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Next generation solid-state batteries (SSB) will need to leverage high voltage cathodes, as well as metallic anodes to achieve the realistic performance targets necessary to replace liquid electrolyte-based batteries in cutting-edge applications including electric vehicles. However, limitations arising from mass and charge transports, kinetics and chemo-mechanical degradation at the electrode | electrolyte interface limit the performance of present day SSBs. Optimizing composite cathode architecture, which is an integral part of solid-state batteries, is vital to realize the high-energy density and high-performance goals for next-generation solid-state batteries. Cathode architecture needs to be optimized for high loadings of active material, well-percolated ion and electron transport pathways and increased resilience against electrochemical stresses. This paper provides a first report of framework for geometric modeling of composite cathode architectures and evaluates the impact of cathode architecture on cell-level energy density using hierarchical models. Packing around primary and secondary active material particles are simulated for a range of active material particle size and solid electrolyte size distributions in the composite cathode. Impact of packing architecture on processing parameters of a given cathode composition and thickness, as well as on achievable energy density is evaluated for a range of commonly used solid electrolyte and cathode materials. Overall, the proposed framework offers a facile exploratory methodology for establishing initial metrics for scalable processing of practical and competent SSBs.

Artificial barriers, usually with either electrochemically active or inactive coating materials, are deployed on cathode material surfaces to mitigate detrimental side reactions by suppressing direct contact of cathode and electrolyte called surface coatings. These surface coatings are commonly known to increase the wettability of liquid electrolyte and reduce the interfacial charge transfer resistance. An important caveat is the selection of appropriate coating material with appropriate thickness for achieving enhanced electrochemical performance. As modern battery materials are increasingly developed with some type of surface coating, a careful and thorough examination of their role in mitigating the cycle life issues of cathode materials is paramount. This comprehensive review article extensively covers the selection criteria of coating materials based on their chemical and physical properties and electrochemical functionalities. Additionally, the article discusses the concept of critical coating thickness and methods of achieving homogeneous coating architectures that deliver desired performance benefits. Furthermore, this comprehensive article summarizes the recent advancements, effectiveness, necessity of cathode surface coatings and identifies the key aspect of structure-property correlation between coating type/thickness and lithium-ion diffusion through coating layers as the linchpin that validates surface coating approaches especially for high capacity nickel-rich cathodes.

Here we report dual ion conduction capability of Na-based NASICON type super ion conductor materials using Na1+xMnx/2Zr2–x/2(PO4)3 (NMZP) as a candidate system. This method enables the use of Na-ba...

The emergence and dominance of lithium-ion batteries in expanding markets such as consumer electronics, electric vehicles, and renewable energy storage are driving enormous interests and investments in the battery sector. The explosively growing demand is generating a huge number of spent lithium-ion batteries, thereby urging the development of cost-effective and environmentally sustainable recycling technologies to manage end-of-life batteries. Currently, the recycling of end-of-life batteries is still in its infancy, with many fundamental and technological hurdles to overcome. Here, the authors provide an overview of the current state of battery recycling by outlining and evaluating the incentives, key issues, and recycling strategies. The authors highlight a direct recycling strategy through discussion of its benefits, processes, and challenges. Perspectives on the future energy and environmental science of this important field is also discussed with respect to a new concept introduced as the Battery Identity Global Passport (BIGP).

As lithium-ion battery (LIB) active material and cell manufacturing costs continue to drop with wider adoption of electric vehicles, electrode and cell processing costs remain too high in terms of reaching the ultimate U.S. Department of Energy (DOE) cell cost target of $80/kWh. This paper primarily covers major materials chemistry advancements made over the last 10 ​years ​at Oak Ridge National Laboratory (ORNL) in the space of advanced manufacturing science for LIBs with the aim of simultaneously meeting the ultimate cost target, 500 ​Wh/kg gravimetric energy density, 10-15-min fast charge times, and 1000 deep discharge cycles. Aqueous electrode processing with a variety of active anode and cathode materials is now a standard procedure at the DOE Battery Manufacturing R&D Facility at ORNL (BMF), including the latest processes developed for Ni-rich cathodes. New results on cobalt-free LiNi0.8Fe0.1Al0.1O2 (NFA 811) are also included and discussed in an electrode processing advantage context. In addition, colloidal processing advancements have been made for Si/C composite anodes for achieving >600 ​mA ​h/g capacities. Optimization of electrode coating parameters and drying protocols have been completed, which has elucidated how key processing variables need to be changed when parameters such as slurry solids loading, solvent type, and wet electrode thickness are changed. ORNL has also increased the line speeds at which thick cathodes can be processed using ultra-fast electron beam (EB) curing and substantially decreased formation cycling times to

