Dual-ion Batteries Research Articles

Ultra-high capacity dual-ion batteries realized by few-layered reduced graphene oxide and cathode structure design

As the development of dual-ion batteries (DIBs) is limited by the capacity of anions intercalation, we put forward an innovative design idea of DIB. Compared with the traditional graphite cathodes, few-layered reduced graphene oxide (rGO) has a large specific surface area and can greatly improve the utilization ratio of carbon layers for fast redox reaction process. In addition, the carbon paper current collector with porous network structure facilitates the uniform distribution of active materials, rapid penetration of electrolyte and fast migration of ions, and also relieves the volume strain caused by PF6− intercalation/de-intercalation. Under the effects of the above two aspects, the lithium-rGO DIB demonstrates significantly enhanced electrochemical performance compared with conventional DIBs. It possesses an ultra-high discharge capacity of 405 mA h g−1 with a coulombic efficiency of > 98% after 1000 cycles at 1 A g−1 in the voltage range of 3.0–5.0 V. The detailed mechanism of electrochemical performance enhancement is also discussed.

Enhanced intercalation behaviors of edge-rich flakes-stacked graphite for Al-graphite dual-ion battery

Graphite has been almost proven to be the positive material with the highest voltage and superior cycle stability for Al-graphite dual-ion battery. However, the limited energy density of graphite as positive material still blocks the future practical application. It is of great significance to further improve the energy density of the battery to satisfy the growing demand. In this regard, an edge-rich flakes-stacked graphite prepared by intentionally eroding the outer dense graphitic layer of graphite paper is demonstrated to apply in Al-graphite dual-ion battery that the chloroaluminate anions can be directly transported from edge-rich graphene nanoflakes and diffused into interior graphitic layers, which will greatly shorten the diffusion pathway, thus revealing better rate capability. The edge-rich flakes-stacked graphite paper enables to deliver a reversible capacity of ~87 mAh g−1 at 50 mA g−1, significantly higher than that of the untreated graphite paper electrode. More importantly, owing to the ultrahigh areal mass loading advantage, the as-assembled batteries exhibit much enhanced areal capacity (1.2 mAh cm−2), which is distinctly the highest among the reported graphite-based electrodes.

Li-based all‑carbon dual-ion batteries using graphite recycled from spent Li-ion batteries

Recycling and regeneration of spent Li-ion batteries have become an important research topic for a sustainable future. This is predominantly because of the exponentially increasing production & usage of lithium ion batteries (LIBs) leading to an intense reflux as spent/failed/end-of-life batteries in the near future. Research on recycling/regenerating cathode materials has been a major attraction while ignoring the anode part, the graphite. In the present work, we demonstrate the possibility of recycling graphite recovered from spent Li-ion batteries for Li-ion based all‑carbon dual-ion battery (ACDIB) application. Graphite electrodes recovered from failed commercial batteries were thermally treated at different temperatures to optimize their electrochemical activity. Thermally processed graphite was characterized by X-ray diffraction, field-emission scanning electron microscopy, Raman and infrared spectroscopy. The electrochemical performances of both anode and cathode half-cells were optimized and finally all‑carbon dual-ion battery was fabricated and tested with the best performing electrodes. For the anode half-cell, spent graphite thermally processed at 800 °C delivered the highest specific capacity of 250 mAh/g at 372 mA/g and cycling stability over 300 cycles. While for cathode half-cell, the spent graphite processed at 650 °C delivered first discharge capacity of about 65 mAh/g at a specific current of 100 mA/g and reasonable stability for 100 cycles. Coupling these anode and cathode, ACDIB displayed an initial discharge capacity of 58 mAh/g corresponding to an energy density of 255 Wh/kg.

Tetrafluoroborate Anion Intercalation into Graphite Electrode from Sulfolane

Electrolyte solutions of lithium tetrafluoroborate dissolved in sulfolane are applied in dual-ion batteries. A graphite positive electrode in this kind of solutions delivers a reversible anion storage capacity over 80 mAh g−1 at potentials over 4.5 V vs. Li/Li+. The structures of anion-graphite intercalation compounds are investigated in detail by the combination of in situ X-ray diffraction (XRD) and in situ Raman spectroscopic measurements.

