Atomic/Molecular Layer Deposition of an All-Solid-State Thin-Film Battery Based on Organic Electrode Materials

Mikko Nisula

Atomic/Molecular Layer Deposition of an All-Solid-State Thin-Film Battery Based on Organic Electrode Materials

Julkaisun otsikon käännös: Orgaanisiin elektrodimateriaaleihin pohjautuvan ohutkalvo-litiumioniakun valmistus atomi/molekyylikerroskasvatusmenetelmällä

Mikko Nisula

Tutkimustuotos: Doctoral Thesis › Collection of Articles

Abstrakti

Kiinteisiin elektrolyytteihin perustuvia ohutkalvoakkuja pidetään nykyisin lupaavimpana energianvarastointimenetelmänä mikroelektroniikan sovelluksiin. Niiden käyttöönottoa kuitenkin rajoittaa niiden rajallinen energia- ja tehotiheys. Käyttämällä kolmiulotteisia rakenteita ohutkalvoakkujen substraattina, niiden efektiivistä pinta-alaa ja siten energia- ja tehotiheyttä voitaisiin huomattavasti parantaa. Yksi ainoista tähän tarkoitukseen sopivista ohutkalvojen valmistusmenetelmistä on atomikerroskasvatus (atomic layer deposition, ALD). Potentiaalistaan huolimatta ALD:n hyödyntäminen litiumioniakkujen kehityksessä on toistaiseksi ollut vähäistä, sillä litiumpohjaisten materiaalien valmistus ALD:llä on verrattain uusi tutkimusala. Tässä väitöskirjatyössä selvitettiin ALD-menetelmän soveltumista kokonaisen akkukenno valmistukseen. Kullekin ohutkalvoakkuun tarvittavalle sähkökemiallisesti aktiiviselle komponentille kehitettiin uusi ALD-prosessi ja nämä yhdistämällä valmistettiin toimiva ohutkalvoakkukenno. Litiumiin pohjautuva ALD-kemia on tavanomaisesta huomattavasti poikkeavaa, ja prosessisuunnittelussa kiinnitettiin huomiota erityisesti tähän ongelmaan. Lisäksi välttämällä siirtymämetallien käyttöä, akkujen kierrätettävyysnäkökulma pyrittiin huomioimaan. Kiinteää elektrolyyttiä varten kehitettiin uusi ALD-prosessi litiumfosforioksinitridille (LiPON), jota pidetään yhtenä parhaista materiaaleista tähän sovellukseen. Aiemmin sen valmistus ALD-menetelmällä on ollut haasteellista johtuen sen monimutkaisesta koostumuksesta. Tässä työssä keskeinen oivallus oli käyttää lähtöaineena dietyylifosforiamidaattia. Tämä yhdessä litiumbis(trimetyylisilyyli)amiinin kanssa käytettynä mahdollisti kvaternaarisen LiPONin valmistuksen binaarisella ALD-prosessilla. Menetelmä tuotti tasalaatuisia pinnoituksia 3D-mikrorakenteille ja lisäksi materiaalille mitattiin yksi korkeimmista ALD:lla valmistetuille kiinteille elektrolyyteille raportoiduista ioninjohtavuusarvoista. Elektrodimateriaaleina käytettiin konjugoituneita karbonyyliyhdisteitä, joita ei aikaisemmin ole tutkittu ohutkalvoakuissa. Hiilivetyihin perustuvina niiden ympäristönkuormitus on epäorgaanisia vastineitaan alhaisempaa. Näiden materiaalien valmistukseen sovellettiin atomi/molekyylikerroskasvatus (ALD/MLD) -yhdistelmää; ensimmäistä kertaa litiumpohjaisille materiaaleille. Akun negatiivielektrodia varten kehitettiin valmistusprosessi lithiumtereftalaatille, joka on yksi tämän materiaaliryhmän suorituskykyisimpiä. Positiivielektrodimateriaali, dilitium-1,4-bentseenidiolaatti (Li2Q) on täysin uusi materiaali, jota ei ennen tätä työtä ole raportoitu. Ohutkalvomuodossa kumpikin materiaali osoittautui erittäin suorituskykyiseksi; Li2Q:lla saavutettiin jopa 0.25 s. lataus/purkuaikoja. Nämä materiaalit yhdistämällä saatiin ALD/MLD-menetelmällä valmistettua täysin orgaaninen ohutkalvoakku jolla saavutettiin usean sadan lataus-purkusyklin käyttöikä.

