• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a flexible structure (6) comprising a strain gauge (7) of elongated shape along a longitudinal axis X1, intended to measure the deformations of the structure. the flexible structure in a direction X parallel to the axis X1, the support (71) of the gauge being bonded to the flexible structure only by its lateral ends (75, 76). A particularly targeted application is the bonding of strain gauges on a flexible lithium battery pack, such as a Li-ion battery.
    公开号:FR3018911A1
    申请号:FR1452264
    申请日:2014-03-19
    公开日:2015-09-25
    发明作者:David Brun-Buisson；Sylvie Genies
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    [0001] STRUCTURE SC UPLE WITH JAUG; ei DE DE 'A> i L01%.' '' LPPLICAT7: 7.7 AU ,; SUMMARY OF THE INVENTION The present invention relates to the field of measuring deformations of a flexible structure by means of at least one embodiment of the present invention. minus a strain gauge glued to said structure. It is more p. to a new realizationcollage between a strain gauge and the flexible structure which one seeks to determine the deformations that it undergoes. The main application targeted by the invention is the measurement of deformations of flexible packaging electrochemical accumulators lithi, such as Li-ion accumulators. The invention thus relates to an electrochemical accumulator comprising at least one electrochemical cell constituted by at least one anode and a cathode on either side of an electrolyte, two current collectors, one of which is connected to the anode and the other at the cathode, and a flexible package arranged to contain the electrochemical cell (s) with sealing while traversed by a portion of the current collectors forming the pale. Although described below with reference to the main application, the invention is also applicable to any other flexible structure whose deformation is sought to measure it by means of a strain gauge. "Flexible structure" means a mechanical structure of which the constituent material (s) is (are) flexible (s), that is to say a suitable material (s) (x). s) to undergo deformation under low stress; that is to say still with a weak Young's modulus. By way of example, a structure of polymer material (s) is considered to be flexible when its Young's modulus is less than 10 GPa. STATE OF THE ART As schematically illustrated in FIGS. 1 and 2, a lithium-ion battery or accumulator usually comprises at least one electrochemical cell C consisting of an electrolyte constituent 1, impregnated in a separator making it possible to isolate electrically the electrodes, between a positive electrode or cathode 2 and a negative electrode or anode 3, a current collector 4 connected to the cathode 2, a current collector 5 connected to the anode 3 and finally, a package 6 arranged to contain the electrochemical cell with sealing while being traversed by a portion of current collectors 4, 5. The architecture of conventional lithium-ion batteries is an architecture that can be described as monopolar, because with a single electrochemical cell comprising an anode, a cathode and electrolyte. Several types of monopolar architecture geometry are known: a cylindrical geometry, with winding around cylindrical axis as disclosed in US patent application 2006/0121348, a prismatic geometry, with winding around parallelepipedal axis as disclosed in US Patents 7348098. , US 7338733; stack geometry as disclosed in US Patent Application Serial Nos. 2008/060189, US 2008/0057392, and US Pat. No. 7335448. Electrolyte component 1 may be of solid, liquid or gel form. In the latter form, the constituent may comprise a polymer separator, ceramic or microporous composite soaked with organic electrolyte (s) or ionic liquid type that allows the displacement of the lithium ion from the cathode to the cathode. anode during the charging process and vice versa during the discharge process, which in this case generates the current, by displacement of electrons in the external circuit. The electrolyte is generally a mixture of organic solvents, for example carbonates in which is added a lithium salt typically LiPF6. The positive electrode or cathode 2 consists of Lithium cation insertion materials, such as LiFePO4, LiCoO2, LiNi0.33Mn0.33C00 3302. The negative electrode or anode 3 is very often made of graphite carbon or Li4Ti0'5012 ( titanate material), possibly also based on silicon or silicon-based composite formed. A negative electrode of a lithium-ion battery can be formed from a single alloy, or a mixture of alloys, or a mixture of alloy (s) and other lithium insertion material (s). (graphite, in synthetic or natural form, Lia Tis012, TiO2 .