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WO2018010922A1 - Dilatomètre pour une pile d'électrodes - Google Patents

Dilatomètre pour une pile d'électrodes Download PDF

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Publication number
WO2018010922A1
WO2018010922A1 PCT/EP2017/065179 EP2017065179W WO2018010922A1 WO 2018010922 A1 WO2018010922 A1 WO 2018010922A1 EP 2017065179 W EP2017065179 W EP 2017065179W WO 2018010922 A1 WO2018010922 A1 WO 2018010922A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode stack
force
dilatometer
power transmission
expansion
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.)
Ceased
Application number
PCT/EP2017/065179
Other languages
German (de)
English (en)
Inventor
Daniel Sauerteig
Christoph Schlund
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.)
Robert Bosch GmbH
Original Assignee
Robert Bosch GmbH
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 Robert Bosch GmbH filed Critical Robert Bosch GmbH
Publication of WO2018010922A1 publication Critical patent/WO2018010922A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L1/00—Measuring force or stress, in general
    • G01L1/005—Measuring force or stress, in general by electrical means and not provided for in G01L1/06 - G01L1/22
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a dilatometer for detecting an expansion tendency of the electrode stack occurring when charging an electrode stack.
  • the volume change of the electrodes described above must be in the corresponding battery cells or battery modules
  • Electrolytes wetted comprise a first electrode and a second electrode.
  • the first electrode is formed of porous, nanoscale, electrically conductive material.
  • the second electrode serves as
  • the arrangement comprises two contacts which are each connected to a different one of the two electrodes and between which an electrical voltage for charging the two electrodes can be applied. If the two electrodes are electrically charged by an electrical voltage applied between the two contacts, the nanoporous material of the first electrode expands or contracts.
  • the first electrode is further between a fixed support and a first end of a
  • Positioning element arranged such that the first electrode, the carrier and the positioning element over two opposite
  • the positioning member has a second end connected to an inductive displacement sensor. By means of the displacement sensor can occur during charging of the two electrodes expansion or
  • a dilatometer for detecting an electrode stack which is formed when a battery cell, in particular, is being charged
  • the dilatometer comprises a carrier unit with a carrier for receiving the electrode stack.
  • the dilatometer further comprises two contact elements, via which an electrical charging of the electrode stack can take place when the Electrode stack rests with a substantially perpendicular to a first direction oriented first outer surface on the support.
  • the dilatometer further comprises a power transmission unit with a
  • the force transmission element is provided to contact a substantially perpendicular to the first direction oriented second outer surface of the electrode stack by means of a first end during charging of the electrode stack and to allow taking place along the first direction free expansion of the electrode stack.
  • the force transmission element is provided to always contact the second outer surface of the electrode stack by means of the first end during charging of the electrode stack and one of the free expansion
  • Dilatometer further comprises a measuring unit, which is for detecting the
  • the power transmission element is provided so that when charging the electrode stack the
  • the outer surface of the electrode stack is the same as when charging the
  • Electrode stack occurring movement of the power transmission element is. This also means that an expansion of the electrode stack occurring during the charging of the electrode stack along the first direction can be determined on the basis of the movement of the force transmission element measured by the measuring unit. An increase in the charge occurring when charging the electrode stack
  • Electrode stack In other words, the expansion of the electrode stack along the first direction is a charge state dependent expansion.
  • the movement measured by the measuring unit is a measure of the free expansion of the electrode stack.
  • the movement measured by the measuring unit is a measure of an expansion of the electrode stack which is slowed down by the first force.
  • Force transmission element and the first force can measure.
  • measuring results of the measuring unit can also be used to determine an influence of the first force on the expansion of the electrode stack.
  • a constant mechanical counterforce represented by the first force is applied to the electrode stack.
  • the expansion of the electrode stack as a function of the constant mechanical counterforce examined and thus a
  • volumetric work of the electrode stack can be determined.
  • the first force during different measuring operations may have different amounts of force, so that the charging of the electrode stack may take place under different mechanical pressure conditions.
  • the measuring unit based on measurement results of the measuring unit, the
  • information about the Expansionsbesteben occurring during charging of the electrode stack or expansion behavior of the Electrode stack can be obtained.
  • Such information is very valuable, especially when the electrode stack is a battery cell intended for incorporation in battery modules or systems.
  • This information can be used to optimize a design of electrodes to be used in the electrode stack for mechanical stress so as to minimize expansion of the electrode stack.
