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Advances in Materials Sciences Energy Technology and Environmental Engineering Proceedings of the International Conference on Materials Science MSETEE
2016 Zhuhai China May 28 29 2016 1st Edition Aragona
Robert J. Howlett, Bournemouth University and KES International, Shoreham-by-Sea, UK
John Littlewood, School of Art and Design, Cardiff Metropolitan University, Cardiff, UK
Lakhmi C. Jain, KES International, Shoreham-by-Sea, UK
The book series aims at bringing together valuable and novel scientific contributions that address the critical issues of renewable energy, sustainable building, sustainable manufacturing, and other sustainability science and technology topics that have an impact in this diverse and fast-changing research community in academia and industry.
The areas to be covered are
• Climate change and mitigation, atmospheric carbon reduction, global warming
• Sustainable transport, smart vehicles and smart roads
• Information technology and artificial intelligence applied to sustainability
• Big data and data analytics applied to sustainability
• Sustainable food production, sustainable horticulture and agriculture
• Sustainability of air, water and other natural resources
• Sustainability policy, shaping the future, the triple bottom line, the circular economy
High quality content is an essential feature for all book proposals accepted for the series. It is expected that editors of all accepted volumes will ensure that contributions are subjected to an appropriate level of reviewing process and adhere to KES quality principles.
The series will include monographs, edited volumes, and selected proceedings.
Ambesh Dixit · Vijay K. Singh · Shahab Ahmad
Editors
Energy Materials and Devices
Proceedings of E-MAD 2022
Editors
Ambesh Dixit
Department of Physics
Indian Institute of Technology Jodhpur
Jodhpur, Rajasthan, India
Shahab Ahmad
Department of Physics
Indian Institute of Technology Jodhpur
Jodhpur, Rajasthan, India
Vijay K. Singh
Department of Physics
Indian Institute of Technology Jodhpur
Jodhpur, Rajasthan, India
ISSN 2662-6829
ISSN 2662-6837 (electronic)
Advances in Sustainability Science and Technology
ISBN 978-981-99-9008-5 ISBN 978-981-99-9009-2 (eBook) https://doi.org/10.1007/978-981-99-9009-2
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Patrons
Professor Santanu Chaudhury, Director, IIT Jodhpur
Professor S. R. Vadera, Deputy Director, IIT Jodhpur
Volume Editors
Professor Ambesh Dixit
Dr. Vijay Kumar Singh
Dr. Shahab Ahmed
Editorial Board
Professor A. Manthiram, University of Texas, Austin, USA
Professor Ram Katiyar, University of Puerto Rico, USA
Professor Sungjune Park, JBNU, South Korea, (Currently at SKKU, Korea)
Dr. Narendra Kumar, Ex-Director, DLJ
Professor M. S. R. Rao, IIT Madras
Professor Ashish Garg, IIT Kanpur
Professor K. L. Yadav, IIT Roorkee,
Professor Laltu Chandra, IIT BHU, (Currently at IIT Kanpur)
Professor Neeraj Khare, IIT Delhi
Professor Raju Gupta, IIT Kanpur
Professor Rajeev Prakash, IIT BHU
Professor L. M. Das, IIT Delhi
Professor Sagar Mitra, IIT Bombay
Professor Pratibha Sharma, IIT Bombay
Professor Yogesh K. Sharma, IIT Roorkee
Professor Amreesh Chandra, IIT Kharagpur
Professor Prabeer Barpanda, IISc Bangalore
Professor Sudakar Chandran, IIT Madras
Professor Preetam Singh, IIT BHU
Professor Gopukumar, CECRI, Karaikudi
Professor K. Ramesha, CECRI, Karaikudi
Professor Ashutosh K. Dubey, IIT BHU
Professor Shobhana Narasimhan, JNCASR, Bangalore
Dr. M. B. Sahana, ARCI, Madras
Preface
IIT Jodhpur has taken initiative to address the current challenges and opportunities in renewable energy towards India’s Urja Aatmnirbharta Mission. This conference is an effort along the same line. Energy Materials and Device (EMAD) technologies emphasized on current developments in designing novel materials for renewable energy generation, storage, and their integration for real applications such as high energy density batteries and green hydrogen for hybrid electric vehicles (HEVs), hydrogen fuel cell for distributed energy needs.
This national conference on energy materials and devices (NCEMAD 2022) is organized during December 16–18, 2022 at Indian Institute of Technology Jodhpur, India. The conference provided a platform for more than hundred delegates from different parts of India, actively participated in the conference and shared their findings. In addition, several renowned speakers were invited for talks and sharing their experiences in the field of renewable energy. This conference provides the status in the field of renewable energy including lithium and beyond lithium-ion energy storage technologies and green hydrogen generation/storage together with the current issues and challenges, especially in Indian Context.
Jodhpur, India
Vijay K. Singh
Shahab Ahmad
Ambesh Dixit
Director’s Message
It gives me immense pleasure in hosting a National Conference on EnergyMaterials and Devices (EMAD) 2022, during 16–18 December 2022 at Indian Institute of Technology Jodhpur (IITJ). It has initiated research and development efforts towards energy secured Aatmnirbhar Bharat, i.e., self-reliant India, in aligned with the policies of Government of India towards zero carbon emission by 2070. IIT Jodhpur has realized:
• to move from conventional singular educational approach towards interdisciplinary creativity-oriented approach.
• to explore the design and research methodology in the areas of artificial intelligence, design engineering, digital twin, health and energy to address the last person, meeting the socio-economic challenges with cost effective solutions.
• to create work pool of scientists/researchers with core strengths in science and engineering capable of finding innovative solutions with entrepreneur spirit. ix
The energy is one of the most important vertical for country’s self-reliance, which is the primary ingredient for industrial growth in conjunction with every day needs. The challenges and solutions in energy related issues are multidisciplinary and solutions cannot be driven from a single research domain. In continuation with the above inter/multi-disciplinary philosophy, the National Conference on Energy Materials and Devices (EMAD) 2022 during December 16–18, 2022 is focused on energy storage solutions even beyond commercially available lithium ion energy storage. It seems essential for country like India, where lithium’s dependency is on other countries. Thus, sustainable energy storage for India should look for equivalent or better alternatives. Further, hydrogen is another important vertical in energy sector and EMAD-2022 is equally focusing on its generation, storage, and applications including hydrogen vehicles.
The conference brings design and development of materials together with their technological and industrial applications ranging from small scale to large scale applications such as hybrid/electric vehicles (H/E-Vs), and even fuel cells for hydrogen vehicles (HVs). EMAD 2022 consists of experts in energy domains and their knowledge sharing will throw light on real issues and challenges with potential solutions for energy problems. Thus, EMAD will provide the most recent updates in the field of energy and the outcomes will be a milestone towards Aatmnirbhar Bharat, emphasizing on Energy for All. I am hopeful that the researchers especially young minds will be motivated to contribute further towards the country’s energy needs. I wish all the best for the success of EMAD 2022.
With Season’s greetings!