An engaging area of research in sodium-ion batteries (SIBs) has been focusing on discovery, design, and synthesis of high-capacity cathode materials in order to boost energy density to levels close enough to that of state-of-the-art lithium-ion batteries. Of particular interest, P2-type layered oxide, Na2/3Fe1/2Mn1/2O2, has been researched as a potential cathode in SIBs based on its high theoretical capacity of 260 mA h/g and use of noncritical materials. However, the reported synthesis methods are not only complex and energy-demanding but also often yield inhomogeneous and impure materials with capacities less than 200 mA h/g under impractical test conditions. Here, we report a novel synthesis route using low-temperature eutectic reaction to produce highly homogeneous, crystalline, and impurity-free P2-NaxFe1/2Mn1/2O2 with enhanced Na-ion diffusivity and kinetics. The overall electrochemical performances of the Na-ion cells have been improved by pairing the P2-cathode with presodiated hard carbon anodes, leading to reversible capacities in the range of 180 mA h/g. This new approach is a contribution toward the simplification of synthesis and scalability of sodium-based cathodes with high crystallinity and fine-tuned morphology and the realization of a sodium-ion battery system with lower cost and improved electrochemical performance.

Solid-state battery (SSB) is the new avenue for achieving safe and high energy density energy storage in both conventional but also niche applications. Such batteries employ a solid electrolyte unlike the modern-day liquid electrolyte-based lithium-ion batteries and thus facilitate the use of high-capacity lithium metal anodes thereby achieving high energy densities. Despite this promise, practical realization and commercial adoption of solid-state batteries remain a challenge due to the underlying material and cell level issues that needs to be overcome. This chapter thus covers the specific challenges, design principles and performance improvement strategies pertaining to the cathode, solid electrolyte and anode used in solid state batteries. Perspectives and outlook on specific applications that can benefit from the successful implementation of solid-state battery systems are also discussed. Overall, this chapter highlights the potential of solid-state batteries for successful commercial deployment in next generation energy storage systems.

Here we demonstrate a composite material exhibiting dual multifunctional properties of a structural material and a redox-active battery. This incorporates three-dimensional aligned carbon nanotube interfaces that weave together a structural frame, redox-active battery materials, and a Kevlar-infiltrated solid electrolyte that facilitates ion transfer. Relative to the total measured composite material mass, we demonstrate energy density up to ∼1.4 Wh/kg, elastic modulus of 7 GPa, and tensile strength exceeding 0.27 GPa. Mechano-electrochemical analysis demonstrates stable battery operation under mechanical loading that validates multifunctional performance. These findings demonstrate how battery materials that are normally packaged under compression can be reorganized as elements in a structurally reinforced composite material.

Here we report a room-temperature sodium metal battery, where the sodium initially stored in a Na3V2(PO4)3 cathode is plated, upon charging, onto an aluminum current collector coated with a thin nucleation layer. To maximize the battery performance, conventional sodium-ion anode materials, including non-graphitized carbons and sodium-alloying metals, were evaluated as nucleation layers to facilitate stable electroplating of sodium metal. Among several materials studied, carbon black and bismuth showed the highest sodium plating–stripping coulombic efficiencies in half-cell testing, averaging 99.9% and 99.85%, respectively, over 50 cycles at 0.5 mA cm−2. Building on these findings, anode-free cells with Na3V2(PO4)3 cathodes were assembled in a discharged state, demonstrating energy densities up to 318 W h kg−1 at 0.25 mA cm−2 (∼C/6), a first-cycle coulombic efficiency up to 92%, a stable discharge voltage at 3.35 V, an average round-trip energy efficiency of 98%, and a capacity retention of 82.5% after 100 cycles at 0.5 mA cm−2 (∼C/3). With its unique performance highlighted in this work, the anode-free sodium battery emerges as a low-cost, high-performance option for stationary electric storage.

