science on interfacial ion dynamics for solid state ionics … · 2020. 4. 7. · project title:...

Newsletter Vol.1

Interface lonics towardSustainable Society

Science on Interfacial Ion Dynamics for Solid State Ionics Devices

2019 – 2023 Japan Society for the Promotion of ScienceGrant-in-Aid for Scientific Research on Innovative Areas

Greetings | Contents2

Contents

Solid-solid interfaces generate entirely new functions that differ from the

intrinsic nature of the solid material. In this project, the unique interfacial ion

dynamics around the hetero/homo interfaces of solid-state ionics materials

(SSIMs) are systematically investigated. The goal is to establish design prin-

ciples for fast ion transport and concentrated ion storage around interfaces,

that is, “Interface IONICS.”

“Interface IONICS” is closely related to the development of a sustainable

society. For example, “Interface IONICS” clarifies issues related to electrode/

solid electrolyte interfaces in advanced energy storage devices such as all-

solid-state batteries and all-solid-state capacitors. Additionally, it provides

clear guidelines of interface regulations to further improve devices toward

faster charge-discharge reactions and higher energy densities.

We appreciate your support.

Principal Investigator

Nagoya University, Yasutoshi IRIYAMA

Greetings

Project Outline 3

Research Objectives 3

Missions and Members 4

Model Interface (Gp-A01) 6

7 Advanced Analysis (Gp-A02) 7

8 Computational & Data Science (Gp-A03) 8

9 Design of Functional Interface (Gp-A04) 9

Research Achievements 10

3Project Outline | Research Objectives

Interface IONICS

Solid-State IONICS Materials (SSIMs)

φEL

EF

φSE

M+

Interface

IonElectrical Factor

Insertion Electrode

Electron Energy

Semiconductor Engineering

Conduction Band Conduction Band

V

Valence BandValence Band

Strain

Orientation

Mutual DiffusionLayer

Reaction PhaseFormation

ActivityConcentration

p -TypeSemiconductor

Solid Electrolyte

Chemical Factor

ElectrochemicalFactor

Mechanical (or Structural) Factor

Correlation Image of Complex Factorse.g. Insertion Electrode/Solid Electrolyte Interface

Project Outline

Research Objectives

Project Title : Science on Interfacial Ion Dynamics for Solid State Ionics Devices

(Interface IONICS)

Research Project Number : 19H05812 (Grant-in-Aid for Scientific Research on Innovative Areas)

Researcher Number : 30335195

Project Term : FY2019–2023

Budget Allocation : 1,127,800 Thousand Yen (ca. 10 million dollars)

Homepage Address : https://interface-ionics.jp/en/index.html

There are two types of solid-state ionics materials (SSIMs): insertion electrode materials (electrodes) and solid electrolytes. In the former, electrons or holes move faster than ions. In contrast, ions move faster than electrons or holes in the latter. When these two SSIMs combine, an equilibrium state is reached through the rearrangement of all charged carriers (electrons, holes, and ions). At equilibrium, their electrochemical potentials become equal. Consequently, the electrode/solid electrolyte interface realizes unique properties with each intrinsic SSIM due to factors such as space charge layer formation and mechanical relaxation (strain distribution) that provide unique interfacial ion dynamics. The aim of this project is to investigate the physical and chemical modulations around interfaces in detail and establish interface design principles, which will make it possible to generate novel functions around

interfaces. This project integrates chemistry, physics, advanced measurements, computational and data sci-ence, and material science. It consists of four research groups.

Gp-A01 fabricates model interfaces using materials such as single crystalline substrates and epitaxial thin films and investigates their interfacial ion dynamics. Gp-A02 analyzes the properties around the interface including the modulation and distribution of voltage, ion concentration, chemical potential, and local struc-ture using advanced measurements. Gp-A03 clarifies the distribution of ions and electrons and their dynam-ics around the interface using multi-scale theoretical calculations and informatics analyses. Gp-A04 devel-ops advanced materials with an emphasis on metasta-ble phases with lattice defects and lattice strains by combining crystalline and amorphous SSIMs.