Prof. Santanu Chaudhury Director, IIT Jodhpur
Akhilesh Pandey and Ambesh Dixit
Jitendra K. Yadav, Brajesh Tiwari, and Ambesh Dixit
Kruti K. Halankar and Balaji P. Mandal 5 Diffusion and Ion-Ion Correlations in
Hema Teherpuria, Sapta Sindhu Paul Chowdhury, Sipra Mohapatra, Prabhat K. Jaiswal, and Santosh Mogurampelly 6
Shahab Ahmad
Ganji Rithvik, Kartik Kumar, Ramdutt Arya, and Kapil Pareek
8
Bharti Rani, Jitendra Kumar Yadav, and Ambesh Dixit
9
Low-Cost Aqueous Rechargeable Iron-Ion Battery in Ambient Conditions Using C3 N4 -Based Cathode .......................... 103
Jitendra Kumar Yadav, Bharti Rani, and Ambesh Dixit
10 High-Performance Aqueous Asymmetric Supercapacitor Based on Hybrid Electrodes 115 Ravi Vikash Pateriya, Shweta Tanwar, and A. L. Sharma
11 Exfoliated Graphite as a Potential Host for Zinc Oxide Nanorods-Based Symmetric Flexible Supercapacitor 125 Priyanka Saini, Bharti Rani, Jitendra Kumar Yadav, Piyush Choudhary, Priyambada Sahoo, and Ambesh Dixit
12 SrTiO3 /CNT/PANI Ternary Composite for Supercapacitor Applications ..................................................
Rosmy Joy and Suja Haridas
13 Enhance the Electrochemical Parameters of Supercapacitor Using ZnO Based Electrode Material ........................... 149 Manisha Yadav, Sanju Choudhari, Pradeep Kumar, Parmeshwar Lal Meena, Himmat Singh Kushwaha, and Pura Ram
14 Characterization and Analysis of (1-x) Ba0.96 Sr0.04 Zr0.1 Ti0.9 O3 –xNaNbO3 : A Study on Structural, Dielectric and Energy Storage Behaviour ........................
K. L. Yadav and Hemraj Lakra
Part II Hydrogen Generation and Storage
15 Recent Progress and Challenges in Hydrogen Storage Medium and Transportation for Boosting Hydrogen Economy 183 Anant Prakash Pandey, Vijay K. Singh, and Ambesh Dixit
16 Concentrated Solar Thermal-Based Hydrogen Generation: Some Recent Findings and a Proposal for Experiment Setup ...... 205 Deepank Arya, Kuldeep Awasthi, Gaurav Hedau, and Laltu Chandra
17 Waste Plastic Generated High-Performance Nanocomposites for Modern EDLC and LIB: A Two-Way Sustainable Approach .....................................................
Kriti Shrivastava and Ankur Jain
18 Effect of La-Ni-Based Alloys on Hydrogenation/ Dehydrogenation Properties of MgH2 ...........................
Mukesh Jangir, Priyanka Chholak, I. P. Jain, Tarun Patodia, and Ankur Jain
19 Au Nanoparticle Decorated g-C3 N4 /Bi2 S3 Photoanodes for Photoelectrochemical Water Splitting ........................ 259
Merin Joseph, Bhagatram Meena, Sebastian Nybin Remello, Challapalli Subrahmanyam, and Suja Haridas
20 Nanostructured Binder-Free Cost Effective SnS2
Electrocatalyst for Efficient Hydrogen Evolution Reaction 275
Minakshi Sharma, Yogesh Yadav, Chandra Prakash, Vijay K. Singh, and Ambesh Dixit
21 Nano-Engineered Vanadium Doped NiS Catalyst for Efficient
Electrochemical Water Splitting ................................ 287 Chandra Prakash, Priyambada Sahoo, Vijay K. Singh, and Ambesh Dixit
22 High Efficiency Zero Carbon Emission Oxy-Hydrogen (HHO) Generator .................................................... 299
S. Vinayak, Chandra Prakash, Ankit K. Yadav, Vijay K. Singh, Sudipto Mukhopadhyay, and Ambesh Dixit
Part III Energy Harvesting
23 Morphological Impact on ZnO Material for Designing Hydroelectric Cell—A Way to Harness Green Electricity by Water Splitting 313
Priyambada Sahoo, Chandra Prakash, Jyoti Shah, Ambesh Dixit, and R. K. Kotnala
24 Modeling Germanene Monolayer: Interaction Potentials and Insights into the Phonon Thermal Conductivity 325 Sourav Thapliyal, Sapta Sindhu Paul Chowdhury, and Santosh Mogurampelly
25 Synthesis and Characterization of SnS Nanoparticles by Hydrothermal Method ...................................... 337 Sanju Choudhari, Manisha Yadav, Pradeep Kumar, Parmeshwar Lal Meena, and Pura Ram
26 Performance Optimization of CuSbS2 Solar Cells by Numerical Simulation Using SCAPS-1D ...................... 349 Shankar Lal, Kinjal Patel, Jaymin Ray, Usha Parihar, Sushila, and S. S. Sharma
About the Editors
Dr. Ambesh Dixit (M.S. and Ph.D. from Wayne State University, MI, USA, and Masters and Bachelor from the University of Allahabad, Allahabad, India) is professor at the Indian Institute of Technology Jodhpur. He has wide experience in computational and experimental materials and device physics with a special emphasis on the design and development of materials for different applications. He is leading Advanced Materials and Device (A-MAD) Laboratory, and his current research efforts are in developing functional nanomaterials and related products for energy generation and storage including lithium and beyond lithium-ion energy storage materials and devices, H2 generation, and storage. He is an expert in multifunctional materials and was the first one to demonstrate that iron vanadate (FeVO4) is a multiferroic system to the scientific community. He has published more than 100 research articles, and two Indian patents are in progress.
Dr. Vijay K. Singh received his Master from Indian Institute of Technology Kanpur India, Bachelor and Ph.D. from Banaras Hindu University, Varanasi India. Then he moved to Jeonbuk National University, Jeonju, South Korea, for Postdoctoral Research. He is currently working as an inspire faculty in the Department of Physics Indian Institute of Technology Jodhpur, India. He has wide expertise in the atomically controlled synthesis and applications of carbon and transition metal chalcogenides-based quantum materials. He has developed high-speed 2D FET, 2D-0D heterostructure-based UV photodetector, and biosensor for cancer detection. His current research efforts are in developing the quantum materials-based next-generation electronic, optical, and biosensing devices. He is also working on generation, storage, and applications of green hydrogen. He has published more than 20 research articles in the journals of international repute.
Dr. Shahab Ahmad is working as an associate professor at the Department of Physics, Indian Institute of Technology (IIT) Jodhpur. Dr. Shahab has received Ph.D. in Physics from IIT-Delhi, India, in 2014. During Ph.D., he has been visiting researcher at NanoPhotonics Centre, Cavendish Laboratory, University
of Cambridge, UK. He has worked as a post-doctoral fellow at NanoManufacturing Centre, Department of Engineering, University of Cambridge, UK, from 2014–2017. Dr. Shahab has worked as an assistant professor at IIT Jodhpur and Centre for Nanoscience and Nanotechnology, Jamia Millia Islamia (Central University), New Delhi, India for two years. So far, he has authored more than 40 research articles in internationally reputed journals including Advanced Materials, Nano Letters, Advanced Energy Materials, Nature, ACS Nano, JACS, etc.
Part I
Batteries and Supercapacitors
Chapter 1
Na-Rich Layered Oxide Cathode Materials for High-Capacity Na-Ion Batteries: A Review
Priti Singh and Mudit Dixit
Abstract Over the last few decades, lithium-ion batteries (LIBs) have dominated the market of energy storage devices due to their wide range of applications ranging from grid–scale energy storage systems to electric vehicles (EVs). However, the increasing demand for sustainable energy sources and scarcity of lithium draws attention to other alternatives, such as Sodium-ion batteries (SIBs). SIBs are potential candidates for sustainable energy storage devices due to their high natural abundance and low cost of Na-based materials. However, the low specific capacity of standard cathodes and the poor cycle life of Na-rich cathodes still limit the practical application of SIBs for high-energy applications. This review summarizes the challenges and recent progress in the development of Na-rich layered cathode materials. We highlight some of the critical parameters that modulate the anionic redox in high-capacity Na-ion batteries. This review provides the present state of understanding and is expected to be helpful for the future design and development of improved Na-based cathode materials for high-energy applications.
