EP1673820A2 - Couche et procede de protection de microbatteries par une bicouche ceramique-metal - Google Patents
Couche et procede de protection de microbatteries par une bicouche ceramique-metalInfo
- Publication number
- EP1673820A2 EP1673820A2 EP04791533A EP04791533A EP1673820A2 EP 1673820 A2 EP1673820 A2 EP 1673820A2 EP 04791533 A EP04791533 A EP 04791533A EP 04791533 A EP04791533 A EP 04791533A EP 1673820 A2 EP1673820 A2 EP 1673820A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- layer
- coating
- protective layer
- insulating layer
- 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.)
- Withdrawn
Links
- 239000002184 metal Substances 0.000 title claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims description 20
- 239000010410 layer Substances 0.000 claims abstract description 46
- 239000011241 protective layer Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 10
- 238000004146 energy storage Methods 0.000 claims abstract description 6
- 238000009413 insulation Methods 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000005538 encapsulation Methods 0.000 claims description 15
- 230000000930 thermomechanical effect Effects 0.000 claims description 13
- 239000000919 ceramic Substances 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 238000005240 physical vapour deposition Methods 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052790 beryllium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 150000004767 nitrides Chemical group 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910020068 MgAl Inorganic materials 0.000 claims description 2
- 238000010884 ion-beam technique Methods 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000000615 nonconductor Substances 0.000 claims 2
- 229910052737 gold Inorganic materials 0.000 claims 1
- 150000003568 thioethers Chemical group 0.000 claims 1
- 229910010293 ceramic material Inorganic materials 0.000 abstract 1
- 238000005336 cracking Methods 0.000 abstract 1
- 239000003570 air Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- 238000000151 deposition Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910012305 LiPON Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- -1 sodium and potassium Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910015617 MoNx Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 229910008328 ZrNx Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G2/00—Details of capacitors not covered by a single one of groups H01G4/00-H01G11/00
- H01G2/12—Protection against corrosion
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/40—Printed batteries, e.g. thin film batteries
-
- 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
- H01M10/04—Construction or manufacture in general
- H01M10/0436—Small-sized flat cells or batteries for portable equipment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
- H01M50/128—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
- H01M50/134—Hardness
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/233—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions
- H01M50/24—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions adapted for protecting batteries from their environment, e.g. from corrosion
-
- 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 invention relates generally to energy storage systems.
- the invention relates more particularly to the protection of these systems against air, in particular for systems deposited on a substrate.
- Electrode storage systems are very often miniaturized. They include inter alia microbatteries and micro-supercapacitors, that is to say systems obtained by depositing materials on a substrate. These materials are, most of the time, reactive to air and / or its compounds (oxygen, nitrogen, humidity).
- microbattery includes both electrochemical systems comprising lithium and its compounds such as glasses based on lithium, as electrochemical systems comprising alkali metals such as sodium and potassium, or even alkaline earths such as beryllium or magnesium.
- micro-supercapacity groups in particular storage systems whose electrodes can be based on carbon or oxides of metals such as the oxides of ruthenium, iridium, tantalum, manganese.
- Microbatteries are mostly obtained in thin layers on a rigid silicon, ceramic or glass substrate, or on a flexible polymer substrate such as kapton or the benzocyclobutene polymer. They can also be associated with integrated circuits. Microbatteries include reactive elements; the anode in particular very often consists of lithium. Metallic lithium reacts quickly to exposure to atmospheric elements such as oxygen, nitrogen, carbon dioxide and water vapor. To ensure good performance of the systems and allow sustainable operation, it therefore provides protection against air.
- microbattery such as cathode films or the electrolyte
- cathode films or the electrolyte even if they are normally less reactive than the anode, also benefit from protection against air.
- 5,561,004 thus suggests the use of polymers including in particular parylene, the use of iron, aluminum, titanium, nickel, vanadium, manganese or chromium, or else the use of LiPON, that is to say a phosphorus and lithium oxynitride on a lithium electrode.
- polymers are not impermeable to air or water vapor, due in particular to their porosity.
- other ceramics have been proposed than LiPON, for example in document WO 02/47187, but the ceramics are fragile and do not withstand mechanical stresses.
