Development of Li-Organic Battery Materials with Atomic/Molecular Layer Deposition

Juho Heiska

Development of Li-Organic Battery Materials with Atomic/Molecular Layer Deposition

Julkaisun otsikon käännös: Litiumorgaanisten akkumateriaalien kehitys atomi/molekyylikerroskasvatuksella

Juho Heiska

Tutkimustuotos: Doctoral Thesis › Collection of Articles

Abstrakti

Litiumioniakut ovat yksi tärkeä osa ilmasto- ja energiakriisin ratkaisemisessa, mikä kiihdyttää niiden käyttöönottoa. Käytön yleistyessä huoli kasvaa raaka-aineiden kestävän kehityksen mukaisesta käytöstä, saatavuudesta ja kierrätettävyydestä. Akut olisi syytä myös suunnitella kestämään mahdollisimman pitkään. Litiumioniakun elinkaaren purku- ja lataussyklien määrää voidaankin kasvattaa suojaamalla aktiiviset materiaalit pinnoitteella. Tässä väitöskirjassa tutkittiin (i) uusia, vaihtoehtoisia ja kestävän kehityksen mukaisia orgaanisia akkumateriaaleja ja (ii) kehitettiin litiumorgaanisia pinnoitteita akkujen aktiivisten materiaalien päällystykseen. Työssä hyödynnettiin atomi/molekyylikerroskasvatus (ALD/MLD) menetelmää, joka tarjoaa ainutlaatuisen lähestymistavan molempiin sovelluskohteisiin. Työ keskittyi uusien litiumorgaanisten ALD/MLD ohutkalvojen kasvatus prosessien kehittämiseen, mistä julkaistua tietoa on olemassa vielä vain vähän. Päämäärä oli osoittaa ALD/MLD tekniikan soveltuvuus ja sen potentiaali litiumioniakkujen kehittämisessä. Työssä kehitettiin viisi uutta ALD/MLD prosessia orgaanisille anodimateriaaleille ja empiirinen tapa optimaalisen lähdelämpötilan arvioimiseksi ALD/MLD prosesseille termogravimetrian avulla. Ohutkalvojen sähkökemiallinen karakterisointi osoitti, että niiden ominainen käyttäytyminen vastasi aiempia tuloksia tavanomaisista elektrodeista. Ohutkalvoelektrodit eivät kuitenkaan sisällä lainkaan lisäaineita, joita normaalisti käytetään elektrodien valmistamisessa. Tämä tekee ohutkalvoelektrodeista erinomaisia mallielektrodeja, jonka avulla voidaan tutkia materiaalien luontaisia ominaisuuksia. Ohutkalvoelektrodien käytön jälkeisissä (post-mortem) diffraktio tutkimuksissa havaittiin, että näyte muuttuu amorfiseksi ja todettiin tämän muutoksen yhteys purku-latauskäyrän käyttäytymiseen. Tämä voi johtua aromaattisen hiilirungon litioitumisesta ja sen sivureaktiosta nestemäisen elektrolyytin kanssa. Työssä tehtiin uraauurtavaa kehitystä litiumorgaanisten ALD/MLD pinnoitteiden parissa. Yksi prosesseista käytti ensimmäisenä hiilidioksidia lähtöaineena litiumkarbonaattiesterien valmistuksessa ohutkalvoina. Litiumkarbonaattiesterit ovat mielenkiintoinen funktionaalinen ryhmä, koska niitä muodostuu elektrodin ja elektrolyytin kiinteässä rajapinnassa (Solid Electrolyte Interphase, SEI). Tämän kehityksen ansiosta voidaan nyt valmistaa täysin keinotekoinen SEI. Toinen ALD/MLD prosessi kehitettiin dilitium-1,4-bentseenidisulfonaatille, jonka diffraktogrammi ja (sähkö)kemialliset ominaisuudet arvioitiin. Litiumorgaanisten materiaalien suorituskykyä on pystyttävä parantamaan ja niiden toiminta tulee testata oikean elektrodimateriaalin päällä. Pohjatyö on kuitenkin nyt aloitettu.