Keywords Sodium-ion batteries · Density functional theory · Anionic redox · Layered-oxide based cathode materials
1 Introduction
Over the last decade, the demand for renewable energy has increased rapidly due to the adverse effect of the combustion of fossil fuels (which led to climate change, the greenhouse effect, and global warming). Presently, Li-ion batteries (LIBs) are known to dominate the market for large-scale energy storage devices and electrical vehicles
P. Singh · M. Dixit (B)
Advanced Materials Lab, CSIR-Central Leather Research Institute (CSIR-CLRI), Sardar Patel Road, Adyar, Chennai 600020, India
e-mail: muditdixit@clri.res.in
M. Dixit
Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, Uttar Pradesh 201002, India
A. Dixit et al. (eds.), Energy Materials and Devices, Advances in Sustainability Science and Technology, https://doi.org/10.1007/978-981-99-9009-2_1 3
Fig. 1 Screenshot to represent statistical update for growth in the sodium-ion batteries (SIBs) market depending upon the global demand. (Data from: www.custommarketinsights.com)
(EVs) due to their long cycle life, high coulombic efficiency, and high energy density [1]. However, the limitation of the low abundance of lithium and the high cost of Li-based materials make it challenging to fulfil the continuously growing demand for LIBs. The scarcity of lithium resources opens the door for new avenues to identify new materials that can be utilized for superior battery technologies. Among the various types of battery technologies, SIBs are recognized as one of the most promising candidates for sustainable energy technology due to the even global distribution of sodium and the low cost of Na-based raw materials [2, 3]. The global demand for SIBs has become visible from the gradual growth in the Na+ -ion battery market (Fig. 1).
In addition to various research communities, the leading industries are also working to utilize SIBs, such as Faradion, Aquion Energy, HiNa Battery Technology Co. Ltd, AMTE Power, Natron Energy, Contemporary Amperex Technology Co. Ltd (CATL), and Indigenous Energy Storage Technologies Pvt. Ltd. Although, lithium and sodium show similar chemical behavior, higher ionic radius (Na+ ,1.02 ´ Å, Li+ , 0.76 ´ Å)) and lower reduction potential of Na (Li, 3.04 V and Na, 2.71 V) than Li leads to lower specific capacity and power density of SIBs than LIBs. Similar to Li-ion batteries, SIBs also exhibit “rocking chair” behavior where Na-ion shuffles between cathode and anode through the electrolyte and vice versa; however, electrons pass through external circuits during charging and discharging [4]. Generally, cathode materials play an important role in dictating the properties of SIBs. In recent years, several research efforts have been made to improve the performance of SIBs. A number of research groups investigated the properties of different components (cathode, anode, and electrolyte) of SIBs. Various classes of cathode materials have
been identified that include polyanionic compounds [5–9], Prussian blue analogs (PBA) [10–12], organic compounds [13], and layered oxide cathode materials [3, 14–17]. Among the different classes of cathode materials, layered oxide-based cathode materials have gained significant attention due to the possibility to (i) use Van der Waals gaps for facile (de)intercalation and (ii) tune the electronic structure. However, the challenge of limited specific capacity in standard layered oxide cathode materials for SIBs still remains unsolved. Many strategies have been employed, such as structural modification, where the activity of cathode material can be tuned by alkali or transition metal substitution. A practical approach to achieve high specific capacity is the activation of anionic redox (redox due to oxygen) in Na-rich cathode materials in addition to the conventional cationic redox (redox due to the oxidation of transition metal). In the anionic redox process, the anions (oxygen ions) participate in the redox process (apart from conventional cationic redox) and leading to extra capacity. For instance, Na2 Mn3 O7 (Na-rich cathode material), delivers a high specific capacity (160 mAh g 1 ) due to the active participation of oxygen in the redox process [18]. There are various cathode materials reported previously that deliver a reasonable capacity, such as P2-Na0.67 Mn0.8 Fe0.2-x Tix O2 [19], P2-Na0.3 Ni0.3 Mn0.6 O2 [20], O3-NaVO2 [21], NaMn1/2 Fe1/2 PO4 [22]. Similarly, several Na-rich layered oxidebased cathode materials have been reported that deliver high specific capacity such as Na2 SeO3 ,[23]O3-Na(Ni2/3 Ru1/3 )O2 [24], Na2 Ru1-x Snx O3 [25], Na2 Zr1-x Yx O3 [26].
This review is focused on the recent progress on Na-rich layered oxide-based cathode materials for the development of high-energy-density SIBs. Herein, we highlight the challenges in attaining the reversible anionic redox in 3d-transition metal-based cathode material. Additionally, we discuss how 4d-/5d-transition metalbased cathode materials offer reversible anionic redox for high-capacity SIBs. We also discuss the effect of elemental doping (4d or 5d transition metal substitution in 3d transition metal-based cathode material) on dealing with some of the major limitations of SIBs, such as phase transitions, voltage hysteresis, capacity fading, and molecular O2 loss. Further, we discuss the key parameters that are required to obtain reversible anionic redox in Na-ion batteries. We highlight some of the important challenges and opportunities to improve the performance of existing cathode materials.
2 Layered-Oxide Cathode Materials
Layered oxide-based cathode materials are generally represented as Ax MO2 (A=Li+ / Na+ ,M = transition metal). These cathode materials are further classified as O3, O3’, P3, O2, and P2 type of layered structures where O represents the octahedral arrangement of Na+ -ion and 3 shows the number of transition metal oxide layers [27]. On the other hand, the P2-type structure represents the prismatic coordination of Na+ -ion, where ‘2’ indicates the number of transition metal oxide layers within the unit cell. In the case of O3-type cathode material, transition metal layer (MO6 ) and
Na-layers (NaO6 ) are arranged in the ABCABC type of stacking pattern, whereas in the case of P2-type structure ABBAABBA type of layered arrangement is observed. Generally, O3-type materials exhibit relatively higher capacity than corresponding P2-type layered cathode materials, whereas P2-type materials have typically a lower Na+ -ion diffusion barrier than O3-type layered oxide materials. The O3’ represents the monoclinic distortion (due to the gliding of the TMO-layer) in the O3 phase. Despite the favorable properties of layered materials, Na-based layered oxide cathode materials fail to deliver as high a capacity as Li-based cathode materials. This could be addressed by introducing stable and reversible anionic redox in Na-rich sodium-ion batteries.