Anion Solvation Regulation Enables Long Cycle Stability of Graphite Cathodes

Graphite is useful as a low-cost and high-voltage cathode of dual-ion batteries (DIBs) to allow anion (de-)intercalation, yet its practical applications are hindered by low Coulombic efficiencies (...

Locally Ordered Graphitized Carbon Cathodes for High-Capacity Dual-Ion Batteries.

Dual-ion batteries (DIBs) inherently suffer from limited energy density. Proposed here is a strategy to effectively tackle this issue by employing locally ordered graphitized carbon (LOGC) cathodes. Quantum mechanical modeling suggests that strong anion-anion repulsions and severe expansion at the deep-charging stage raise the anion intercalation voltage, therefore only part of the theoretical anion storage sites in graphite is accessible. The LOGC interconnected with disordered carbon is predicted to weaken the interlaminar van der Waals interactions, while disordered carbons not only interconnect the dispersed nanographite but also partially buffer severe anion-anion repulsion and offer extra capacitive anion storage sites. As a proof-of-concept, ketjen black (KB) with LOGC was used as a model cathode for a potassium-based DIB (KDIB). The KDIB delivers an unprecedentedly high specific capacity of 232 mAh g-1 at 50 mA g-1 , a good rate capability of 110 mAh g-1 at 2000 mA g-1 , and excellent cycling stability of 1000 cycles without obvious capacity fading.

Fast and stable K-ion storage enabled by synergistic interlayer and pore-structure engineering

Carbon-based material has been regarded as one of the most promising electrode materials for potassium-ion batteries (PIBs). However, the battery performance based on reported porous carbon electrodes is still unsatisfactory, while the in-depth K-ion storage mechanism remains relatively ambiguous. Herein, we propose a facile “in situ self-template bubbling” method for synthesizing interlayer-tuned hierarchically porous carbon with different metallic ions, which delivers superior K-ion storage performance, especially the high reversible capacity (360.6 mAh·g−1@0.05 A·g−1), excellent rate capability (158.6 mAh·g−1@10.0 A·g−1) and ultralong high-rate cycling stability (82.8% capacity retention after 2,000 cycles at 5.0 A·g−1). Theoretical simulation reveals the correlations between interlayer distance and K-ion diffusion kinetics. Experimentally, deliberately designed consecutive cyclic voltammetry (CV) measurements, ex situ Raman tests, galvanostatic intermittent titration technique (GITT) method decipher the origin of the excellent rate performance by disentangling the synergistic effect of interlayer and pore-structure engineering. Considering the facile preparation strategy, superior electrochemical performance and insightful mechanism investigations, this work may deepen the fundamental understandings of carbon-based PIBs and related energy storage devices like sodium-ion batteries, aluminum-ion batteries, electrochemical capacitors, and dual-ion batteries.

Status of rechargeable potassium batteries

Future renewable energy integrated grid systems require rechargeable batteries with low cost, high safety, and long cycle life. The much higher abundance of sodium and potassium compared to lithium in earth crust indicates that rechargeable sodium and potassium batteries are attractive replacements for lithium-ion batteries. Rechargeable potassium batteries have gained tremendous attention during the past decade. However, the development of rechargeable potassium batteries is still in its infancy. This review summarizes the recent technological developments in rechargeable potassium batteries. First, we summarize the latest achievements of active materials design, mechanistic understanding, and exploration of new active materials. We propose new directions in tuning the architecture and enhancing the electrochemical performances of high-performance anodes and cathodes. Second, we also summarize the advances that have been achieved in the new configurations of rechargeable potassium battery systems (potassium-ion capacitors, potassium dual ion batteries, potassium-sulfur batteries, and potassium-oxygen batteries). Finally, we propose future directions and design strategies that could be employed to advance rechargeable potassium batteries toward commercial applications. In this review, a large family of rechargeable batteries based on potassium as charge carrier are summarized. Rechargeable potassium ion batteries include potassium-ion batteries, potassium-ion capacitors, potassium-ion-based dual ion batteries, potassium-sulfur batteries, and potassium-oxygen batteries. Future directions and design strategies that could be employed to advance rechargeable potassium batteries toward commercial applications are proposed. • Rechargeable potassium ion battery as a promising rechargeable battery system. • Current status and future research trends of rechargeable potassium batteries. • Strategies for developing practical anodes and cathodes for potassium batteries. • Recent advances of different configurations of rechargeable potassium batteries.