Julkaisun otsikon käännös	Litiumorgaanisten akkumateriaalien kehitys atomi/molekyylikerroskasvatuksella
Alkuperäiskieli	Englanti
Pätevyys	Tohtorintutkinto
Myöntävä instituutio	Aalto-yliopisto
Valvoja/neuvonantaja	Karppinen, Maarit, Vastuuprofessori
Kustantaja	Aalto University
Painoksen ISBN	978-952-64-0331-1
Sähköinen ISBN	978-952-64-0332-8
Tila	Julkaistu - 2021
OKM-julkaisutyyppi	G5 Tohtorinväitöskirja (artikkeli)

Tutkimusalat

atomi/molekyylikerroskasvatus
litiumioniakku
orgaaninen elektrodi
litiumorgaaninen pinnoite

YK:n kestävän kehityksen tavoitteet

Tämä tuotos edistää seuraavia kestävän kehityksen tavoitteita:

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http://urn.fi/URN:ISBN:978-952-64-0332-8

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@phdthesis{2791bea85676464196710585f7ffb2cd,

title = "Development of Li-Organic Battery Materials with Atomic/Molecular Layer Deposition",

abstract = "Li-ion battery (LIB) is a piece of the puzzle for solving the present climate and energy crisis. Hence, the adaptation of LIBs is rapidly increasing, which has evoked severe concerns about the abundance, sustainability, and recyclability of the electrode raw materials. Cycle life is one of the main parameters regarding the sustainability of the LIBs, and it can be improved by protecting the active materials with suitable coatings. The scope of this thesis was twofold: (i) to challenge new organic electrode (OE) materials as more sustainable alternatives to current electrode materials, and (ii) to develop new Li-organic protective coating materials for the LIB electrodes. The gas-phase atomic/molecular layer deposition (ALD/MLD) thin-film technique provides unique advantages for both applications, and it was comprehensively utilized in this thesis. The focus was on developing new Li-organic ALD/MLD processes, which are still scarce in the literature. The overall goal was to show the applicability, benefits, and uniqueness of ALD/MLD technology to deposit various Li-organic materials for potential battery applications. In addition to five new ALD/MLD processes for OE anode materials, an empirical method for simplifying source temperature's optimization in ALD/MLD based on thermogravimetric analysis was developed. The OE anode materials showed similar intrinsic electrochemical performance metrics as previously measured with conventional electrodes with bulk materials. As the thin-film electrodes deposited from the gas phase do not contain any additives that are usually mixed with the active material, they can be considered a perfect model for studying the electrode materials' intrinsic properties. The post-mortem X-ray analysis of the cycled electrodes showed amorphization of the active material whenever the charge-discharge voltage plateau was lost. The performance decay is proposed to be caused by the excess lithiation of the aromatic core and subsequent side reaction. Pioneering work with three new ALD/MLD processes for possible Li-organic protective coatings was accomplished in this thesis. One of the processes utilized CO2 for the first time in the ALD/MLD process to deposit lithium alkyl carbonates. The lithium alkyl carbonates are an exciting group of materials because they are abundant in the organic part of the solid electrolyte interphase (SEI), forming naturally in the LIBs. This development allows the depositions of artificial SEI coatings. Furthermore, films of dilithium-1,4-benzenedisulfonate were deposited, diffraction patterns reported, and performance evaluated. The performance still needs to be improved, and the Li-organic coatings applied on conventional electrodes, but the groundwork is now laid down.",

keywords = "atomic/molecular layer deposition, lithium-ion battery, organic electrode, lithium-organic coating, atomi/molekyylikerroskasvatus, litiumioniakku, orgaaninen elektrodi, litiumorgaaninen pinnoite, atomic/molecular layer deposition, lithium-ion battery, organic electrode, lithium-organic coating",

author = "Juho Heiska",

year = "2021",

language = "English",

isbn = "978-952-64-0331-1",

series = "Aalto University publication series DOCTORAL DISSERTATIONS",

publisher = "Aalto University",

number = "48",

address = "Finland",

school = "Aalto University",

}

TY - THES

T1 - Development of Li-Organic Battery Materials with Atomic/Molecular Layer Deposition