3 Origin of Reversible/Irreversible Anionic Redox
In 2013, Sathiya et al. demonstrated the cumulative participation of cationic and anionic redox in Sn-doped Li2 RuO3 cathode material using detailed experimental and computational methods [25]. Subsequently, Seo et al., based on their in-depth computational study, explained how specific structural features (linear Li-O-Li configuration) can be responsible for anionic redox in Li-rich cathode materials, Fig. 2 [28]. The authors reported that Li-rich cathode material exhibits linear Li-O-Li and Li-O-M (M = transition metal) type of arrangements. In these linear Li-O-Li configurations, the corresponding oxygen atom’s orbitals resemble the unhybridized O-2p state and occupy a high energy level (near the Fermi level), Fig. 2a, b, and d. Therefore the oxygen contribution near the Fermi level is increased in Li-/Na-rich cathode materials, resulting in the participation of oxygen in the redox process. However, in the case of linear Li-O-M (M = transition metal) type of arrangement (as noticed in the case of Li/NaTMO2 -type standard materials), the O2p state is unable to interact with the neighboring unhybridized O2p orbital due to the strong covalent bond between the TM and oxygen. Consequently, the cationic redox dominates over the anionic redox. Another strategy to increase the contribution of oxygen redox is the incorporation of electrochemically inactive elements. Seo et al. noticed that if Li-rich cathode material consists of linear Li-O-M’ (M’ = electrochemically inactive elements) configuration (in addition to Li-O-Li type of arrangement), the O2p states (corresponding to LiO-M’ arrangement) are free to interact with neighboring unhybridized O2p orbitals due to less directional bond between M’ and O. In the pursuit of understanding the fundamental chemistry of anionic redox, Yahia et al. identified the number of holes (ho ) as an indicator of anionic redox. They suggested that if the ho ≥ 1/3, reversible anionic redox takes place, Fig. 2c[29]. Additionally, the authors explained that the reversibility of anionic redox could also be defined in terms of charge transfer (ΔCT ) energy of the TM d-bands (the difference between bonding and antibonding states of the TM d-orbitals). They suggested that if ΔCT > Δσ O-O , then the reversible anionic redox is possible, whereas if the TM d-bands are present between σ* and π* orbitals, (Δσ O-O > ΔCT > Δπ O-O ), voltage hysteresis takes place due to formation of peroxo type of species (O2 2 ) and the third scenario is where the Δπ O-O > ΔCT , leading to an
irreversible anionic redox. Similarly, Doublet et al. explained the relation between the Mott-Hubbard parameter (U) and charge transfer (ΔCT ) energy in the following works [30]. The U-parameter represents the coulombic repulsion in d-orbitals of transition metal. They suggested that (i) if U << ΔCT , the coulombic repulsion within the d-orbitals is low, therefore, the TM-O bond exhibits a strong ionic bonding character. Consequently, the TM d-orbital occupies a high energy state above the O2p state (near Fermi level), and cationic redox occurs. (ii) If U/2 ~ ΔCT , the TM d-orbital shifts at the lower energy level and overlaps significantly with the O-2p band. This leads to a reductive coupling mechanism. (iii) The 3d, 4d or 5d transition metals with do electrons generally have U >> ΔCT , as explained in Fig. 2e. Therefore, O-2p bands are observed near to Fermi level, activating the anionic redox.
Fig. 2 Screenshots for a, b representation of specific structural feature responsible for oxygen participation in Li/Na-rich cathode material (Reprinted with permission from Ref. [32]. Copyright 2016 Springer Nature). c, d Graphical representation to observe reversible/irreversible anionic redox (Reprinted with permission from Ref. [33]. Copyright 2019 Springer Nature). e Pictorial representation of the relation between Hubbard U parameter and charge transfer parameter for anionic redox in SIBs (Reprinted with permission from Ref. [33]. Copyright 2017 Springer Nature)
4
3d Transition Metal-Based Cathode Material
In the case of LIBs, most of the 3d-transition metal-based layered oxide materials, LiMO2, are found to exhibit irreversible phase transitions during the delithiation process (except for Co3+ and Ni3+ ), whereas in the case of SIBs, the layered cathode materials, Nax MO2 (M=Ti to Ni) are found to show relatively favorable phase transition [31]. Billaud et al. reported that the β-NaMnO2 cathode material delivers a high specific capacity of 190 mAh g 1 [32]. The O3-NaCrO2 cathode material exhibits a reversible capacity of 120 mAh g 1 within the 2.0 to 3.6 V voltage window [33]. The O3-type NaFeO2 [34] and NaNiO2 [35], cathode materials were found to deliver high theoretical capacity. Gao et al. carried out a theoretical investigation on Narich Na2 MnO3 cathode material (Fig. 3a-b). The authors found that the Na2 MnO3 shows a high theoretical capacity, 315 mAh g 1 , due to the major contribution of oxygen in the redox process than cationic redox [36]. In this material, at high Na+ -ion de-intercalation levels, structural distortion takes place due to the absence of sufficient covalent bonding interaction between Mn4+ and oxygen. Although 3d transition metal-based Na-rich cathode material theoretically delivers high capacity (especially through the participation of oxygen in the redox process), the anionic redox leads to the formation of molecular oxygen and structural degradation at high voltages.
5 4d or 5d-Transition Metal-Based Cathode Materials
In contrast to 3d metals, 4d and 5d transition metals show strong covalent bonding interaction with lattice oxygen, which inhibits the release of molecular oxygen. Narich such as Na2 RuO3 [26, 37–39], Na2 ZrO3 [26], Na2 IrO3 [40] cathode materials involve the active participation of oxygen during the redox and still deliver a high capacity for SIBs. Tamaru et al. conducted structural and electrochemical analyses of Na-rich layered material (Na2 RuO3 )[37]. They observed that the Na2 RuO3 delivers a moderate capacity (~140 mAhg 1 ) through the cationic redox process (Ru4+ → Ru5+ ) at 2.8 V. Additionally, the authors also utilized the X-ray diffraction (XRD) technique to confirm the honeycomb type of ordering in TMO layer which is beneficial in extracting more than one electron during sodiation/de-sodiation process. Later on, moving one step ahead, Boisse et al. computed the density of states (DOS) for Ru and O and confirmed that Na2 RuO3 shows active participation of oxygen during the redox process (Fig. 3c) [38]. They reported that the honeycomb ordering in Na2 RuO3 helps raise the σ* antibonding state near the Fermi level, activating anionic redox and delivering a high capacity of 180 mAh g 1 . Kim and co-workers performed experimental and theoretical investigations to examine the range of the anionic redox reaction and structural changes to reveal how different interactions between cations and anions change as a function of Na deintercalation.[41]The authors suggested that at the initial degrees of desodiation (0.0 ≤ x ≤ 0. 5), cationic redox takes place where Na+ -ion was removed from 4 h site and the volume of
Fig. 3 Graphical screenshot to represent a the stacking pattern in Na2 MnO3 , b projected density of states (PDOS) for Mn and O (Reprinted with permission from Ref. [39]. Copyright 2019 John Wiley and Sons). c Schematic representation to show the effect of structural changes on the position of oxygen antibonding (σ * )energystatesinNa2 RuO3 (Reprinted with permission from Ref. [40]. Copyright 2016 Springer Nature). Screenshot for d voltage profile for Na3 RuO4 , e Raman spectra to show formation of peroxo species. (Reprinted with permission from Ref. [45]. Copyright 2018 Royal Society of Chemistry). Structural representation for f Li-doped NaMnO2 (Na0.6 Li0.2 Mn0.8 O2 ), g projected density of states to show oxygen participation (Reprinted with permission from Ref. [49]. Copyright 2016 American Chemical Society). Graphical screenshot for h projected density of states of NaNi1/3 Fe1/3 Mn1/3 O2 , i F -doped NaNi1/3 Fe1/3 Mn1/3 O2 cathode material. j and k screenshot to show the Na+ -ion diffusion pathway (Reprinted with permission from Ref. [49]. Copyright 2023 Elsevier)
the lattice increases due to increasing electrostatic repulsion between the oxygen of TMO layers (O2 - ∎ -O2 ). The anionic redox was observed for the composition of Na1-x Ru0.5 O1.5 (0.0 ≤ x ≤ 0.75). However, on further desodiation (0.75 ≤ x ≤ 1.0) the lattice structure gets destabilized due to the oxidation of lattice oxygen. Therefore, the Na-rich layered material with composition Na1-x Ru0.5 O1.5 (0.0 ≤ x ≤ 0.75) involves cumulative participation of cationic and anionic redox to deliver high capacity. Qiao et al. proposed the prototype Na-rich transition metal oxide cathode material, Na3 RuO4 which delivers a high capacity of 321 mAh g 1 after removal of 2.7 equivalent of Na+ -ion per formula unit [42]. Based on the advanced in-situ Raman spectroscopy technique, the authors suggested that the oxygen shows a major
contribution during the redox process due to the high oxidation state of Ru (Ru5+ ). In addition to this, the X-ray photoelectron spectroscopy (XPS) analysis for Ru5+ and On depict a significant shift in the peak position of oxygen during the charging and discharging process (peak position at 530.7 eV corresponds to the peroxo type of species). However, based on Ru-XPS spectra analysis, the participation of Ru was not clear. Later on, Otoyama et al. utilized X-ray powder diffraction-Scanning electron microscopy to elucidate the structural and electrochemical properties of Na3 RuO4 on Na+ -ion de-intercalation [43]. Additionally, the authors performed density functional theory (DFT + U) calculations to explain the change in oxidation state of Ru (Ru5+ → Ru6+ ) on desodiation. The experimental and computational investigations confirmed the participation of both cationic and anionic redox in this material (Fig. 3d-e). Hu et al. used the mRIXS (full-range mapping of resonant inelastic X-ray scattering) technique to confirm the participation of both Ru and O in the redox process [44]. Perez et al. reported a reversible anionic redox in Na-rich Na2 IrO3 cathode material, using projected density of states (PDOS) and crystal orbital overlap population (COOP) the authors demonstrated strong covalent interactions between Ir and O that might be responsible in stabilizing oxygen redox [40].