Theoretical Analysis

AnalysisExperimental

Model SamplesPrincipal Investigator

Yasutoshi IRIYAMANagoya Univ., Electrochemistry


Yoshitaka TATEYAMANIMS, Computational Interface Science

A03 Computational & Data Science

Co-Investigators

Tsuyoshi OHNISHI NIMS, Thin-Film Growth

Toshinori TAISHI Shinshu Univ., Bulk Crystal Growth

Yumi TANAKA Tokyo Univ. of Science, Solid-State Ionics

Kaoru DOKKO Yokohama National Univ., Electrochemistry

Masaki MATSUI Kobe Univ., Inorganic Materials Chemistry

Co-Investigators

Gen INOUE Kyushu Univ., Macro-Transport Simulation

Hieu Chi DAM JAIST, Data-Driven AI

Masanobu NAKAYAMA Nagoya Institute of Technology, Materials Simulation

Shunsuke MUTO Nagoya Univ., Properties of Nanomaterials

A01 ModelInterface

Fabrication of Model Interfaces of Solid-State Ionics Materials and their Fundamental Research on Interfacial Ion Dynamics

Theoretical, Computational, and Data Science of the Interfacial Ion Dynamics in Solid-State Ionics Materials

Collaborative network for research on Interface IONICS

Shigeaki ZAIMA ProfessorMeijo Univ.Semiconductor Engineering

Masahiro TATSUMISAGO PresidentOsaka Prefecture Univ.Inorganic Materials Chemistry

Shinji TSUNEYUKIProfessorThe Univ. of TokyoCondensed Matter Physics Theory, Computational Physics

Minoru INABAProfessorDoshisha Univ.Electrochemistry, Inorganic Industrial Chemistry


Expe

rimen

tal D

ata

4 Missions and Members

Evaluation Committees

Missions and Members

Experimen

tal A

naly

sis


New Devic

es &

Mat

eria

ls

AnalysisExperimental


Naoaki YABUUCHIYokohama National Univ., Solid-State Electrochemistry


Koji AMEZAWATohoku Univ., Solid-State Ionics

A02 Advanced Analysis

A04 Design of Functional Interface

New theory

Co-Investigators

Masashi OKUBO The Univ. of Tokyo, Solid-State Chemistry

Daisuke KAN Kyoto Univ., Solid-State Chemistry

Ayuko KITAJOU Yamaguchi Univ., Inorganic Chemistry

Akitoshi HAYASHI Osaka Prefecture Univ., Inorganic Materials Chemistry

Co-Investigators

Kazutaka IKEDA KEK, Neutron Science

Koji OHARA JASRI, Structural Analysis for Amorphous Materials

Akichika KUMATANI Tohoku Univ., Surface Science

Naoaki KUWATA NIMS, Physical Chemistry

Yukio TAKAHASHI Tohoku Univ., Synchrotron X-ray Imaging

Shigeo MORI Osaka Prefecture Univ., Materials Physics

Kazuo YAMAMOTO JFCC, Electron Microscopy

Physico-Chemical Analysis of Solid-State Ionics Interfaces by Integrating Advanced Measurement Techniques

Development of Novel FunctionalInterfaces of Solid-State Ionics Devices and New Solid-State Ionics Materials

Shu YAMAGUCHISpecially Appointed ProfessorNational Institution for Academic Degrees and Quality Enhancement of Higher EducationSolid-State Ionics

Kohei UOSAKIFellowNational Institute for Materials ScienceSurface Physical Chemistry

Kiyoshi KANAMURA ProfessorTokyo Metropolitan Univ.Electrochemistry, Battery, Energy Chemistry

Hideki IBA Advanced Material Engineering Div. CPEToyota Motor CorporationNew Generation Batteries, Industry-Academia Collaboration

5Mission and Members

Observers

6 Missions and Members

Gp-A01 Model Interface

Yasutoshi IRIYAMA

Nagoya Univ. Electrochemistry

Tsuyoshi OHNISHI

NIMS Thin-Film Growth

Toshinori TAISHI

Shinshu Univ. Bulk Crystal Growth

Yumi TANAKA

Tokyo Univ. of Science Solid-State Ionics

Kaoru DOKKO

Yokohama National Univ.Electrochemistry

Masaki MATSUI

Kobe Univ.Inorganic MaterialsChemistry

Thin-film materials

Members

Single crystallineLixLa(1-x)/3NbO3(LLNbO)

Epitaxial La(2/3-x)Li3xTiO3 (LLTO) thin film

wet process epitaxial

organic solid

Preparation of model materials Tailored interface Fundamental analysis of interfacial ion dynamics

metal/solid electrolyte (blocking) semiconductor/solid electrolyte grain boundary