-- ..). This negative electrode may also contain electronic conductive additives as well as polymeric additives which give it mechanical properties and electrochemical performance appropriate to the lithium-ion battery application or to its implementation method. The current collector 4 connected to the positive electrode is generally made of aluminum. The current collector 5 connected to the negative electrode is generally made of copper, nickel-plated copper or aluminum. A lithium-ion battery or accumulator may of course include a plurality of electrochemical cells which are stacked on each other. Traditionally, a Li-ion battery or accumulator uses a couple of materials at the anode and at the cathode allows it to operate at a high voltage level, typically equal to 3.6 volts. Depending on the type of application targeted, one seeks to achieve either a thin and flexible lithium-ion battery, or a rigid accumulator: the package is then either flexible or rigid and is in the latter case a kind of case. The flexible packages are usually made from a multilayer composite material consisting of a stack of aluminum layers covered by one or more adhesive-laminated polymer film (s). In most of these flexible packages, the polymer covering the aluminum is selected from polyethylene (PE), propylene, polyamide (PA) or may be in the form of an adhesive layer made of polyester-polyurethane. The company Showa Denko markets this type of composite material for use as a battery pack under the references NADR-0N25 / AL40 / CPP40 or No. ADR-0N25 / AL40 / CPP80. The Applicant has also proposed in the patent application FR 2955974 an improved flexible packaging from one or more sheets of polyarylethercetone (PAEK). Rigid packaging (boxes) are as for. they are used when the targeted applications are binding where one seeks a long life, with for example much higher pressures to be supported and a stricter required level of sealing, typically lower than the mbar.1 / s, or in environments with strong constraints such as aeronautics or space. The constituent material of a Li-ion battery pack is usually metal, typically an aluminum alloy or rigid polymer stainless steel such as acrylonitrile butadiene styrene (ABS). During the insertion / deinsertion of the Li + ion, the active materials of the negative and positive electrodes undergo an increase or a decrease of their crystallographic mesh, as figured in example in the table below. LiFePO4 LiNi0,33Mn0.33C00.3302 Graphite Non-Lithiated Lithium Non-Lithiated Lithium Non-Lithiated Lithium a (A) 5,792 6,008 2,832 2,858 2,460 2,485 b (A) 9,821 10,334 2,832 2,858 2,460 2,485 c (A) 4,788 4,683 13,938 14,223 3,350 3,706 volumes ( A3) 272.4 291.3 96.809 100.611 52.67059.458 variation of + 6.5 + 3.8 + 11.4 volume (%) These significant changes in the crystallographic mesh of the alloy can not be absorbed by the intrinsic porosity of the negative electrode. Step by step since all the components of a Li-ion battery, that is to say separator, electrode, collectors and packaging, have a low elasticity, the significant increase in the active materials induces a constraint on the package or a deformation thereof according to its rigidity. In other words, the process of insertion and disinsertion of lithium ions induces swelling / deflation of the active materials, which generates increases in pressure on the packaging of the battery according to its state of charge. Similarly, a degradation of a component can generate the production of gas within the accumulator, which also results in pressure increases on the packaging. Also, by measuring the pressure on the battery pack, the state of health of the battery can be estimated as a function of its aging. The Applicant has already proposed in the French patent application No. FR 13 53708 to use strain gauges, as health status indicators of Li-ion batteries. In this application, the pressures exerted by the inside of the Li-ion accumulator on the rigid packaging (box), causes its deformation directly measurable by a strain gauge glued on the case, this qH provides indicators health status of the Li-ion battery. Measurement results disclosed s. The aforesaid application has been obtained with Li-ion batteries with a rigid metal package on which a strain gauge has been glued. The inventors have found that with conventional adhesives and conventional strain gauge gluing techniques, it was not possible to obtain satisfactory measurements on flexible Li-ion battery packs. There is therefore a need to improve the deformation measurements of flexible electrochemical accumulator lithium packaging, in order to obtain a reliable indicator of the health of the accumulator. More generally, there is a need to improve the deformation measurements of a flexible structure, by