The present invention relates to the general technical field of supercapacitors, i.e. capacitors with a double electrochemical layer (or EDLC acronym of “Electrochemical Double Layer Capacitor”).
A supercapacitor is a means for storing energy with which it is possible to obtain a power density and an intermediate energy density between those of dielectric capacitors and batteries. Their discharge time is generally of the order of a few seconds.
A supercapacitor conventionally comprises a cylindrical wound element comprising at least two electrodes. Each electrode is made from a mixture of active coal (also called “active material”), of carbon black and polymers. During a so-called extrusion step, a conductive paste is deposited on an aluminium collector which is used as a current collector. Both electrodes are separated by a porous separator in order to avoid short-circuits between both electrodes. During a so-called impregnation step, the supercapacitor is filled with an electrolyte. This electrolyte consists of a salt dissolved in a solvent, generally acetonitrile. This salt is separated into two charged species which are called ions (for example: BF4− and TEA+).
The thickness of an electrode is typically 100 μm. The ions have a size of the order of 1/1000th of a μm, i.e. 100,000 times smaller than the thickness of the electrode. Active coal (or active material) is an extremely porous material.
When a voltage is applied with a DC generator between two electrodes of the supercapacitor, the ions move in the porosity very close to the surface of the coal. The greater the amount of ions present at the surface of coal, the larger is the capacitance.
The amount of energy stored in a supercapacitor depends on the voltage applied between both electrodes and on the total capacitance of the supercapacitor.
Many investigations have shown that the higher the operating voltage of the supercapacitors, the shorter is the lifetime, because of very large generation of gas in the supercapacitor.
This gas generation is related to the decomposition of the material forming the electrolyte, this decomposition being a function of the applied voltage between the electrodes of the supercapacitor.
For example, the decomposition voltage of pure acetonitrile is 5.9V.
Presently, the reference voltage applied to the electrodes of supercapacitors is 2.7V (see notably WO 9 815 962 which teaches to the person skilled in the art that the voltage of a supercapacitor should be limited in order not to degrade too much the electrolyte).
In order to remedy this drawback, it is known how to electrically connect several supercapacitors to each other in order to form a module. This allows an increase in the voltage applied to the module.
In order to electrically connect two adjacent supercapacitors, connection means comprising two lids and a strap are used.
Each lid is capable of capping a respective supercapacitor so as to be electrically connected to the latter, for example by soldering.
Each lid further comprises a connection terminal capable of coming into contact with a through-bore of the strap, so as to electrically connect both adjacent supercapacitors.
However, such supercapacitors have drawbacks.
Notably, the volume and the mass of two supercapacitors electrically connected through a strap and two lids are significant.
Moreover, the manufacturing cost related to the purchase and mounting of the straps and lids for connecting both supercapacitors is significant.
Also, the series resistance Rs between two electrically connected supercapacitors—which corresponds to the sum of the resistances of the supercapacitors and of the connection means (strap+lid+solder)—is significant.
The general object of the invention is to propose a supercapacitor, the lifetime of which is increased at the reference voltage.
Another object of the present invention is to propose a supercapacitor in which gas generation is limited.
Another object of the present invention is to propose a supercapacitor capable of supporting a voltage above the reference voltage without undergoing any degradation.
For this purpose, a supercapacitor is provided comprising at least two electrodes and at least one separator between both electrodes, the electrodes and the separator being wound together in turns in order to form a wound element, the supercapacitor further comprising at least one other electrode and at least one other separator, the other electrode and the other separator being wound together in turns around the wound element so as to form at least one consecutive wound element, these successive wound elements being separated by an electronic insulating space.
“Complex” designates the association of a current collector and of at least one electrode, the current collector and the electrode having a common electrically conducting surface.
“Successive complexes” designate two coplanar complexes (before being wound in turns in order to form a wound element) and separated by an electronic insulating space of width d during their being wound.
“Common complex” designates any association of complexes in electronic continuity.
The separator(s) extend(s) beyond the electrodes of each complex facing each other but not beyond the collectors of the complexes being used as a connection to the outside.
Preferred but non-limiting aspects of the module according to the invention are the following:
The invention also relates to a module comprising a casing in which is positioned at least one supercapacitor as described above.
Advantageously, the module may both comprise supercapacitors according to the invention and supercapacitors of the prior art, as illustrated in
Other features, objects and advantages of the present invention will further become apparent from the description which follows, which is purely illustrative and non-limiting and should be read with reference to the appended drawings wherein:
a-7 illustrate different embodiments of wound elements of a supercapacitor according to the invention,
Different embodiments of the supercapacitor according to the invention will now be described with reference to
With reference to
The supercapacitor comprises two complexes 2, 3 positioned face to face and separated by a separator 4.