Insertion electrode/solid electrolyte metal/solid electrolyte (non-blocking) hetero solid electrolyte interface

amorphous

single crystal poly crystal

atomic layer

Ion charge interface

Ion transfer interfaceBulk materials

Co-InvestigatorsPrincipal Investigator

Gp-A01 develops model interface systems such as electrode/solid elec-trolyte interfaces, inorganic/organic solid electrolyte interfaces, and grain boundaries. Interfacial ion dynamics play important roles in the design of solid-state ionics devices such as all-solid-state batteries and capacitors. Gp-A01 uses thin-film technologies (e.g., pulsed laser deposition, atomic layer deposition, and sputtering) and single crystalline materials, among others, to develop model interfaces as well as investigate their interfacial ion transfer and ion accumulation properties using electrochemical methods. The resultant model interfaces are analyzed in Gp-A02.

7Missions and Members

Koji AMEZAWA

Tohoku Univ. Solid-State Ionics

Kazutaka IKEDA

KEK Neutron Science

Co-Investigators

Akichika KUMATANI

Tohoku Univ. Surface Science

Yukio TAKAHASHI

Tohoku Univ. Synchrotron X-ray Imaging

Koji OHARA

JASRI Structural Analysis for Amorphous Materials

Naoaki KUWATA

NIMS Physical Chemistry

Shigeo MORI

Osaka Prefecture Univ. Materials Physics

Kazuo YAMAMOTO

JFCC Electron Microscopy

Gp-A02 Advanced Analysis

MembersPrincipal Investigator

Unique ion transport/storage phenomena at solid-state interfaces are often attributed to anomalous physical/chemical states modulated locally at interfaces. Gp-A02 comprehensively reveals the physical/chemical char-acteristics of anomalous and local states such as ion concentration, elec-tric/chemical/electrochemical potentials, micro/local structures, strain/distortion, and ion diffusion from multiple viewpoints by combining various novel and advanced analytical techniques. Through systematic analyses of Gp-A01’s and Gp-A04’s model interfaces together with Gp-A03’s theoretical calculation, scientific principles to design high performance solid-state interfaces are established based on theoretical rationales.

8 Missions and Members8

Yoshitaka TATEYAMA

NIMSComputational Interface Science

Gen INOUE

Kyushu Univ. Macro-Transport Simulation

Hieu Chi DAM

JAIST Data-Driven AI

Masanobu NAKAYAMA

Nagoya Institute ofTechnology Materials Simulation

Shunsuke MUTO

Nagoya Univ. Properties of Nanomaterials

Co-Investigators

Gp-A03 Computational & Data Science


To construct a theory for “Interface IONICS,” Gp-A03 introduces two strategies; computational and data science approaches. For the former, equilibrium/steady states and dynamics of electrons and ions around solid-solid interfaces are investigated using multiscale computational approaches through DFT (density functional theory) level calculations and continuum models. In addition, data-driven AI science approaches are implemented to elucidate large-scale structure-property relations in the observed images and spectra. Through these findings and deep collabora-tions with the other groups (Gp-A01, A02 and A04), a new theoretical framework for “Interface IONICS” is established.

9Missions and Members

Naoaki YABUUCHI

Yokohama National Univ.Solid-State Electrochemistry

Masashi OKUBO

The Univ. of TokyoSolid-State Chemistry

Daisuke KAN

Kyoto Univ. Solid-State Chemistry

Ayuko KITAJOU

Yamaguchi Univ. Inorganic Chemistry

Akitoshi HAYASHI

Osaka Prefecture Univ. Inorganic Materials Chemistry

E/V

New Materials Interface Engineering

New Functionality through Interface Engineering of Solid-State Ionics Materials

Design of New Solid-State Ionics Materials(Inorganic, Organic, Polymer, and Complex Materials)

Nano/Amorphous Materials

Enriched Grain Boundary ➡ Better Functionality

Conventional LiMnO2

LiMnO2 with Enriched Grain Boundary

Q / mAh/g

Gp-A04 Design of Functional Interface

Co-Investigators


Gp-A04 studies solid-state ionics materials and realizes new functional-ities through interface engineering. For instance, charge accumulation and migration of charge carriers are highly dependent on the interface struc-tures of materials. Nevertheless, the origin is not clearly understood. One example of an electrode material for lithium storage is LiMnO2. Although LiMnO2 prepared by a conventional route shows an insufficient ability for charge accumulation, LiMnO2 with enriched grain boundaries shows a much better functionality as an electrode material. Gp-A04 establishes the basic science related to the interface structures of solid-state ionics materials, which will be the foundation for innovative solid-state energy storage sys-tems and other functional solid-state devices.