- the functioning of the microbattery notably involves variations in the temperature of the elements, and therefore also of any protective layer of these elements. These variations cause significant thermomechanical stresses on these elements and their protective layer. Improvements to the existing protective layers are therefore necessary, in particular as regards their resistance.
- the invention proposes to overcome the drawbacks caused by the existing coating layers.
- the invention relates to a protective layer for a microbattery made of a material, metal or metal alloy, sufficiently soft and / or flexible to absorb significant deformations without revealing cracks.
- the appearance of cracks in a coating layer is indeed detrimental to the operation of an air-sensitive device.
- the protective layer itself be not very reactive with air, and / or not very reactive chemically with the constituents of the element to be protected, and in particular with lithium in the context of microbatteries. It is also preferable that it also has good mechanical compatibility with the constituents of the element to be protected, and in particular good adhesion.
- the material of the layer is selected to have good thermomechanical resistance.
- the material is chosen from rigid materials having a low coefficient of expansion, in particular less than ⁇ .lO "6 ⁇ " 1 : during temperature variations inherent in the operation of a microbattery for example, the material remains identical to itself, without reacting to the stresses generated during thermomechanical stresses.
- the protective layer may consist of a pure metal, or of a nitrided alloy which combines its thermomechanical resistance with reinforced protection against oxidation. It is also possible to opt for a combination of these materials, such as for example a layer of metal combined with a layer of its nitrided alloy.
- the protective layer can also be combined with another protective layer whose material has a very ductile behavior, that is to say that it deforms plastically during thermomechanical stresses without being damaged.
- its Vickers hardness is less than 50, preferably 40, which implies a very low elastic limit.
- the protective layer according to the invention is associated with an insulating layer. This insulating layer can also provide a first barrier against air.
- the protective layer is applied to a microbattery, object of this invention.
- the insulating layer is located on the side of the elements of the microbattery, the layer containing the metal being exterior.
- the preferred embodiment relates to a microbattery totally encapsulated in this layer.
- the invention also relates to a method of protection against air and / or its constituents comprising the coating with a protective layer of metal and / or metal alloy capable of absorbing thermomechanical deformations as described above.
- W and / or Ta and / or Mo and / or Zr and / or WN X and / or TaN x and / or MoN x and / or ZrN x and / or TiN x and / or A1N X are used (x ⁇ 1), possibly associated with Pd and / or Pt and / or Au.
- the method comprises coating with a layer of insulation before coating with the layer containing the metal. It is possible to carry out a preliminary encapsulation before the final coating, which can be kept or eliminated, for example by argon plasma.
- the various coatings are carried out by physical vapor deposition, evaporation, vaporization or spraying, in order to control the coating parameters as much as possible.
- the figure is a schematic representation of the various constituents of a microbattery comprising an encapsulation layer according to the invention.
- a microbattery (10) comprises the substrate (1), the cathode (2a) and anode (2b) collectors, the cathode (3), the electrolyte (4), the anode (5).
- an encapsulation opening is made on the cathode (2a) and anode (2b) collectors.
- the connection of the microbattery to an integrated circuit or to a redistribution substrate is carried out directly on the latter and the connection is carried out directly on the connection pads of an ASIC situated under the microbattery, or by the intermediary of passages ("vias") through the ASIC located under the microbattery.
- the microbattery (10) as such is carried out by known techniques.
- the electrodes (3, 5), in particular when they are made of lithium, are in fact very reactive to air. It is therefore desirable to cover them with a protective layer.
- the other elements (2, 4) can also react with air and it is advantageous to completely encapsulate the microbattery in the bilayer (6, 7).
- the protection of the constituent elements of the microbattery vis-à-vis the air is mainly ensured by a tight metallic layer (7), the metals having a lower air permeability than ceramics and polymers.
- the encapsulation layer according to the invention remains intact and covering, free from cracks.
- thermomechanical stresses In order to reduce the stresses generated during thermomechanical stresses, and to keep these stresses at a low enough level not to cause deterioration, the material is flexible enough to absorb the resulting deformations.
- a rigid material having a low coefficient of expansion is used. This material can be associated with a material having a very ductile behavior allowing it to deform plastically without being damaged.