  • Electrode stack then leads to an optimization of one of the
  • Electrode stack deliverable electrical power.
  • a mechanical tension of the force transmission element by an external system such as by pneumatic or hydraulic piston done.
  • an external system such as by pneumatic or hydraulic piston.
  • the measuring unit comprises a displacement sensor.
  • the displacement sensor is designed to charge one of a second end of the electrode when charging the electrode stack
  • the first end and the second end of the power transmission element are rigidly connected together.
  • the path traveled by the second end of the power transmission member along the first direction is equal to one of the first end of the first end
  • Electrode stack is adversely affected by the first end of the power transmission element by a corresponding path measurement.
  • the measuring unit comprises a force sensor arranged in the carrier unit.
  • the force sensor is further provided to measure the first force during charging of the electrode stack. It should be noted that when charging the
  • Electrode stack the force transmission element always contacted the resting on the carrier electrode stack by means of its first end. It should also be noted that when charging the electrode stack and the force sensor always contacted the carrier. Thereby, the first force from the force transmission element is applied to the electrode stack, of which
  • Force sensor exerted This means that the first force acts unadulterated on the force sensor, so that, by means of the force sensor arranged in this way, a very accurate measurement of the first force can be carried out.
  • a selective contacting of the outer surface of the carrier by the force sensor allows a punctual resting of the carrier on the force sensor. This ensures a full-surface
  • Power transmission element is a corresponding
  • Dilatometer whose force sensor contacts the outer surface of the carrier selectively, self-locking.
  • the power transmission unit comprises an elastic element and a bracing element.
  • the bracing element is provided to generate a force leading to a mechanical strain of the force transmission element contraction of the elastic element for generating the first force. In this way it is achieved that the mechanical tension of the
  • Power transmission element and thus the first force can be generated by means of such incorporated in a corresponding dilatometer components, without the need for an external system must be used.
  • Elastic modulus of the elastic element selected so that when charging the electrode stack of the force transmission element on the
  • Electrode stack exerted first force is less than a second force.
  • the second force is exerted during charging of the electrode stack due to a growing internal pressure of the electrode stack from the electrode stack to the force transmission element. This achieves in a simple manner that when charging the electrode stack, a movement of the second outer surface of the electrode stack is not completely slowed down by the first force. Consequently, when charging the electrode stack a
  • the elastic element is a spring.
  • a spring travel of the spring occurring along the first direction during the contraction of the spring is greater by a predefined factor or at least an order of magnitude than an expansion of the electrode stack along the first direction during charging of the electrode stack.
  • the predefined factor has, for example, a value of 10 3 , 10 4 or 10 5 . In this way it is ensured that a change in the amount of the first force resulting from a due to the expansion of the
  • Electrode stack occurring changing a length of the spring arises is negligible. It should be noted that the length of the spring extends along the first direction.
  • the first force represents a constant mechanical counteracting force counteracting the expansion of the electrode stack.
  • a constant mechanical counterforce is exerted on the electrode stack, which causes an expansion or expansion of the electrode stack
  • Electrode stack along the first direction allows.
  • Elastic modulus of the elastic member selected so that when charging the electrode stack that of the force transmission element on the
  • Electrode stack exerted first force compensates for a second force.
  • the second force is applied to the force transmitting member due to a growing internal pressure of the electrode stack from the electrode stack. In this way it is achieved that during charging of the electrode stack, a movement of the second outer surface of the electrode stack and thus an expansion or expansion of the electrode stack along the first direction are substantially prevented. It should be noted that when charging the electrode stack an expansion - related increase of the
  • Increase in an amount of the second force leads.
  • the increase of the internal pressure and thus the amount of the second force is dependent on mechanical properties of electrodes installed in the electrode stack. Since the first force compensates for the second force when the electrode stack is charged, an increase in the magnitude of the first force also occurs when the electrode stack is charged.
  • the first force represents one of the expansion of the electrode stack
  • the elastic member during charging of the electrode stack, a variable mechanical counterforce is exerted on the electrode stack, which substantially prevents the expansion of the electrode stack occurring along the first direction.
  • a path traveled by the second outer surface of the electrode stack along the first direction is greatly restricted and thereby defined.
  • Electrode stack is applied, which substantially prevents expansion of the electrode stack along the first direction.
  • the elastic element surrounds the force transmission element.
