Layered P2‐Type K 0.65 Fe 0.5 Mn 0.5 O 2 Microspheres as Superior Cathode for High‐Energy Potassium‐Ion Batteries

Deng, Tao; Fan, Xiulin; Chen, Ji; Chen, Long; Luo, Chao; Zhou, Xiuquan; Yang, Junhe; Zheng, Shiyou; Wang, Chunsheng

doi:10.1002/adfm.201800219

Title: Layered P2‐Type K _0.65 Fe _0.5 Mn _0.5 O ₂ Microspheres as Superior Cathode for High‐Energy Potassium‐Ion Batteries

Abstract

Abstract Potassium‐ion batteries have been regarded as the potential alternatives to lithium‐ion batteries (LIBs) due to the low cost, earth abundance, and low potential of K (−2.936 vs standard hydrogen electrode (SHE)). However, the lack of low‐cost cathodes with high energy density and long cycle life always limits its application. In this work, high‐energy layered P2‐type hierarchical K _0.65 Fe _0.5 Mn _0.5 O ₂ (P2‐KFMO) microspheres, assembled by the primary nanoparticles, are fabricated via a modified solvent‐thermal method. Benefiting from the unique microspheres with primary nanoparticles, the K ⁺ intercalation/deintercalation kinetics of P2‐KFMO is greatly enhanced with a stabilized cathodic electrolyte interphase on the cathode. The P2‐KFMO microsphere presents a highly reversible potassium storage capacity of 151 mAh g ⁻¹ at 20 mA g ⁻¹ , fast rate capability of 103 mAh g ⁻¹ at 100 mA g ⁻¹ , and long cycling stability with 78% capacity retention after 350 cycles. A full cell with P2‐KFMO microspheres as cathode and hard carbon as anode is constructed, which exhibits long‐term cycling stability (>80% of retention after 100 cycles). The present high‐performance P2‐KFMO microsphere cathode synthesized using earth‐abundant elements provides a new cost‐effective alternative to LIBs for large‐scale energy storage.

Authors:

Deng, Tao ^[1]; Fan, Xiulin ^[1]; Chen, Ji ^[1]; Chen, Long ^[1]; Luo, Chao ^[1]; Zhou, Xiuquan ^[2]; Yang, Junhe ^[3]; Zheng, Shiyou ^[3];

^[1]

Department of Chemical and Biomolecular Engineering University of Maryland College Park MD 20742 USA
Department of Chemistry and Biochemistry University of Maryland College Park MD 20742 USA
School of Materials Science and Engineering University of Shanghai for Science and Technology Shanghai 200093 P. R. China

Publication Date:: Wed May 30 00:00:00 EDT 2018

Sponsoring Org.:: USDOE

OSTI Identifier:: 1439525

Grant/Contract Number:: DESC0001160

Resource Type:: Publisher's Accepted Manuscript

Journal Name:: Advanced Functional Materials

Additional Journal Information:: Journal Name: Advanced Functional Materials Journal Volume: 28 Journal Issue: 28; Journal ID: ISSN 1616-301X

Publisher:: Wiley Blackwell (John Wiley & Sons)

Country of Publication:: Germany

Language:: English

Citation Formats


                    Deng, Tao, Fan, Xiulin, Chen, Ji, Chen, Long, Luo, Chao, Zhou, Xiuquan, Yang, Junhe, Zheng, Shiyou, and Wang, Chunsheng. Layered P2‐Type K 0.65 Fe 0.5 Mn 0.5 O 2 Microspheres as Superior Cathode for High‐Energy Potassium‐Ion Batteries.  Germany: N. p., 2018. 
Web.  doi:10.1002/adfm.201800219.

