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WO2025084306A1 - Module de capteur - Google Patents

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Publication number
WO2025084306A1
WO2025084306A1 PCT/JP2024/036786 JP2024036786W WO2025084306A1 WO 2025084306 A1 WO2025084306 A1 WO 2025084306A1 JP 2024036786 W JP2024036786 W JP 2024036786W WO 2025084306 A1 WO2025084306 A1 WO 2025084306A1
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WO
WIPO (PCT)
Prior art keywords
storage battery
sensor module
cycles
sensor
discharged
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/036786
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English (en)
Japanese (ja)
Inventor
秀昭 片山
優太 佐藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Maxell Ltd
Original Assignee
Maxell Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Maxell Ltd filed Critical Maxell Ltd
Publication of WO2025084306A1 publication Critical patent/WO2025084306A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • G—PHYSICS
    • G08—SIGNALLING
    • G08C—TRANSMISSION SYSTEMS FOR MEASURED VALUES, CONTROL OR SIMILAR SIGNALS
    • G08C19/00—Electric signal transmission systems
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
    • H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
    • H02J7/34—Parallel operation in networks using both storage and other DC sources, e.g. providing buffering

Definitions

  • the present invention relates to a sensor module.
  • sensor modules equipped with sensors are installed in structures.
  • the sensor module is configured to include, for example, a sensor for measuring specific data related to the structure, a communication device for transmitting the measured data to the outside, and a power source for supplying power to the sensor and communication device, so that the condition of the structure can be monitored remotely.
  • JP 2016-194441 A discloses a sensor module that can be attached to a structure.
  • This sensor module has a sensor device that detects a physical quantity related to the properties of the structure, and an adhesive sheet between the structure and the sensor.
  • JP 2020-119149 A discloses a wireless communication system used in a sensor system fixedly installed on a vibrating structure such as a bridge.
  • This wireless communication system is a wireless communication device equipped with at least an acceleration sensor, and is equipped with a data calculation means that performs a predetermined calculation, including a Fourier transform, on acceleration data measured by the acceleration sensor over a certain period of time to obtain a frequency spectrum, and a transmission means that transmits the frequency spectrum.
  • WO 2022/118928 discloses an all-solid-state battery system including an all-solid-state battery and a charging device.
  • the negative electrode active material of the all-solid-state battery contains lithium titanium oxide
  • Infrastructure facilities such as bridges and tunnels may be monitored for long periods of time, such as decades.
  • existing sensor modules are expected to last for about five years, and after this period they need to be replaced one by one.
  • the objective of the present invention is to provide a sensor module capable of long-term monitoring.
  • the present invention provides a sensor module capable of long-term monitoring.
  • FIG. 1 is a block diagram showing the functional configuration of a sensor module according to an embodiment of the present invention.
  • FIG. 2 is a scatter plot showing the relationship between temperature and degradation rate.
  • Sensor modules are often installed outdoors, and depending on the region in which they are installed, the temperature may drop to around -30°C in winter. On the other hand, in summer, direct sunlight may cause the temperature to rise to around 60°C.
  • secondary batteries it is preferable to use secondary batteries that can operate stably over a wide temperature range.
  • a secondary battery that uses a solid electrolyte (all-solid-state battery) is suitable as a secondary battery that can operate stably over such a wide temperature range.
  • the sensor module Even if an all-solid-state battery capable of stable operation over a wide temperature range is used, there may be cases where the sensor module is exposed to higher than normal temperatures during long-term use. If the sensor module is exposed to higher than normal temperatures even if the frequency is a few times a year or once every few years, and the secondary battery installed therein deteriorates rapidly at the temperatures, the sensor module will ultimately not be able to be used for a long period of time. For this reason, it is preferable that the secondary battery installed in the sensor module is one whose deterioration rate does not increase significantly at higher than normal temperatures, even when the secondary battery is exposed to such temperatures.
  • [Sensor module] 1 is a block diagram showing the functional configuration of a sensor module 10 according to an embodiment of the present invention.
  • the sensor module 10 includes a sensor 11 that measures data, a communication device 12 that transmits the measured data to the outside, a storage battery 13 that supplies power to the sensor 11 and the communication device 12, and a power generation device 14 that charges the storage battery 13.
  • the sensor module 10 further includes a control device 15 that controls the sensor 11, the communication device 12, the storage battery 13, and the power generation device 14.
  • control device 15 includes a communication control unit 151 that controls the sensor 11 and the communication device 12, and a power supply control unit 152 that controls the storage battery 13 and the power generation device 14.