6 Mixed Transition Metal-Based Cathode Materials
Although 4d-and 5d-transition metal-based cathode materials play an important role in reversible anionic redox, the cost of 4d/5d transition metal still limits the practical application of these materials for SIBs. However, tuning the activity of 3d transition metal-based cathode material by minute doping with 4d/5d transition metal could help to stabilize oxygen redox in Na-ion batteries. Komaba et al. suggested that despite various phase transitions, the O3-type layered NaNi0.5 Mn0.5 O2 cathode material delivers a high reversible capacity, 185 mAh g 1 [45]. de la Llave et al. reported that the P2-Na0.6 Li0.2 Mn0.8 O2 delivers a high capacity of ~190 mAh g 1 within the voltage range of 2.0–4.0 V even after 100 cycles (Fig. 3f-g) [46]. Liu et al. studied the structural and electrochemical properties of F doped O3-type layered oxide cathode material, NaNi1/3 Fe1/3 Mn1/3 O1.95 F0.05 using experimental and computational methods (Fig. 3h-k) [47]. The authors noticed that fluorine doping significantly improves the Na+ -ion diffusion rate and enhances the covalent interaction between the transition metal and oxygen. This leads to high cycle stability with 84.1% capacity retention after 100 cycles. Song et al. carried out experimental (Raman and XPS spectroscopic analysis) and computational investigation on Na-rich Na2 TiO3 cathode material that delivers a reversible capacity (~217 mAh g 1 )[48]. To further enhance the performance of SIBs, they doped the Na2 TiO3 with Cr3+ -ion and observed the significant improvement in Na+ -ion diffusion rate, leading to a high capacity ~336 mAh g 1 . Additionally, 74% of capacity retention was observed after 1000 cycles with only 0.026% of capacity decay per cycle. NaFe1-x Nix O2 [34], Nax (Co2/3 Mn1/3 )O2 [49], Na(Ni1/2 Ti1/2 )O2 [50], and Na0.67 (Ni0.2 Mg0.1 Mn0.7 )O2 [51] are some of the structurally modified layered oxide-based cathode material for SIBs.
7 Challenges and Opportunities
Although we listed various successful examples of layered oxide cathode material above, some key limitations still hinder their practical applications. These include voltage hysteresis, irreversible oxygen loss, TM migration, and capacity decay.
Transition metal Migration and Irreversible Capacity loss: It was found that during the process of charging and discharging, TM ions migrate from TMO layers to Na-layers, blocking the Na+ -ion diffusion pathway. This leads to structural degradation and capacity loss. Irreversible TM migration disturbs the complete process of charging and discharging whereas reversible TM migration can be beneficial to the anionic redox process. The introduction of the “pillar effect” can mitigate the TM migration [52, 53].
Irreversible oxygen loss: In the case of Na-rich layered-oxide-based cathode materials, the specific structural feature, linear Na-O-Na configuration, mimics the unhybridized O2p state; hence O2p states are observed near the Fermi level. However, in some of the Na-rich materials, the number of such linear Na-O-Na configurations is more than the Na-O-M type of arrangement. Therefore, the number of labile oxygen increases on higher degrees of desodiation and leads to the formation of highly reactive species (O2 n → O2 ). This could be limited by strong covalent bonding interaction between the transition metal and oxygen. However, to reduce the possibility of irreversible oxygen loss, the Na-based cathode materials can be doped with electrochemically inactive elements (M’) that forms a strong ionic bond with oxygen. This can lead to reversible anionic redox in Na-rich cathode materials [54].
Voltage Hysteresis: The voltage hysteresis is mainly observed during the first cycle of charging/discharging. Structural degradation and voltage decay occur as a function of TM migration or oxygen loss during the first cycle. This could be avoided by introducing the “pillar effect”, where large ionic radius elements are used as dopants. The pillar effect helps to reduce TM migration and achieve reversible structural transformation. Additionally, if the TM forms strong covalent bond, TM migration becomes energetically demanding. Another strategy to avoid voltage fading is the design of the super lattice for cathode material to reduce the possibility of O2 removal [55].
Development of Cost-effective computational methods: Although presently available computational methods provide an in-depth understanding of various properties of Li/Na-based cathode materials, the accuracy and high computational cost still hinder the complete utilization of appropriate theoretical tools. For instance, generally, the GGA method [56] produces reasonable results; however, the self-interaction error leads to the poor estimation of electronic band gaps. The Hubbard U parameter is introduced to deal with the self-interaction error of DFT (GGA + U). In contrast, the U parameter depends upon the oxidation state of a transition metal which causes a severe accuracy issue during electronic structure study [57, 58]. Presently, the metaGGA functional SCAN [59] has been considered one of the most reliable methods to provide highly accurate results for different properties of cathode material. As the accuracy increases, the computational cost of the newly developed method also
increases. Therefore, developing more accurate and cost-effective methods could help design new cathode materials for high-energy Na-ion batteries.
In summary, this review represents the current state of development of cathode materials for high-capacity SIBs. It highlights the active role of doping in improving the performance of SIBs in terms of high specific capacity, improved Na+ -ion diffusion channel, and stable cationic and anionic redox process. Although 4d/5d transition metal-based cathode material promotes reversible anionic redox appreciably, the cost of 4d/5d metal-based cathode materials restricts the practical application of Na-based cathode materials. Therefore, tuning the activity of 3d metal-based cathode material with 4d or 5d elements could help to design materials with reversible cationic and anionic redox. Additionally, a detailed combined experimental and computational study will be helpful to design new cathode material for high-energy sodium-ion batteries.