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                    Deng, Tao, Fan, Xiulin, Chen, Ji, Chen, Long, Luo, Chao, Zhou, Xiuquan, Yang, Junhe, Zheng, Shiyou, & Wang, Chunsheng. Layered P2‐Type K 0.65 Fe 0.5 Mn 0.5 O 2 Microspheres as Superior Cathode for High‐Energy Potassium‐Ion Batteries.  Germany.  https://doi.org/10.1002/adfm.201800219

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                    Deng, Tao, Fan, Xiulin, Chen, Ji, Chen, Long, Luo, Chao, Zhou, Xiuquan, Yang, Junhe, Zheng, Shiyou, and Wang, Chunsheng. Wed .  
"Layered P2‐Type K 0.65 Fe 0.5 Mn 0.5 O 2 Microspheres as Superior Cathode for High‐Energy Potassium‐Ion Batteries".  Germany.  https://doi.org/10.1002/adfm.201800219.

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@article{osti_1439525,

  title        = {Layered P2‐Type K 0.65 Fe 0.5 Mn 0.5 O 2 Microspheres as Superior Cathode for High‐Energy Potassium‐Ion Batteries},

  author       = {Deng, Tao and Fan, Xiulin and Chen, Ji and Chen, Long and Luo, Chao and Zhou, Xiuquan and Yang, Junhe and Zheng, Shiyou and Wang, Chunsheng},

  abstractNote = {Abstract Potassium‐ion batteries have been regarded as the potential alternatives to lithium‐ion batteries (LIBs) due to the low cost, earth abundance, and low potential of K (−2.936 vs standard hydrogen electrode (SHE)). However, the lack of low‐cost cathodes with high energy density and long cycle life always limits its application. In this work, high‐energy layered P2‐type hierarchical K 0.65 Fe 0.5 Mn 0.5 O 2 (P2‐KFMO) microspheres, assembled by the primary nanoparticles, are fabricated via a modified solvent‐thermal method. Benefiting from the unique microspheres with primary nanoparticles, the K + intercalation/deintercalation kinetics of P2‐KFMO is greatly enhanced with a stabilized cathodic electrolyte interphase on the cathode. The P2‐KFMO microsphere presents a highly reversible potassium storage capacity of 151 mAh g −1 at 20 mA g −1 , fast rate capability of 103 mAh g −1 at 100 mA g −1 , and long cycling stability with 78% capacity retention after 350 cycles. A full cell with P2‐KFMO microspheres as cathode and hard carbon as anode is constructed, which exhibits long‐term cycling stability (>80% of retention after 100 cycles). The present high‐performance P2‐KFMO microsphere cathode synthesized using earth‐abundant elements provides a new cost‐effective alternative to LIBs for large‐scale energy storage.},

  doi          = {10.1002/adfm.201800219},

  journal      = {Advanced Functional Materials},

  number       = 28,

  volume       = 28,

  place        = {Germany},

  year         = {Wed May 30 00:00:00 EDT 2018},

  month        = {Wed May 30 00:00:00 EDT 2018}

}

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Title: Layered P2‐Type K 0.65 Fe 0.5 Mn 0.5 O 2 Microspheres as Superior Cathode for High‐Energy Potassium‐Ion Batteries

Abstract

Citation Formats

Layered-to-Rock-Salt Transformation in Desodiated Na x CrO 2 ( x 0.4) journal, February 2016

Insights into the structural effects of layered cathode materials for high voltage sodium-ion batteries journal, January 2017

Electrochemical investigation of the P2–NaxCoO2 phase diagram journal, December 2010

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Advances in Structure and Property Optimizations of Battery Electrode Materials journal, November 2017

Sodium deintercalation from sodium iron oxide journal, June 1994

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Prussian Green: A High Rate Capacity Cathode for Potassium Ion Batteries journal, June 2015

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Earth Abundant Fe/Mn-Based Layered Oxide Interconnected Nanowires for Advanced K-Ion Full Batteries journal, December 2016

Reversible Dendrite-Free Potassium Plating and Stripping Electrochemistry for Potassium Secondary Batteries journal, July 2017

High Voltage Mg-Doped Na 0.67 Ni 0.3– x Mg x Mn 0.7 O 2 ( x = 0.05, 0.1) Na-Ion Cathodes with Enhanced Stability and Rate Capability journal, July 2016

Alternative electrochemical energy storage: potassium-based dual-graphite batteries journal, January 2017

Recent Progress on Spray Pyrolysis for High Performance Electrode Materials in Lithium and Sodium Rechargeable Batteries journal, December 2016