The complexes 2, 3 and the separator 4 are wound together in turns in order to form a first wound element.
The supercapacitor also comprises another complex 1 successive to one 2 of the complexes 2, 3 and another separator 4. The other electrode and the other separator are wound together in turns around the first wound element so as to form at least one second consecutive wound element.
The successive complexes 1, 2 are spaced apart by a distance q along a direction circumferential to the longitudinal axis of the supercapacitor.
Advantageously, the distance q between the successive complexes 1, 2 is provided to be sufficient in order to electrically insulate the successive complexes 1, 2 from each other. In the embodiment illustrated in
A distance q of one millimeter is indeed sufficient in order to prevent the electric field generated between both successive complexes 1, 2 from being too large, which would risk decomposing the electrolytes under normal conditions of use of the supercapacitor.
The complex 3 positioned facing both successive complexes is a so-called “common complex”.
With the separators 4, it is possible to electrically insulate the successive complexes 1, 2 of the common complex 3. One of the separators is positioned between the common complex 3 and the successive complexes 1, 2. The other separator 4 is positioned on the other face of the common complex 3 so that the common complex 3 is located between the separators 4.
Each complex 1, 2, 3 comprises a current collector 11, 21, 31 and at least one electrode consisting of active material, the electrode having an electrically conducting face in common with the current collector 11, 21, 31.
In the embodiment illustrated in
The areas facing the successive and common complexes define two supercapacitor cells, the capacitances of which are determined by their respective lengths. The continuity of the common complex 3 allows both supercapacitor cells to be placed in series.
The complexes 1, 2, 3 and separators 4 respectively consist of one or more superposed sheets.
Advantageously, the successive complexes 1, 2, the common complex 3 and the separators 4 are successively wound together in turns, in order to form a consecutive first wound element and second wound element.
The proposed solution is less costly than the supercapacitors of the prior art described earlier. Indeed, the number of straps, lids and tubes (used as a housing for the wound elements) in order to electrically connect two supercapacitor cells is less than the number of straps, lids and tubes required for electric connection of several supercapacitors of the prior art.
Moreover, the proposed solution above allows a reduction in the series resistance Rs of the system (by the reduction of the number of lids and straps required for connecting the supercapacitor cells as compared with the number of lids and straps required for connecting supercapacitors of the prior art), and a significant increase in the admissible energy per unit volume while optimizing the capacitance.
With the supercapacitor described above, it is thus possible to obtain a compact wound structure:
Other advantages related to the removal of straps and lids for connecting two supercapacity cells in series/parallel are the following:
With reference to
The supercapacitor illustrated in
Two first complexes 2, 3a are positioned face to face. One 2 of both first complexes is positioned between two separators 4. The first two complexes 2, 3a and the separators 4 are wound together in turns in order to form a first wound element.
Two other complexes 1, 3b are successive to the first two complexes 2, 3a and spaced apart (from the first two complexes) by a distance q along a direction circumferential to the supercapacitor.
Both complexes 1, 3b are wound together in turns around the first wound element consisting of the complexes 2, 3a so as to form at least one second consecutive wound element.
In this embodiment, each wound element forms an independent supercapacitor. The series or parallel electric connection of both thereby formed supercapacitors is ensured by the lids 50 as this will be described in more detail in the following.
In
According to an alternative embodiment, the electronic insulating space is formed by a distance q separating two successive wound elements. Advantageously, this distance q is provided to be sufficient in order to prevent direct passage of the current between two successive wound elements. For example, the distance q may be greater than one millimeter.
According to another alternative embodiment, the electronic insulating space may be formed by a reinforcement 40 formed with at least one turn of dielectric insulating material. The use of a reinforcement for electrically separating two successive wound elements facilitates the making of the supercapacitor.
Advantageously, the height of the reinforcement is comprised between the height of active material of the first wound element and the total height of said first wound element.
As illustrated in
In the embodiment illustrated in
In other embodiments as illustrated in
Still in other embodiments, the successive wound elements 10, 20, 30 are of identical height, but their bases are shifted relatively to each other along their longitudinal axis. Such embodiments are illustrated in
In the embodiment of
In the embodiment illustrated in
The successive wound elements of the supercapacitor are intended to be connected together or with wound elements of other adjacent supercapacitors via lids 50 and/or straps.
The different types of the lids 50 will now be described in more detail, which may be used for connecting together the wound elements of a supercapacitor or of different adjacent supercapacitors.