overcoming the limitations of conventional adhesives and / or conventional bonding techniques. The object of the invention is to respond at least in part to this (these) need (s). SUMMARY OF THE INVENTION To this end, one aspect of the invention is a flexible structure comprising a strain gauge of elongate shape along a longitudinal axis X 1 intended to measure the deformations of the flexible structure in one direction. X parallel to the axis X 1, the support of the gauge being bonded to the flexible structure only by its lateral ends. In other words, unlike state-of-the-art strain gage gluing, which consists in adhering the entire surface of the gauge support to the structure, such as on a rigid Li-ion accumulator package, the bonding of the Deformation gauge according to the invention essentially consists of gluing only the lateral ends of the support. Thus, the bonding according to the invention only at the ends of the gauge support makes it possible to avoid hardening the surface of the flexible package, and therefore not to minimize the attenuation of the signal measured by the strain gauge. The bonded lateral ends thus behave like jaws of traction by which the force undergone by the flexible structure is reflected. Preferably, each adhesive bead between the gauge support and the flexible structure is formed along the entire length of a lateral end, that is to say along the entire width of the gauge support. Advantageously, the adhesive between the gauge support and the flexible structure is an adhesive, in the cured state, with a high Young's modulus, typically greater than 5 GPa, or very high. An adhesive with a Young's modulus very high compared to that of the flexible structure is an advantage since the deformation is not absorbed by the adhesive and directly reflected in the strain gauge. Advantageously, the glue is chosen from the family of cyanoacrylates of general formula: CH 2 = C (CN) -COOR with R a methyl, propyl, butyl, ethyl, hextyl, heptyl or octyl radical. According to a preferred application, flexible structure constitutes the flexible packaging of a lithium electrochemical accumulator, such as a Li-ion accumulator. A lithium electrochemical accumulator that can be targeted by the invention comprises at least one electrochemical cell constituted by at least one anode and a cathode on either side of an electrolyte, two current collectors, one of which is connected. at the anode and the other at the cathode, and a flexible package arranged to contain the electrochemical cell (s) with sealing while being traversed by a portion of the current collectors forming the poles. Depending on the type of lithium insertion electrode materials chosen for the electrodes constituting an electrochemical cell according to the invention, the current collector formed by at least one metal sheet may be made of aluminum or metallized on the surface of the electrode. another metal, for example aluminum superimposed on copper. By "electrode of lithium insertion material" is meant here and in the context of the invention, an electrode comprising at least one lithium insertion material and at least one polymer binder. Optionally, the electrode may further comprise an electronic conductor, for example carbon fibers or carbon black. By "lithium insertion material", in particular for the positive electrode, is meant here and in the context of the invention, a material chosen from lithiated oxides comprising manganese of spinel structure, the lithiated oxides of structure lamellar and mixtures thereof, lithiated polyanionic framework oxides of formula LiM, (X0z) ,, with M representing an element selected from Mn, Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr , Ba, Ti, Al, Si, B and Mo, X represent. t an element selected from P, Si, Ge, S and As, y, z and n being positive integers. By "lithium insertion material", in particular for the negative electrode, is also meant a material chosen from: lithiated or non-lithiated titanium oxide, for example Li 4 Ti 50 O 2 or TiO 2. More P. Specifically, the negative electrode material may be selected from carbonaceous materials, non-lithiated titanium oxides and their derivatives and lithiated titanium oxides such as Li4Ti5012 and their derivatives and a mixture thereof. Preferably, the anodes are Li4Ti5012 and the cathodes are LiFePO4. By "separator" is meant here and in the context of the invention, an electrical insulator, ionic conductor formed by at least one polymeric material such as polyvinylidene fluoride (PVDF), polyvinyl acetate (PVA), polymethyl methacrylate (PM), polyoxyethylene (POE), polyethylene terephthalate (PET), a polymer chosen from polyolefins such as polypropylene, polyethylene, cellulose. The electrolyte