Nature of the Cathode–Electrolyte Interface in Highly Concentrated Electrolytes Used in Graphite Dual-Ion Batteries

Dual-ion batteries (DIBs) generally operate beyond 4.7 V vs Li+/Li0 and rely on the intercalation of both cations and anions in graphite electrodes. Major challenges facing the development of DIBs are linked to electrolyte decomposition at the cathode–electrolyte interface (CEI), graphite exfoliation, and corrosion of Al current collectors. In this work, X-ray photoelectron spectroscopy (XPS) is employed to gain a broad understanding of the nature and dynamics of the CEI built on anion-intercalated graphite cycled both in highly concentrated electrolytes (HCEs) of common lithium salts (LiPF6, LiFSI, and LiTFSI) in carbonate solvents and in a typical ionic liquid. Though Al metal current collectors were adequately stable in all HCEs, the Coulombic efficiency was substantially higher for HCEs based on LiFSI and LiTFSI salts. Specific capacities ranging from 80 to 100 mAh g–1 were achieved with a Coulombic efficiency above 90% over extended cycling, but cells with LiPF6-based electrolytes were characterized by <70% Coulombic efficiency and specific capacities of merely ca. 60 mAh g–1. The poor performance in LiPF6-containing electrolytes is indicative of the continual buildup of decomposition products at the interface due to oxidation, forming a thick interfacial layer rich in LixPFy, POxFy, LixPOyFz, and organic carbonates as evidenced by XPS. In contrast, insights from XPS analyses suggested that anion intercalation and deintercalation processes in the range from 3 to 5.1 V give rise to scant or extremely thin surface layers on graphite electrodes cycled in LiFSI- and LiTFSI-containing HCEs, even allowing for probing anions intercalated in the near-surface bulk. In addition, ex situ Raman, SEM and TEM characterizations revealed the presence of a thick coating on graphite particles cycled in LiPF6-based electrolytes regardless of salt concentration, while hardly any surface film was observed in the case of concentrated LiFSI and LiTFSI electrolytes.

Reversible Insertion of I–Cl Interhalogen in a Graphite Cathode for Aqueous Dual-Ion Batteries

Anion storage in cathode of dual-ion batteries provides leeway for new battery chemistries. For high energy density and better safety, it is desirable but challenging to reversibly intercalate chlo...

Organic cation (DMPI) intercalated graphite anode for high voltage next generation dual-ion batteries

Organic cation (DMPI) intercalated anode and AlCl4 anion intercalated cathode for high voltage dual ion battery

Efficient Na+-storage in a Li4Ti5O12 anode to expand the voltage-window for full SIBs of high energy density.

The stable storage of sodium ions always presents some difficulties for sodium-based dual-ion batteries (S-DIBs), such as the irreversibility of guest-storage and kinetic hindrance in the anode. Based on the low strain volume and stable phase structure, herein, lithium titanate (LTO, Li4Ti5O12) was developed to store sodium ions between the working potential (∼0.8 V), which expands the lower plateau over than that of lithium ion storage (∼1.55 V) to obtain a high energy density of full batteries. The spinel lithium titanate shows negligible volume change and extremely stable structure under Na+-storage, which completely overcomes the shortage problems of the Na+-host. Additionally, by the detection of the transfer state of anions and cations in dual-ion batteries, the diffusion coefficient of the sodium ion in the LTO electrode is higher than that of the cathode, which shows that the transport process of sodium ions can meet the kinetic demands of full batteries. Such S-DIBs exhibit a large working voltage of 2.0–4.6 V and stable electrochemical performance over 1280 cycles, which is superior to conventional sodium-based systems, and further exhibit many advantages such as high energy density, environmental friendliness, and low cost.

Preparation of flower-like iron phosphate materials as a novel anode for dual-ion batteries

Dual-ion batteries (DIBs) have exceptional advantages over other electrochemical energy storage devices.

Tailoring the linking patterns of polypyrene cathodes for high-performance aqueous Zn dual-ion batteries

The redox-activity of Cl−-hosting polypyrene cathode in dual-ion batteries can be tuned by tailoring the linking patterns.

