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All Solid State Battery Including A Solid Electrolyte And A Layer Of Ion Conducting Material

Abstract: The invention relates to a method for manufacturing an all-solid-state battery made up of thin layers, including the following consecutive steps: a) depositing a layer including at least one anode material on the conductive substrate thereof; b) depositing a layer including at least one cathode material on the conductive substrate thereof; c) depositing a layer including at least one solid electrolyte material on at least one layer obtained in step a) and/or b); d) depositing a layer of an ion-conducting material with a thickness of less than 10 µm, preferably less than 5 µm, and more preferably less than 2 µm, either on the layer of anode material coated with a layer of solid electrolyte material and/or on the layer of cathode material optionally coated with a layer of solid electrolyte material, or on the layer of cathode material coated with a layer of solid electrolyte material and/or on the layer of anode material optionally coated with a layer of solid electrolyte material; e) drying said layer of said solution of the ion-conducting material obtained in step d) in order to obtain a layer of an ion-conducting material; f) consecutively stacking a layer of anode material obtained in step a), c) or e), face-to-face, with a layer of cathode material obtained in step b), c) or e), with the proviso that the stack includes at least one layer of solid electrolyte material obtained in step c) and at least one layer of an ion-conducting material obtained in step e); and g) thermally treating and/or mechanically compressing the stack obtained in step e) to obtain an all-solid-state battery made up of thin layers.

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Notices, Deadlines & Correspondence

Patent Information

Application #
Filing Date
21 June 2018
Publication Number
45/2018
Publication Type
INA
Invention Field
ELECTRICAL
Status
Email
Parent Application
Patent Number
Legal Status
Grant Date
2023-12-14
Renewal Date

Applicants

I-TEN
12 chemin du Jubin 69570 Dardilly

Inventors

1. GABEN, Fabien
5 montée du Clair 69570 Dardilly
2. WEISS, Cédric
4 avenue de Champagne 69410 Champagne au Mont d'Or
3. SORRIANO, Claire
1 route de Champagne 69130 Ecully