Advances in piezoelectric or triboelectric materials have enabled high-frequency platforms for mechanical energy harvesting (>10 Hz); however, virtually all human motions occur below 5 Hz and therefore limits application of these harvesting platforms to human motions. Here we demonstrate a device configuration based on sodiated black phosphorus nanosheets, or phosphorene, where mechanoelectrochemical stress–voltage coupling in this material is capable of efficient energy harvesting at frequencies as low as 0.01 Hz. The harvester is tested using both bending and pressing mechanical impulses with peak power delivery of ∼42 nW/cm2 and total harvested energy of 0.203 μJ/cm2 in the bending mode and ∼9 nW/cm2 and 0.792 μJ/cm2 in the pressing mode. Our work broadly demonstrates how 2D materials can be effectively leveraged as building blocks in strategies for efficient electrochemical strain energy harvesting.

Increasing amounts of nondegradable waste and rising levels of atmospheric carbon dioxide (CO2) similarly threaten a sustainable future, leaving routes to address these issues at the forefront of ongoing research efforts. Here, we demonstrate a route where electrochemical processing of scrap metals extracts catalytic species to the surface that actively convert CO2 scavenged from the atmosphere to form multiwalled carbon nanotubes (MWCNTs). Our findings demonstrate two distinct pathways for this technique that is generalizable to a broad range of scrap metals. First is the case where the catalytic elements are the primary constituents of the material (e.g., Fe in stainless steel) and the reaction with CO2 consumes the material. Second is the case where the catalytic elements are impurities (e.g., Fe in brass) where reaction with CO2 leads to impurity consumption. Our results demonstrate facile growth of MWCNTs directly from irregular scraps, such as shavings and pipes. Overall, this study presents a route...

The interplay between mechanical strains and battery electrochemistry, or the tunable mechanochemistry of batteries, remains an emerging research area with limited experimental progress. In this report, we demonstrate how elastic strains applied to vanadium pentoxide (V2O5), a widely studied cathode material for Li-ion batteries, can modulate the kinetics and energetics of lithium-ion intercalation. We utilize atomic layer deposition to coat V2O5 materials onto the surface of a shapememory superelastic NiTi alloy, which allows electrochemical assessment at a fixed and measurable level of elastic strain imposed on the V2O5, with strain state assessed through Raman spectroscopy and X-ray diffraction. Our results indicate modulation of electrochemical intercalation potentials by ∼40 mV and an increase of the diffusion coefficient of lithium ions by up to 2.5-times with elastic prestrains of

Until now, research efforts focused on electrochemical conversion of carbon dioxide into stable carbon-based materials have been limited by poor understanding of catalytic effects occurring at surfaces. Here, we demonstrate the capability to simultaneously use atomic layer deposition (ALD), electrode composition control, and current density as a means to direct the formation of iron-based catalysts and grow highly crystalline multi-walled carbon nanotubes at high yields (99%) and with controlled average diameters of 27.5 nm from ambient carbon dioxide captured and dissolved in molten carbonate electrolytes. ALD of passive alumina coatings on a Ni anode prevents electrode corrosion processes and adverse deposition of Ni on the cathode that results in increased CNT diameters, lower CNT quality, and non-CNT products. On the cathode side where CNT growth occurs, our results elucidate the fine balance of iron catalyst accessibility from the cathode interior and the surface chemical properties in order to achieve high yield and high quality CNT growth. Our work provides an intersection between decades of research understanding on catalytic gas-phase growth of CNT materials and the ability to leverage these ideas to sustainably capture ambient carbon dioxide and produce functional CNT materials.

Here we demonstrate an isothermal technique that enables rapid vapor infiltration of sulfur into carbon templates to overcome scalability and performance bottlenecks associated with common melt infiltration techniques. Building on straightforward thermodynamic principles of capillary condensation, self-limited sulfur loadings up to 82 wt % can be achieved in as little as 10 min at temperatures between 155 and 175 °C. We demonstrate a broad range of device performance criteria using a carbon black–single-walled carbon nanotube binder-free cathode framework, including a side-by-side comparison to melt infiltrated electrodes with 74 wt % loading that shows improved capacity (1015 mAh/g vs 768 mAh/g), ∼92% capacity retention after 200 cycles at 0.5 C, and ∼98% Coulombic efficiency as a result of enhanced uniformity and conductivity. Further, we demonstrate this technique over a range of different electrodes (1) electrodes with high sulfur loading (82 wt %) with high initial discharge capacity of 1340 mAh/g, (...