Exploration of K 2 Ti 8 O 17 as an anode material for potassium-ion batteries journal, January 2016

A New, Safe, High-Rate and High-Energy Polymer Lithium-Ion Battery journal, August 2009

Self-Templated Formation of P2-type K 0.6 CoO 2 Microspheres for High Reversible Potassium-Ion Batteries journal, January 2018

Na 0.67 Mn 1−x Mg x O 2 (0 ≤ x ≤ 0.2): a high capacity cathode for sodium-ion batteries journal, January 2014

Potassium secondary cell based on Prussian blue cathode journal, February 2004

Mg rechargeable batteries: an on-going challenge journal, January 2013

P2-type Na0.67Mn0.65Fe0.2Ni0.15O2 Cathode Material with High-capacity for Sodium-ion Battery journal, January 2014

Update on anode materials for Na-ion batteries journal, January 2015

Role of Nitrogen-Doped Graphene for Improved High-Capacity Potassium Ion Battery Anodes journal, October 2016

A Practical High-Energy Cathode for Sodium-Ion Batteries Based on Uniform P2-Na 0.7 CoO 2 Microspheres journal, April 2017

A Novel Potassium-Ion-Based Dual-Ion Battery journal, March 2017

Porous Fe-Mn-O nanocomposites: Synthesis and supercapacitor electrode application journal, June 2016

The Li-Ion Rechargeable Battery: A Perspective journal, January 2013

Radially aligned hierarchical columnar structure as a cathode material for high energy density sodium-ion batteries journal, April 2015

Potassium intercalation into graphite to realize high-voltage/high-power potassium-ion batteries and potassium-ion capacitors journal, November 2015

Potassium-Ion Oxygen Battery Based on a High Capacity Antimony Anode journal, November 2015

A high-voltage solid-state secondary cell based on chromium hexacyanometallates journal, May 2003

Hard Carbon Microspheres: Potassium-Ion Anode Versus Sodium-Ion Anode journal, November 2015

K-Ion Batteries Based on a P2-Type K 0.6 CoO 2 Cathode journal, May 2017

Structure of the high voltage phase of layered P2-Na 2/3−z [Mn 1/2 Fe 1/2 ]O 2 and the positive effect of Ni substitution on its stability journal, January 2015

Research Development on Sodium-Ion Batteries journal, October 2014

Electrochemical ammonia compression journal, January 2017

A comprehensive review of sodium layered oxides: powerful cathodes for Na-ion batteries journal, January 2015

Non-Aqueous K-Ion Battery Based on Layered K 0.3 MnO 2 and Hard Carbon/Carbon Black journal, January 2016

Suppressing the P2-O2 Phase Transition of Na 0.67 Mn 0.67 Ni 0.33 O 2 by Magnesium Substitution for Improved Sodium-Ion Batteries journal, May 2016

Potassium–Sulfur Batteries: A New Member of Room-Temperature Rechargeable Metal–Sulfur Batteries journal, August 2014

Potassium Prussian Blue Nanoparticles: A Low-Cost Cathode Material for Potassium-Ion Batteries journal, December 2016

Potassium Secondary Batteries journal, October 2016

First-Principles Study of Alkali and Alkaline Earth Ion Intercalation in Iron Hexacyanoferrate: The Important Role of Ionic Radius journal, October 2013

Low-Cost High-Energy Potassium Cathode journal, January 2017

Energy and Capacity Projections for Practical Dual-Graphite Cells journal, January 2000

Lithium-ion batteries. A look into the future journal, January 2011

Hierarchical Porous Carbonized Co 3 O 4 Inverse Opals via Combined Block Copolymer and Colloid Templating as Bifunctional Electrocatalysts in Li-O 2 Battery journal, July 2017

Hard-Soft Composite Carbon as a Long-Cycling and High-Rate Anode for Potassium-Ion Batteries journal, May 2017

P2-type Nax[Fe1/2Mn1/2]O2 made from earth-abundant elements for rechargeable Na batteries journal, April 2012