  • the elastic element on each two the force transmission element enclosing open end regions. The contracted by means of the bracing element elastic
  • Element presses with a first of its two open end portions against a side facing away from the first end of the force transmission element side of a first end portion of the force-transmitting element. The first end of the
  • Power transmission element comprises the first end of the
  • the power transmission unit comprises a first housing which the
  • the first housing has an open end area.
  • the open end portion of the first housing encloses the power transmission element.
  • Clamping element is a first screw-threaded element and has a continuous along its screw-in cavity.
  • Bracing element may further in the open end of the first
  • Housing be inserted. This can be done so that the first
  • screwable element surrounds the force transmission element and generates the contraction of the elastic element by screwing into the open end of the first housing.
  • the mechanical tension of the elastic element and consequently also the first force can be generated in a simple manner by screwing in the first screw-in element.
  • the power transmission unit comprises a rotation-preventing element, which is designed to co-rotate the power transmission element during
  • Power transmission unit a centering element, which is intended to center the enclosed by the first screw-threaded element force transmission element. In this way it is achieved that one, in particular of one Operator of the dilatometer caused misalignment of the power transmission element is prevented.
  • the carrier is designed in the form of a shell.
  • the force transmission element is designed in the form of a piston.
  • a first outer surface of the piston extending at its first end is larger than a second outer surface of the piston extending at a second end of the piston rigidly connected to the first end. In this way, one over the first outer surface of the
  • Electrode stack of the carrier uncomplicated and easily done.
  • a previously described dilatometer comprises a second screw-in element and two holes associated therewith.
  • Power transmission unit each have one of the two holes.
  • the carrier unit and the power transmission unit can be detachably connected to one another by screwing in the second screw-in element into the two bores positioned adjacent to one another.
  • a detachable connection between the carrier unit and the power transmission unit is provided in a simple manner.
  • at least one further second screw-threaded element can be provided which is formed in the same way as the second screw-in element.
  • At least one of the holes in each case has an insulating layer. In this way it is achieved that no electrical connection between the carrier unit and the power transmission unit can be produced via the second screw-in element.
  • a previously described dilatometer comprises a between the carrier unit and the
  • Power transmission unit mounted insulating. In this way, a full-surface electrical insulation and thus a full-surface
  • a previously described dilatometer comprises a sealing element enclosing the carrier.
  • a previously described dilatometer comprises a further sealing element enclosing the force transmission element.
  • Electrolyte ensured and penetration of contaminants, such as
  • At least one further sealing element can be provided, which is formed in the same way as a previously described sealing element.
  • the two contact elements preferably comprise a first contact element installed in the support and a second contact element installed in the force transmission element.
  • the two contact elements are preferably designed in the form of plug sockets.
  • a previously described dilatometer allows an on-site feasible measurement of a charge state-dependent expansion or expansion of an electrode stack, in particular in the form of a battery cell. According to some previously described
  • Figure 1 is a sectional view of a first dilatometer according to a first embodiment of the invention
  • Figure 2 is a sectional view of a second dilatometer according to a second embodiment of the invention.
  • FIG. 3 shows a plurality of progressions measured by means of the first dilatometer for different mechanical pressure conditions, which shows a plurality of charge-state-dependent expansions of FIG
  • FIG. 1 shows a first dilatometer 1 according to a first embodiment of the invention.
  • the first dilatometer 1 comprises a carrier unit 10 with a carrier in the form of a shell 1 1 for receiving a
  • Electrode stack 12 The electrode stack 12 is formed in the form of a battery cell.
  • the first dilatometer 1 further comprises a
  • the first dilatometer 1 comprises two contact elements (not shown) in the form of plug sockets, via which an electrical contacting of electrodes (not shown) present in the electrode stack 12 can take place. Charging of the electrode stack 12 can take place via the two contact elements when the electrode stack 12 rests on the shell 1 1 with a first outer surface oriented essentially perpendicular to a first direction R1.
  • the two contact elements comprise a built in the shell 1 1 first contact element and a built-in the piston 21 second
  • the electrodes of the electrode stack 12 comprise an anode and a cathode, are each coated on one side with active material and electrically insulated from one another by an ion-conducting separator.
  • the electrode stack 12 further comprises an electrolyte.
  • the electrode stack 12 is designed in particular in the form of a lithium-ion battery cell.
  • the piston 21 is provided to a substantially perpendicular to the first direction R1 oriented second outer surface of the electrode stack 12 by means of a located at a first end face over the entire surface
  • the piston 21 always contacted the second outer surface of the electrode stack 12 by means of its first end over the entire surface.