Acknowledgements M.D. and P.S. acknowledge the Core Research Grant (CRG/2020/005626) of SERB, India, for financial support toward the completion of this work. We acknowledge National Supercomputing Mission (NSM) for providing computing resources of Param Porul HPC System, which is implemented by C-DAC and supported by the Ministry of Electronics and Information Technology (MeitY) and Department of Science and Technology (DST), Government of India.
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Chapter 2
In-Situ X-Ray Diffraction Studies of Battery Electrode Materials for the Microscopic Understanding of the Phase Stability and Performance
Correlation
Akhilesh Pandey and Ambesh Dixit
Abstract In any electrochemical energy storage system capacity fading is a crucial concern and poses challenges to their long-term stability for any practical uses. There are various characterization techniques for understanding the electrode material, yet it is difficult to nail down the microscopic regions of failure. X-ray diffraction is one of the most important techniques, used for understanding the crystallographic characteristics of the material together with any residual stress, volume change, and other related information. The electrode materials used in rechargeable batteries undergo lithium/sodium ion insertion/extraction process during cycling, causing changes in the electrode materials. The changes may include even permanent structural changes in some cases together with changes like localized strain, volume expansion/contraction, and even complete structural collapse. These cause cyclic instability, and even causing fire accidents in some cases. The in-situ XRD can be integrated to monitor such changes during charging/discharging cycling and thus, may provide a wealth of information to design and develop a robust electrode material for enhanced stability during charging/discharging cycling. The presented review will discuss a few case studies (both Li and Na ion rechargeable batteries) to track such changes in respective cathode materials and thus provide the use of in-situ XRD measurements in electrochemical storage devices.
A. Dixit et al. (eds.), Energy Materials and Devices, Advances in Sustainability Science and Technology, https://doi.org/10.1007/978-981-99-9009-2_2
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The Project Gutenberg eBook of Head-hunters, black, white, and brown
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Title: Head-hunters, black, white, and brown
Author: Alfred C. Haddon
Release date: February 3, 2024 [eBook #72861]
Language: English
Original publication: London: Methuen & Co, 1901
Credits: Peter Becker and the Online Distributed Proofreading Team at https://www.pgdp.net (This file was produced from images generously made available by The Internet Archive)
*** START OF THE PROJECT GUTENBERG EBOOK HEADHUNTERS, BLACK, WHITE, AND BROWN ***
HEAD-HUNTERS
BLACK, WHITE, AND BROWN
THE SCOTT-KELTIE FALLS, MOUNT DULIT, BARAM DISTRICT, SARAWAK
HEAD-HUNTERS
BLACK, WHITE, AND BROWN
BY
ALFRED C. HADDON, S .D., F.R.S.
FELLOW OF CHRIST’S COLLEGE AND UNIVERSITY LECTURER IN ETHNOLOGY, CAMBRIDGE
WITH THIRTY-TWO PLATES, FORTY ILLUSTRATIONS IN THE TEXT AND SIX MAPS
METHUEN & CO.
36 ESSEX STREET W.C. LONDON 1901 TO MY WIFE AND TO THE MEMORY OF MY MOTHER
WHO FIRST TAUGHT ME TO OBSERVE I DEDICATE THIS RECORD OF MY TRAVELS
PREFACE
In 1888 I went to Torres Straits to study the coral reefs and marine zoology of the district; whilst prosecuting these studies I naturally came much into contact with the natives, and soon was greatly interested in them. I had previously determined not to study the natives, having been told that a good deal was known already about them; but I was not long in discovering that much still remained to be learned. Indeed, it might be truly said that practically nothing was known of the customs and beliefs of the natives, even by those who we had every reason to expect would have acquired that information.
Such being the case, I felt it to be my duty to gather what information I could when not actually engaged in my zoological investigations. I found, even then, that the opportunities of learning about the pagan past of the natives were limited, and that it would become increasingly more difficult, as the younger men knew comparatively little of the former customs and beliefs, and the old men were dying off.
On my return home I found that my inquiries into the ethnography of the Torres Straits islanders were of some interest to anthropologists, and I was encouraged to spend some time in writing out my results. Gradually this has led me to devote myself to anthropological studies, and, not unnaturally, one of my first projects was to attempt a monograph on the Torres Straits Islanders. It was soon apparent that my information was of too imperfect a nature to make a satisfactory memoir, and therefore I delayed publishing until I could go out again to collect further material.
In course of time I was in a position to organise an expedition for this purpose, which, being mainly endowed from University funds, had the honour of being closely associated with the University of Cambridge. It was my good fortune to be able to secure the co-
operation of a staff of colleagues, each of whom had some special qualification.
For a long time it had appeared to me that investigations in experimental psychology in the field were necessary if we were ever to gauge the mental and sensory capabilities of primitive peoples. This expedition presented the requisite opportunity, and the organisation of this department was left to Dr. W. H. R. Rivers, of St. John’s College, the University lecturer in physiological and experimental psychology. The co-operation of Dr. C. S. Myers, of Caius College, had been secured early, and as he is a good musician, he specialised more particularly in the study of the hearing and music of the natives. Mr. W. McDougall, Fellow of St. John’s College, also volunteered to assist in the experimental psychology department of the expedition.
When the early arrangements were being made one of the first duties was to secure the services of a linguist, and the obvious person to turn to was Mr. Sidney H. Ray, who has long been a recognised authority on Melanesian and Papuan languages. Fortunately, he was able to join the expedition.
Mr. Anthony Wilkin, of King’s College, took the photographs for the expedition, and he assisted me in making the physical measurements and observations. He also investigated the construction of the houses, land tenure, transference of property, and other social data of various districts.
When this book was being brought out the sad news arrived in England of the death by dysentery of my pupil, friend, and colleague in Cairo on the 17th of May (1901), on his return home from a second winter’s digging in Upper Egypt. Poor Wilkin! barely twentyfour years of age, and with the promise of a brilliant career before him. I invited him to accompany me while he was still an undergraduate, having been struck by his personal and mental qualities. He was a man of exceptional ability and of frank, pleasing manner, and a thorough hater of humbug. Although he was originally a classical scholar, Wilkin read for the History Tripos, but his interests were wider than the academic course, and he paid some
attention to sociology, and was also interested in natural science. In his early undergraduate days he published a brightly written book, On the Nile with a Camera. Immediately after his first winter’s digging in Egypt with Professor Flinders Petrie, he went with Mr. D. Randall-Maciver to Algeria to study the problem of the supposed relationship, actual or cultural, of the Berbers with the Ancient Egyptians. An interesting exhibition of the objects then collected was displayed at the Anthropological Institute in the summer (1900), and later in the year Wilkin published a well-written and richly illustrated popular account of their experiences, entitled, Among the Berbers of Algeria. Quite recently the scientific results were published in a sumptuously illustrated joint work entitled, Libyan Notes. Wilkin was an enthusiastic traveller, and was projecting important schemes for future work. There is little doubt that had he lived he would have distinguished himself as a thoroughly trained field-ethnologist and scientific explorer.
Finally, Mr. C. G. Seligmann volunteered to join the party. He paid particular attention to native medicine and to the diseases of the natives as well as to various economic plants and animals.
Such was the personnel of the expedition. Several preliminary communications have been published by various members; but the complete account of our investigations in Torres Straits is being published by the Cambridge University Press in a series of special memoirs. The observations made on the mainland of British New Guinea and in Sarawak will be published in various journals as opportunity offers.
The book I now offer to the public contains a general account of our journeyings and of some of the sights we witnessed and facts that we gleaned.