  • the communication control unit 151 and the power supply control unit 152 are mounted on the substrate 16.
  • the substrate 16 has predetermined wiring formed on at least one of its two surfaces.
  • the wiring on the substrate 16 is electrically connected to the sensor 11, the communication device 12, the storage battery 13, the power generation device 14, the communication control unit 151, and the power supply control unit 152.
  • the communication control unit 151 and the power supply control unit 152 are mounted on the substrate 16. Elements other than the communication control unit 151 and the power supply control unit 152 may also be mounted on the substrate 16.
  • the sensor module 10 is installed in a structure (not shown) and is used to acquire predetermined data about the structure over a predetermined period of time. Specifically, the sensor module 10 measures data about the structure using a sensor 11 and transmits the measured data to the outside using a communication device 12. With this configuration, the state of the structure can be monitored remotely.
  • Structures that are the subject of monitoring by the sensor module 10 include, but are not limited to, bridges and tunnels.
  • the sensors 11 include, but are not limited to, acceleration sensors, acoustic sensors, strain sensors, surface acoustic wave sensors, thermometers, water level gauges, etc.
  • acceleration sensors for example, by attaching an acceleration sensor to a structure, the inclination of the structure can be monitored.
  • a strain sensor to a structure such as a bridge made of concrete, cracks caused by deterioration of the concrete can be monitored.
  • landslides can be monitored.
  • the resistance of reinforcing bars, metal beams, etc. can be measured to monitor deterioration due to corrosion.
  • the communication device 12 may be a wireless communication device or a wired communication device, but is preferably a wireless communication device.
  • the storage battery 13 is an all-solid-state battery. The detailed configuration of the storage battery 13 will be described later.
  • the power generation device 14 is, but is not limited to, for example a vibration power generation device, a solar power generation device, a thermal power generation device using a thermal power generation element, or a wind power generation device. By providing the sensor module 10 with the storage battery 13 and the power generation device 14, it can be used for a longer period of time without replacing the battery, compared to when the power source is a primary battery.
  • the white arrows indicate the flow of power.
  • the power for charging the storage battery 13 may be supplied wirelessly.
  • the sensor module 10 is provided with a power receiving antenna instead of the power generation device 14 (or in addition to the power generation device 14), and the power transmission radio waves sent from outside the sensor module 10 are received by the power receiving antenna, and the power supply control unit 152 converts the power transmission radio waves into electricity to charge the storage battery 13.
  • the control device 15 has a memory and a processor, and executes various operations according to programs stored in the memory.
  • the control device 15 includes a communication control unit 151 and a power supply control unit 152.
  • the communication control unit 151 and the power supply control unit 152 may each be an independent device, or may be integrated.
  • the communication control unit 151 and the power supply control unit 152 may each have an independent memory and processor, or may share a single memory and processor.
  • the communication control unit 151 of the control device 15 receives data from the sensor 11, stores it in memory, and passes the stored data to the communication device 12 at a predetermined interval, causing the communication device 12 to transmit the data to the outside.
  • the data transmitted to the outside may be data detected by the sensor 11 that has been subjected to arithmetic processing, or the processor may be equipped with such a arithmetic processing function.
  • the power supply control unit 152 of the control device 15 adjusts the timing of charging and discharging, and the distribution of power supply to each device.
  • the power supply control unit 152 of the control device 15 may be composed of multiple devices, such as a control unit for power management and a control unit for driving other devices.
  • the power supply control unit 152 since a sensor module installed outdoors in particular is likely to be used over a wide temperature range, it is preferable that the power supply control unit 152 be able to perform charging control such as adjusting the charging voltage and charging current according to the temperature of the storage battery.
  • the power supply control unit 152 is preferably equipped with a sensor for detecting the temperature of the storage battery 13, and preferably operates by switching charging conditions based on the temperature detected by the sensor.
  • the storage battery 13 is an all-solid-state battery. By using an all-solid-state battery as the storage battery 13, the operable temperature range can be expanded compared to the case of using a secondary battery containing an electrolytic solution in which an electrolyte is dissolved in an organic solvent.
  • the storage battery 20 is preferably operable in a temperature range from -40°C to 80°C.
  • operable refers to a case in which, assuming that the capacity when discharged at a current value of 0.2C at 25°C is 100, the discharge capacity at 0.2C at each temperature is 10 or more.
  • the deterioration rate of the storage battery 13 does not increase abruptly even when exposed to a temperature higher than normal. Specifically, it is preferable that the deterioration rate at 105°C does not deviate significantly from the value predicted from the deterioration rate in the normal temperature range.
