 33 measures the voltage between the terminals of storage battery 41 according to an instruction (for example, every 5 minutes) from measurement control unit 31, and outputs measurement data to measurement control unit 31.
- Internal resistance measurement unit 34 measures an internal resistance between terminals of storage battery 41 using an instruction from measurement control unit 31 as a trigger, and outputs measurement data to measurement control unit 31.
- the sine wave generation unit 35 generates sine waves of a plurality of frequencies as described above, and a current (for example, 3 A or less) at each frequency is supplied to the storage battery 41.
- the internal resistance at each frequency is calculated based on measurement data of the current value at this time and the voltage value between the terminals.
- the accuracy of the deterioration determination can be improved by measuring the internal resistance with a plurality of frequencies selected at least one each from a low frequency region of less than 200 Hz and a high frequency region of 200 Hz or more and less than 2000 Hz. it can.
- the accuracy can be further improved by measuring by adding another different frequency in the above-mentioned frequency domain.
- the present embodiment includes, for example, a high frequency region of at least about 1 kHz (for example, 350 Hz or more and less than 2000 Hz, preferably 800 Hz or more but less than 1200 Hz) and a low frequency region less than 100 Hz (a frequency that does not interfere with commercial power).
- the internal resistance is to be measured at three frequencies obtained by adding a frequency in the middle frequency range (for example, 100 Hz or more and less than 350 Hz) as the frequency.
- the conventional products 1 to 3 are measuring devices for measuring the internal resistance with a single frequency according to the prior art, and the measurement frequencies are different (high frequency range (350 Hz or more and less than 2000 Hz)), middle frequency range (100 Hz or more and 350 Hz) Less), low frequency region (less than 100 Hz)).
- the developed products 1 and 2 are the state measurement device 30 of the present embodiment, and a plurality of frequency regions (the developed product 1 is high frequency region (200 Hz or more and less than 2000 Hz) and low frequency region (less than 200 Hz) 2 measures internal resistance by the measurement frequency which belongs to a high frequency area (more than 350 Hz and less than 2000 Hz), a middle frequency area (more than 100 Hz and less than 350 Hz) and a low frequency area (less than 100 Hz).
- the fully charged state of the storage battery refers to a state where the storage battery is charged for 48 hours or more at a limited current of 13.38 V / 10A.
- the measured value (actual capacity) of the 5HR capacity after charging, leave in an open circuit state for 24 hours in an atmosphere of 25 ⁇ 2 ° C, and then discharge at 25 ⁇ 2 ° C with a discharge current value of 20A. The discharge capacity was determined from the discharge duration until the voltage of 10.5 V was reached.
- the battery left for 24 hours in a 25 ⁇ 2 ° C atmosphere after full charge is discharged at a discharge current value of 100A
- the discharge capacity was determined from the discharge duration time to reach a voltage of 9.6 V.
- the relative ratio to the discharge capacity of the new state is calculated.
- the discharge capacity is the internal resistance
- the initial value of Discharge capacity initial value of discharge capacity ⁇ (1- (measured value of internal resistance-initial value of internal resistance) / initial value of internal resistance)
- a weighted average value obtained by performing predetermined weighting on the measured values of two or three internal resistances is used. It shall be applied to the above equation. For example, in the case of measurement at low rate discharge, a large weighting value is set with respect to the internal resistance value measured at the frequency in the high frequency region as compared to the internal resistance measured at the frequency in the medium frequency region. Also, in the case of high-rate discharge measurement, a larger weight value is set relative to the internal resistance measured at the frequency in the middle frequency range, compared to the internal resistance measured at the frequency in the high frequency range. A large weighting value is set for the internal resistance measured at the frequency in the frequency domain and the internal resistance measured at the frequency in the intermediate frequency domain.
- the battery capacity can be estimated in a short time and with high accuracy as a whole compared to the conventional products 1 to 3 (measurement of internal resistance at a single frequency). Also, according to the developed product 2 (measurement of internal resistance at three frequencies), the battery capacity can be estimated in a shorter time and with higher accuracy than that of the developed product 1 (measurement of internal resistance at two frequencies) I understand.