I would like to take this opportunity of expressing my thanks to my comrades for all the assistance they have rendered me, both in the field and at home. I venture to prophesy that when all the work of the expedition is concluded my colleagues will be found to have performed their part in a most praiseworthy manner.
Our united thanks are due to many people, from H.H. the Rajah of Sarawak down to the least important native who gave us information. Wherever we went, collectively or individually, we were hospitably received and assisted in our work. Experience and information were freely offered us, and what success the expedition has attained must be largely credited to these friends.
I cannot enumerate all who deserve recognition, but, taking them in chronological order, the following rendered us noteworthy service.
The Queensland Government, through the Hon. T. J. Byrnes, then Premier, sent us the following cordial welcome by telegraph on our arrival at Thursday Island:—
“Permit me on behalf of Government to welcome you and your party to Queensland and to express our sincere hope that your expedition will meet with the success which it deserves. We shall be glad if at any time we can afford any assistance towards the object of the expedition or to its individual members, and trust that you will not hesitate to advise us if we can be of service to you. Have asked Mr. Douglas to do anything in his power and to afford you any information concerning the objects of your mission he may be in a position to impart.”
The Hon. John Douglas, . . ., the Government Resident at Thursday Island, not merely officially, but privately and of his spontaneous good nature, afforded us every facility in his power. Through his kind offices the Queensland Government made a special grant of £100 towards the expenses of the expedition, and in connection with this a very friendly telegram was sent by the late Sir James R. Dickson, . . . ., who was then the Home Secretary.
The Government of British New Guinea did what it could to further our aims. Unfortunately, His Excellency Sir William Macgregor, . . . ., . ., S .D., the then Lieutenant-Governor of the Possession, was away on a tour of inspection during my visit to the Central District; but he afterwards showed much kindness to
Seligmann. The Hon. A. Musgrave, of Port Moresby, was most cordial and helpful, and we owe a great deal to him. The Hon. D. Ballantine, the energetic Treasurer and Collector of Customs, proved himself a very good friend and benefactor to the expedition. The Hon. B. A. Hely, Resident Magistrate of the Western Division, helped us on our way, and we are greatly indebted in many ways to Mr. A. C. English, the Government Agent of the Rigo District.
All travellers to British New Guinea receive many benefits directly and indirectly from the New Guinea Mission of the London Missionary Society. Everywhere we went we were partakers of the hospitality of the missionaries and South Sea teachers; the same genuine friendliness and anxiety to help permeates the whole staff, so much so that it seems invidious to mention names, but the great assistance afforded us by the late Rev. James Chalmers deserves special recognition, as does also the kindness of Dr. and Mrs. Lawes. The Mission boats were also freely placed at our disposal as far as the service of the Mission permitted; but for this liberality on the part of Mr. Chalmers we should several times have been in an awkward predicament. If any words of mine could induce any practical assistance being given to the Mission I would feel most gratified, for I sadly realise that our indebtedness to the Mission can only be acknowledged adequately by proxy.
It is a sad duty to chronicle the irreparable loss which all those who are connected with British New Guinea have undergone in the tragic death of the devoted Tamate. Mrs. Chalmers died in the autumn of 1900 under most distressing circumstances in the Mission boat when on her way to Thursday Island. A few months later, when endeavouring to make peace during a tribal war on the Aird River, Chalmers crowned a life of hardship and self-sacrifice by martyrdom in the cause of peace. A glorious end for a noble life. With him were murdered twelve native Mission students and the Rev. O. Tomkins, a young, intelligent, and enthusiastic missionary, from whom much was expected.
Very pleasing is it to record the brotherly kindness that we received at the hands of the Sacred Heart Mission. None of our party belonged to their Communion, but from the Archbishop to the
lowliest Brother we received nothing but the friendliest treatment. Nor would we omit our thanks to the good Sisters for the cheerful way in which they undertook the increased cares of catering which our presence necessitated. The insight which we gained into the ethnography of the Mekeo District is solely due to the good offices of the various members of the Sacred Heart Mission.
In the course of the following pages I often refer to Mr. John Bruce, the Government Schoolmaster on Murray Island. It would be difficult to exaggerate the influence he exerts for good by his instruction, advice, and unostentatious example. His help and influence were invaluable to us, and when our researches are finally published, anthropologists will cordially admit how much their science owes to “Jack Bruce.”
We found Mr. Cowling, of Mabuiag, very helpful, not only at the time but subsequently, as he has since sent us much valuable information, and he also deserves special thanks.
Our visit to Sarawak was due to a glowing invitation I received from Mr. Charles Hose, the Resident of the Baram District. I have so frequently referred in print and speech to his generosity and erudition, that I need only add here that his University has conferred on him the greatest honour it is in her power to bestow—the degree of Doctor in Science honoris causa.
But it was Rajah Sir Charles Brooke’s interest in the expedition that made many things possible, and to him we offer our hearty thanks, both for facilities placed at our disposal and for the expression of his good-will.
At Kuching we received great hospitality from the white residents. Particular mention must be made of the Hon. C. A. Bampfylde, Resident of Sarawak; on our arrival he was administrating the country in the absence of the Rajah, who was in England; nor should Dr. A. J. G. Barker, Principal Medical Officer of Sarawak, and Mr. R. Shelford, the Curator of the Museum, be omitted.
Great kindness and hospitality were shown us by Mr. O. F. Ricketts, Resident of the Limbang District. We had a most enjoyable
visit to his beautiful Residency, and he arranged for us all the details of our journey up-river.
One fact through all our journeyings has continually struck me. Travellers calmly and uninvitedly plant themselves on residents by whom they are received with genuine kindness and hospitably entertained with the best that can be offered. Experience, information, and influence are cheerfully and ungrudgingly placed at the disposal of the guests, who not unfrequently palm off, without acknowledgment, on an unsuspecting public the facts that others have gleaned.
The warm welcome that one receives is as refreshing to the spirit as the shower-bath is to the body and daintily served food to the appetite when one has been wandering in the wilds.
In order to render my descriptions of the places and people more continuous I have practically ignored the exact order in which events happened or journeys were made. For those who care about chronology I append a bare statement of the location of the various members of the expedition at various times. I have also not hesitated to include certain of my experiences, or some of the information I gained, during my first expedition to Torres Straits in 1888-9; but the reader will always be able to discriminate between the two occasions.
1898
March 10th. Left London.
April 22nd. Arrived Thursday Island, where joined by Seligmann.
April 30th. Left Thursday Island.
May 6th. Arrived Murray Island.
May 23rd. Haddon, Ray, Wilkin, and Seligmann left for New Guinea.
June 25th. Seligmann went to Rigo.
July 20th. Haddon, Ray, and Wilkin returned from New Guinea to Murray Island.
August 24th. Myers and McDougall left Murray Island for Sarawak.
Sept. 8th. Haddon, Rivers, Ray, and Wilkin left Murray Island for Kiwai.
Sept. 12th. Seligmann arrived at Saguane.
Sept. 15th. Haddon, Rivers, Wilkin, Seligmann left Saguane for Mabuiag.
Sept. 17th. Arrived Mabuiag.
Oct. 3rd. Ray came from Saguane.
Oct. 19th. Rivers left to return home.
Oct. 21st. Wilkin left to return home.
Oct. 22nd. Haddon, Ray, Seligmann left for Saibai, etc.
Nov. 15th. Left Thursday Island.
Nov. 28th. Arrived Hongkong.
Dec. 3rd. Left Hongkong.
Dec. 9th. Arrived Singapore.
Dec. 10th. Left Singapore.