- the protective layer (7) consists of either a pure metal or an alloy, chosen from the following elements or compounds: W, Ta, Mo, Zr, WN X , TaN x , MoN x , ZrN x , TiN x , A1N X , (x ⁇ 1). It can also consist of a multilayer of these metals and / or alloys.
- the metals were chosen because they are refractory materials with a low coefficient of expansion (W, Ta, Mo, Zr), less than 6.10 "6 ° C _1 .
- W, Ta, Mo, Zr are very resistant to oxidation.
- the protective layer (7) can be a multilayer comprising a highly ductile metal, which has a very low yield strength (Vickers hardness less than 50, preferably less than 40
- Pd, Pt , At are chosen because they offer the additional advantage of being stainless.
- a first layer of electrical insulating coating (6) is applied in direct contact with the microbattery and its substrate.
- This layer is also chemically stable and mechanically compatible with the microbattery. Furthermore, this layer can provide a first barrier against air.
- this layer (6) will be chosen in particular from: a) an oxide whose oxide is more stable than lithium oxide: namely the oxides of Mg, Ca, Be, Ce and La ; b) a “simple” oxide: Si0 2 , MgAl 2 0 4 , Al 2 0 3 , Ta 2 0 5 ; c) a sulfide: zinc sulfide: ZnS; d) a “simple” nitride: Si 3 N 4 , BN; e) a carbide: SiC, B 4 C, WC.
- the encapsulation (6, 7) thus produced is in particular impermeable to H 2 0, 0 2 , N 2 .
- microbatteries as such are produced in a conventional manner in equipment, consisting of a succession of frames, allowing the successive deposition of the different materials constituting the microbattery. The transfer between each frame is carried out via a hermetic enclosure under protection of dried argon making it possible to limit exposure to air.
- This very fine temporary pre-encapsulation layer may be produced for example by chemical vapor deposition from a HMDSO type precursor (Hexamethyldisiloxane).
- HMDSO type precursor Hexamethyldisiloxane
- the type of spraying frame will be of the radiofrequency or ion beam spraying type (IBS) or any other suitable equipment.
- IBS radiofrequency or ion beam spraying type
- PVD physical vapor deposition
- IBS very low deposition temperatures (up to less than 100 ° C).
- the provisional pre-encapsulation layer may be eliminated by a first step of argon plasma or left as it is if it does not harm the adhesion of the ceramic layer.
- the ceramic deposition is carried out at the desired thickness, preferably between 25 nm and 10,000 nm, or even less than 5,000 nm; the rate of deposition of ceramic layers is of the order of 200 nm / hour.
- a second metallic deposit is then carried out in the same way by a PVD technique or by evaporation. This step usually takes place in another deposition frame: in fact, the configuration of the spraying frame for metals is generally different, of the magnetron or direct current type.
- nitrogen is moreover introduced into the deposit frame for the production of a deposit by reactive spraying.
- the speed of deposition of the metal layers is of the order of 2 ⁇ m / hour; the thickness is generally between 50 nm and 10,000 nm.
- the waterproofing of the layers was tested by placing the microbatteries encapsulated in a strongly oxidizing temperature atmosphere (85 ° C / 85% relative humidity), ZnS deposit (100 nm) + W (100 nm) MgO deposit (100 nm) + Ta (100 nm) - Si0 2 deposit ( 100 nm) + W (100 nm) + WN X (100 nm) deposition Si0 2 (100 nm) + AlN x (100 nm) deposition A1 2 0 3 (100 nm) + W (100 nm) No deterioration of the characteristics of the microbatteries after a stay of 200 h have been observed.