- FIG. 4 is a flowchart showing an outline of an example of control processing of measurement timing of voltage and temperature in the measurement control unit 31 of the state measurement device (child unit) 30.
- the predetermined time is an interval at which the child device 30 periodically measures the parameter of the storage battery 41 by itself, and, for example, 5 minutes when the state of the child device 30 is not in the “sleep state”, “normal time” In the case of the "sleep state", for example, a time interval of one day or the like is used.
- the “sleep state” in the present embodiment refers to a state in which the measurement frequency of the voltage or temperature in the slave unit 30 is lowered by an instruction from the upper-level monitoring device 10 (not to stop). .
- step S01 is repeated until the predetermined time has elapsed. If the predetermined time has elapsed, the temperature measuring unit 32 measures the temperature of the storage battery 41, and the voltage measuring unit 33 measures the voltage between the terminals of the storage battery 41 (S02). The temperature and voltage are measured by the temperature measurement unit 32 and the voltage measurement unit 33, and when the measurement control unit 31 acquires measurement data, the measurement data of the temperature and voltage is recorded in the internal memory 37 along with the time stamp (S03) ).
- This predetermined time may be, for example, the same as the predetermined time in step S01, and is, for example, 5 minutes when the state of the slave unit is "normal", for example, 1 when the "sleep state" is It can be a time interval such as a day. If this predetermined time has not elapsed, the process returns to step S01, and the above-described series of processing is repeated. If the predetermined time has passed, the unsent ones of the measurement data recorded and stored in the internal memory 37, which are acquired in step S03, are transmitted to the upper monitoring device 10 via the parent device 20 ( S05). After the transmission, the process returns to step S01 to repeat the above-described series of processes. In the higher-level monitoring apparatus 10, an abnormality or life including a sudden failure of the storage battery 41 is estimated based on the transmitted measurement data of temperature and voltage.
- FIG. 5 is a flowchart showing an outline of an example of control processing of charge and discharge of the storage battery 41 by the upper level monitoring device 10.
- the upper-level monitoring apparatus 10 When the upper-level monitoring apparatus 10 is activated and starts control processing, first, it waits for transmission of measurement data from each base unit 20 by the base unit 30 and receives measurement data (S11). Next, it is determined whether the voltage data of the storage battery 41 included in the measurement data is lower than a predetermined overdischarge prevention voltage (S12). At this time, as described above, the deterioration determination unit 13 separately performs a process of estimating the state and the life of the storage battery 41 based on the received measurement data.
- S11 measurement data
- S12 overdischarge prevention voltage
- step S12 If it is determined in step S12 that the voltage does not fall below the overdischarge prevention voltage, it is determined that the target storage battery 41 is operating in a predetermined partial charge state, and then the power supply including the target storage battery 41 for a predetermined period or longer. It is determined whether or not a measurement command of internal resistance is issued to the control / power supply device 50 corresponding to the device 40 (S13). When a measurement command of the internal resistance is issued within a predetermined period, and measurement data of the internal resistance is acquired through the parent device 20, the discharge circuit is connected for the target storage battery 41 (power supply device 40) and the storage battery is A command is issued to the control / power supply device 50 so as to discharge from 41 (S14), and the process proceeds to step S17. In this case, the upper monitoring device 10 can estimate the state of the storage battery 41 at a timing close to time, and it is determined that the state of the storage battery 41 has no problem because it is operating on that. The reason is that
- step S13 If it is determined in step S13 that the measurement command of the internal resistance is not issued for a predetermined period or more, the process proceeds to step S17.
- the predetermined period in step S13 can be, for example, one week.
- the "connection" in step S14 includes continuing as it is when it is already connected to the discharge circuit.
- the slave 30 corresponding to the target storage battery 41 is in the above-mentioned "sleep state", the release is also included.
