Title of Invention

ELECTROCHEMICAL GENERATOR ELEMENT WITH DIFFERENT THICKNESS OF ELECTRODE LAYER

Abstract

ABSTRACT IN/PCT/2002/01294/CHE The invention concerns an electrochemical generator element (102) comprising successively a first electrode layer having a polarity (114), a first electrolyte layer (110), a second electrode layer with reverse polarity (108), a second electrolyte layer (112), a second electrode layer with said polarity (116). The electrode layers of said polarity (114, 116) are connected by a parallel connection. It comprises current collectors (118, 120) connected to the electrode layers with said polarity (114,116). The thickness of the first electrode layer with said polarity (114) is different from the thickness of said second electrode layer with said polarity (116). The invention is applicable to lithium-polymer storage batteries. [Figure 3]

Full Text

The present invention relates to an electrochemical generator element successively comprising a first electrode layer of one polarity, a first electrolyte layer, an electrode layer of a reverse polarity, a second electrolyte layer and a second electrode layer of said polarity, said electrode layers of said polarity being connected by a connection in parallej, the element forther comprising current collectors, connected to the electrode layers of said polarity. Electrochemical cells are known for example from the documents US-A-5840087, WO99/60651, US-A-4315061, and EP298800. However, none of these documents discloses an electrochemical cell having positive electrodes with different thickness. Also none of these documents mentions this feature in order to improve the specific capacity of the cell. The invention is applicable, for example, to lithium-polymer electrochemical batteries for electric vehicles or steady-state applications. Electrochemical generators with lithium having a polymer electrolyte are known. Such generators generally comprise elements consisting of two half-elements electrically connected in parallel. Each half-element consists of a cathode layer which is applied via an electrolyte layer onto one of the two faces of a lithium layer. The current is drawn by current collectors arranged on the free surface of the cathodes and of the collecting leads connected to the lithium layer. The cathode layers on the two sides of the lithium layer have the same thickness (Figure 1). To increase the specific energy (energy per unit mass) of such an electrochemical generator, the thickness, which has the same value for both cathode layers, is increased. Correspondingly, the thickness of the lithium layer is also increased. This has the effect that the maximum specific power (power per unit mass) decreases as the resistance of the element increases. The aim of the invention is to alleviate this drawback and to provide an electrochemical element in which the specific energy is substantially independent of the 5 maximum specific power. To this end, the subject of the invention is sn electrochemical generator element of the aforementioned type, characterized in that the thickness of said first electrode layer of said polarity is different from the thickness of said second electrode layer of said polarity. The subject of the invention is also an electrochemical battery comprising at least one electrochemical generator element of the type defined above. The invention will be better understood on reading the following description, given solely by way of example and made with reference to the appended drawings in which: - Figure 1 is a cross section through a known lithium-polymer electrochemical generator element; - Figure 2 shows the specific energy and the specific power of an electrochemical element of the prior art as the function of the cathode thickness; - Figure 3 is a cross section through a lithium-polymer electrochemical generator element according to the invention; and - Figure 4 shows the specific energy and the specific power of the electrochemical elements according to the invention and indicates the ratio of the two elements as a function of the cathode thickness. For the effect of the invention to be better unaerstood, tne problem posed by the prior art will first of all be described with reference to figures 1 and 2. Figure 1 shows an electrochemical generator element 2 of the prior art in cross section. The element comprises two haIf-elements 4, 6, each of which consists of a common lithium layer 8, an electrolyte layer 10, 12, a positive electrode layer 14, 16 and a current collector 18, 20, Electrical conductors 22, 2 4 are connected to the collectors 18, 20 and an electrical conductor 26 is connected to the lithium layer 8. Depending on the accumulator type, the conductors 24, 2 6 may be connected directly to the positive electrode layers 14, 16, such that the current is collected by the conductors 24, 26. The two electrical conductors 22, 2 4 are connected to one side of a user {not shown) , while the electrical conductor 2 6 is connected to the other side of the user such that a parallel connection of the two half-si ements 4, 6 is formed. The electrolyte layers 10, 12 each have a thickness of 30 (jm and separate the positive electrode layers 14, 16 from the common lithium layer 8 which acts as a -legative electrode. The lithium layer has a thickness between 10 \xm and 150 (im, preferably between 30 jim and 70 |Jjn. i^ach of the positive electrode layers 14, 16 has (in :his example) a thickness of 90 [am and are manufactured :rom a material which contains a certain proportion Y 3f V2O5, generally more than 50%. This proportion of V2O5 ietermines the specific capacity which is, if Y = 54%, 153 Ah/kg. As a variant, nickel, cobalt, manganese oxide or a mixture of these oxides can be used instead of V2O5. 