EP3545577A1 - Cellule de stockage d'énergie électrochimique à base d'ions li - Google Patents

Cellule de stockage d'énergie électrochimique à base d'ions li

Info

Publication number
EP3545577A1
EP3545577A1 EP17808385.3A EP17808385A EP3545577A1 EP 3545577 A1 EP3545577 A1 EP 3545577A1 EP 17808385 A EP17808385 A EP 17808385A EP 3545577 A1 EP3545577 A1 EP 3545577A1
Authority
EP
European Patent Office
Prior art keywords
layer
cathode
energy storage
current collector
anode
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Withdrawn
Application number
EP17808385.3A
Other languages
German (de)
English (en)
Inventor
Stephan Buecheler
Alejandro Nicolas FILIPPIN
Michael Rawlence
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eidgenoessische Materialprufungs und Forschungsanstalt EMPA
Original Assignee
Eidgenoessische Materialprufungs und Forschungsanstalt EMPA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Eidgenoessische Materialprufungs und Forschungsanstalt EMPA filed Critical Eidgenoessische Materialprufungs und Forschungsanstalt EMPA
Publication of EP3545577A1 publication Critical patent/EP3545577A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H01M4/662—Alloys
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • 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
    • 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 present invention describes a multi-layered thin film Li-ion based electrochemical energy storage cell, according to the preamble of claim 1, a rechargeable thin-film Li-ion based solid state battery in form of a stack of a multiplicity of multi-layered thin film Li-ion based electrochemical energy storage cells and a method for production of a multi-layered thin film Li-ion based electrochemical energy storage cell, by in-situ deposition steps followed by annealing process steps at elevated temperatures.
  • Lithium-ion accumulators, secondary or rechargeable batteries or battery cells can be used for electrically powered vehicles, as well as in computer technology, in particular for notebooks, smartphones or tablets.
  • Lithium-ion battery cells have a positive cathode and a negative anode, sandwiching an electrolyte in between.
  • a cathode current collector and an anode current collector are placed in direct electrical contact with the cathode and the anode respectively.
  • Charged lithium ions can move between both electrodes, while the discharge process from anode to cathode takes place.
  • Thin film batteries comprising different substrates and metal or metal oxide cathode current collectors are disclosed with thicknesses of less than 3 micrometers.
  • EP2897203 a composite current collector for an energy storage device electrode is disclosed, comprising at least copper, aluminum, nickel, gold, silver, and alloys thereof with a thickness from 1 to 100 pm.
  • EP2738852 discloses a current collector for a bipolar lithium ion secondary battery, wherein the metal layer contains at least one metal material selected from the group consisting of aluminum, nickel, copper, iron, titanium, and an alloy, a metal carbide, a metal nitride and a metal oxide of these metals.
  • Cathode current collectors in conventional Li-ion battery technology and especially in solid state batteries are predominantly based on aluminum due to its low cost and electrochemical stability at high voltage, exhibiting minor electrochemical reactions in the 3.5-5 V vs Li+/Li range due to the formation of a passivation layer.
  • aluminum melts already at 660 °C, which is incompatible with state-of-the-art battery materials, such as the high-voltage cathode LiMnl .5Ni0.5O4 and LiCo02 that require up to 750 °C to crystallize fully or solid-state electrolytes like LLZO (Li 7 La3Zr 2 0i2) demanding equal temperatures for crystallization.
  • the manufacturing of the electrochemical energy storage cells is still problematic, due to the temperatures used while depositing different material layers.
  • the object of the present invention is to create a multi-layered Li- based solid state electrochemical energy storage cell, which can easily be produced in an in-situ production process, which can resist elevated temperatures of more than 700°C, showing a high lithium resistance and high electrical conductivity even after a heat treatment in air/oxygen. With the high preparation temperatures, the prepared layers of the multi-layered solid state electrochemical energy storage cell are stable against oxidation and reactions with lithium.