- step S12 If it is determined in step S12 that the voltage is less than the overdischarge prevention voltage, it is determined that the target storage battery 41 is operating in the overdischarge state, and the discharge circuit is opened for the target storage battery 41 (power supply device 40). A command is issued to the control / power supply device 50 so as to stop the discharge from 41 (S15). Furthermore, in order to avoid unnecessary measurement processing for the target storage battery 41, a command is issued to the corresponding slave unit 30 to be in the "sleep state" (S16). Thereafter, the process returns to step S11 to wait for the transmission of measurement data from each of the masters 20 by the slave 30.
- step S17 it is determined whether the voltage data of the storage battery 41 included in the measurement data exceeds the predetermined overcharge prevention voltage (S17). If the overcharge protection voltage is not exceeded, it is determined that the target storage battery 41 is operating in a predetermined partial charge state, and the charging circuit is connected for the target storage battery 41 (power supply device 40) to To the control / power supply device 50 to charge the storage battery 41 (S18). Thereafter, the process returns to step S11 to wait for the transmission of measurement data from each of the masters 20 by the slave 30.
- S17 the predetermined overcharge prevention voltage
- step S17 If it is determined in step S17 that the overcharge prevention voltage is exceeded, it is determined that the target storage battery 41 is operating in the overcharge state, and then the storage battery 41 obtained by the current detection function of the control / power supply device 50 It is determined whether the charging current to the battery is below a predetermined value (S19). If the charging current is not lower than the predetermined value, that is, if the value of the internal resistance is smaller than a predetermined degree and it is determined that the storage battery 41 is not deteriorated so much, the process proceeds to step S18 described above. Regarding the (power supply device 40), a command is issued to the control / power supply device 50 to connect the charging circuit and charge the storage battery 41 from the power generation facility 70.
- step S19 If it is determined in step S19 that the charging current is lower than the predetermined value, that is, if it is determined that the value of the internal resistance is larger than the predetermined degree and the storage battery 41 may be degraded, the corresponding slave 30 Is instructed to measure the internal resistance value (S20). Further, the control / power supply device 50 is instructed to open the charging circuit of the target storage battery 41 (power supply device 40) and stop the charging of the storage battery 41 from the power generation facility 70 (S21). Thereafter, the process returns to step S11 to wait for the transmission of measurement data from each of the masters 20 by the slave 30.
- FIG. 6 is a flowchart showing an example of control processing of measurement timing of the internal resistance in the measurement control unit 31 of the state measurement device (child unit) 30.
- slave unit 30 When slave unit 30 is activated and measurement processing of various parameters of storage battery 41 is started, first, a command to measure the internal resistance value in step S20 of FIG. It is determined whether or not there is (S31). When the measurement command of the internal resistance value is not issued, step S01 is repeated until a predetermined time passes.
- the internal resistance measurement unit 34 measures the internal resistance of the storage battery 41 (S32).
- the sine wave generation unit 35 generates sine waves of a plurality of frequencies, and currents (eg, 3 A or less) at each frequency are supplied to the storage battery 41, and the current value at this time and the voltage value between the terminals
- the internal resistance at each frequency is calculated based on the measurement data of and.
- the plurality of frequencies include a high frequency of at least about 1 kHz and a low frequency of less than 100 Hz, and it is possible to add different frequencies to this.
- the internal resistance measurement unit 34 measures the internal resistance, and when the measurement control unit 31 acquires measurement data, the measurement data of the internal resistance is recorded in the internal memory 37 together with the time stamp (S33).
- a predetermined time is elapsed since the measurement data was transmitted to the parent device (S34).
- the predetermined time may be, for example, a time interval of 5 minutes. If this predetermined time has not elapsed, the process returns to step S31, and the above-described series of processing is repeated. If the predetermined time has passed, the unsent ones of the measurement data recorded and stored in the internal memory 37, which are acquired in step S33, are transmitted to the upper monitoring device 10 via the parent device 20 ( S35). After the transmission, the process returns to step S01 to repeat the above-described series of processes.
- the deterioration determination unit 13 separately estimates the deterioration tendency of the storage battery 41 in a plurality of deterioration modes based on the received measurement values of the internal resistance measured at a plurality of received frequencies.