according to the invention may be a liquid formed by a mixture of carbonate and at least one lithium salt. By "lithium salt" is preferably meant a salt selected from LiPF6, LiC104, LiBF4 and L1AsF6. Alternatively, the electrolyte may comprise one or more ionic liquid, based on lithium ions, namely a salt consisting of lithium cations, complexed with inorganic or barley anions, which has the property of being in the state. at room temperature An ionic liquid, depending on the nature of the anion, may be hydrophilic or hydrophobic Examples of ionic liquids include ionic liquids based on hydrophobic anions such as trifluoromethanesulfonate (CF 3 SO 3 ), bis (trifluoromethanesulfonate imide [(CF 3 SO 2) 21 V] and tris (trifluoromethanesulfonate) methide [(CF 3 SO 2) 3 C]. The deposition of each electrode on the electrical conductive portion forming a current collector of at least one of the devices can to be realized by a conventional coating or printing technique such as screen printing, heliography, flexography, spray, etc. According to another of its aspects, a method of co A strain gauge is provided on a flexible structure, in which the gauge support is bonded to the flexible structure only at its lateral ends. DETAILED DESCRIPTION Other advantages and features will become more apparent upon reading the detailed description, given by way of illustration with reference to the following figures, of which FIG. 1 is an exploded schematic perspective view showing the various elements of a lithium-ion accumulator. FIG. 2 is a front view showing an accumulator with its flexible packaging according to the state of the art; FIG. 3 is a view from above illustrating a strain gauge according to the state of the art; FIG. FIG. 4 is a perspective view illustrating the bonding of a strain gauge on a rigid package of a Li-ion battery according to the state of the art; - Figure 5 is a perspective view illustrating the bonding of a strain gauge on a flexible package of a Li-ion battery according to the invention; FIG. 6 shows the measurement of deformation by linear strain gauges instrumented on a flexible Li-ion accumulator package, respectively according to a bonding according to the state of the art, according to a bonding according to the invention during the time of an imposed strain rate tensile test. For the sake of clarity, the same reference 6 is used for a flexible or rigid packaging of a lithium-ion battery according to the state of the art and a flexible package of a lithium-ion battery according to the invention for FIGS. 1 to 5. A lithium ion battery according to the invention comprises at least one electrochemical cell C consisting of at least one anode and one cathode on either side of an electrolyte impregnated in a separator. The anode and the cathode of lithium insertion material and may be deposited in a conventional manner in the form of an active layer on a metal foil is a current collector. For example, the anode is Li4Ti5012, the LiFePai cathode and the aluminum current collector sheets. The Li-ion accumulator has two current collectors, one of which is connected to the anode and the other to the cathode of each cell C.
    [0002] The flexible package 6 of the accumulator is arranged to contain the electrochemical cell (s) with e ety while being traversed by a portion of the current collectors forming the terminals (the poles). It is specified that the various elements according to the invention are shown only for the sake of clarity and that they are not to scale.
    [0003] The terms "longitudinal" and "lateral" are to be considered in relation to the elongated geometric shape along a longitudinal axis X1 of the strain gauge. Thus, the two longitudinal edges of the support of the gauge are those which extend parallel to the longitudinal axis X1. The two lateral edges of the gauge support are those at the lateral ends and extend orthogonally to the longitudinal axis X1. Figures 1 and 2 have already been discussed in detail in the preamble. They are therefore not described below.
    [0004] As represented in FIG. 3, a strain gauge 7 has an elongate shape along a longitudinal axis X1, and is constituted by a very thin metal wire 70 bonded to a support 71 of small thickness, typically made of polyimide. The wire 70 is arranged in a looped form 74, i.e., most of its length is distributed parallel to the longitudinal axis X1. Larger strands 72 serve to weld the outlets, to cables connecting the instruments shown, through the pads 73, called measuring pads. When it is desired to know the elongation of a structure along a given direction X, the gauge 7 is glued with the strands parallel to this direction X. The gauge 7 is thus qualified as a linear strain gauge.