Here, we report a wet synthesis-based titanium doping strategy to improve the structural stability and electrochemical performances, such as cycling stability and rate capability, of P2-type Na0.67Fe0.5Mn0.5O2 layered oxide cathodes. Through Ti4+ doping aimed at replacing some of the Mn and Fe atoms in the crystal structure, effective mitigation of the Jahn Teller distortion caused by active Mn3+ before charging and Fe4+ after charging was achieved. X-ray diffraction (XRD), Raman spectroscopy, Electrochemical Impedance Spectroscopy (EIS) and Mossbauer spectroscopy were used to investigate the effects of the Ti4+ dopant before and after cycling. It was observed that Ti4+ doping increased the Na layer thickness, minimized the lattice volume strain, showed better structural stability, minimally decreased Fe migration to the Na layer, and lowered charge transfer resistance in these P2-type cathodes. Overall, our reported synthesis methodology and electrochemical characterizations highlight the feasibility of Ti doping in sodium layered oxide P2-type cathodes.

Despite the promise of surface engineering to address the challenge of polysulfide shuttling in sulfur–carbon composite cathodes, melt infiltration techniques limit mechanistic studies correlating engineered surfaces and polysulfide anchoring. Here, we present a controlled experimental demonstration of polysulfide anchoring using vapor phase isothermal processing to fill the interior of carbon nanotubes (CNTs) after assembly into binder-free electrodes and atomic layer deposition (ALD) coating of polar V2O5 anchoring layers on the CNT surfaces. The ultrathin submonolayer V2O5 coating on the CNT exterior surface balances the adverse effect of polysulfide shuttling with the necessity for high sulfur utilization due to binding sites near the conductive CNT surface. The sulfur loaded into the CNT interior provides a spatially separated control volume enabling high sulfur loading with direct sulfur-CNT electrical contact for efficient sulfur conversion. By controlling ALD coating thickness, high initial discha...

Sodium-ion batteries (SIBs) have been pursued as a more cost-effective and more sustainable alternative to lithium-ion batteries (LIBs), but these advantages come at the expense of energy density. In this work, we demonstrate that the challenge of energy density for sodium chemistries can be overcome through an anode-free architecture enabled by the use of a nanocarbon nucleation layer formed on Al current collectors. Electrochemical studies show this configuration to provide highly stable and efficient plating and stripping of sodium metal over a range of currents up to 4 mA/cm2, sodium loading up to 12 mAh/cm2, and with long-term durability exceeding 1000 cycles at a current of 0.5 mA/cm2. Building upon this anode-free architecture, we demonstrate a full cell using a presodiated pyrite cathode to achieve energy densities of ∼400 Wh/kg, far surpassing recent reports on SIBs and even the theoretical maximum for LIB technology (387 Wh/kg for LiCoO2/graphite cells) while still relying on naturally abundant ...

Here we report the first mechanistic study investigating the effect of carbon defects on the evolution of different sodium–red phosphorus (red P) alloy states for stable high capacity sodium ion battery anodes. Using tunable sp2/sp3 carbon composites containing controlled single-walled carbon nanotube (SWCNT) and single-walled carbon nanohorn (SWCNH) compositions, we identify potentials over which both stable and unstable alloying of red P occurs with sodium. Examination of the stable alloy region includes both NaP and Na5P4 formation that occurs between 0.40 and 0.15 V where alloying is mostly independent of the carbon composite matrix chemistry. However, an unstable region corresponding to Na3P formation below 0.15 V results in capacity degradation that directly correlates with the density of carbon defects. In the unstable region, defects are observed to initiate deep alloying and poor reversibility due to the formation of irreversible Na3P products that form over the carbon surface. Our results present a mechanistic roadmap to guide the design of red P–carbon composite anodes to approach high theoretical sodium ion capacity (2596 mA h g−1) while simultaneously addressing chemical interactions that compromise performance stability.

Here we present the first full-cell battery device that is developed entirely from scrap metals of brass and steel – two of the most commonly used and discarded metals. A room temperature chemical process is developed to convert brass and steel into functional electrodes for rechargeable energy storage that transforms these multicomponent alloys into redox-active iron-oxide and copper-oxide materials. The resulting steel-brass battery exhibits cell voltages up to 1.8 V, energy density up to 20 Wh/kg, power density up to 20 kW/kg, and stable cycling over 5000 cycles in alkaline electrolytes. Further, we show the versatility of this technique to enable processing of steel and brass materials of different shapes, sizes, and purity, such as screws and shavings, to produce functional battery components. The simplicity of this approach, building from commonly available chemicals enables a simple pathway to the local recovery, processing, and assembly of storage systems based on materials that would otherwise be discarded.