Pomegranate-Structured Conversion-Reaction Cathode with a Built-in Li Source for High-Energy Li-Ion Batteries journal, May 2016

Carbon Electrodes for K-Ion Batteries journal, September 2015

Short-Range Order in Mesoporous Carbon Boosts Potassium-Ion Battery Performance journal, October 2017

Layered P2-Na 0.66 Fe 0.5 Mn 0.5 O 2 Cathode Material for Rechargeable Sodium-Ion Batteries journal, August 2013

Scalable synthesis of Na 3 V 2 (PO 4 ) 3 /C porous hollow spheres as a cathode for Na-ion batteries journal, January 2015

High-Performance Olivine NaFePO 4 Microsphere Cathode Synthesized by Aqueous Electrochemical Displacement Method for Sodium Ion Batteries journal, August 2015

Activated carbon from the graphite with increased rate capability for the potassium ion battery journal, October 2017

Potassium Ion Batteries with Graphitic Materials journal, October 2015

Title: Layered P2‐Type K _0.65 Fe _0.5 Mn _0.5 O ₂ Microspheres as Superior Cathode for High‐Energy Potassium‐Ion Batteries

Layered-to-Rock-Salt Transformation in Desodiated Na _x CrO ₂ ( x 0.4)
journal, February 2016

Insights into the structural effects of layered cathode materials for high voltage sodium-ion batteries
journal, January 2017

Electrochemical investigation of the P2–NaxCoO2 phase diagram
journal, December 2010

Investigation of Potassium Storage in Layered P3-Type K _0.5 MnO ₂ Cathode
journal, August 2017

Advances in Structure and Property Optimizations of Battery Electrode Materials
journal, November 2017

Sodium deintercalation from sodium iron oxide
journal, June 1994

New-type K0.7Fe0.5Mn0.5O2 cathode with an expanded and stabilized interlayer structure for high-capacity sodium-ion batteries
journal, May 2017

Prussian Green: A High Rate Capacity Cathode for Potassium Ion Batteries
journal, June 2015

A fundamental parameters approach to X-ray line-profile fitting
journal, April 1992

Tin-based composite anodes for potassium-ion batteries
journal, January 2016

Superior Stable Self-Healing SnP ₃ Anode for Sodium-Ion Batteries
journal, June 2015

Earth Abundant Fe/Mn-Based Layered Oxide Interconnected Nanowires for Advanced K-Ion Full Batteries
journal, December 2016

Reversible Dendrite-Free Potassium Plating and Stripping Electrochemistry for Potassium Secondary Batteries
journal, July 2017

High Voltage Mg-Doped Na _0.67 Ni _{0.3– x} Mg _x Mn _0.7 O ₂ ( x = 0.05, 0.1) Na-Ion Cathodes with Enhanced Stability and Rate Capability
journal, July 2016

Alternative electrochemical energy storage: potassium-based dual-graphite batteries
journal, January 2017

Recent Progress on Spray Pyrolysis for High Performance Electrode Materials in Lithium and Sodium Rechargeable Batteries
journal, December 2016

Exploration of K ₂ Ti ₈ O ₁₇ as an anode material for potassium-ion batteries
journal, January 2016

A New, Safe, High-Rate and High-Energy Polymer Lithium-Ion Battery
journal, August 2009

Self-Templated Formation of P2-type K _0.6 CoO ₂ Microspheres for High Reversible Potassium-Ion Batteries
journal, January 2018

Na _0.67 Mn _1−x Mg _x O ₂ (0 ≤ x ≤ 0.2): a high capacity cathode for sodium-ion batteries
journal, January 2014

Potassium secondary cell based on Prussian blue cathode
journal, February 2004

Mg rechargeable batteries: an on-going challenge
journal, January 2013

P2-type Na0.67Mn0.65Fe0.2Ni0.15O2 Cathode Material with High-capacity for Sodium-ion Battery
journal, January 2014

Update on anode materials for Na-ion batteries
journal, January 2015

Role of Nitrogen-Doped Graphene for Improved High-Capacity Potassium Ion Battery Anodes
journal, October 2016