  • the unit of T in formulas (1) and (2) is ° C.
  • the deterioration rate of a storage battery varies in proportion to the inverse of the temperature within a normal temperature range.
  • the lower limit of k100 is not particularly limited, but is, for example, 90% of f100 (Th), preferably 95% of f100 (Th).
  • the upper limit of k200 is preferably 105% of f200 (Th).
  • the lower limit of k200 is, for example, 90% of f200 (Th), preferably 95% of f200 (Th).
  • the positive electrode layer contains a positive electrode active material and a solid electrolyte, and further contains a conductive assistant, a binder, etc., as required.
  • the negative electrode layer similarly contains a negative electrode active material and a solid electrolyte, and further contains a conductive assistant, a binder, etc., as required.
  • the solid electrolyte layer contains a solid electrolyte, and further contains a binder, etc., as required.
  • the solid electrolyte contained in the positive electrode layer, the solid electrolyte contained in the negative electrode layer, and the solid electrolyte contained in the solid electrolyte layer may each be a different compound or may be the same compound.
  • the positive electrode active material is, but is not limited to, for example, a lithium composite oxide.
  • the positive electrode active material include spinel-type lithium manganese composite oxide represented by LiM x Mn 2-x O 4 (wherein M is at least one element selected from the group consisting of B, Mg, Ca, Sr, Ba, Ti, V, Cr, Fe, Co, Ni, Cu, Al, Sn, Sb, In, Nb, Mo, W, Y, Ru, and Rh, and 0.01 ⁇ x ⁇ 0.5), Li x Ni (1-y-z) Mn y M z O (2-k) F l a layered compound represented by LiCo1-xMxO2 (wherein M is at least one element selected from the group consisting of Co, Mg, Al, B, Ti, V, Cr, Fe, Cu, Zn, Zr, Mo, Sn, Ca, Sr, and W, and 0.8 ⁇ x ⁇ 1.2, 0 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0.5, k+l ⁇ 1, -0.1 ⁇
  • the positive electrode active material preferably has a reaction suppression layer on its surface for suppressing the reaction with the solid electrolyte.
  • the reaction suppression layer may be made of a material that has ion conductivity and can suppress the reaction between the positive electrode active material and the solid electrolyte.
  • materials that can form the reaction suppression layer include oxides containing Li and at least one element selected from the group consisting of Nb, P, B, Si, Ge, Ti, and Zr, more specifically, Nb-containing oxides such as LiNbO 3 , Li 3 PO 4 , Li 3 BO 3 , Li 4 SiO 4 , Li 4 GeO 4 , LiTiO 3 , LiZrO 3 , etc.
  • the reaction suppression layer may contain only one of these oxides, or may contain two or more of them, and further, a plurality of these oxides may form a composite compound. Among these oxides, it is preferable to use an Nb-containing oxide, and it is more preferable to use LiNbO 3 .
  • the reaction suppression layer is preferably present on the surface in an amount of 0.1 to 1.0 part by mass per 100 parts by mass of the positive electrode active material. Methods for forming the reaction suppression layer on the surface of the positive electrode active material include the sol-gel method, the mechanofusion method, the CVD method, the PVD method, and the like.
  • the negative electrode active material is preferably, but not limited to, lithium titanium oxide.
  • lithium titanium oxide By using lithium titanium oxide, operation at low temperatures can be stabilized compared to the graphite-based negative electrode active material that is often used in secondary batteries.
  • lithium titanium oxide is one represented by the following general composition formula (A).
  • M1 is at least one element selected from the group consisting of Na, Mg, K, Ca, Sr, and Ba
  • M2 is at least one element selected from the group consisting of Al, V, Cr, Fe, Co, Ni, Zn, Ym, Zr, Nb, Mo, Ta, and W, and 0 ⁇ s ⁇ 1/3 and 0 ⁇ t ⁇ 5/3.
  • the lithium titanium oxide represented by the general composition formula (A) a part of the Li site may be substituted with the element M1 .
  • s representing the ratio of the element M1 is preferably less than 1/3.
  • Li does not have to be substituted with the element M1 , so s representing the ratio of the element M1 may be 0.
  • the element M2 is a component for enhancing the electronic conductivity of the lithium titanium oxide, and when t representing the ratio of the element M2 is 0 ⁇ t ⁇ 5/3, the effect of improving the electronic conductivity can be well secured.
  • a negative electrode active material other than lithium titanium oxide which is used in lithium ion secondary batteries, etc., can also be used together with lithium titanium oxide.