5 The internal surface resistance of a haIf-element is calculated by the following formula; where Rs_Li/ei is the surface resistance of the interface between the electrolyte 10, 12 and the lithium anode layer 8. Its value is 10 Qcm^. rs_ei is the specific resistance of the electrolyte 10, 12 (rs_ei = 0.2 Qcm^/ym). rs_cath is the specific resistance of the cathodes 14, 16 at 80% discharge {rs_cath =3,5 Qcm'/iim} . Gel and ecath are the thickness of the electrolyte layer 10, 12 (eel = 30 \xrci) and the thickness of the cathode layer 14, 16 (e^ath = 90 |jjn) . The surface resistances indicated are valid for a temperature of 90°C. The electrical resistances of the current collectors 22, 24, 26 and of the lithium 8 are considered to be negligible compared to the surface resistances of the interface, electrolyte and cathode. For the given electrochemical element 2, a half-element 4, 6 therefore has the surface resistance: The internal surface resistance of such an element is calculated from the following formula (parallel connection): For the given example, the surface resistance is The maximum surface power produced by such a lithium-polyme:f element 2 is given by the following equation: (1.2.) where Uo is the voltage in vacuo of the element 2 (2.2 V at 80% discharge). The energy per unit area is given by the following formula: Es_e = ^s_dei + E;s_de2 = (Scathl + ScathS) X Pcath X Y X Es X U^viean ( 1 • 2 . ) where Es_dex is the surface energy of the half-element 1 or 2; Scathx is the thickness of the corresponding cathode, p is the density of the cathode (p 2.1 g/cm^) , Y is the V2O5 content of the cathode in % weight (54%), Eg is the specific capacity of V2O5 (153 Ah/kg) and U^ean is the mean voltage of 2.55 V. Eg e = 7.98 mWh/cm^ for the example given. In order to increase the specific surface energy of a lithium-polymer element 2, it has already been proposed to increase the thickness of the two cathode layers 14, 16. This has the result that the surface resistance of the two half-elements 4, 6 increases while the voltage in vacuo of the elements 2 remains constant and thus the surface power and, consequently, the specific power of the element 2 decreases. The thickness of the lithium layer remains constant. The ratio of the maximum power of the element 2 to the specific energy of the element 2 decreases as the thickness of the cathode layers increases. Table 1 shows, as a function of the cathode thickness, the values of surface resistance, of surface power at 80% discharge, of surface energy, the ratio of the surface power to the surface energy, the surface mass, the specific power and the specific energy. The values were measured at a temperature of 90°C. Figure 2 is a graph showing the specific energy and the specific power as a function of the cathode thickness of a known electrochemical element. It is observed that an increase in the specific energy of a lithium-polymer cell by increasing the thicknesses of the two cathode layers by the same value is not possible without reducing the specific power. Now the invention will be described with reference to Figures 3 and 4. Figure 3 shows an electrochemical generator element 102 with lithium having a polymer electrolyte according to the invention, in cross section. In Figure 3, elements similar to those in Figure 1 are denoted by reference numbers increased by 100. The electrochemical generator element 102 comprises, like the element of Figure 1, two half-elements 104, 106 each one comprising part of a common lithium Layer 108, an electrolyte layer 110, 112 and a cathode layer 114, 116 together with a layer forming a collector 118, 120. The thicknesses of the lithiura layer 108 and of the electrolyte layers 110, 112 are the same as those of the layers 8, 11 and 12 of the element 2 of Figure 1. However, the thicknesses of the two cathode layers 114, 116 are different from each other while their sum is equal to that of the two cathode layers 14, 16 of the element 2 of Figure 1. The thickness of the first layer 114 is, for example, 150 μm. For this example, it may be between 130 μm and 170 μm, preferably between 140 μm and 160 )im. The thickness of the second layer 116 is 30 [xm, and may be between 10 ^m and 50 (im, preferably between 20 niri and 40 ]xm. In general, the thicker layer may have a thickness between 80 )im and 200 )im, preferably between 100 and 160 )JJTi. In order to be able to compare the power and the energy of the two elements 2 and 102, the surface resistance of the element 102 will be calculated according to the invention as follows. The electrical surface resistance of each of the two half-elements is calculated using formula (1.1.) for respective thickness values of the cathode layers 114, 116. Here again, the electrical surface resistances of the current collectors 118, 120 and of the lithium layer 108 are considered to be negligible. The values of the specific resistances at an operating temperature of 90°C remain the same. For an element consisting of an assembly of two half-elements comprising cathode layers of 30 \m. and 150 ^mi respectively, the calculation of the internal surface resistance of the two half-elements 104, 106 gives the following values: The surface resistance of the complete element l02 is calculated by the following formula