  • the power transmission unit 20 comprises a spring 22 in the form of a spring
  • the power transmission unit 20 further includes a first housing 24 which encloses the piston 21 and the spring 22.
  • the first housing 24 has a piston 21 enclosing the open end region 25.
  • the first screw-in element 23 can be inserted into the open end region 25 of the first housing 24 such that the first screw-in element 23 encloses the piston 21 and by screwing into the open end region 25 of the first housing 24 causes a contraction of the spring 22. Due to the contraction of the spring 22, a mechanical tension of the piston 21 is generated, so that the piston 21 presses against the electrode stack 12 with a first force resulting from the contraction of the spring 22.
  • Electrode stack 12 counteracting mechanical counterforce.
  • the power transmission unit 20 comprises a rotation-preventing element designed in the form of an axial needle bearing 27, which is provided to prevent co-rotation of the piston 21 when the first screw-in element 23 is screwed in.
  • the axial needle bearing 27 is disposed between the spring 22 and the piston 21.
  • the power transmission unit 20 further comprises a centering element in the form of a centering ring 28, which is intended to center the piston 21 enclosed by the first screw-in element 23.
  • the first dilatometer 1 comprises a measuring unit which has a force sensor 14 arranged in the carrier unit 10, on which the bowl 1 1 rests punctually.
  • the force sensor 14 is provided to measure the first force. Characterized in that the sound 1 1 rests selectively on the force sensor 14, a full-surface edition of the first end of the piston 21 extending end face of the piston 21 on the electrode stack 12 and consequently on an electrode stack 12 contacting inner surface of the shell 1 1 is ensured , Thus, the first dilatometer 1 is self-locking. This also achieves a full-surface mechanical contacting of the electrodes arranged in the electrode stack 12.
  • the measuring unit further comprises a displacement sensor 26 arranged in the force unit 20.
  • the displacement sensor 26 is designed to charge the battery during charging Electrode stack 12 to measure one of a protruding from the open end portion 25 of the first housing 24 second end of the piston 21 along the first direction R1 path traveled.
  • the second end of the piston 21 is rigidly connected to the electrode stack 12 contacting first end of the piston 21. Consequently, that of the second end of the
  • the displacement sensor 26 is for example a differential transformer displacement sensor (LVDT) or a capacitive displacement sensor.
  • LVDT differential transformer displacement sensor
  • the carrier unit 10 and the power transmission unit 20 are releasably connected to one another via a second screw-in element designed in the form of a screw 30.
  • a second screw-in element designed in the form of a screw 30.
  • Power transmission unit 20 each one of two holes and are positioned by screwing the screw 30 in the two adjacent to each other
  • the first dilatometer 1 further comprises an insulating element mounted between the carrier unit 10 and the power transmission unit 20 and formed in the form of a polyethylene ring 40.
  • Power transmission unit 20 are electrically insulated and sealed via the polyethylene ring 40.
  • the first dilatometer 1 may also comprise a sealing element enclosing the shell 11 and formed in the form of a sealing ring 41.
  • the first dilatometer 1 may further comprise a sealing element enclosing the piston 21 and formed in the form of a further sealing ring 42.
  • the sealing rings 41, 42 can to ensure a tightness in the Electrode stack 12 located electrolytes and to prevent ingress of impurities, such as water from the air, are provided. These sealing rings 41, 42 are not necessary when the first dilatometer 1 is operated in a dry space or within a protective atmosphere, such as in a glovebox.
  • the spring 22 for mechanical tension of the piston 21 can be omitted.
  • a free expansion of the electrode stack 12 along the first direction R1 can take place and be determined by means of the displacement sensor 26.
  • the spring 22 can be dispensed with for the mechanical tensioning of the piston 21 and the mechanical tensioning of the piston 21 can take place externally by means of pneumatic or hydraulic pistons.
  • FIG. 2 shows a second dilatometer 2 according to a second embodiment of the invention.
  • the second dilatometer 2 differs from the first dilatometer 1 in that the spring 22 is replaced by a metal sleeve 102.
  • Housing 24 causes a contraction of the metal sleeve 102.
  • a change in length of the metal sleeve 102 occurring during the contraction of the metal sleeve 102 along the first direction R1 is by several
  • the first force when charging the electrode stack 12, the first force must compensate for the second force exerted on the piston 21 from the electrode stack 12 due to a growing internal pressure of the electrode stack 12 to increase the expansion along the first direction R1
  • the first force represents a variable mechanical counterforce, which is measured by the force sensor 14.