Small diameter carbon nanotube (CNTs) are synthesized directly from a parent CNT forest using a floating catalyst chemical vapor deposition (CVD) method. To support a new CNT generation from an existing forest, an alumina coating was applied to the CNT forest using atomic layer deposition (ALD). The new generation of small diameter CNTs (8 nm average) surround the first generation, filling the interstitial regions. The hierarchical forests exhibit a 5-10-fold increase in stiffness, and the two generations are electrically addressable in spite of the interfacial alumina layer between them. This work enables the design of complex CNT architectures with hierarchical features that bring tailored properties such as high specific surface area and robust mechanical properties that can benefit a range of applications.

Despite widespread focus on porous carbons for lithium-sulfur battery cathode materials, electrode design to preserve mass-specific performance and sustained extended cycling stability remains a challenge. Here, we demonstrate electrochemically etched porous silicon as a sacrificial template to produce a new class of functional mesoporous carbons optimized for dual chemical and physical confinement of soluble polysulfides in lithium-sulfur battery cathodes. Melt infiltration loading of sulfur at 60 wt% enables initial discharge capacity of 1350 mAh/gsulfur at rates of 0.1 C - approaching theoretical capacity of 1675 mAh/gsulfur. Cycling performance measured at 0.2 C indicates 81% capacity retention measured over 100 cycles with 830 mAh/gsulfur capacity. Unlike other carbons, this template combines structural properties necessary for sulfur containment and polysulfide confinement to achieve high specific capacity, but also boasts surface-bound oxygen-containing functional groups that are able to chemically anchor the soluble Li2Sn species on the interior of the mesoporous carbon to sustain cycling performance. In turn, this elucidates a scalable and competitive material framework that is capable, without the addition of additional membranes or inactive anchoring materials, of providing the simultaneous anchoring and confinement effects necessary to overcome performance limitations in lithium sulfur batteries.

In this work, we report solution-based doping and coating strategies to improve the electrochemical performance of the Co-free layered oxide cathode LiNi0.5Mn0.5O2 (NM-50/50). Small amounts of d0 dopants (e.g., Mo6+and Ti4+, 0.5–1 at. %) increase the cathode's specific capacity, cycling stability, and rate capability. For example, a Mo-doped cathode with the nominal composition LiNi0.495Mn0.495Mo0.01O2 exhibits a high reversible capacity of 180 mA h/g at 20 mA/g compared to only 156 mA h/g for undoped NM-50/50. Effects of 1 at.% Mo dopant on the cathode structure were studied using a suite of characterization tools including X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy. These measurements demonstrate that Mo6+ dopant is enriched near the particle surface and improves the electrochemical performance of LiNi0.5Mn0.5O2 by: (i) reducing Li+/Ni2+ cation mixing which facilitates Li+ transport, (ii) mitigating undesirable phase transformations near the cathode surface, and (iii) altering the cathode/electrolyte interfacial chemistry. This work also reports the use of an inorganic Mn2P2O7 coating which enhances the cycling stability of Mo-doped NM-50/50, presumably through formation of a stable cathode electrolyte interphase (CEI) layer. Overall, the synthesis approaches reported herein are quite general and can potentially be expanded to other high voltage Li-ion battery cathodes.

Separation of cathode materials from the current collector remains a challenging task for the recycling of both spent lithium-ion batteries and cathode scraps. Dissolving the organic binder polyvinylidene difluoride (PVDF) with an organic solvent to recover both cathode materials and Al foils is an efficient and promising method. However, the use of toxic solvents limits their practical application in recycling large amounts of cathode scraps generated during the manufacturing process. Cyrene, a bioderived green solvent, is proposed here for a solvent-based separation process. This study investigated a closed-loop recovery process to reclaim cathode materials, Al foils, and PVDF binder from cathode scraps. Additionally, the reuse of the Cyrene solvent led to a circular recycling process. The Cyrene-based separation process embraces a sustainable electrode recovery and reuse platform and paves the way for battery recycling.