relating to the parallel connection of the two elements. resistance of the half-element X (X e [1,2]). For the given assembly, the total surface resistance of the element is; The maximum power (at 80% discharge) per unit area is then, using formula 1.2.: The energy contained per unit area of the element 102 is calculated by the equation of formula 1.3.; The ratio of the surface power to the surface energy is then ; which means an increase of 60% with respect to the element of the prior art which has a ratio It is understood that, for an equivalent total cathode thickness {180 fjm) , the increase in thickness of the first cathode 114 from 90 |im to 150 )im, on the one hand, and the decrease in thickness of the second cathode 116 from 90 |im to 30 )im, on the other hand, makes it possible to decrease the internal surface resistance of the element from 160.5 Qcm^ to 121 Qcm^. For a constant specific energy density, since the mass and volume have not changed, the specific power is considerably increased. Table 2 shows the surface resistances of two half-elements 114, 116 of different thicknesses for an element 102 with a total cathode thickness of 180 fun. It furthermore shows the resulting surface resistance of the corresponding element, and the power gain with respect to an element 2 with cathode layers of Figure 1 each having a thickness equal to 90 μm. Figure 4 is a graph showing the specific power, the specific energy and the ratio between the two as a function of the thinnest cathode layer thickness for an element according to the invention, the cathode layers of which have a total thickness of 180 μm. It is observed that it is possible, by increasing the thickness of one layer to 170 μm and decreasing the thickness of the other layer to 10 μm, to increase the specific power by a factor of 2.5 with respect to the available power of an element, the positive electrodes of which each have a thickness of 90 μm. The invention therefore makes it possible to increase the specific power and, consequently, the power density available in an electrochemical generator element with lithium having a polymer electrolyte at constant specific energy. It makes it possible to change the power to energy ratio depending on the application envisaged for a given energy density. It is clear that the invention is not limited to the example given. The thicknesses of the electrode layers may be changed over large ranges and the sum of the thicknesses of the cathode layers is not limited to 180 μm but may also be changed. The invention may also be applied to electricity generating cells which use positive or negative electrode materials other than lithium and polymer. The invention may also be applied to any type of electricity generating cell with a thin-layer assembly. As a variant, the invention may also be applied to cells having a common positive electrode layer and two negative electrode layers having different thicknesses, one layer of which is placed on each of the two sides of the positive electrode layer. We claim: 1. An electrochemical generator element (102) successively comprising a first electrode layer of one polarity (114), a first electrolyte layer (110), an electrode layer of a reverse polarity (108), a second electrolyte layer (112) and a second electrode layer of said polarity (116), said electrode layers of said polarity (114, 116) being connected by a connection in parallel, the element comprising current collectors (118, 120), connected to the electrode layers of said polarity (114, 116), characterized in that the thickness of said first electrode layer of said polarity (114) is different from the thickness of said second electrode layer of said polarity (116). 2. The element as claimed in claim 1, wherein the electrode layers of said polarity are positive electrode layers (114, 116), and in that the electrode layer of said reverse polarity is a negative electrode layer. 3. The element as claimed in claim 2, wherein said negative electrode layer (108) is made of lithium or of a lithium-based alloy, said electrolyte layers (llO, 112) are made of a solid polymer and said positive electrode layers (114, 116) are made of a composite comprising vanadium, nickel, cobalt or manganese oxide or a mixture thereof. 4. The element as claimed in claim 2 or claim 3, wherein the thickness of said first positive electrode layer (U4) is between 80 |im and 200 ^un, preferably between 100μmand 160 μm. 5. The element as claimed in claim 2 or claim 3, wherein the thickness of said first positive electrode layer (114) is between 130 μm and 170μm, preferably between 140 μm and 160 μm 6. The element as claimed in claim 4 or claim 5, wherein the thickness of said second positive electrode (116) is between 10 yon and 50 \im, preferably between 20 μm and 40 μm. 7. An electrochemical battery comprising at least one element according to any one of claims 1 to 6.

Documents:

in-pct-2002-1294-che abstract.pdf

in-pct-2002-1294-che claims-duplicate.pdf

in-pct-2002-1294-che claims.pdf

in-pct-2002-1294-che correspondence-others.pdf

in-pct-2002-1294-che correspondence-po.pdf

in-pct-2002-1294-che description (complete)-duplicate.pdf

in-pct-2002-1294-che description (complete).pdf

in-pct-2002-1294-che drawings.pdf

in-pct-2002-1294-che form-1.pdf

in-pct-2002-1294-che form-18.pdf

in-pct-2002-1294-che form-26.pdf

in-pct-2002-1294-che form-3.pdf

in-pct-2002-1294-che form-5.pdf

in-pct-2002-1294-che pct-search report.pdf

in-pct-2002-1294-che pct.pdf

in-pct-2002-1294-che petition.pdf