Julkaisun otsikon käännös	Orgaanisiin elektrodimateriaaleihin pohjautuvan ohutkalvo-litiumioniakun valmistus atomi/molekyylikerroskasvatusmenetelmällä
Alkuperäiskieli	Englanti
Pätevyys	Tohtorintutkinto
Myöntävä instituutio	Aalto-yliopisto
Valvoja/neuvonantaja	Karppinen, Maarit, Vastuuprofessori
Kustantaja	Aalto University
Painoksen ISBN	978-952-60-7840-3
Sähköinen ISBN	978-952-60-7841-0
Tila	Julkaistu - 2018
OKM-julkaisutyyppi	G5 Artikkeliväitöskirja

Tutkimusalat

atomikerroskasvatus
molekyylikerroskasvatus
lithiumioniakku
ohutkalvoakku

YK:n kestävän kehityksen tavoitteet

Tämä tuotos edistää seuraavia kestävän kehityksen tavoitteita:

Pääsy asiakirjaan

http://urn.fi/URN:ISBN:978-952-60-7841-0Lisenssi: Määrittelemätön

OtaNano
Rissanen, A. (Manager)
Aalto-yliopisto
Laitteistot/tilat: Facility
OtaNano Nanomikroskopiakeskus
Seitsonen, J. (Manager) & Rissanen, A. (Other)
OtaNano
Laitteistot/tilat: Facility
Raaka-aineiden tutkimusinfrastruktuuri
Karppinen, M. (Manager)
Kemian tekniikan korkeakoulu
Laitteistot/tilat: Facility

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@phdthesis{434f49954bc242e6b94273a7c96a3fb3,

title = "Atomic/Molecular Layer Deposition of an All-Solid-State Thin-Film Battery Based on Organic Electrode Materials",

abstract = "All-solid-state Li-ion batteries in thin-film format are currently the most promising concept for the energy storage needs of miniature electronic devices. Their applicability is however restricted by their inherently poor energy and power densities. By using 3D substrates, the effective surface area and thus the energy density could be markedly increased. Atomic layer deposition (ALD) is one of the few methods capable in producing conformal layers on such complex structures. As the basic research on new ALD processes for Li-containing thin films is only in early stage, the true impact of the ALD technique in the Li-ion battery field is yet to be demonstrated. The aim of this theses was to advance the field with the introduction of novel deposition processes for each of the active components of a thin-film Li-ion battery. An ultimate goal was to manufacture a fully functional all-solid-state thin-film battery. For each material, the process design needs to take into account the fundamental difficulties related to lithium-based ALD chemistries. Additionally, by avoiding the use of metal components other than Li in the materials, the environmental impact of the newly designed and fabricated thin-film battery could potentially be reduced. For the solid electrolyte, a novel thermal-ALD process was developed for one of the most promising thin-film battery electrolyte material, i.e. lithium phosphorus oxynitride (LiPON). Due to its complex composition, it had been considered highly challenging compound for the ALD synthesis. In this thesis, the key innovation was the use of a novel ALD precursor, diethyl phosphoramidate. In combination with lithium bis(trimethylsilyl)amide, the quaternary target material could be deposited with a simple binary ALD process. The conformality on high-aspect-ratio substrates was confirmed and the measured ionic conductivity value is among the highest reported for ALD-grown solid electrolytes. For the electrode materials, a completely new approach was demonstrated. By utilizing combined atomic/molecular layer deposition (ALD/MLD) technique the range of available electrode materials was broadened to those based on conjugated carbonyl systems. Based on their fully organic backbones, such lithium organic electrode materials should be less harmful than their inorganic counterparts. The negative electrode material, lithium terephthalate, was known as one of the top performing organic electrode materials, whereas a completely novel material, dilithium-1,4-benezenediolate (Li2Q), was developed to function as the positive electrode. Excellent rate performance was demonstrated for both materials; in particular, charge/discharge times as low as 0.25 s were observed for Li2Q. Moreover, these materials were combined into an all-solid-state thin-film battery that was able to undergo extended charge/discharge cycling.",

keywords = "atomic layer deposition, molecular layer deposition, lithium-ion battery, thin film battery, atomikerroskasvatus, molekyylikerroskasvatus, lithiumioniakku, ohutkalvoakku, atomic layer deposition, molecular layer deposition, lithium-ion battery, thin film battery",

author = "Mikko Nisula",

year = "2018",

language = "English",

isbn = "978-952-60-7840-3",

series = "Aalto University publication series DOCTORAL DISSERTATIONS",

publisher = "Aalto University",

number = "23",

address = "Finland",

school = "Aalto University",

}

TY - BOOK

T1 - Atomic/Molecular Layer Deposition of an All-Solid-State Thin-Film Battery Based on Organic Electrode Materials