Research Achievements10

Peer-reviewed Papers and Proceedings (8)Keynote/Invited lectures (36)

Highlight from Interface IONICSA sodium-ion sulfide solid electrolyte with unprecedented conductivityat room temperature

A. Hayashi, N. Masuzawa, S. Yubuchi, F. Tsuji, C. Hotehama, A. Sakuda and M. Tatsumisago

Nature Communications, 10: 5266 (2019). DOI: https://doi.org/10.1038/s41467-019-13178-2Published on November 20, 2019

AbstractA key material for realizing all-solid-state recharge-

able batteries is an excellent inorganic superionic con-ductor. Here, we demonstrate a sulfide superionic conductor, Na2.88Sb0.88W0.12S4, with conductivity supe-rior to that of the benchmark electrolyte, Li10GeP2S12. Partial substitution of antimony in Na3SbS4 with tung-sten induces the generation of sodium vacancies and tetragonal to cubic phase transition, resulting in the highest room-temperature conductivity of 32 mS cm−1

for a sintered body, Na2.88Sb0.88W0.12S4. Moreover, this

Research Achievements (Jul.2019 - Dec.2019)

sulfide has additional advantages: it generates a negli-gible amount of harmful hydrogen sulfide in humid atmosphere and it can be densified at much lower sin-tering temperatures than those (>1000°C) of typical oxide sodium ion conductors, Na3Zr2Si2PO12 and β-alumina. The discovery of the superior sodium ion conductor boosts the ongoing research for solid-state rechargeable battery technology with high safety, cost-effectiveness, large energy, and power density.

Osaka Prefecture University press release URL (Japanese)https://www.osakafu-u.ac.jp/press-release/pr20191121/

Group URLhttp://www2.chem.osakafu-u.ac.jp/ohka/ohka2/english/index.html

11

AbstractHigh interfacial resistance between a cathode and

solid electrolyte (SE) has been a long-standing problem for all-solid-state batteries (ASSBs). Though thermody-namic approaches suggested possible phase transfor-mations at the interfaces, direct analyses of the ionic and electronic states at the solid/solid interfaces are still crucial. Here, we used our newly constructed scheme for predicting heterogeneous interface structures via the swarm-intelligence-based crystal structure analysis by particle swarm optimization method, combined with density functional theory calculations, and systemati-cally investigated the mechanism of Li-ion (Li+) trans-port at the interface in LiCoO2 cathode/β-Li3PS4 SE, a representative ASSB system. The sampled favorable interface structures indicate that the interfacial reac-tion layer is formed with both mixing of Co and P cations

Highlight from Interface IONICSLi+ Transport Mechanism at Heterogeneous Cathode/Solid Electrolyte Interface in All-Solid-State Battery via First-Principles Structure Prediction Scheme

Bo Gao, Randy Jalem, Yanming Ma, Yoshitaka Tateyama

Chem. Mater. 32, 85-96 (2020).DOI: https://doi.org/10.1021/acs.chemmater.9b02311Published on November 20, 2019

and mixing of O and S anions. The calculated site- dependent Li chemical potentials μLi(r) and potential energy surfaces for Li+ migration across the interfaces reveal that interfacial Li+ sites with higher μLi(r) values cause dynamic Li+ depletion with the interfacial elec-tron transfer in the initial stage of charging. The Li+-depleted space can allow oxidative decomposition of SE materials. These pieces of evidence theoretically confirm the primary origin of the observed interfacial resistance in ASSBs and the mechanism of the resis-tance decrease observed with oxide buffer layers (e.g., LiNbO3) and oxide SE. The present study also provides a perspective for the structure sampling of disordered heterogeneous solid/solid interfaces on the atomic scale.

NIMS press release URL (Japanese)https://www.nims.go.jp/news/press/2019/11/201911210.html

Group URLhttps://www.nims.go.jp/group/cs/en/

Publisher/ContactOffice for Scientific Research on Innovative Areas:Science on Interfacial Ion Dynamics for Solid State Ionics Devices

TEL: +81-52-789-3576E-mail: [email protected]://interface-ionics.jp/en/index.html Date of issue: March 2020

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