Dec. 12th. Arrived Kuching.
1899.
Jan. 4th. Left Kuching for Baram.
Jan. 8th. Arrived Limbang.
Jan. 16th. Left Limbang.
Jan. 28th. Arrived Marudi (Claudetown).
April 20th. Left Marudi.
April 25th. Left Kuching.
May 31st. Arrived in London.
The following is the system of spelling which has been adopted in this book:—
a as in “father.”
ă as in “at.”
e as a in “date.”
ĕ as in “debt.”
i as ee in “feet.”
ĭ as in “it.”
o as in “own.”
ŏ as in “on.”
ö as German ö in “schön.”
ò as aw in “law.”
u as oo in “soon.”
ŭ as in “up.”
ai as in “aisle.”
au as ow in “cow.”
The consonants are sounded as in English.
ng as in “sing.”
ngg as in “finger.”
CONTENTS
PART I
CHAPTER I
THURSDAY ISLAND TO MURRAY ISLAND
Port Kennedy, Thursday Island—l’assage in the Freya to Murray Island—Darnley Island— Arrival at Murray Island—Reception by the natives Page 1-10
CHAPTER II
THE MURRAY ISLANDS
Geographical features of the islands of Torres Straits—Geology of the Murray Islands— Climate—The Murray Islanders—Physical and other characteristics—Form of Government Page 11-21
CHAPTER III
WORK AND PLAY IN MURRAY ISLAND
The Expedition Dispensary—Investigations in Experimental Psychology: visual acuity, colour vision, mirror writing, estimation of time, acuity of hearing, sense of smell and taste, sensitiveness to pain—The Miriam language— Methods of acquiring information—Rain-making —Native amusements—Lantern exhibition— String puzzles—Top-spinning—Feast—Copper Maori Page 22-41
CHAPTER IV
THE MALU CEREMONIES
Initiation ceremonies—Secret societies—Visit to Las —Representation of the Malu ceremonies— Models of the old masks—The ceremonies as formerly carried out—“Devil belong Malu” Page 42-52
CHAPTER V. ZOGOS
The Murray Island oracle, Tomog Zogo—The village of Las—Tamar—The war-dance at Ziriam Zogo —Zabarker—Wind-raising—Teaching Geography at Dam—Tamar again—A Miriam “play”—How Pepker made a hill—Iriam Moris, the fat man—Zogo of the girl of the south-west —Photographing zogos—The coconut zogo—A turtle zogo—The big women who dance at night —The Waiad ceremony Page 53-70
CHAPTER VI
VARIOUS INCIDENTS IN MURRAY ISLAND
Our “boys” in Murray Island—“Gi, he gammon”— Character of some of our native friends—Ulai— Rivalry between Debe Wali and Jimmy Rice— Our Royal Guests—The Papuan method of smoking—A domestic quarrel—Debe and Jimmy fall out—An earthquake—Cause of a hurricane—The world saved from a comet by three weeks of prayer—an unaccounted-for windstorm—New Guinea magic—“A woman of Samaria”—Jimmy Rice in prison—A yam zogo —Rain-makers—A death-dealing zogo— Mummies—Skull-divination—Purchasing skulls —A funeral Page 71-94
CHAPTER VII
KIWAI AND MAWATTA
Leave Murray Island in the Nieue—Daru—Arrive at Saguane—Mission-work—Visit Iasa—Long Page 95-116
clan houses—Totems and totemistic customs— Bull-roarers and human effigies as garden charms and during initiation ceremonies— Head-hunting—Stone implements—Origin of Man—Origin of Fire—Primitive dwellings at Old Mawatta—Shell hoe—Katau or Mawatta— Election of a chief—A love story—Dances— Bamboo beheading-knife
CHAPTER VIII MABUIAG
Mabuiag revisited—Character of the island— Comparison between the Murray Island and Mabuiag natives—Barter for skulls—Economic condition of Mabuiag—Present of food—Waria, a literary Papuan—Death of Waria’s baby— Method of collecting relationships and genealogies—Colour-blindness—The Mabuiag language—A May Meeting followed by a wardance Page 117-131
CHAPTER IX
TOTEMISM AND THE CULT OF KWOIAM
Totemism in Mabuiag—Significance of Totemism— Advantage of Totemism—Seclusion of girls— The Sacred Island of Pulu—The scenes of some of Kwoiam’s exploits—The Pulu Kwod— The stone that fell from the sky—The Kwoiam Augŭds—Death dances—Test for bravery— Bull-roarer—Pictographs—The Cave of Skulls —The destruction of relics—Outline of the Saga of Kwoiam—Kwoiam’s miraculous water-hole— The death of Kwoiam Page 132-147
CHAPTER X
DUGONG AND TURTLE FISHING
A dugong hunt—What is a dugong?—The dugong Page 148-157
platform—Dugong charms—Turtle-fishing— How the sucker-fish is employed to catch turtle —Beliefs respecting the gapu—The agu and bull-roarers—Cutting up a turtle
CHAPTER XI
MARRIAGE CUSTOMS AND STAR MYTHS
M C : How girls propose marriage among the western tribe—A proposal in Tut— Marital relations—A wedding in church—An unfortunate love affair—Various love-letters. S M : The Tagai constellation—A stellar almanack, its legendary origin—The origin of the constellations of Dorgai Metakorab and Bu —The story of Kabi, and how he discovered who the Sun, Moon, and Night were Page 158-169
CHAPTER XII
VISITS TO VARIOUS WESTERN ISLANDS
Our party breaks up. S : Clan groupings— Vaccination marks turned to a new use—Triplecrowned coconut palm—A two-storied native house. T : Notes of a former visit—Brief description of the old initiation ceremonies— Relics of the past. Y : A Totem shrine. N : The decoration of Magau’s skull “old-time fashion”—Divinatory skulls—The sawfish magical dance—Pictographs in Kiriri. M : Visit to Prince of Wales Island in 1888—A family party—War-dance Page 170-189
CHAPTER XIII
CAPE YORK NATIVES
Visit to Somerset—Notes on the Yaraikanna tribe— Initiation ceremony—Bull-roarer—Knocking out a front tooth—The ari or “personal totem” Page 190-194
CHAPTER XIV
A TRIP DOWN THE PAPUAN COAST
The Olive Branch—Passage across the Papuan Gulf—Delena—Tattooing—A Papuan amentum —A sorcerer’s kit—Borepada—Port Moresby— Gaile, a village built in the sea—Character of the country—Kăpăkăpă—Dubus—The Vatorata Mission Station—Dr. and Mrs. Lawes—Sir William Macgregor’s testimony to mission work —A dance Page 197-210
CHAPTER XV
THE HOOD PENINSULA
Bulaa by moonlight—Hospitality of the South Sea teachers—Geographical character of the Hood Peninsula—Kalo—Annual fertility ceremony at Babaka—Canoe-making at Keapara—The fishing village of Alukune—The Keapara bullies —Picking a policeman’s pocket—Tattooing—A surgical remedy—Variations in the character of the Papuan hair—Pile-raising—Children’s toys and games—Dances—Second visit to Vatorata —Visit Mr. English at Rigo Page 211-234
CHAPTER XVI
PORT MORESBY AND THE ASTROLABE RANGE
Port Moresby—Ride inland—Vegetation—View from the top of Warirata—The Taburi village of Atsiamakara—The Koiari—Tree houses—The Agi chief—Contrasts—A lantern show—The mountaineers—Tribal warfare—The pottery trade of Port Moresby—The Koitapu and the Motu—Gunboats Page 235-251