AU - Nisula, Mikko

PY - 2018

Y1 - 2018

N2 - All-solid-state Li-ion batteries in thin-film format are currently the most promising concept for the energy storage needs of miniature electronic devices. Their applicability is however restricted by their inherently poor energy and power densities. By using 3D substrates, the effective surface area and thus the energy density could be markedly increased. Atomic layer deposition (ALD) is one of the few methods capable in producing conformal layers on such complex structures. As the basic research on new ALD processes for Li-containing thin films is only in early stage, the true impact of the ALD technique in the Li-ion battery field is yet to be demonstrated. The aim of this theses was to advance the field with the introduction of novel deposition processes for each of the active components of a thin-film Li-ion battery. An ultimate goal was to manufacture a fully functional all-solid-state thin-film battery. For each material, the process design needs to take into account the fundamental difficulties related to lithium-based ALD chemistries. Additionally, by avoiding the use of metal components other than Li in the materials, the environmental impact of the newly designed and fabricated thin-film battery could potentially be reduced. For the solid electrolyte, a novel thermal-ALD process was developed for one of the most promising thin-film battery electrolyte material, i.e. lithium phosphorus oxynitride (LiPON). Due to its complex composition, it had been considered highly challenging compound for the ALD synthesis. In this thesis, the key innovation was the use of a novel ALD precursor, diethyl phosphoramidate. In combination with lithium bis(trimethylsilyl)amide, the quaternary target material could be deposited with a simple binary ALD process. The conformality on high-aspect-ratio substrates was confirmed and the measured ionic conductivity value is among the highest reported for ALD-grown solid electrolytes. For the electrode materials, a completely new approach was demonstrated. By utilizing combined atomic/molecular layer deposition (ALD/MLD) technique the range of available electrode materials was broadened to those based on conjugated carbonyl systems. Based on their fully organic backbones, such lithium organic electrode materials should be less harmful than their inorganic counterparts. The negative electrode material, lithium terephthalate, was known as one of the top performing organic electrode materials, whereas a completely novel material, dilithium-1,4-benezenediolate (Li2Q), was developed to function as the positive electrode. Excellent rate performance was demonstrated for both materials; in particular, charge/discharge times as low as 0.25 s were observed for Li2Q. Moreover, these materials were combined into an all-solid-state thin-film battery that was able to undergo extended charge/discharge cycling.

AB - All-solid-state Li-ion batteries in thin-film format are currently the most promising concept for the energy storage needs of miniature electronic devices. Their applicability is however restricted by their inherently poor energy and power densities. By using 3D substrates, the effective surface area and thus the energy density could be markedly increased. Atomic layer deposition (ALD) is one of the few methods capable in producing conformal layers on such complex structures. As the basic research on new ALD processes for Li-containing thin films is only in early stage, the true impact of the ALD technique in the Li-ion battery field is yet to be demonstrated. The aim of this theses was to advance the field with the introduction of novel deposition processes for each of the active components of a thin-film Li-ion battery. An ultimate goal was to manufacture a fully functional all-solid-state thin-film battery. For each material, the process design needs to take into account the fundamental difficulties related to lithium-based ALD chemistries. Additionally, by avoiding the use of metal components other than Li in the materials, the environmental impact of the newly designed and fabricated thin-film battery could potentially be reduced. For the solid electrolyte, a novel thermal-ALD process was developed for one of the most promising thin-film battery electrolyte material, i.e. lithium phosphorus oxynitride (LiPON). Due to its complex composition, it had been considered highly challenging compound for the ALD synthesis. In this thesis, the key innovation was the use of a novel ALD precursor, diethyl phosphoramidate. In combination with lithium bis(trimethylsilyl)amide, the quaternary target material could be deposited with a simple binary ALD process. The conformality on high-aspect-ratio substrates was confirmed and the measured ionic conductivity value is among the highest reported for ALD-grown solid electrolytes. For the electrode materials, a completely new approach was demonstrated. By utilizing combined atomic/molecular layer deposition (ALD/MLD) technique the range of available electrode materials was broadened to those based on conjugated carbonyl systems. Based on their fully organic backbones, such lithium organic electrode materials should be less harmful than their inorganic counterparts. The negative electrode material, lithium terephthalate, was known as one of the top performing organic electrode materials, whereas a completely novel material, dilithium-1,4-benezenediolate (Li2Q), was developed to function as the positive electrode. Excellent rate performance was demonstrated for both materials; in particular, charge/discharge times as low as 0.25 s were observed for Li2Q. Moreover, these materials were combined into an all-solid-state thin-film battery that was able to undergo extended charge/discharge cycling.

KW - atomic layer deposition

KW - molecular layer deposition

KW - lithium-ion battery

KW - thin film battery

KW - atomikerroskasvatus

KW - molekyylikerroskasvatus

KW - lithiumioniakku

KW - ohutkalvoakku

KW - atomic layer deposition

KW - molecular layer deposition

KW - lithium-ion battery

KW - thin film battery

M3 - Doctoral Thesis

SN - 978-952-60-7840-3

T3 - Aalto University publication series DOCTORAL DISSERTATIONS

PB - Aalto University

ER -

Atomic/Molecular Layer Deposition of an All-Solid-State Thin-Film Battery Based on Organic Electrode Materials

Abstrakti

Tutkimusalat

YK:n kestävän kehityksen tavoitteet

Pääsy asiakirjaan

Sormenjälki

Laitteet

OtaNano

OtaNano Nanomikroskopiakeskus

Raaka-aineiden tutkimusinfrastruktuuri

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