  • the proportion of the negative electrode active material other than lithium titanium oxide in the total amount of the negative electrode active material is 30 mass% or less.
  • Solid electrolytes include, but are not limited to, sulfide-based solid electrolytes, hydride-based solid electrolytes, oxide-based solid electrolytes, etc., with sulfide-based solid electrolytes being preferred.
  • the sulfide-based solid electrolyte is not particularly limited, but examples thereof include a compound in a glassy or glass-ceramic state represented by xLi 2 S.(100-x)P 2 S 5 (where 70 ⁇ x ⁇ 80) and a compound in a glassy or glass-ceramic state represented by yLiI.zLiBr.(100-y-z)(xLi 2 S.(1-x)P 2 S 5 ) (where 0.7 ⁇ x ⁇ 0.8, 0 ⁇ y ⁇ 30, 0 ⁇ z ⁇ 30).
  • the sulfide-based solid electrolyte may be a compound represented by Li 4-x Ge 1-x PxS 4 (where 0 ⁇ x ⁇ 1), which is so-called LGPS.
  • at least a part of Ge may be substituted with at least one of Sb, Si, Sn, B, Al, Ga, In, Ti, Zr, V, and Nb.
  • at least a part of P may be substituted with at least one of Sb, Si, Sn, B, Al, Ga, In, Ti, Zr, V, and Nb.
  • at least a part of Li may be substituted with at least one of Na, K, Mg, Ca, and Zn.
  • at least a part of S may be substituted with a halogen (at least one of F, Cl, Br, and I).
  • the sulfide-based solid electrolyte may also be an argyrodite-based compound represented by Li7 -x- 2yPS6 -x-yXx , Li8 -x- 2ySiS6 -x-yXx , Li8-x- 2yGeS6-x -yXx , etc.
  • X is at least one of F, Cl, Br, and I, and x and y satisfy 0 ⁇ x, 0 ⁇ y.
  • Examples of the hydride-based solid electrolyte include LiBH 4 , solid solutions of LiBH 4 and the following alkali metal compounds (for example, those in which the molar ratio of LiBH 4 to the alkali metal compound is 1:1 to 20:1), and the like.
  • the alkali metal compound in the solid solution includes at least one selected from the group consisting of lithium halides (LiI, LiBr, LiF, LiCl, etc.), rubidium halides (RbI, RbBr, RbF, RbCl, etc.), cesium halides (CsI, CsBr, CsF, CsCl, etc.), lithium amide, rubidium amide, and cesium amide.
  • the hydride-based solid electrolyte may also be a salt of Li with a closo complex hydride such as [B 12 H 12 ] 2- , [CB 11 H 12 ] - , or [CB 9 H 10 ] - .
  • oxide-based solid electrolyte for example, a garnet-type solid electrolyte represented by Li7 -xLa3 ( Zr2 - xNbx ) O12 (where 0 ⁇ x ⁇ 2) can be used.
  • the oxide-based solid electrolyte may be a perovskite-based compound represented by (Li,La) TiO3 , (Li,La) NbO3 , (Li,Sr)(Ta,Zr) O3 , or the like.
  • the oxide-based solid electrolyte may also be a Nasicon-type compound such as Li(Al,Ti)( PO4 ) 3 or Li(Al,Ga)( PO4 ) 3 .
  • the oxide-based solid electrolyte may also be a phosphoric acid-based compound represented by Li3PO4 or a compound in which a part of O in Li3PO4 is replaced by N.
  • the oxide-based solid electrolyte may also be a boric acid-based compound represented by Li3BO3 or a compound in which a part of O in Li3BO3 is replaced by C.
  • the solid electrolyte may be a mixture of the above-mentioned compounds.
  • the proportion of the sulfide-based solid electrolyte in the total amount of the solid electrolyte is preferably 70 mass% or more.
  • the proportion of the sulfide-based solid electrolyte in the total amount of the solid electrolyte is more preferably 80 mass% or more, and even more preferably 90 mass% or more.
  • the above describes the sensor module 10 according to one embodiment of the present invention.
  • This embodiment provides a sensor module capable of long-term monitoring.
  • a negative electrode mixture was prepared by mixing lithium titanate (Li 4 Ti 5 O 12 , negative electrode active material) having an average particle size of 2 ⁇ m, a sulfide-based solid electrolyte (Li 6 PS 5 Cl) having an average particle size of 0.7 ⁇ m, and graphene (conductive additive) in a mass ratio of 50:41:9.