- each storage battery 41 As described above, according to the storage battery state monitoring system 1 of the embodiment of the present invention, a plurality of solar cells, which are charged by power generated using natural energy such as solar cells, are always connected to the device The condition of each storage battery 41 by automatically measuring or acquiring parameters including the voltage, the internal resistance, and the direct current resistance at the time of discharging and charging other than the temperature for the storage battery 41 and measuring the internal resistance at a plurality of frequencies. It is possible to estimate the life with high accuracy and to control the storage battery 41 to operate in a predetermined partial charge state.
- the hierarchical configuration of the high-level monitoring device 10, the parent device 20, and the child device 30 is taken, and wireless communication is performed between the parent device 20 and the child device 30, thereby measuring various parameters of a large number of storage batteries 41. It becomes possible to do efficiently.
- the present invention is not limited to the above-mentioned embodiment, and can be variously changed in the range which does not deviate from the gist. Needless to say.
- the present invention is applicable to a storage battery state monitoring system in which a storage battery is always connected to a device, such as a backup application or output fluctuation application, and the storage battery is energized to monitor and estimate the state.
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Abstract
Description
例えば、公園の電灯や時計、人が少ない地域における街灯や信号機など、電力を必要とする屋外機器に商用電源を使用することが困難もしくは効率がよくない場合がある。このような屋外機器を稼働させるため、例えば、太陽電池などの自然エネルギーを利用した自立型電源が用いられる場合がある。この電源システムは、上述したように、電力平準化のために蓄電池が組み合わせて構成され、日照量(太陽電池の発電量)に応じて、余剰電力の蓄電池への充電と蓄電池からの放電による負荷(屋外機器)への電力供給を制御する。
図1は、本発明の一実施の形態である蓄電池状態監視システムの構成例について概要を示した図である。蓄電池状態監視システム1は、例えば電源装置40などの、直列に接続された複数の蓄電池41からなる組電池を備える機器において、各蓄電池41について各種パラメータを自動で測定もしくは取得することで、各蓄電池41の状態や寿命を推定するシステムである。この蓄電池状態監視システム1は、1つ以上の電源装置40の各蓄電池41に対して1つずつ固定して設置され、当該蓄電池41についての各種パラメータを測定する状態測定装置30と、状態測定装置30で測定されたデータを収集して蓄電池41の状態や寿命を推定する処理を一元的に行う上位監視装置10とを有する。また、上位監視装置10と各状態測定装置30との間に、各状態測定装置30から送信された測定データを中継して上位監視装置10に送信するデータ中継装置20を有する。
・電池A 蓄電池規格UP300-12(12V/100Ah/5HR)の新品
・電池B 電池Aと同等の電池に対して電解液を10%減じたもの