Specification

Technical area The present invention relates to the field of batteries including lithium ion batteries. It relates more particularly lithium ion batteries ( "Li-ion batteries") completely solid, and a new such batteries manufacturing process. State of the art There are several known manufacturing methods for lithium ion batteries ( "Li-ion batteries"). The electrodes of Li-ion batteries can be manufactured using known printing or deposition techniques in the art, including the filing by roller coating ( "roll coating") or doctor ( " doctor blade "), or the deposit by tape casting (" cast tape "). These techniques consist in coating an ink containing micrometer-sized particles of active material on metallic current collectors for depositing layers having a thickness typically between 50 and 400 μηη. Depending on the thickness of the electrode, its porosity and the particle size of the active materials, the power and battery power may be modulated. These batteries have the feature of containing liquid electrolytes or in the form of gelled polymers to ensure the transport of lithium ions between the individual active particles of the electrodes. These electrolytes consist of aprotic solvents in which were dissolved lithium salts. However, these electrolytes tend to degrade in the electric potential effect and / or high temperatures. This degradation can be violent and fast in case of internal short circuit, and promote thermal runaway of the whole cell battery. Besides the operation and durability of safety problems inherent in the use of electrolytes based on aprotic solvents, these architectures do not allow either to optimize the electrochemical performance of the cell. The porosity necessary for wetting the electrodes causes a loss of volumetric energy densities and mass of the electrodes. The realization of Li-ion batteries completely solid, not liquid electrolytes based on aprotic solvents, would significantly increase the performance of Li-ion batteries. To achieve a high density of energy density would require of battery electrodes in the form of compact thin layers, in which the lithium ions can easily diffuse, without having to add electrolyte conductive of lithium ions or conductive particles electricity in the electrodes. Such electrodes and entirely solid batteries can be deposited using deposition techniques in vacuum such as PVD and / or CVD. Are thus obtained fully solid battery electrodes, without porosity and or binder containing only or organic electrolyte or electronic conductors in the electrodes. These techniques also allow to deposit electrolyte layers on the electrodes. These deposits are conformaux perfectly follow the surface roughness, are very adherent and do not require high-temperature heat treatment. vacuum deposition techniques and allow for an accurate definition of the interface between the electrode and the electrolyte, no inter-diffusion of one layer into the other, or risk of ill-point mechanical contact between the two layers. This gives quality interfaces resistive bit, well adapted to the realization of entirely solid batteries with high power densities. However, these vacuum deposition techniques are costly to implement and does not allow access to complex chemical compositions, with more than two or three separate chemical elements. Moreover thicknesses available with these techniques are limited and not exceed rarely 5 μηη. More recently filed thin electrophoretic nanoparticles. This technique is easier to implement than vacuum deposition techniques, it also allows for electrodes with more complex chemical formulations, see electrodes consist of two distinct phases. The nanoparticles thus deposited layers may be consolidated by simple drying or by thermal treatments at relatively low temperatures. This limits the inter-diffusion at the interfaces, an undesirable phenomenon that can give rise to new chemical compounds, ionic conductivity properties and / or electronics may be very different from those of the original component. Thus obtained electrode layers and completely solid electrolyte, The techniques using inks fail to make the deposit very thin layers. And if these techniques were to be used to fully solid electrodes, there should be a debinding annealing to burn organic products that have been used to achieve inks, and it would consolidate the layers. The consolidation is typically by high temperature heat treatment, called sintering. The sintering leads to the narrow portion, it does not allow to work directly on metal substrates without the risk of cracking. Moreover, because of the high temperature sintering promotes inter-diffusion at the various interfaces with the disadvantages described above. To reduce the porosity between the particles without the use of high temperature sintering is used solid ionic conductors and relatively fuses to bond the electrodes and electrolyte particles together or to bind the electrolyte particles together. This also improves the integrity of the encapsulation layer of the final battery. The quality of the encapsulation is of paramount importance for Li-ion batteries. Indeed, to ensure their shelf life calendar, Li-ion batteries must be completely encapsulated and protected from the external environment. Deposition techniques by ALD (Atomic layer deposition) are particularly well suited for coating surfaces fully waterproof and compliant manner battery cells. The encapsulation layers thus obtained generally consist of oxides, the Al 2 0 3or otherwise, of a thickness of the order of about fifty nanometers. These layers are therefore mechanically very fragile and require a rigid support surface. Depositing a brittle layer on a soft surface would lead to the formation of cracks, resulting in loss of integrity of this protective layer. Furthermore, to allow industrially a relatively high deposition rate, these layers must be deposited at a relatively high temperature between 200 and 300 ° C. However, the conventional electrolytes based on polymers containing lithium salts do not withstand such temperatures and do not exhibit a sufficiently rigid surface to ensure the realization of encapsulation quality with ALD deposition processes. A first object of the present invention is to provide a method of manufacturing batteries in fully solid thin layers, does not induce the appearance of phases at the interface between the two layers of electrolytes to assemble but also between the layers electrolyte and electrode. Another object of the present invention is to provide a battery manufacturing process, which may consist of multilayer assemblies completely solid and efficient cells, at low temperature without causing interdiffusion phenomenon at the interfaces with the electrodes, or any glass transition of the solid electrolyte film induced by methods too hot assemblies. Another object of the invention is to assemble low-temperature thin films of solid electrolyte of different types in order to optimize the choice of electrolytes on each of the electrodes so as to get the best compromise in terms of stability chemical interfaces, ionic conductivity and electrical insulation. Another object of the present invention is to facilitate the encapsulation of the battery. Another object of the present invention is to ensure the mechanical rigidity necessary for the achievement of quality encapsulation. Yet another object is to obtain in the battery sufficiently low internal resistance, that is to say a sufficiently high ionic conduction in the electrolyte to allow the battery to deliver a high power density. Another object of the invention is to manufacture thin film batteries by a process which can be implemented industrially fairly simply. Objects of the Invention A first object of the invention relates to a method of manufacturing a battery in fully solid thin film comprising the following successive steps: a) a layer comprising at least an anode material (referred to herein as "layer of anode material") on the conductive substrate, preferably selected from the group consisting of a metal foil, a metal strip, an insulating sheet metallized, a metallized insulating strip, a metallized insulating film, said conductive substrates, or their conductive elements, can be used as an anode current collector; b) a layer comprising at least a cathode material (referred to herein as "layer of cathode material") on the conductive substrate, preferably selected from the group consisting of a metal foil, a metal strip, a metallized insulating sheet, a metallized insulating strip, a metallized insulating film, said conductive substrates, or their conductive elements, can be used as a cathode current collector, it being understood that steps a) and b) can be reversed; c) a layer comprising at least one solid electrolyte material (Referred to herein as "layer of electrolyte material") on at least one layer obtained in step a) and / or b); d) depositing a layer of a solution of an ion-conductive material, preferably, at least one lithium salt: o either the anode material layer coated with a layer of solid electrolyte material and / or the cathode material layer or not coated with a layer of solid electrolyte material; o either the cathode layer material coated with a layer of solid electrolyte material and / or coated on the anode material layer or without a layer of solid electrolyte material; e) drying said layer of said solution of the ionic conductive material obtained in step d) to obtain a layer of an ionically conductive material; the thickness of the layer of said ion-conductive material being less than 10 μηη, preferably less than 5 μηη, and even more preferably less than 2 micrometres; f) are stacked face to face successively a layer of anode material obtained in step a), c) or e) with a cathode material layer obtained in step b), c) or e), being understood that the stack comprises at least one layer of solid electrolyte material obtained in step c) and at least one layer of an ionic conductive material obtained in step e); g) performing a thermal treatment and / or mechanical compression of the stack obtained in step e) to obtain a fully solid battery in thin layers. Advantageously, a recrystallization heat treatment or consolidation of the anode layer and / or cathode and / or electrolyte is effected at a temperature between 300 ° C and 1000 ° C, preferably between 400 ° C and 800 ° C, and even more preferably between 500 ° C and 700 ° C. Advantageously, the recrystallization heat treatment of the anode layer and / or cathode and / or electrolyte is carried out after step a) and / or b) of depositing the anode layer and / or cathode and / or after step c) of depositing the electrolyte layer. Advantageously, after step a) and / or b) of depositing the anode layer and / or cathode, and / or after step c) of depositing the electrolyte layer, a recrystallization heat treatment respectively of the anode layer and / or cathode and / or electrolyte is preferably carried out at a temperature between 300 ° C and 1000 ° C, more preferably between 400 ° C and 800 ° C, and more preferably between 500 ° C and 700 ° C. Preferably, the ion-conductive material used in step d) is selected from: a. silicates, preferably selected from Li 2 If 2 05 Li 2 Si0 3 , Li 2 If 2 0 6 , LiAISi0 4 , Li 4 Si0 4 , LiAISi 2 0 6 b. the ceramic compounds selected from mixtures Li 3 B03-Li 2 S04, Li 3 B0 3 -Li 2 Si0 4 , Li 3 B0 3 -Li 2 S0 4 Li 2 Si0 4 , c. ionic conductors lithium ions selected from: LiCl, LiBr, LiI, LiF, LiBH4, LiH, LiOH, LiB0 2 , LiP0 3 , LIN0 3 , Li 3 N, Li 2 S0 4 , LiV0 3 , Li 2 Mo0 4 , Li 2 B 4 0 7 , or a mixture of these compounds. d. the solid electrolytes anti-perovskite type selected from Li 3 OA with A a halide or mixture of halides, preferably at least one element selected from F, Cl, Br, I or a mixture of two or three or four thereof; Li (3-x) Mx / 2 OA with 0 0, b> 0, a + b <2, 0 0, b> 0, a + b <2, 0 0 , b> 0, a + b> 0, a + b <2, 0 0, b>0, a+b<2, 0 0, b> 0, a + b <2, 0 0, b> 0, a + b <2, 0 0, b> 0, a + b> 0, a + b < 2, 0 0, b> 0, a + b <2, 0