A Practical High-Energy Cathode for Sodium-Ion Batteries Based on Uniform P2-Na _0.7 CoO ₂ Microspheres
journal, April 2017

A Novel Potassium-Ion-Based Dual-Ion Battery
journal, March 2017

Porous Fe-Mn-O nanocomposites: Synthesis and supercapacitor electrode application
journal, June 2016

The Li-Ion Rechargeable Battery: A Perspective
journal, January 2013

Radially aligned hierarchical columnar structure as a cathode material for high energy density sodium-ion batteries
journal, April 2015

Potassium intercalation into graphite to realize high-voltage/high-power potassium-ion batteries and potassium-ion capacitors
journal, November 2015

Potassium-Ion Oxygen Battery Based on a High Capacity Antimony Anode
journal, November 2015

A high-voltage solid-state secondary cell based on chromium hexacyanometallates
journal, May 2003

Hard Carbon Microspheres: Potassium-Ion Anode Versus Sodium-Ion Anode
journal, November 2015

K-Ion Batteries Based on a P2-Type K _0.6 CoO ₂ Cathode
journal, May 2017

Structure of the high voltage phase of layered P2-Na _2/3−z [Mn _1/2 Fe _1/2 ]O ₂ and the positive effect of Ni substitution on its stability
journal, January 2015

Research Development on Sodium-Ion Batteries
journal, October 2014

Electrochemical ammonia compression
journal, January 2017

A comprehensive review of sodium layered oxides: powerful cathodes for Na-ion batteries
journal, January 2015

Non-Aqueous K-Ion Battery Based on Layered K _0.3 MnO ₂ and Hard Carbon/Carbon Black
journal, January 2016

Suppressing the P2-O2 Phase Transition of Na _0.67 Mn _0.67 Ni _0.33 O ₂ by Magnesium Substitution for Improved Sodium-Ion Batteries
journal, May 2016

Potassium–Sulfur Batteries: A New Member of Room-Temperature Rechargeable Metal–Sulfur Batteries
journal, August 2014

Potassium Prussian Blue Nanoparticles: A Low-Cost Cathode Material for Potassium-Ion Batteries
journal, December 2016

Potassium Secondary Batteries
journal, October 2016

First-Principles Study of Alkali and Alkaline Earth Ion Intercalation in Iron Hexacyanoferrate: The Important Role of Ionic Radius
journal, October 2013

Low-Cost High-Energy Potassium Cathode
journal, January 2017

Energy and Capacity Projections for Practical Dual-Graphite Cells
journal, January 2000

Lithium-ion batteries. A look into the future
journal, January 2011

Hierarchical Porous Carbonized Co ₃ O ₄ Inverse Opals via Combined Block Copolymer and Colloid Templating as Bifunctional Electrocatalysts in Li-O ₂ Battery
journal, July 2017

Hard-Soft Composite Carbon as a Long-Cycling and High-Rate Anode for Potassium-Ion Batteries
journal, May 2017

P2-type Nax[Fe1/2Mn1/2]O2 made from earth-abundant elements for rechargeable Na batteries
journal, April 2012

Pomegranate-Structured Conversion-Reaction Cathode with a Built-in Li Source for High-Energy Li-Ion Batteries
journal, May 2016

Carbon Electrodes for K-Ion Batteries
journal, September 2015

Short-Range Order in Mesoporous Carbon Boosts Potassium-Ion Battery Performance
journal, October 2017

Layered P2-Na _0.66 Fe _0.5 Mn _0.5 O ₂ Cathode Material for Rechargeable Sodium-Ion Batteries
journal, August 2013

Scalable synthesis of Na ₃ V ₂ (PO ₄ ) ₃ /C porous hollow spheres as a cathode for Na-ion batteries
journal, January 2015

High-Performance Olivine NaFePO ₄ Microsphere Cathode Synthesized by Aqueous Electrochemical Displacement Method for Sodium Ion Batteries
journal, August 2015

Activated carbon from the graphite with increased rate capability for the potassium ion battery
journal, October 2017

Potassium Ion Batteries with Graphitic Materials
journal, October 2015