  • LiCoO 2 positive electrode active material
  • LiNbO 3 coating layer formed on its surface LiNbO 3
  • Si 6 PS 5 Cl sulfide-based solid electrolyte having an average particle size of 0.7 ⁇ m
  • graphene were mixed in a mass ratio of 65:30.7:4.3 to prepare a positive electrode mixture.
  • a powder of sulfide-based solid electrolyte (Li 6 PS 5 Cl) having an average particle size of 0.7 ⁇ m was placed in a powder molding die, and pressure molding was performed at 70 MPa using a press to form a provisionally molded layer of the solid electrolyte layer. Furthermore, the negative electrode mixture was placed on the upper surface of the provisionally molded layer of the solid electrolyte layer and pressure molding was performed at 50 MPa, and a provisionally molded layer of the negative electrode was further formed on the provisionally molded layer of the solid electrolyte layer.
  • the positive electrode mixture was placed on the top surface of the provisionally molded layer of the solid electrolyte layer in the mold (the side opposite the surface having the negative electrode), and the entire structure was pressurized and molded at a surface pressure of 1400 MPa to produce two unit electrode bodies with a diameter of 9.5 mm and a thickness of 2.7 mm, in which the negative electrode, solid electrolyte layer, and positive electrode are integrated.
  • Capacity reduction rate (1 ⁇ discharge capacity after charge/discharge cycles/initial discharge capacity) ⁇ 100
  • the actual degradation rate k 100 after 100 cycles was 0.201 (%/cycle), and the actual degradation rate k 200 after 200 cycles was 0.131 (%/cycle), which were 110% or less of f 100 (Th) and f 200 (Th), respectively.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'un module de capteur capable de surveillance à long terme. La solution selon l'invention porte sur un module de capteur (10) qui comprend un capteur (11) destiné à mesurer des données, un dispositif de communication (12) destiné à transmettre les données mesurées vers l'extérieur, une batterie de stockage (13) destiné à fournir de l'énergie électrique au capteur (11) et au dispositif de communication (12), et un générateur d'énergie (14) destiné à charger la batterie de stockage (13). Selon l'invention : la batterie de stockage (13) est une batterie tout solide ; et une valeur mesurée réelle k100 d'un taux de réduction de capacité moyen par cycle lorsque la batterie de stockage (13) est soumise à 100 cycles de charge-décharge à Th = 105 °C est au plus égale à 110 % d'une valeur prédite f100 (Th) obtenue en substituant T=Th dans une formule de prédiction f100 (T) obtenue par substitution du taux de réduction de capacité moyen f100 (T) par cycle lorsque la batterie de stockage (13) est soumise à 100 cycles de charge-décharge à T = 25 °C, T = 37 °C et T = 45 °C dans la formule (1), et détermination des coefficients A100 et B100 par la méthode des moindres carrés.　(1) : f100 (T) = A100/(273+T)+B100. L'unité de T dans la formule (1) est le °C.
PCT/JP2024/036786 2023-10-17 2024-10-16 Module de capteur Pending WO2025084306A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023178872 2023-10-17
JP2023-178872 2023-10-17

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WO2025084306A1 true WO2025084306A1 (fr) 2025-04-24

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008226728A (ja) * 2007-03-14 2008-09-25 Geomatec Co Ltd 薄膜固体二次電池及びこれを備えた複合型機器
JP2015076158A (ja) * 2013-10-07 2015-04-20 富士通株式会社 全固体二次電池、全固体二次電池の製造方法、及びセンサシステム
JP2018510487A (ja) * 2015-02-02 2018-04-12 サクティスリー・インコ—ポレイテッド 固体エネルギー貯蔵デバイス
JP2018159581A (ja) * 2017-03-22 2018-10-11 Tdk株式会社 状態検出装置
CN116454370A (zh) * 2023-03-31 2023-07-18 清华大学深圳国际研究生院 复合固态电解质、其制备方法及锂金属电池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008226728A (ja) * 2007-03-14 2008-09-25 Geomatec Co Ltd 薄膜固体二次電池及びこれを備えた複合型機器
JP2015076158A (ja) * 2013-10-07 2015-04-20 富士通株式会社 全固体二次電池、全固体二次電池の製造方法、及びセンサシステム
JP2018510487A (ja) * 2015-02-02 2018-04-12 サクティスリー・インコ—ポレイテッド 固体エネルギー貯蔵デバイス
JP2018159581A (ja) * 2017-03-22 2018-10-11 Tdk株式会社 状態検出装置
CN116454370A (zh) * 2023-03-31 2023-07-18 清华大学深圳国际研究生院 复合固态电解质、其制备方法及锂金属电池

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