Documents

Application Documents

# Name Date
1 201817023227-TRANSLATIOIN OF PRIOIRTY DOCUMENTS ETC. [21-06-2018(online)].pdf 2018-06-21
2 201817023227-STATEMENT OF UNDERTAKING (FORM 3) [21-06-2018(online)].pdf 2018-06-21
3 201817023227-FORM 1 [21-06-2018(online)].pdf 2018-06-21
4 201817023227-DECLARATION OF INVENTORSHIP (FORM 5) [21-06-2018(online)].pdf 2018-06-21
5 201817023227-COMPLETE SPECIFICATION [21-06-2018(online)].pdf 2018-06-21
6 201817023227-Proof of Right (MANDATORY) [31-08-2018(online)].pdf 2018-08-31
7 201817023227-FORM-26 [31-08-2018(online)].pdf 2018-08-31
8 201817023227-FORM 3 [31-08-2018(online)].pdf 2018-08-31
9 201817023227-Power of Attorney-310818.pdf 2018-09-05
10 201817023227-OTHERS-310818.pdf 2018-09-05
11 201817023227-Correspondence-310818.pdf 2018-09-05
12 201817023227.pdf 2018-09-24
13 201817023227-Proof of Right (MANDATORY) [23-11-2018(online)].pdf 2018-11-23
14 201817023227-OTHERS-271118.pdf 2018-11-30
15 201817023227-Correspondence-271118.pdf 2018-11-30
16 201817023227-FORM 18 [03-10-2019(online)].pdf 2019-10-03
17 201817023227-certified copy of translation [26-08-2020(online)].pdf 2020-08-26
18 201817023227-Certified Copy of Priority Document [26-08-2020(online)].pdf 2020-08-26
19 201817023227-OTHERS [04-02-2021(online)].pdf 2021-02-04
20 201817023227-FER_SER_REPLY [04-02-2021(online)].pdf 2021-02-04
21 201817023227-COMPLETE SPECIFICATION [04-02-2021(online)].pdf 2021-02-04
22 201817023227-CLAIMS [04-02-2021(online)].pdf 2021-02-04
23 201817023227-ABSTRACT [04-02-2021(online)].pdf 2021-02-04
24 201817023227-FER.pdf 2021-10-18
25 201817023227-US(14)-HearingNotice-(HearingDate-20-11-2023).pdf 2023-11-01
26 201817023227-Duplicate-US(14)-HearingNotice-(HearingDate-20-11-2023).pdf 2023-11-01
27 201817023227-Correspondence to notify the Controller [17-11-2023(online)].pdf 2023-11-17
28 201817023227-FORM-26 [18-11-2023(online)].pdf 2023-11-18
29 201817023227-Written submissions and relevant documents [04-12-2023(online)].pdf 2023-12-04
30 201817023227-PETITION UNDER RULE 137 [04-12-2023(online)].pdf 2023-12-04
31 201817023227-PatentCertificate14-12-2023.pdf 2023-12-14
32 201817023227-IntimationOfGrant14-12-2023.pdf 2023-12-14

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