With reference to
This first lid embodiment 50 is intended to cap a supercapacitor, the wound elements of which have bases shifted relatively to each other. In order to electrically connect wound elements of identical height non-shifted relatively to each other (such as illustrated in
Advantageously, the lid 50 is conducting on the whole of its surface, and allows the successive wound elements of a supercapacitor to be placed in electric contact so as to form a common terminal for these wound elements.
The other face of the supercapacitor may be capped with a conducting lid 50 over the whole of its surface in order to electrically connect in parallel the successive wound elements of the supercapacitor.
The other face of the supercapacitor may also be capped with a lid 50 comprising electrically conducting portions, the conducting portions being separated from each other by electrically insulating portions, each electrically conducting portion being respectively in electric contact with a wound element so as to connect the wound elements in series.
Embodiments of lids comprising electrically conducting portions intended to respectively come into electric contact with one of the wound elements are illustrated in
In the embodiment illustrated in
In the embodiment illustrated in
Of course, the lid 50 may comprise more than three electrically conducting portions, the number of conducting portions depending on the number of wound elements of the supercapacitor.
Depending on the application, the lid 50 may substantially extend in a plane, or have an indented cross-section as illustrated in
Moreover, the electrically conducting portions may have other shapes. Lids 50 are illustrated in
In the embodiment illustrated in
In the embodiment in
Once the supercapacitor is capped with one of the lids 50 described earlier with reference to
With reference to
More specifically, each strap 70 is substantially flat. The main body of the connecting strap 70 is rectangular. The ends 80 of the strap are of triangular shape. The size and the shape of these ends 80 are provided to be sufficient for coming into contact with a respective conducting portion S1, S2, S3 of the lid 50, without covering the insulating portion separating two conducting portions of the lid 50. Thus, the connecting straps 70 are insulated from each other. By avoiding the contact between the straps 70, the electric insulation of the straps 70 are guaranteed so as to avoid a short-circuit.
With reference to
The connecting strap 70 comprises two (or more than two) electrically conducting portions insulated from each other (respectively the ones from the others) by one (or more) electrically insulating portions. Each electrically conducting portion is respectively intended to come into contact with a conducting portion S1, S2, S3 of the lid 50. Each electrically conducting portion comprises a protruding connecting element 90 at the ends 80 of the connecting strap 70. Each of these elements which protrude is intended to come into contact with a respective conducting portion S1, S2, S3 of the lid 50.
With reference to
The connecting strap 70 is substantially flat. The lid comprises electrically insulating areas extending at the contact surface between the lid and the strap. These electrically insulating areas are positioned so that each conducting portion of the strap is electrically in contact with a single conducting portion of the lid. With this, the wound elements of the thereby connected supercapacitors may be electrically connected two by two.
Advantageously, the supercapacitor may be dissymmetrical, i.e. the electrodes of the different complexes may be different in terms of length and/or thickness and/or nature of the material making them up.
By working with a dissymmetrical supercapacitor, it is possible to optimize:
The dissymmetry of the supercapacitor may for example be obtained by varying the thickness of the electrodes of the wound elements, so that the positive and negative electrodes of each wound element have different volumes.
The dissymmetry of the supercapacitor may also be obtained by varying the thicknesses and/or lengths of the electrodes of the wound elements.
The dissymmetry may also be obtained by varying the nature of the constituents of the electrodes of the wound elements. For example, in an embodiment, the electrodes of a wound element are of identical thickness but are made up of different materials so as to have different faradic densities.
The supercapacitors may have different shapes, for example the supercapacitors may be cylindrical.
The supercapacitors may also have a hexagonal or triangular, or octagonal, or rectangular shape, or further elliptical shape, orthogonally to the winding axis. With this, the dead volume may be limited between two adjacent supercapacitors. The angles of the wound elements may be non-protruding.
As described earlier, the supercapacitor according to the invention allows reduction of the volume associated with the series or parallel electric connection of two supercapacitors as compared with the modules of the prior art.
Such a module of the prior art is illustrated in
In order to demonstrate the gain in volume of the supercapacitor according to the invention as compared with the module of the prior art, the following parameters are required:
C: capacitance to be obtained (F)
ξ: faradic density (F/cm3)
h: activated height (cm)
H: total height (cm)
e: thickness of the wound separator/electrode/collector/electrode/separator/electrode/collector/electrode (cm)
φint: inner diameter around which begins the winding (φint>0) (cm)
The output data are the following:
k: number of turns
φext: outer diameter of a winding of capacitance C comprising k turns (cm)
Cn: capacitance of n parallel nested windings (F)
φext n: Outer Diameter of the Capacitor Cn (Cm)
Vn: volume of the n-nested capacitor of value Cn (cm3)
V: volume of n capacitors of value C in parallel (cm3)
In the following numerical examples, the value of capacitance of each winding is assumed to be identical, which in practice means that windings of larger diameters have smaller thickness than the windings of smaller diameters, the winding length being identical for each capacitor.
