Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/08—Structural combinations, e.g. assembly or connection, of hybrid or EDL capacitors with other electric components, at least one hybrid or EDL capacitor being the main component
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/10—Multiple hybrid or EDL capacitors, e.g. arrays or modules
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/66—Current collectors
  • H01G11/72—Current collectors specially adapted for integration in multiple or stacked hybrid or EDL capacitors
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/78—Cases; Housings; Encapsulations; Mountings
  • H01G11/82—Fixing or assembling a capacitive element in a housing, e.g. mounting electrodes, current collectors or terminals in containers or encapsulations
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/40—Structural combinations of fixed capacitors with other electric elements, the structure mainly consisting of a capacitor, e.g. RC combinations
• • 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
  • Y02E60/13—Energy storage using capacitors
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the invention relates to an energy storage device comprising a battery and at least one supercapacitor.
• Hybrid storage devices associating a supercapacitor and a battery connected in parallel have in particular been described in US Pat. No. 6,117,585, US Pat. No. 6,187,061 and the article by A. Rufer “The supercapacitor and the battery combine to supply energy »(Electronics, CEP Communication, Paris, n ° 100, February 2000). These devices combine the advantages of their two components and allow in particular to store a large amount of energy while having a high instantaneous power. However, none of these devices can be integrated into a chip.
• a lithium micro-battery in the form of thin films, the thickness of which is between 7 ⁇ m and 30 ⁇ m (preferably of the order of 15 ⁇ m) and which is formed by vapor deposition techniques by the chemical (“chemical vapor deposition”: CVD) or physical (“physical vapor deposition”: PVD), is for example described in document WO-A-9848467.
• Charging of a micro-battery is generally complete after a few minutes of charging.
• the duration of the charge of the micro-batteries constitutes nevertheless an obstacle to their use in numerous applications (smart cards, smart labels, feeding of microsystems, etc.) which impose the possibility of rapid recharging while having sufficient energy capacity.
• An energy storage device integrated into a smart card used for banking transactions must, for example, be able to be recharged in less than a second.
• the object of the invention is to provide an energy storage device which does not have the above drawbacks and, more particularly, allowing rapid recharging without reducing the energy capacity, while being integrable in a chip.
• a device in which the battery and the supercapacitor are respectively constituted by a micro-battery and a micro-supercapacitor, produced in the form of thin films, the micro-supercapacitor. being connected between two terminals of a charge control circuit comprising means for controlling the closing of at least one electronic switch, normally open, so as to connect in parallel the micro-supercapacitor and the microbattery for recharging the micro- battery from micro-supercapacitor.
• the micro-battery and the micro-supercapacitors are formed on the same insulating substrate, either side by side, or superimposed.
• FIG. 1 represents, in section, a particular embodiment of a microbattery which can be used in an energy storage device according to the invention.
• FIG. 2 represents, in section, a particular embodiment of a micro-supercapacitor which can be used in an energy storage device according to the invention.
• FIG. 3 illustrates the connections between a micro-battery and micro-supercapacitors of a device according to the invention.
• Figures 4 and 5 illustrate, respectively in top view and in section along A-A, a first embodiment of a device according to the invention.
• Figures 6 and 7 illustrate, respectively in top view and in section along B-B, a second embodiment of a device according to the invention.
• the operating principle of a micro-battery is based on the insertion and deactivation of an alkali metal ion or a proton in the positive electrode of the micro-battery, preferably a lithium Li + ion from '' a metallic lithium electrode.
• the micro-battery 1 is formed on an insulating substrate 2 by a stack of layers obtained by CVD or PVD deposition, constituting respectively two current collectors 3a and 3b, a positive electrode 4, a solid electrolyte 5, a negative electrode 6 and, optionally, an encapsulation (not shown).
• the elements of the micro-battery 1 can be made of various materials:
• the metallic current collectors 3a and 3b can, for example, be based on platinum (Pt), chromium (Cr), gold (Au) or titanium (Ti).
• the positive electrode 4 can consist of LiCo0 2 , LiNi0 2 , LiMn 2 0 4 , CuS, CuS 2 , WO y S z , TiO y S z , V 2 0 5 or V 3 0 8 as well as lithiated forms of these vanadium oxides and metal sulfides.
• the solid electrolyte 5 a good ionic conductor and electrical insulator, can consist of a glassy material based on boron oxide, lithium oxides or lithium salts.