- the microbattery thus protected can, depending on the types of application, be encapsulated and interconnected by various techniques known within systems (known for example under the
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0350690A FR2861218B1 (fr) | 2003-10-16 | 2003-10-16 | Couche et procede de protection de microbatteries par une bicouche ceramique-metal |
PCT/FR2004/002621 WO2005038957A2 (fr) | 2003-10-16 | 2004-10-14 | Couche et procede de protection de microbatteries par une bicouche ceramique-metal |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1673820A2 true EP1673820A2 (fr) | 2006-06-28 |
Family
ID=34385403
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP04791533A Withdrawn EP1673820A2 (fr) | 2003-10-16 | 2004-10-14 | Couche et procede de protection de microbatteries par une bicouche ceramique-metal |
Country Status (5)
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US (1) | US20070091543A1 (fr) |
EP (1) | EP1673820A2 (fr) |
JP (1) | JP2007508673A (fr) |
FR (1) | FR2861218B1 (fr) |
WO (1) | WO2005038957A2 (fr) |
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US8445130B2 (en) | 2002-08-09 | 2013-05-21 | Infinite Power Solutions, Inc. | Hybrid thin-film battery |
US8404376B2 (en) | 2002-08-09 | 2013-03-26 | Infinite Power Solutions, Inc. | Metal film encapsulation |
US8535396B2 (en) | 2002-08-09 | 2013-09-17 | Infinite Power Solutions, Inc. | Electrochemical apparatus with barrier layer protected substrate |
US8394522B2 (en) | 2002-08-09 | 2013-03-12 | Infinite Power Solutions, Inc. | Robust metal film encapsulation |
US8236443B2 (en) | 2002-08-09 | 2012-08-07 | Infinite Power Solutions, Inc. | Metal film encapsulation |
US8431264B2 (en) | 2002-08-09 | 2013-04-30 | Infinite Power Solutions, Inc. | Hybrid thin-film battery |
US20070264564A1 (en) | 2006-03-16 | 2007-11-15 | Infinite Power Solutions, Inc. | Thin film battery on an integrated circuit or circuit board and method thereof |
US8021778B2 (en) | 2002-08-09 | 2011-09-20 | Infinite Power Solutions, Inc. | Electrochemical apparatus with barrier layer protected substrate |
US8728285B2 (en) | 2003-05-23 | 2014-05-20 | Demaray, Llc | Transparent conductive oxides |
US7959769B2 (en) | 2004-12-08 | 2011-06-14 | Infinite Power Solutions, Inc. | Deposition of LiCoO2 |
KR101127370B1 (ko) | 2004-12-08 | 2012-03-29 | 인피니트 파워 솔루션스, 인크. | LiCoO2의 증착 |
US8062708B2 (en) | 2006-09-29 | 2011-11-22 | Infinite Power Solutions, Inc. | Masking of and material constraint for depositing battery layers on flexible substrates |
US8197781B2 (en) | 2006-11-07 | 2012-06-12 | Infinite Power Solutions, Inc. | Sputtering target of Li3PO4 and method for producing same |
WO2009086038A1 (fr) | 2007-12-21 | 2009-07-09 | Infinite Power Solutions, Inc. | Procédé pour pulvérisation cathodique de cibles pour des films d'électrolyte |
US8268488B2 (en) | 2007-12-21 | 2012-09-18 | Infinite Power Solutions, Inc. | Thin film electrolyte for thin film batteries |
EP2229706B1 (fr) | 2008-01-11 | 2014-12-24 | Infinite Power Solutions, Inc. | Encapsulation de films minces pour batteries à film mince et autres dispositifs |
EP2266183B1 (fr) | 2008-04-02 | 2018-12-12 | Sapurast Research LLC | Commande de sûr/sous tension passive et protection pour des dispositifs de stockage d'énergie associes a un captage d'énergie |
CN102119454B (zh) | 2008-08-11 | 2014-07-30 | 无穷动力解决方案股份有限公司 | 具有用于电磁能量收集的一体收集器表面的能量设备及其方法 |
US8260203B2 (en) | 2008-09-12 | 2012-09-04 | Infinite Power Solutions, Inc. | Energy device with integral conductive surface for data communication via electromagnetic energy and method thereof |
FR2936106B1 (fr) | 2008-09-16 | 2010-10-01 | Commissariat Energie Atomique | Micro-batterie au lithium comportant une couche d'encapsulation et procede de fabrication. |