  • cathode current collectors of stainless steel, tungsten, nickel and chromium react/oxidize in the potential range 4-4.5 V vs Li+/Li or oxidize below 600 °C.
  • NixAI is electrochemically stable in the potential range 2-4.7 V vs Li+/Li, but shows, only in the first cycle, a minor reaction from 3.5-5 V vs Li/Li+ which we attributed to the formation of a passivation layer with the electrolyte.
  • Another object of the subject matter of the invention is to provide a manufacturing method for such multilayered Li-based solid state electrochemical energy storage cell and rechargeable Li-ion based batteries made of these multilayered Li-based solid state electrochemical energy storage cells.
  • Figure 1 shows a schematic sectional view of one embodiment of a multi-layer solid state Li-based electrochemical energy storage cell
  • Figure 2 shows a schematic sectional view of second embodiment of an electrochemical energy storage cell with an additional cathode interlayer and anode interlayer.
  • Figures 3 are showing schematic sectional views of the layer by layer production of a multi-layer solid state Li-based electrochemical energy storage cell according steps a) to e).
  • Figure 4 shows a schematic sectional view of a rechargeable Li-ion based battery, made of the aforementioned cells with and without an anode current collector.
  • the electrochemical solid state energy storage cell 0 comprises at least the following layers in subsequent order: a substrate layer 1, a cathode current collector layer 2, a cathode layer 3, a solid electrolyte layer 4, an anode layer 5 and an anode current collector layer 6. Aside from the substrate layer 1, the thicknesses of each layer 2, 3, 4, 5, 6 should be between 100 nm and 50 microns.
  • Current leads 7 and 7' are connected to the cathode current collector, layer 2, and the anode current collector, layer 6.
  • Solid state refers to the use of a solid electrolyte in layer 4, a promising new development which makes very thin, robust energy storage cells 0 possible.
  • solid electrolyte materials applicable as solid electrolyte layer 4 known.
  • Li 7 La 3 Zr 2 0i2 (LLZO), with thicknesses between 100 nm and 2 microns, in particular 500 nm.
  • (Li, La)(Ti, M)0 3 is the general formula for denoting the perovskite family of Li-ion conductor, where M denotes a rare metal oxide which might be present or absent (as in lanthanum lithium titanate) in the compound.
  • the substrate layer different metals and non-metals such as glass can be used .
  • stainless steel which is temperature resistant well above 700°C, in particular in form of a stainless steel foil.
  • the cathode current collector layer 2 has to be electrochemical stable, high temperature corrosion resistant at temperatures higher than 700 °C and resistant to reactions with lithium. We found, that a NixAI composition showed good results, leading to a simplified production method and showing desired oxidation resistance and lithium resistance.
  • the x lies between 0.3 and 9, in particular between 1 and 3. While the aluminium amount increases the oxidation resistance, the nickel amount increases the resistance against lithium.
  • NixAI alloys lithium resistance and the electrical conductivity after a heat treatment in air/oxygen (oxidizing atmosphere) of NixAI alloys is interesting . So far, the prior art did not mention these properties of NixAI alloys, when in contact with lithium containing layers. Therefore it was not obvious for the person skilled in the art, to restrict x between 1 and 3. An unusual try and extensive experiments were necessary to identify the x-range between 1 and 3.
  • the thickness of the cathode current collector layer 2 should lie between 50 nm and 5 microns, in particular 1 micron.
  • the NixAI composition regardless of the x range and substrate will be a conductive intermetallic compound in the form of a solid . Continuous films of NixAI less than 20-50 nm thickness could be grown by atomic layer deposition (ALD) by alternating layers of aluminum and nickel, followed by post annealing in vacuum or inert atmosphere. So, even forming islands, the cathode current collector layer 2 is working .