• the negative electrode 6 can be constituted by metallic lithium deposited by thermal evaporation, by a metallic alloy based on lithium or by an insertion compound of the SiTON, SnN x , lnN x , Sn0 2 type , etc.
• the purpose of possible encapsulation is to protect the active stack from the external environment and, more specifically, from humidity. It can be constituted by ceramic, by a polymer (hexamethyldisiloxane, parylene, epoxy resins), by a metal or by a superposition of layers of these different materials.
• the operating voltage of a micro-battery is between 2V and 4V, with a surface capacity of the order of 10O ⁇ Ah / cm 2 .
• the production techniques used make it possible to obtain all the shapes and all the surfaces desired, but the recharging of the micro-battery is generally complete only after a few minutes of charging.
• micro-supercapacitors have been produced in the form of thin films in the laboratory, with the same type of technology as micro-batteries.
• a micro-supercapacitor 7 is constituted by the stacking, on an insulating substrate 2, preferably made of silicon, of thin layers constituting respectively a lower current collector 8, a lower electrode 9, a solid electrolyte 10, an upper electrode 11 and an upper current collector 12. Encapsulation (not shown) can optionally be added, in the same way as for a microbattery, although the components of micro-supercapacitor 7 are less sensitive to looks like lithium.
• the elements of the micro-supercapacitor 7 can be made of various materials.
• the electrodes 9 and 11 may be based on carbon or on metal oxides such as Ru0 2 , Ir0 2 , Ta0 2 or Mn0 2 .
• the solid electrolyte 10 can be a glassy electrolyte of the same type as that of micro-batteries.
• the micro-supercapacitor 7 can be formed on the insulating substrate 2, in silicon, for example in five successive deposition steps:
• the lower current collector 8 is, for example, formed by depositing a layer of platinum of 0.2 ⁇ 0.1 ⁇ m in thickness, by radiofrequency sputtering.
• the lower electrode 9, for example made of ruthenium oxide (Ru0 2 ) is produced from a metallic ruthenium target, by reactive radio frequency sputtering in a mixture of argon and of oxygen (Ar / 0 2 ) at room temperature.
• the layer formed has, for example, a thickness of 1.5 ⁇ 0.5 ⁇ m.
• It is a conductive glass of the Lipon type (Li 3 PO 25 N 03 ), obtained by cathode sputtering under partial pressure of nitrogen with a target of Li 3 P0 4 or 0.75 (Li 2 O) -
• the upper electrode 11, made of ruthenium oxide (Ru0 2 ) for example, is produced in the same way as the lower electrode 9 during the second step.
• the upper current collector 12, made of platinum, is formed in the same way as the lower current collector 8 during the first step.
• the micro-supercapacitor 7 thus obtained can have a surface capacity of the order of 10 ⁇ Ah / cm 2 and its full charge can be obtained in less than a second, typically in a few hundred microseconds. Its low surface capacity, requiring too frequent recharging, does not allow its use as an energy source in many applications.
• the fast recharging energy storage device has sufficient capacity thanks to the combination of a micro-battery 1 and at least one micro-supercapacitor 7.
• the micro-battery 1 provides sufficient energy capacity
• micro-supercapacitors allow high recharging speeds, compatible with the various applications envisaged (smart cards, smart labels, microsystems powering, etc.).
• the micro-supercapacitors then charge the micro-battery 1 for the time necessary.
• the thickness of a micro- battery or micro-supercapacitor is 10 to 30 times lower than that of a mini-battery or a mini-supercapacitor, using liquid electrolytes, which allows the integration of the storage device according to the invention in a chip.
• the energy storage device comprises a micro-battery 1 and three micro-supercapacitors 7a, 7b and 7c.
• the three micro-supercapacitors 7a, 7b and 7c are connected in series between two terminals of an integrated circuit 13.
• the integrated circuit 13 supplied by supply terminals connected to the micro-battery 1, controls the charge, rapid ( less than a second), micro-supercapacitors from an external energy source 14. This recharging can be carried out in any known manner, for example by contact or by radio frequency when a chip card comprising the circuit integrated 13 and the energy storage device according to the invention is introduced into a reader.
• the integrated circuit 13 causes, by means of a control signal S controlling the closing of at least one electronic switch 15, normally open, the parallel connection of the micro-battery 1 and of the series circuit constituted by the three micro-supercapacitors, so as to recharge the micro-battery for the time necessary (for example a few minutes).