    [0005] Thus, when a deformation appears in the direction of the measured deformations, the length of the wire 70 is increased. A continuous measurement of the resistance of the wire by an electrical connection of a Wheatstone bridge on the measurement pads 73 makes it possible to obtain a signal directly proportional to the linear deformation undergone by the support 71 according to the equation: R = p * 1 / S in which R is the resistance of the linear strain gauge 7, p the resistivity of the material, 1 the length of the wire 71 and S the surface of the wire 71. It is represented in FIG. linear deformation 7 on a packaging of a Li-ion accumulator as it is made according to the state of the art: the entire lower surface of the gauge support 71 is glued by the glue 8. Up to now, the adhesives 8 envisaged for bonding the strain gauges 7 on a flexible package are the glues of the cyanoacrylate family because they prove to be the most effective binders for adhering to a polymeric material, such as the polyimide of the gauge support 71.
    [0006] Also, the inventors were able to analyze the reasons why a bonding technique according to the state of the art as shown in FIG. 4 was not efficient for measuring the deformations of a flexible Li-ion battery pack.
    [0007] Thus, the cyanoacrylates have the disadvantage of hardening much on drying. And, in a gluing configuration according to FIG. 4, the deformation undergone by the flexible package 6 can not be completely measured by the gauge 7 because of an attenuation of the deformation by the too rigid cyanoacrylate glue 8 is present on the entire lower surface of the support 71. In other words, the difference in modulus of elasticity between the cyanoacrylate adhesive 8 and the material (s) of the flexible packaging 6 is very important and this difference is an obstacle to a measurement deformation performance. The inventors have thus proposed a bonding technique different from the prior art, which advantageously makes it possible to use very rigid glues in the cured state, such as cyanoacrylate adhesives. FIG. 5 shows a bonding of a linear strain gauge 7 on a packaging of a Li-ion accumulator, according to the invention: only the lateral ends 75, 76 of the support 71 of the gauge are glued along their entire length to the flexible package 6 by glue beads 80, 81. As can be seen in this figure 5, unlike the gluing technique according to the state of the art, a major part of the lower surface of the support 71 of gauge 7, in substance the surface of the support 71 on which the wire 70 and the pads are present, is then devoid of glue.
    [0008] Preferably, the bonding is done at most 0.5 cm of width of each lateral end 75 and 76. Preferably also, the glue 81, is not opposite to the measuring wire 70 of the gauge 7. Thus, the invention consists of gluing on a p. only lateral 75, 76 support 71 of the gauge, that is to say only on the lateral ends 75, 76 of the support 71 which are transverse to the axis Xi, that is to say orthogonal to the direction X of the deformation. Thanks to such a partial bonding, it avoids a hardening of the surface of the flexible package 6 bonded, and therefore it does not minimize the attenuation of the signal measured by the gauge 7. It can be assimilated the mechanical behavior of the bonded areas 80, 81 to the jaws of tractions through which the deformation experienced by the flexible package 6 is reflected. Unlike the bonding according to the state of the art, a very high Young's modulus of the glue 80, 81 with respect to the flexible packaging 6 is an advantage since the deformation is not absorbed by the adhesive and directly passed on to the gauge 7. In order to validate the improvement of the measurement provided by the bonding according to the invention, the inventors have proceeded to comparative tests. These tests are tensile tests that have been carried out on two rec. flexible packaging of Li-ion battery, of identical dimensions namely a width of 2 cm and a length of 20 cm. The flexible packaging used for the tapes is a tri-layer material: a polyamide layer, an aluminum layer and a polyethylene layer. Each of the two strips was instrumented with a linear strain gauge 7 as shown in FIG. 3. More precisely: a strain gauge 7 was glued on one of the two strips as in the state of the art, ie as shown in Figure 4, with the entire surface of the support 71 glued on the flexible packaging 6; a strain gauge 7 has been glued on the other of the two strips as according to the invention, ie as shown in FIG. 5, with only the lateral ends 75, 76 of the support 1 glued to the flexible package 6. It has been then carried out tensile tests on the two bands thus instrumented.