C=600F ξ=30F/cm3 h=8 cm H=10 cm
e=0.05 cm φint=2.5 cm
C=2600F ξ=30F/cm3 h=8 cm H=10 cm
e=0.05 cm φint=2.5 cm
C=5000F ξ=30F/cm3 h=8 cm H=10 cm
e=0.05 cm φint=2.5 cm
As described earlier, with the supercapacitor according to the invention, it is possible to reduce the mass associated with the series or parallel electric connection of two supercapacitors as compared with the modules of the prior art.
In order to demonstrate the gain in mass of the supercapacitor according to the invention as compared with the module of the prior art, the following parameters are required:
ec: thickness of the lid (cm)
et: thickness of the tube (cm)
muC: mass of the capacitor C (g)
d: specific gravity of the material of the tube and of the lid (g/cm3)
The output data are the following:
mcC: mass of the lid of a capacitor of value C (g)
mtC: mass of the tube of a capacitor of value C (g)
m: total mass of n capacitors of value C in parallel (g)
mn: total mass of the n-nested capacitor of value Cn (g)
mcC=πφext2ecd
mtC=πφextetHd
m=n(muC+2mcC+mtC)
m
n
=m
u
Cn+2mcCn+mtCn
ec=0.4 cm et=0.05 cm
d(specific gravity of aluminium)=2.7 g/cm3
mn600F=75 g mu2600F=325 g
ec=0.4 cm et=0.05 cm
d(specific gravity of aluminium)=2.7 g/cm3
mu600F=75 g
ec=0.4 cm et=0.05 cm
d(specific gravity of aluminium)=2.7 g/cm3
mu2600F=325 g
ec=0.4 cm et=0.05 cm
d(specific gravity of aluminium)=2.7 g/cm3
mu5000F=650 g
Regardless of the number of co-wound elements, the simultaneous gain in mass and volume exists relatively to a series or parallel assembly of several wound elements as proposed in the prior art.
This novel system therefore corresponds to a significant increase in bulk and mass energy density.
It is important to specify that the mass of each electrode, the thickness of the coating, of the collector, the type of carbon and the overall width may be different, as shown by the different descriptive diagrams.
Among the examples which we have mentioned, we have taken the simplest cases and they may easily be multiplied over and over again. Regardless of the type of arrangement, the gain in mass and in volume is targeted in an advantageous way. This gain may also be accomplished in terms of voltage, according to arrangements of the type described in
Each electrode may be symmetrical (the simplest and generally applied case) relatively to a specific collector so as to double the amount of active material of the thereby formed capacitance and to drastically increase the bulk capacitance of the assembly, and therefore the maximum admissible energy. The case of dissymmetry should not be set aside:
In
With reference to
With reference to
More specifically, the bases of each supercapacitor are capped with lids (of the type illustrated in
The advantage of this circuit is that the electric connection of both supercapacitors does not require the use of a connecting strap. It is quite obvious that in the case of the electric connection of two adjacent supercapacitors, the same circuit may be achieved by using particular connecting straps (such as the connecting strap illustrated in
With reference to
More specifically, the lower base of the supercapacitor is capped with a conducting lid over the whole of its surface, and the upper base of the supercapacitor is capped with a lid of the type illustrated in
With reference to
More specifically, the bases of each supercapacitor are capped with conducting lids over the whole of their surface and are connected through conducting connecting straps over the whole of their surface.
The supercapacitors according to the invention therefore allow a large number of electric circuits to be made, much more ergonomically than the supercapacitors of the prior art.
The reader will have understood that many modifications may be made to the supercapacitor described earlier without materially departing from the novel teachings and advantages described herein.
Therefore, all the modifications of this type are intended to be incorporated within the scope of the supercapacitor as defined in the appended claims.
This type of element design may also find all its application for batteries or battery cells of any nature (Li-ion, lithium polymer, Ni—Cd, Ni—MH), or further even for fuel cells.
The supercapacitor according to the invention has many advantages:
Finally, in a module comprising a plurality of supercapacitors connected to each other, at least half of the series resistance of the module is a connection technology resistance between the coils and the lids. In a module comprising a plurality of supercapacitors according to the invention, the series resistance of the module is strongly reduced, due to the reduction in the number of junctions required between lid and coil as compared with a module comprising a plurality of standard supercapacitors.
Number | Date | Country | Kind |
---|---|---|---|
0851056 | Feb 2008 | FR | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/EP2009/051665 | 2/12/2009 | WO | 00 | 11/10/2010 |