  • the physical and chemical properties of the NixAI are the essential properties related to the application of this intermetallic compound as current collector in thin film all-solid-state Li-ion batteries.
  • a third component can be added to the NixAI, in particular in form of an amount of chromium.
  • the composition of the cathode current collector layer 2 should comprise up to 30% weight of chromium. But amounts below 10% of chromium are desirable to limit the diffusion of this element into the cathode layer 3.
  • the missing layers 3, 4, 5, 6 will be deposited, which is at least partly associated with an annealing step after some deposition steps. These annealing steps at elevated temperatures up to 700°C and more, are harmful for cathode current collectors known from the prior art. But the above described cathode current collector layer 2 is resistant against the elevated temperatures.
  • NixAI thin film cathode current collector layers 2 are high temperature oxidation resistant above 1000 °C, electrochemically stable up to at least 4.5 V vs Li+/Li and lithium resistance at high temperatures at least up to 700 °C.
  • NixAI does not present any reaction with lithium when annealed for example with LiMnl .5Ni0.5O4 or Li20 at a temperature of 750 °C. Furthermore, above a 10% atomic percentage of Al in the superalloy, NixAI can effectively withstand annealing in oxygen at more than 1000 °C for long periods of time. Noble metals such as gold and platinum tend to alloy with lithium and have a prohibitive cost to be used in mass produced batteries.
  • the cathode layer 3 directly neighbouring the cathode current collector layer 2, is deposited subsequently onto the cathode current collector layer 2.
  • Lithium comprising material as LiMnl .5Ni0.5O4, LiCo0 2 , LiNii / 3Coi / 3Mni /3 0 2 , LiNiCoAI0 2 are among the suitable candidates.
  • the thickness of cathode layer 3 is between 100 nm and 50 microns.
  • an annealing step has to follow the deposition step of the cathode layer 3 unless deposition at elevated temperature is carried out.
  • the solid electrolyte layer 4 Directly connected to the cathode layer 3 is the solid electrolyte layer 4 as stated above.
  • the anode layer 5 may be made of silicon, lithium, LiTi 4 0 5 or aluminium, tin and/or alloys thereof and is also deposited onto the solid electrolyte layer 4.
  • the chosen thickness is in the order of the thickness of the cathode layer 3.
  • the anode current collector layer 6 is subsequently deposited onto the anode layer 5 and may be made from an electrically conductive material such as copper, titanium, nickel, gold, silver, platinum, molybdenum, manganese, metal alloys, conductive ceramics, conductive semiconductors and the like.
  • the thickness of the anode current collector layer 6 varies between 100 nm and 1 millimetre. The anode current collector layer 6 would not need to resist elevated temperatures.
  • Figure 2 shows an electrochemical energy storage cell 0' in the multi- layered setup as known from figure 1, wherein the same parts are marked with the same references. The differences are the arrangements of a cathode interlayer 34, between adjacent cathode layer 3 and solid electrolyte layer 4 and an anode interlayer 45 between solid electrolyte layer 4 and anode layer 5.
  • each interlayer 34, 45 should be between 10 nm to 50 nm.
  • the interlayers 34, 45 are comprising a Li- comprising compound, wherein the cathode interlayer 34 could comprise LiF, LiAIF 6 , Li 2 ZrF 6 , LiNb0 3 , while the anode interlayer 45 could comprise LiF, LiAIF 6 , Li 2 ZrF 6 , Li 3 N, Li 2 S.
  • FIG. 3a) to e) are showing the productions steps, beginning with providing a substrate layer 1.
  • the production method starts with the deposition of the cathode current collector layer 2, by any adequate technique, on any processable substrate layer 1, preferably of flexible nature, which is not restricted to conductive substrates but it would be desirable.
  • cathode current collector layer 2 Possible deposition techniques for the cathode current collector layer 2 are electron beam evaporation, thermal evaporation, atomic layer deposition, pulsed laser deposition, sputtering, thin-film printing . In particular electron beam evaporation or magnetron sputtering will be applied .