WO2010042594A1 (fr) | 2008-10-08 | 2010-04-15 | Infinite Power Solutions, Inc. | Module de capteurs sans fil alimenté par l’environnement |
FR2938977B1 (fr) * | 2008-11-21 | 2011-04-01 | Commissariat Energie Atomique | Microbatterie sur substrat a encapsulation monolithique |
FR2946461B1 (fr) * | 2009-06-09 | 2011-07-22 | Commissariat Energie Atomique | Dispositif d'encapsulation flexible d'une micro-batterie |
KR101792287B1 (ko) | 2009-09-01 | 2017-10-31 | 사푸라스트 리써치 엘엘씨 | 집적된 박막 배터리를 갖는 인쇄 회로 보드 |
EP2577777B1 (fr) | 2010-06-07 | 2016-12-28 | Sapurast Research LLC | Dispositif électrochimique à haute densité rechargeable |
US8900743B2 (en) * | 2011-10-27 | 2014-12-02 | Sakti3, Inc. | Barrier for thin film lithium batteries made on flexible substrates and related methods |
FR2977729B1 (fr) | 2011-07-08 | 2014-06-20 | Commissariat Energie Atomique | Accumulateur electrique et ses moyens d'encapsulation |
JP7035538B2 (ja) * | 2015-11-30 | 2022-03-15 | 大日本印刷株式会社 | 電池用包装材料、電池、電池用包装材料の製造方法 |
FR3076061B1 (fr) * | 2017-12-21 | 2019-11-22 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Realisation d'un collecteur de dispositif microelectronique |
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DE1139560B (de) * | 1960-04-08 | 1962-11-15 | Siemens Ag | Verfahren zum feuchtedichten Einbau von Kondensatoren oder anderen elektrischen Bauelementen |
DE2829031C3 (de) * | 1977-07-07 | 1982-05-19 | Matsushita Electric Industrial Co., Ltd., Kadoma, Osaka | Galvanische Zelle mit einem festen Elektrolyten aus Lithiumjodid |
JPS59226472A (ja) * | 1983-06-06 | 1984-12-19 | Hitachi Ltd | 薄膜リチウム電池 |
JPS63318066A (ja) * | 1987-06-22 | 1988-12-26 | Ricoh Co Ltd | 薄型電池 |
US5326652A (en) * | 1993-01-25 | 1994-07-05 | Micron Semiconductor, Inc. | Battery package and method using flexible polymer films having a deposited layer of an inorganic material |
US5561004A (en) * | 1994-02-25 | 1996-10-01 | Bates; John B. | Packaging material for thin film lithium batteries |
US6200704B1 (en) * | 1998-09-01 | 2001-03-13 | Polyplus Battery Company, Inc. | High capacity/high discharge rate rechargeable positive electrode |
US6168884B1 (en) * | 1999-04-02 | 2001-01-02 | Lockheed Martin Energy Research Corporation | Battery with an in-situ activation plated lithium anode |
US6790556B1 (en) * | 1999-12-06 | 2004-09-14 | E.C.R. - Electro Chemical Research, Ltd. | Electrochemical energy storage device having improved enclosure arrangement |
US7433655B2 (en) * | 2000-03-24 | 2008-10-07 | Cymbet Corporation | Battery-operated wireless-communication apparatus and method |
US20020071989A1 (en) * | 2000-12-08 | 2002-06-13 | Verma Surrenda K. | Packaging systems and methods for thin film solid state batteries |
WO2002065573A1 (fr) * | 2001-02-15 | 2002-08-22 | Matsushita Electric Industrial Co., Ltd. | Cellule d'electrolyse solide et procede de production de cette derniere |
-
2003
- 2003-10-16 FR FR0350690A patent/FR2861218B1/fr not_active Expired - Fee Related
-
2004
- 2004-10-14 WO PCT/FR2004/002621 patent/WO2005038957A2/fr active Application Filing
- 2004-10-14 EP EP04791533A patent/EP1673820A2/fr not_active Withdrawn
- 2004-10-14 JP JP2006534794A patent/JP2007508673A/ja active Pending
- 2004-10-14 US US10/574,756 patent/US20070091543A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO2005038957A2 * |
Also Published As
Publication number | Publication date |
---|---|
FR2861218B1 (fr) | 2007-04-20 |
WO2005038957A3 (fr) | 2006-05-18 |
JP2007508673A (ja) | 2007-04-05 |
WO2005038957A2 (fr) | 2005-04-28 |
US20070091543A1 (en) | 2007-04-26 |
FR2861218A1 (fr) | 2005-04-22 |
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