・電池C 電池Aと同等の電池に対して25℃トリクル寿命試験により5年相当経過させた状態のもの
・電池D 電池Aと同等の電池に対して25℃トリクル寿命試験により15年相当経過させた状態のもの
・電池E 電池Cと同等の電池に対して電解液減少分を補液したもの
・電池F 電池Dと同等の電池に対して電解液減少分を補液したもの
の6種類の蓄電池(電池A~F)を作成した。
放電容量=放電容量の初期値×
(1-(内部抵抗の測定値-内部抵抗の初期値)/内部抵抗の初期値)
の式により表される。従って、新品状態の放電容量(放電容量の初期値)に対する相対比は、
相対比=1-(内部抵抗の測定値-内部抵抗の初期値)/内部抵抗の初期値
の式により算出することができる。
図4は、状態測定装置(子機)30の測定制御部31における電圧および温度の測定タイミングの制御処理の例について概要を示したフローチャートである。子機30が起動して蓄電池41の各種パラメータの測定処理を開始すると、まず、直近の処理から所定の時間が経過しているか否かを判定する(S01)。この所定の時間とは、子機30が自ら定期的に蓄電池41のパラメータを測定する間隔であり、子機30の状態が“スリープ状態”ではない“通常時”の場合は、例えば5分、“スリープ状態”の場合は、例えば1日などの時間間隔とする。ここで、本実施の形態における“スリープ状態”とは、上位監視装置10からの指令により子機30における電圧や温度の測定頻度が下げられた状態を指すものとする(停止するわけではない)。
10…上位監視装置、11…インタフェース部、12…監視制御部、13…劣化判定部、14…測定履歴、15…設定情報、
20…データ中継装置(親機)、
30…状態測定装置(子機)、31…測定制御部、32…温度測定部、33…電圧測定部、34…内部抵抗測定部、35…正弦波発生部、36…通信部、37…内部メモリ、38…外部メモリ、39…温度センサ、
40…電源装置、41…蓄電池、
50…制御・電源装置、
60…ネットワーク、
70…発電設備。
Claims (11)
- 複数の蓄電池が直列に接続された組電池と自然エネルギーによる発電設備とを備えた機器に対して、前記各蓄電池の状態を監視する蓄電池状態監視システムであって、
前記各蓄電池の電流を検出する電流検出部と、
前記各蓄電池における温度、電圧、および少なくとも2種類以上の周波数における内部抵抗を測定する状態測定部と、
前記各蓄電池に対応する前記状態測定部から測定データを取得するとともに、前記制御部および前記状態測定部に対して動作に係る指令を出す上位監視部とを有し、
前記上位監視部は、前記状態測定部が測定した温度、電圧、内部抵抗、および前記各蓄電池の充放電時における前記電流検出部が検出した電流の値の変化分と前記状態測定部が測定した電圧の値の変化分との比から得た前記各蓄電池の直流抵抗のうち、少なくとも1つ以上の値に基づいて前記各蓄電池の劣化を推定することを特徴とする蓄電池状態監視システム。 - 請求項1に記載の蓄電池状態監視システムにおいて、
前記蓄電池について、負荷に対する放電と前記発電設備からの余剰電力による充電とを制御する制御部を有し、
前記上位監視部は、前記状態測定部から取得した前記蓄電池の電圧の測定値が所定の過放電防止電圧以上である場合は、前記制御部に対して前記蓄電池を負荷に対する放電回路に接続させるよう指令を行い、前記電圧の測定値が前記過放電電圧未満である場合は、前記制御部に対して前記蓄電池を前記放電回路から開放させるよう指令を行い、
また、前記電圧の測定値が所定の過充電防止電圧以下である場合、および前記電圧の測定値が前記過充電防止電圧を超え、かつ前記電流検出部により検出された前記蓄電池の充電電流が所定の値以上である場合は、前記制御部に対して前記蓄電池を前記発電設備からの充電回路に接続させるよう指令を行い、前記電圧の測定値が前記過充電防止電圧を超え、かつ前記電流検出部により検出された前記蓄電池の充電電流が所定の値未満である場合は、前記状態測定部に対して前記蓄電池の内部抵抗の値を取得するよう指令を行うとともに、前記制御部に対して前記蓄電池を前記充電回路から開放させるよう指令を行うことを特徴とする蓄電池状態監視システム。 - 請求項2に記載の蓄電池状態監視システムにおいて、
前記上位監視部は、前記状態測定部から取得した前記蓄電池の電圧の測定値が前記過放電防止電圧未満である場合、前記制御部に対して前記蓄電池を前記放電回路から開放させるよう指示を行うとともに、前記状態測定部に対して前記蓄電池のパラメータの測定間隔を長くする指令を行うことを特徴とする蓄電池状態監視システム。 - 請求項1~3のいずれか1項に記載の蓄電池状態監視システムにおいて、
前記状態測定部は、少なくとも、200Hz未満の第1の周波数と、200Hz以上2000Hz未満の第2の周波数とをそれぞれ含む、2種類以上の周波数によって前記蓄電池の内部抵抗を測定することを特徴とする蓄電池状態監視システム。 - 請求項1~3のいずれか1項に記載の蓄電池状態監視システムにおいて、
前記状態測定部は、前記第1の周波数を100Hz未満とし、前記第2の周波数を350Hz以上2000Hz未満とし、さらに、100Hz以上350Hz未満の第3の周波数を含む3種類の周波数によって前記蓄電池の内部抵抗を測定することを特徴とする蓄電池状態監視システム。 - 請求項1~5のいずれか1項に記載の蓄電池状態監視システムにおいて、