• the serial connection of several micro-supercapacitors provides sufficient voltage to charge micro-battery 1.
• microbattery 1 and the micro-supercapacitors 7 are preferably formed on the same substrate 2, either side by side ( Figures 4 and 5) or superimposed ( Figures 6 and 7).
• the substrate 2 also preferably supports the integrated circuit 13 and the electronic switches 15. Thin film deposition techniques of the same type can be used for the manufacture of the micro-battery and micro-supercapacitors.
• Micro-battery 1 and micro- supercapacitors 7 preferably comprise identical materials for the current collectors, on the one hand, and for the solid electrolyte, on the other hand, which makes it possible to reduce the manufacturing time.
• the micro-battery and the micro-supercapacitors are placed side by side on the substrate 2. This makes it possible to simultaneously produce certain layers of the micro-battery and the micro-supercapacitors , but requires a larger surface area than the second embodiment, illustrated in FIGS. 6 and 7, in which the micro-battery and the micro-supercapacitors are superimposed.
• the micro-battery 1 and three micro-supercapacitors 7a, 7b and 7c are installed side by side on an insulating substrate 2 in silicon, with a surface area of 9 cm 2 .
• the micro-battery 1 is constituted by a stack of Pt / TiOS / Lipon / Li layers. It has an average operating voltage of around 2V and a capacity of 400 ⁇ Ah.
• Each micro-supercapacitor, having a voltage close to 1V and a capacity of the order of 15 ⁇ Ah, is constituted by a stack of Pt / Ru0 2 / Lipon / Ru0 2 layers.
• the serial coupling of three micro-supercapacitors provides a voltage of the order of 3V, necessary for full recharging of the microbattery.
• the micro-battery and the three micro-supercapacitors can be formed in seven successive stages of deposition: - In a first stage, represented in FIG. 4, the current collectors 3a and 3b of the micro-battery and the lower current collectors 8a, 8b and 8c of the three micro-supercapacitors are formed side by side on the substrate 2 by radiofrequency sputtering of a layer of platinum (Pt), 0.2 ⁇ 0.1 ⁇ m thick.
• Pt platinum
• the lower electrodes 9a, 9b and 9c, micro-supercapacitors, made of ruthenium oxide (Ru0 2 ), are produced from a metallic ruthenium target, by reactive radio frequency cathode sputtering in a mixture of 'argon and oxygen (Ar / 0 2 ) at room temperature.
• the layer formed has a thickness of 1.5 + 0.5 ⁇ m.
• This layer is obtained from a metal titanium (Ti) target by reactive radio frequency sputtering in a mixture of argon and hydrogen sulfide (Ar / H 2 S) at room temperature.
• a layer of 1.2 ⁇ 0.4 ⁇ m thick constituting the solid electrolyte 5 of the micro-battery and the solid electrolyte 10 of each of the micro-supercapacitors, is formed.
• It is a conductive glass of the Lipon type (Li 3 PO 2 5 N 03 ), obtained by reactive cathode sputtering under partial pressure of nitrogen with a target of Li 3 P0 4 or 0.75 (Li 2 O) -0, 25 (P 2 O 5 ).
• the upper electrodes 11a, 11b and 11c of the micro-supercapacitors, made of ruthenium oxide (Ru0 2 ) are produced in the same way as the lower electrodes during the second step.
• a lithium (Li) layer 5 ⁇ 2 ⁇ m thick, constituting the negative electrode 6 of the micro-battery, is formed by evaporation under secondary vacuum by heating metallic lithium by Joule effect in a crucible at 450 ° C.
• the upper current collectors 12a, 12b and 12c of the three micro-supercapacitors, made of platinum, are formed in the same way than the lower current collectors during the first stage.
• FIG. 5 illustrates, in section, the three micro-supercapacitors obtained at the end of the seventh step.
• the upper collectors 12a and 12b come into contact respectively with the collectors 8b and 8c of the adjacent micro-supercapacitor, thus automatically making the series connection of the three micro-supercapacitors during the seventh step.
• the connections between the micro-battery and the micro-supercapacitors, by means of the electronic switches 15, as well as their connections to the integrated circuit 13, are made subsequently by any suitable means.
• the entire device is then preferably protected from the external environment by encapsulation, for example by successive deposits of layers of polymer and metal.
• the second and third steps can optionally be reversed. The same applies to the fifth and sixth stages and, respectively, to the sixth and seventh stages.