AU - Heiska, Juho

PY - 2021

Y1 - 2021

N2 - Li-ion battery (LIB) is a piece of the puzzle for solving the present climate and energy crisis. Hence, the adaptation of LIBs is rapidly increasing, which has evoked severe concerns about the abundance, sustainability, and recyclability of the electrode raw materials. Cycle life is one of the main parameters regarding the sustainability of the LIBs, and it can be improved by protecting the active materials with suitable coatings. The scope of this thesis was twofold: (i) to challenge new organic electrode (OE) materials as more sustainable alternatives to current electrode materials, and (ii) to develop new Li-organic protective coating materials for the LIB electrodes. The gas-phase atomic/molecular layer deposition (ALD/MLD) thin-film technique provides unique advantages for both applications, and it was comprehensively utilized in this thesis. The focus was on developing new Li-organic ALD/MLD processes, which are still scarce in the literature. The overall goal was to show the applicability, benefits, and uniqueness of ALD/MLD technology to deposit various Li-organic materials for potential battery applications. In addition to five new ALD/MLD processes for OE anode materials, an empirical method for simplifying source temperature's optimization in ALD/MLD based on thermogravimetric analysis was developed. The OE anode materials showed similar intrinsic electrochemical performance metrics as previously measured with conventional electrodes with bulk materials. As the thin-film electrodes deposited from the gas phase do not contain any additives that are usually mixed with the active material, they can be considered a perfect model for studying the electrode materials' intrinsic properties. The post-mortem X-ray analysis of the cycled electrodes showed amorphization of the active material whenever the charge-discharge voltage plateau was lost. The performance decay is proposed to be caused by the excess lithiation of the aromatic core and subsequent side reaction. Pioneering work with three new ALD/MLD processes for possible Li-organic protective coatings was accomplished in this thesis. One of the processes utilized CO2 for the first time in the ALD/MLD process to deposit lithium alkyl carbonates. The lithium alkyl carbonates are an exciting group of materials because they are abundant in the organic part of the solid electrolyte interphase (SEI), forming naturally in the LIBs. This development allows the depositions of artificial SEI coatings. Furthermore, films of dilithium-1,4-benzenedisulfonate were deposited, diffraction patterns reported, and performance evaluated. The performance still needs to be improved, and the Li-organic coatings applied on conventional electrodes, but the groundwork is now laid down.

AB - Li-ion battery (LIB) is a piece of the puzzle for solving the present climate and energy crisis. Hence, the adaptation of LIBs is rapidly increasing, which has evoked severe concerns about the abundance, sustainability, and recyclability of the electrode raw materials. Cycle life is one of the main parameters regarding the sustainability of the LIBs, and it can be improved by protecting the active materials with suitable coatings. The scope of this thesis was twofold: (i) to challenge new organic electrode (OE) materials as more sustainable alternatives to current electrode materials, and (ii) to develop new Li-organic protective coating materials for the LIB electrodes. The gas-phase atomic/molecular layer deposition (ALD/MLD) thin-film technique provides unique advantages for both applications, and it was comprehensively utilized in this thesis. The focus was on developing new Li-organic ALD/MLD processes, which are still scarce in the literature. The overall goal was to show the applicability, benefits, and uniqueness of ALD/MLD technology to deposit various Li-organic materials for potential battery applications. In addition to five new ALD/MLD processes for OE anode materials, an empirical method for simplifying source temperature's optimization in ALD/MLD based on thermogravimetric analysis was developed. The OE anode materials showed similar intrinsic electrochemical performance metrics as previously measured with conventional electrodes with bulk materials. As the thin-film electrodes deposited from the gas phase do not contain any additives that are usually mixed with the active material, they can be considered a perfect model for studying the electrode materials' intrinsic properties. The post-mortem X-ray analysis of the cycled electrodes showed amorphization of the active material whenever the charge-discharge voltage plateau was lost. The performance decay is proposed to be caused by the excess lithiation of the aromatic core and subsequent side reaction. Pioneering work with three new ALD/MLD processes for possible Li-organic protective coatings was accomplished in this thesis. One of the processes utilized CO2 for the first time in the ALD/MLD process to deposit lithium alkyl carbonates. The lithium alkyl carbonates are an exciting group of materials because they are abundant in the organic part of the solid electrolyte interphase (SEI), forming naturally in the LIBs. This development allows the depositions of artificial SEI coatings. Furthermore, films of dilithium-1,4-benzenedisulfonate were deposited, diffraction patterns reported, and performance evaluated. The performance still needs to be improved, and the Li-organic coatings applied on conventional electrodes, but the groundwork is now laid down.

KW - atomic/molecular layer deposition

KW - lithium-ion battery

KW - organic electrode

KW - lithium-organic coating

KW - atomi/molekyylikerroskasvatus

KW - litiumioniakku

KW - orgaaninen elektrodi

KW - litiumorgaaninen pinnoite

KW - atomic/molecular layer deposition

KW - lithium-ion battery

KW - organic electrode

KW - lithium-organic coating

M3 - Doctoral Thesis

SN - 978-952-64-0331-1

T3 - Aalto University publication series DOCTORAL DISSERTATIONS

PB - Aalto University

ER -

Development of Li-Organic Battery Materials with Atomic/Molecular Layer Deposition

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