前記状態測定部が測定した前記蓄電池の温度および/または電圧の値が所定の値を超え、もしくは所定の値より低下した場合に、前記蓄電池に異常があると判定し、
また、前記状態測定部が測定した前記蓄電池の内部抵抗および/または前記蓄電池の放電時における直流抵抗の値の初期値からの変化率に基づいて、前記蓄電池の劣化を推定することを特徴とする蓄電池状態監視システム。 - 請求項1~6のいずれか1項に記載の蓄電池状態監視システムにおいて、
前記状態測定部からなる子機と、
前記上位監視部からなる上位監視装置とを有し、
さらに、前記上位監視装置と前記子機との間での通信を中継する親機を有し、
前記上位監視装置には1つ以上の前記親機が通信可能に接続され、前記各親機には、1つ以上の前記子機が通信可能に接続される構成を有することを特徴とする蓄電池状態監視システム。 - 請求項7に記載の蓄電池状態監視システムにおいて、
前記親機と前記子機との間の通信は無線通信であることを特徴とする蓄電池状態監視システム。 - 請求項7または8に記載の蓄電池状態監視システムにおいて、
前記子機は、前記親機を介した前記上位監視装置からの指示に基づいて、前記蓄電池の内部抵抗を測定することを特徴とする蓄電池状態監視システム。 - 請求項7~9のいずれか1項に記載の蓄電池状態監視システムにおいて、
前記子機は、前記親機を介した前記上位監視装置への測定データの送信が、前回の送信から所定の時間以上経過していない場合は、行わないことを特徴とする蓄電池状態監視システム。 - 請求項7~10のいずれか1項に記載の蓄電池状態監視システムにおいて、
前記子機は、前記蓄電池に固定して設置されることを特徴とする蓄電池状態監視システム。
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PL12847257T PL2778697T3 (pl) | 2011-11-08 | 2012-08-01 | System monitorowania stanu akumulatora |
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EP12847257.8A EP2778697B1 (en) | 2011-11-08 | 2012-08-01 | Battery-state monitoring system |
US14/356,778 US9453885B2 (en) | 2011-11-08 | 2012-08-01 | Battery-state monitoring system |
JP2013542884A JP5816906B2 (ja) | 2011-11-08 | 2012-08-01 | 蓄電池状態監視システム |
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WO (3) | WO2013069328A1 (ja) |
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US9453885B2 (en) | 2016-09-27 |
EP2778697B1 (en) | 2019-05-15 |
EP2778697A1 (en) | 2014-09-17 |
CN103917884B (zh) | 2016-08-24 |
EP2778698A1 (en) | 2014-09-17 |
EP2778697A4 (en) | 2015-07-29 |
JPWO2013069346A1 (ja) | 2015-04-02 |
PL2778697T3 (pl) | 2019-11-29 |
TW201319602A (zh) | 2013-05-16 |
US9459323B2 (en) | 2016-10-04 |
JP5403191B2 (ja) | 2014-01-29 |
US20140312915A1 (en) | 2014-10-23 |
CN103917882A (zh) | 2014-07-09 |
US20140285156A1 (en) | 2014-09-25 |
EP2778699A4 (en) | 2015-07-29 |
JPWO2013069328A1 (ja) | 2015-04-02 |
EP2778699A1 (en) | 2014-09-17 |
JP5924346B2 (ja) | 2016-05-25 |
EP2778698A4 (en) | 2015-07-29 |
JP5816906B2 (ja) | 2015-11-18 |
US20140306667A1 (en) | 2014-10-16 |
CN103917883B (zh) | 2016-04-27 |
TWI443357B (zh) | 2014-07-01 |
US9297859B2 (en) | 2016-03-29 |
CN103917884A (zh) | 2014-07-09 |
CN103917882B (zh) | 2016-12-21 |
JPWO2013069423A1 (ja) | 2015-04-02 |
WO2013069328A1 (ja) | 2013-05-16 |
WO2013069423A1 (ja) | 2013-05-16 |
CN103917883A (zh) | 2014-07-09 |
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