    [0009] The deformation measurements as a function of time of the tensile test are shown in FIG. 6 in the form of curves among which: the curve in solid lines represents the deformation at constant speed imposed by the traction bench; the curve in solid lines symbolized with circles corresponds to the signal measured by the gauge glued according to a technique of the state of the art; the curve in solid lines symbolized with crosses corresponds to the signal measured by the glued gauge according to a technique according to the invention. From these curves, it appears that the bonding according to the invention improves by a factor substantially equal to three, the sensitivity of a strain gauge.
    [0010] The invention is not limited to the examples which have just been described; it is possible in particular to combine with one another characteristics of the illustrated examples within non-illustrated variants.
    权利要求:
    Claims (6)
    [0001]
    REVENDICATIONS1. Flexible structure (6) comprising a strain gauge (7) of elongate shape along a longitudinal axis Xl, intended to measure the deformations of the flexible structure in a direction X parallel to the axis XI, the support (71) of the gauge being adhered to the flexible structure only by its lateral ends (75, 76).
    [0002]
    2. flexible structure (6) according to claim 1, each bead of adhesive (80, 81) between gauge support (71) and flexible structure being formed over the entire length of a lateral end.
    [0003]
    3. Flexible structure according to claim 1 or 2, the glue between gauge support and flexible structure being a glue, in the cured state, high Young's modulus, typically greater than 5 GPa, or very high.
    [0004]
    4. Flexible structure according to one of the preceding claims, the adhesive being selected from the family of cyanoacrylates of general formula: CH2 = C (CN) -COOR with R radical methyl, propyl, butyl, ethyl, hextyl, heptyl or octyl .
    [0005]
    5. Flexible structure according to one of the preceding claims, constituting the flexible package of a lithium electrochemical accumulator, such as a Li-ion accumulator.
    [0006]
    6. A method of bonding a strain gauge (7) on a flexible structure (6), which is bonded to the support (71) of the gauge to the flexible structure only by its lateral ends (75, 76).
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    同族专利:
    公开号 | 公开日
    US20170141360A1|2017-05-18|
    EP3120399A1|2017-01-25|
    WO2015140721A1|2015-09-24|
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    法律状态:
    2015-01-30| PLFP| Fee payment|Year of fee payment: 2 |
    2016-03-31| PLFP| Fee payment|Year of fee payment: 3 |
    2017-03-30| PLFP| Fee payment|Year of fee payment: 4 |
    2018-03-30| PLFP| Fee payment|Year of fee payment: 5 |
    2020-03-31| PLFP| Fee payment|Year of fee payment: 7 |
    2021-12-10| ST| Notification of lapse|Effective date: 20211105 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1452264A|FR3018911B1|2014-03-19|2014-03-19|FLEXIBLE STRUCTURE WITH DEFORMATION GAUGE, APPLICATION TO LITHIUM ACCUMULATORS WITH SOFT PACKAGING|FR1452264A| FR3018911B1|2014-03-19|2014-03-19|FLEXIBLE STRUCTURE WITH DEFORMATION GAUGE, APPLICATION TO LITHIUM ACCUMULATORS WITH SOFT PACKAGING|
    US15/127,669| US10170733B2|2014-03-19|2015-03-17|Flexible structure with strain gauge, application to electrochemical lithium-ion batteries in a flexible packaging|
    PCT/IB2015/051961| WO2015140721A1|2014-03-19|2015-03-17|Flexible structure with strain gauge, application to electrochemical lithium-ion batteries in a flexible packaging|
    EP15714947.7A| EP3120399B1|2014-03-19|2015-03-17|Flexible structure with strain gauge, application to electrochemical lithium-ion batteries in a flexible packaging|
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