• the micro-battery 1 and three micro-supercapacitors 7a, 7b and 7c are superimposed on an insulating substrate 2 made of silicon, with an area of 8 cm 2 .
• the materials used are the same as in the first embodiment.
• the superimposition makes it possible to increase the surface available for the micro-battery as well as for each of the micro-supercapacitors, and consequently to increase their energy capacity. It is thus possible to obtain a micro-battery having a capacity of 800 ⁇ Ah and a capacity of 80 ⁇ Ah for all the micro-supercapacitors. In return, the number of deposit steps is greater.
• the micro-battery and the three micro-supercapacitors can be formed in eighteen successive deposition steps, the characteristics of the different layers being identical to those of the first embodiment:
• the current collectors 3a and 3b, the positive electrode 4, the electrolyte 5 and the negative 6 of the micro-battery electrode are successively formed by stacking layers platinum (Step 1), TiOS (2 nd stage) of Lipon (step 3) and lithium (step 4).
• an electrically insulating layer 16 is formed on the micro-battery before forming the micro-supercapacitors.
• the insulating layer 16 is constituted by a solid electrolyte layer, made of Lipon.
• the three micro-supercapacitors are then successively formed, in a superimposed manner, above the insulating layer 16.
• the upper collector 12a of the first micro-supercapacitor 7a also constitutes the lower collector of the second micro-supercapacitor 7b.
• the upper collector 12b of the second micro-supercapacitor 7b also constitutes the lower collector of the third micro-supercapacitor 7c.
• the three micro-supercapacitors are thus automatically connected in series.
• the second micro-supercapacitor 7b is then formed by stacking on the current collector 12a, constituting its lower current collector, a layer of Ru0 2 (H th step) constituting the lower electrode 9b, a layer of Lipon ( 2nd stage) constituting the solid electrolyte 10b, of a layer of Ru0 2 (13 th step) constituting the upper electrode 11b and of a platinum layer (14 th step) constituting the upper current collector 12b.
• the storage device thus obtained is shown in Figures 6 and 7, respectively in top view and in section.
• the current collectors 8a, 12a, 12b and 12c formed respectively during the 6 th , 10 th , 14 th and 18 th stages each have a zone 17 projecting on one side and constituting the output terminals, offset, of the micro-supercapacitors .
• the zones 17 of the current collectors 8a and 12c are intended to be connected to the integrated circuit 13 and, by means of electronic switches 15, to the micro-battery.
• the zones 17 of the current collectors 12b and 12c are not essential, but they can be used if it is desired to have intermediate voltages.
• the insulating layer 16 can be removed if the device has only one electronic switch 15, to connect the upper current collector 12c of the third micro-supercapacitor 7c to the current collector 3a of the micro-battery.
• the lower current collector 8a of the first micro-supercapacitor 7a is then directly in contact with the negative electrode 6 of the micro-battery.
• the solid electrolyte layers 10a, 10b and 10c can completely cover the preceding layers, with the exception of the zones 17 of the current collectors of the micro-supercapacitors and of part of the current collectors 3a and 3b of the micro-battery to allow subsequent connections. They thus constitute an electrical insulator coating almost all of the lateral faces of the stack.
• all the steps for manufacturing the storage device can be carried out at ambient temperature, without subsequent annealing.
• the modular architecture of the device in particular the surface of the various elements, the number of micro-supercapacitors connected in series and the materials used determining the operating voltage and the surface capacity of the micro-battery and the micro-supercapacitors, is adapted to each application, in particular to its energy consumption and its recharging frequency.

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• Power Engineering (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Manufacturing & Machinery (AREA)
• Secondary Cells (AREA)
• Electric Double-Layer Capacitors Or The Like (AREA)

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• 2001
  • 2001-10-22 FR FR0113568A patent/FR2831318B1/fr not_active Expired - Fee Related
• 2002
  • 2002-10-21 EP EP02793171A patent/EP1543533A2/de not_active Withdrawn
  • 2002-10-21 CN CNA028061233A patent/CN1639816A/zh active Pending
  • 2002-10-21 WO PCT/FR2002/003588 patent/WO2003036670A2/fr not_active Application Discontinuation
  • 2002-10-21 US US10/250,769 patent/US20040161640A1/en not_active Abandoned
  • 2002-10-21 JP JP2003539066A patent/JP2005507544A/ja not_active Withdrawn
  • 2002-10-21 AU AU2002358840A patent/AU2002358840A1/en not_active Abandoned

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