High-performance dual-ion Zn batteries enabled by a polyzwitterionic hydrogel electrolyte with regulated anion/cation transport and suppressed Zn dendrite growth

We described the fabrication of a novel dual-ion Zn/PANI battery based on a solid-state polyzwitterion hydrogel electrolyte with regulated anion/cation transport and suppressed Zn dendrite growth.

A diffusion encouraged core–shell heterostructured Co3Sn2@SnO2 anode towards emerging dual ion batteries with high energy density

A novel core–shell heterostructured Co3Sn2@SnO2 anode is explored for lithium dual ion batteries (LDIBs). The optimized Co3Sn2@SnO2 anode and expanded graphite cathode in an LDIB delivered notable energy density (334.5 W h kg−1).

Polydiphenylamine as a promising high-energy cathode material for dual-ion batteries

Polydiphenylamine (PDPA)-based cathodes exhibited record energy densities among all known polymer-based cathodes for dual-ion batteries.

Doped graphene encapsulated SnP2O7 with enhanced conversion reactions from polyanions as a versatile anode material for sodium dual-ion battery

Tin-based ternary oxides have obtained much attention for energy storage systems due to high capacity based on alloying/dealloying reactions and improved cycling performance resulted from the inactive buffer matrix. Herein, SnP2O7 particles are encapsulated into N/P dual-doped graphene (SnP2O7/NPG), which is served as an universal anode material for sodium-ion batteries (SIBs) and sodium-based dual-ion batteries (SDIBs). Benefiting from the unique structure of tin-based ternary oxides and synergy effect of multicomponent, the obtained SnP2O7/NPG delivers a good reversible capacity of 412.9 mAh g−1 at 0.05 A g−1, superior cycling performance of 86.2 mAh g−1 at 2 A g−1 after 1000 cycles, and exceptional rate performance of 182.3 mAh g−1 at 2 A g−1 in Na+ half cells. Especially, assembly of SnP2O7/NPG with the graphite cathode could yield a SnP2O7/NPG-graphite SDIBs, which shows high rate performance (up to 2 A g−1) and good cycling stability over 100 cycles with a capacity retention of 63.2%. Furthermore, the Na+ insertion/extraction mechanism is systematically investigated using the extensive kinetics investigation. This work provides inspirations as to extending the wider application prospect of tin-based ternary oxides in energy storage systems.

Intercalation Behavior of Tetrafluoroborate Anion in a Graphite Electrode from Mixed Cyclic Carbonates

In a dual-ion battery with an electrolyte solution, the anion storage behavior of graphite positive electrode is heavily dependent on anion solvation. In 1 M LiBF4 solutions dissolved in cyclic car...

Polycyclic Aromatic Hydrocarbons as Prospective Cathodes for Aluminum Organic Batteries

Aluminum dual-ion batteries (DIBs) have been identified as a possible future alternative for lithium-ion batteries, possessing several attractive properties like high abundance, high energy density, and environmental friendly. Graphite and graphite-like materials are being explored to improve the cathodic performance in Al DIBs. Very recently, several organic materials with p-type redox activity are also gaining attention due to their flexibility, low cost, and easy availability for usage as electrodes in DIBs. In this work, we have evaluated four lightweight polycyclic aromatic hydrocarbons (PAHs) (pyrene, perylene, triphenylene, and coronene) as prospective cathode materials for Al DIBs using first-principles calculation. Binding energy calculations show favorable intercalation of AlCl4–, maintaining its tetrahedral geometry inside the flexible lattices and subsequent charge transfer from the PAH systems displaying their redox activity. The charge transfer also initiates semiconducting to metallic transformation ensuring the electronic conductivity during the redox reactions in Al DIBs. Pyrene and coronene are found to deliver good electrochemical performance with ultrahigh specific capacity. Triphenylene also exhibits good voltage (∼1.9 V) even at a lower specific capacity. The flexible arrangement of PAH molecules is expected to compensate for a slightly higher diffusion energy barrier values due to subsequent expansion with increasing concentration of AlCl4– intercalation. These results motivate us toward use of PAH materials and further exploration of similar organic materials as cathodes for Al DIBs.