  • an expansion-related development of the first force acting on the electrode stack 12 can be measured by means of the force sensor 14.
  • the overall height of a corresponding dilatometer 2 can be reduced by approximately along the first direction R1 extending length of the spring 22, whereby a very compact construction of such a dilatometer 2 is made possible.
  • FIG. 3 shows a first course V1 of a charge state-dependent first expansion of a first lithium-ion battery cell as a function of time measured by means of the first dilatometer 1.
  • the first expansion is measured during the first charging of the first battery cell.
  • the piston 21 exerts a first force on the first battery cell with such an amount that the first battery cell is exposed to a first mechanical pressure of 79 kPa.
  • the first expansion is given on a first axis s in microns ⁇ .
  • the time is given on a second axis t in hours h.
  • FIG 3 further shows a second curve V2 of a first voltage, which is shown as a function of time and bears against the first battery cell during the first charging of the first battery cell.
  • the first voltage is given on a parallel to the first axis oriented third axis U in volts V.
  • the first battery cell has a state of charge that changes between 0 and 1 during the first charging of the first battery cell.
  • FIG. 3 shows a third course V3 of a charge state-dependent second expansion of a second lithium-ion battery cell as a function of time measured by means of the first dilatometer 1.
  • the first and the second battery cells are identical.
  • the second expansion is measured during the first charging of the second battery cell.
  • the piston 21 exerts a first force on the second battery cell with an amount such that the second battery cell is exposed to a second mechanical pressure of almost 156 kPa, which is almost double the first pressure.
  • the second expansion is also indicated on the first axis s in microns ⁇ .
  • FIG. 3 further shows a fourth curve V4 of a second voltage, which is shown as a function of time and bears against the second battery cell during the first charging of the second battery cell.
  • the second voltage is also indicated on the third axis U in volts V.
  • the second battery cell has a state of charge that changes between 0 and 1 during the first charging of the second battery cell.
  • the first expansion of the first battery cell is greater than the second expansion of the second battery cell.
  • the first expansion of the first battery cell taking place during the first pressure is greater by a factor of approximately 1.5 than the second expansion taking place during the second pressure when the first battery cell and the second battery cell each have a charge state of 1. This means that a large increase in a mechanical pressure applied to an electrically charged lithium-ion battery cell becomes a leads to significant reduction of a charge state-dependent expansion of this battery cell.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Secondary Cells (AREA)
  • Battery Mounting, Suspending (AREA)

Abstract

L'invention concerne un dilatomètre (1) servant à détecter une tendance d'extension d'une pile d'électrodes (12) survenant lors d'une charge de la pile d'électrodes (12). Le dilatomètre comporte une unité porteuse (10), dotée d'un support (11) pour recevoir la pile d'électrodes (12), et deux éléments de contact par le biais desquels peut se produire une charge électrique de la pile d'électrodes (12) lorsqu'une première surface externe de la pile d'électrodes (12) repose sur le support (11). Le dilatomètre (1) comporte en plus une unité de transmission de force (20) dotée d'un élément de transmission de force (21) qui sert, lors de la charge de la pile d'électrodes (12), à contacter en permanence une seconde surface externe de la pile d'électrodes (12) au moyen d'une première extrémité et à permettre une extension libre de la pile d'électrodes (12) et/ou à exercer sur la pile d'électrodes (12) une première force s'opposant à l'extension libre. Le dilatomètre (1) comporte en outre une unité de mesure (14, 26) qui est conçue pour, lors de la charge de la pile d'électrodes (12), mesurer un mouvement de l'élément de transmission de force (21) et/ou la première force.
PCT/EP2017/065179 2016-07-11 2017-06-21 Dilatomètre pour une pile d'électrodes Ceased WO2018010922A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016212556.7 2016-07-11
DE102016212556.7A DE102016212556A1 (de) 2016-07-11 2016-07-11 Dilatometer für Elektrodenstapel

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WO2018010922A1 true WO2018010922A1 (fr) 2018-01-18

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CN110953980A (zh) * 2019-11-27 2020-04-03 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） 一种检测深海耐压电池单体鼓胀的方法
CN110953980B (zh) * 2019-11-27 2022-04-19 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） 一种检测深海耐压电池单体鼓胀的方法

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