  • the reason for adding the cathode current collector layer 2 is to increase lithiation resistant and conductivity of the layers, after annealing in air/ oxygen in a later step, in particular, if such an annealing step of the solid electrolyte layer at or above 700°C is necessary.
  • the annealing step provides crystallization of the cathode layer 3.
  • the annealing step can be done by heating the setup up to 750 °C in oxygen atmosphere.
  • the annealing can also be done by photonic curing .
  • LiPON is a solid state electrolyte with a poor Lithium-ion conductivity around ⁇ 10 "6 S/cm, the solid state electrolyte we mention (LLZO) has a much higher and suitable ionic conductive ( ⁇ 10 ⁇ 3 S/cm).
  • anode material will be deposited forming the anode layer 5 onto the solid electrolyte layer 4.
  • another annealing step can be carried out.
  • the deposition of the anode current collector layer 6, for example copper or nickel, is performed, without an annealing step.
  • a rechargeable Li-ion based solid state battery 8 is producible by a stack of a multiplicity of in-situ prepared electrochemical energy storage cell 0, 0'. The concept of such a stacking of double layered cells in the field of thin film Li-ion based electrochemical energy storage cells 0', 0" is new.
  • a first electrochemical energy storage cell 0' comprising a substrate layer 1, a cathode current collector layer 2, a cathode layer 3, cathode interlayer 34, solid electrolyte layer 4, anode interlayer 45, anode layer 5 and anode current collector layer 6 are deposited and annealed as stated above.
  • a second electrochemical energy storage cell 0" is prepared in the same way, but without an anode current collector layer 6.
  • the second electrochemical energy storage cell 0" will be rotated and connected to the anode current collector layer 6 of the first electrochemical energy storage cell 0', such that the anode layer 5' of the second electrochemical energy storage cell 0" connects to the anode current collector layer 6 of the first electrochemical energy storage cell 0'.
  • Current leads 7, 7' can be connected to cathode current collector layers 2, 2' and the anode current collector layer 6.
  • a multiplicity of such thin-film solid state energy storage cells 0, 0', 0" is forming an electrochemical battery or rechargeable battery 8.
  • the electrochemical energy storage cells 0 or rechargeable batteries 8 can be used in a variety of application as stated above from hearing aids to electrically powered vehicles.
  • We show a novel cathode current collector layer 2 for next-generation bulk and thin film Li-ion batteries 8 based on a thin film of a Ni-AI superalloy with a composition in the range NixAI, x 0.3-9, deposited by magnetron sputtering at 300 °C in a low pressure argon atmosphere.
  • This cathode current collector shows a sufficient high temperature oxidation and lithium resistance and is electrochemically stable, for bulk and thin film Li-ion batteries.
  • state-of-the-art solid state electrolytes that require high temperatures such as the garnet Li7La3Zr2012 which requires at least 700 °C in oxygen atmosphere, can be directly deposited, annealed and electrically characterized to reach their proper crystallization.
  • NixAI thin film cathode current collector 2 By tuning the composition of NixAI thin film cathode current collector 2 to a richer nickel superalloy (x>2.9), the reaction between aluminium and the more mobile lithium of the solid electrolyte layer 4 at high temperatures can be avoided/minimized.
  • NixAI thin films Fabrication by magnetron sputtering and characterization of NixAI thin films with different compositions were carried out. Annealing experiments in the presence of other materials (LiMn l .5Ni0.5O4, Li7La3Zr2012, Li20) and under oxygen atmosphere were carried out along with electrochemical ones.
  • the thickness of the substrate layer 1 lies between 5 microns and 1 millimetre
  • the thickness of the solid electrolyte layer 4 lies between 100 nm and 2 microns
  • the thickness of the anode current collector layer 6 lies between lOOnm and 1 millimetre.

Abstract

La présente invention concerne une cellule de stockage d'énergie électrochimique à base d'ions Li à film mince multicouche, préparée in-situ dans des processus de dépôt subséquents, dans lequel les couches déposées subséquentes résistent à des températures élevées supérieures ou égales à 700 °C. Ceci est atteint par une cellule de stockage d'énergie électrochimique à base d'ions Li à film mince multicouche, comprenant une couche de substrat, sous la forme d'un composé métallique ou non métallique résistant à la température à au moins 700 °C et plus élevée, une couche de collecteur de courant de cathode, comprenant au moins deux éléments métalliques, déposée directement sur la couche de substrat, une couche de cathode comprenant un composé de lithium, qui cristallise à des températures élevées à ou au-dessus de 700 °C, une couche d'électrolyte solide comprenant du lithium, qui se cristallise à des températures élevées à ou au-dessus de 700 °C, une couche d'anode et une couche de collecteur de courant d'anode.
EP17808385.3A 2016-11-23 2017-11-20 Cellule de stockage d'énergie électrochimique à base d'ions li Withdrawn EP3545577A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16200316.4A EP3327837A1 (fr) 2016-11-23 2016-11-23 Cellule de stockage d'énergie électrochimique à base de li-ion
PCT/EP2017/079730 WO2018095845A1 (fr) 2016-11-23 2017-11-20 Cellule de stockage d'énergie électrochimique à base d'ions li

Publications (1)

Publication Number Publication Date
EP3545577A1 true EP3545577A1 (fr) 2019-10-02

Family

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Family Applications (2)

Application Number Title Priority Date Filing Date
EP16200316.4A Withdrawn EP3327837A1 (fr) 2016-11-23 2016-11-23 Cellule de stockage d'énergie électrochimique à base de li-ion
EP17808385.3A Withdrawn EP3545577A1 (fr) 2016-11-23 2017-11-20 Cellule de stockage d'énergie électrochimique à base d'ions li

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP16200316.4A Withdrawn EP3327837A1 (fr) 2016-11-23 2016-11-23 Cellule de stockage d'énergie électrochimique à base de li-ion

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EP (2) EP3327837A1 (fr)
WO (1) WO2018095845A1 (fr)

Families Citing this family (6)

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Publication number Priority date Publication date Assignee Title
EP4293940A3 (fr) 2017-05-12 2024-02-14 Koninklijke Philips N.V. Récepteur, émetteur, réseau de communication, signal de données et procédé pour améliorer un processus de retransmission dans un réseau de communication
CN108550907B (zh) * 2018-06-05 2020-08-21 北京卫蓝新能源科技有限公司 原位复合固态电解质及其应用、全固态电池及其制备方法
CN112189239B (zh) * 2018-10-01 2022-08-12 松下知识产权经营株式会社 卤化物固体电解质材料和使用该材料的电池
EP3863028A4 (fr) * 2018-10-01 2021-12-08 Panasonic Intellectual Property Management Co., Ltd. Matériau d'électrolyte solide à base d'halogénure et batterie l'utilisant
WO2020070957A1 (fr) * 2018-10-01 2020-04-09 パナソニックＩｐマネジメント株式会社 Matériau d'électrolyte solide à base d'halogénure et batterie l'utilisant
JPWO2020070956A1 (ja) * 2018-10-01 2021-09-16 パナソニックＩｐマネジメント株式会社 ハロゲン化物固体電解質材料およびこれを用いた電池

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8021778B2 (en) * 2002-08-09 2011-09-20 Infinite Power Solutions, Inc. Electrochemical apparatus with barrier layer protected substrate
CN101931097B (zh) * 2004-12-08 2012-11-21 希莫菲克斯公司 LiCoO2的沉积
CN101689635B (zh) * 2007-03-26 2013-03-27 西姆贝特公司 用于锂薄膜电池的基材
JP2011141982A (ja) * 2010-01-06 2011-07-21 Sumitomo Electric Ind Ltd 非水電解質電池
JP5770553B2 (ja) 2011-07-26 2015-08-26 日産自動車株式会社 双極型リチウムイオン二次電池用集電体
JP6078977B2 (ja) * 2012-04-18 2017-02-15 富士通株式会社 全固体二次電池及びその封止材
WO2014042080A1 (fr) 2012-09-14 2014-03-20 日産化学工業株式会社 Collecteur de courant composite destiné à une électrode de dispositif de stockage d'énergie, et électrode
KR20150073192A (ko) 2012-10-15 2015-06-30 사임베트 코퍼레이션 유리 또는 세라믹 기판을 포함하는 박막 전지

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Publication number Publication date
EP3327837A1 (fr) 2018-05-30
WO2018095845A1 (fr) 2018-05-31

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