Recently, rapid fluctuations in cobalt prices have created a worsening supply chain constraint that has become a serious cause of concern amidst global battery manufacturers. To address this challenge, here we report a new class of cobalt-free, nickel-rich layered cathode material termed the NFA class with general formula LiNixFeyAlzO2 (x + y + z = 1). Using co-precipitation reaction in a continuous stirred tank reactor, we synthesized NFA(OH)2 precursors with the constituent Ni, Fe and Al elements successfully incorporated. The obtained LiNFAO2 cathode was characterized using X-Ray diffraction, Mossbauer spectroscopy and scanning electron microscopy. Electrochemical behavior was assessed using cyclic voltammetry, galvanostatic charge/discharge, electrochemical impedance spectroscopy and galvanostatic intermittent titration technique at various states of lithiation/delithiation. Electrochemical performance evaluations revealed that our cobalt-free material delivers high capacity of 190 mAh/g at 0.1C. Rate and cycling performance evaluations also indicated good rate capability and cycling stability with 88% capacity retention after 100 cycles at C/3. Using NFA cathodes, we also fabricated a 0.5Ah (C/3) cobalt-free Li-ion battery which demonstrated reasonable cycling stability with ~72% capacity retained after 200 cycles. Overall, our work demonstrates the immense potential of the cobalt-free NFA class cathodes as viable candidates towards development of next generation cost effective lithium ion batteries.

LiMn1.5Ni0.5O4 is one of the most promising cathode materials for use in either next generation lithium-ion batteries or all solid-state batteries. However, despite the significant Research and Development (R&D) carried out throughout the last two decades the material has not made serious inroads into market. One of the major reasons is the lack of consistency in the reported intrinsic properties and electrochemical performance owing to major controversies in synthesis, crystal structure and bulk and interfacial properties of LiMn1.5Ni0.5O4, notably in contact with electrolytes. This paper is a compelling review providing an assessment on the mainstream R&D dealing with the various crystal structures of LiMn1.5Ni0.5O4 and their evolutions observed during synthesis and cycling in correlation with their electrochemical performance. Influence of electrolytes and additives along with modifications through doping and surface treatments are interrelated, and the electronic and ionic transport properties of the ordered and disordered LiMn1.5Ni0.5O4 phases are discussed. Overall, this review provides a detailed assessment on LiMn1.5Ni0.5O4 and the underlying mechanisms governing its electrochemical performance broadly providing a focused framework for further advancement towards commercialization.

In recent years, cobalt has become a critical constraint on the supply chain of the Li-ion battery industry. With the ever-increasing projections for electric vehicles, the dependency of current Li-ion batteries on the ever-fluctuating cobalt prices poses serious environmental and sustainability issues. To address these challenges, a new class of cobalt-free materials with general formula of LiNix Fey Alz O2 (x + y + z = 1), termed as the lithium iron aluminum nickelate (NFA) class of cathodes, is introduced. These cobalt-free materials are synthesized using the sol-gel process to explore their compositional landscape by varying aluminum and iron. These NFA variants are characterized using electron microscopy, neutron and X-ray diffraction, and Mossbauer and X-ray photoelectron spectroscopy to investigate their morphological, physical, and crystal-structure properties. Operando experiments by X-ray diffraction, Mossbauer spectroscopy, and galvanostatic intermittent titration have been also used to study the crystallographic transitions, electrochemical activity, and Li-ion diffusivity upon lithium removal and uptake in the NFA cathodes. NFA compositions yield specific capacities of ≈200 mAh g-1 , demonstrating reasonable rate capability and cycling stability with ≈80% capacity retention after 100 charge/discharge cycles. While this is an early stage of research, the potential that these cathodes could have as viable candidates in next-generation cobalt-free lithium-ion batteries is highlighted here.

Here we demonstrate a full-cell battery design that bridges the energy density and rate capability between that of supercapacitors or pseudocapacitors with that of traditional lithium-ion batteries. This is accomplished by pairing an anode that enables ultrafast ion co-intercalation, an open framework cathode that allows rapid ion diffusion, and linear ether based electrolyte that sustains cell-level stability and high rate performance. We show this platform to be suitable for both sodium and potassium batteries using graphite as the co-intercalation anode, and Prussian blue as the open framework cathode. Our devices exhibit active material energy densities >100 W h kg-1 with power density >1000 W kg-1 with cycling durability approaching ∼80% energy density retention over 2000 cycles. This work brings together state-of-the-art concepts for fast-charging batteries into a full-cell configuration.

Carbon nanotubes exhibit mechanical properties ideally suited for reinforced structural composites and surface area and conductivity attractive for electrochemical capacitors. Here we demonstrate the multifunctional synergy between these properties in a composite material exhibiting simultaneous mechanical and energy storage properties. This involves a reinforcing electrode developed using dense, aligned carbon nanotubes grown on stainless steel mesh that is layered in an ion conducting epoxy electrolyte matrix with Kevlar or fiberglass mats. The resulting energy storage composites exhibit elastic modulus over 5 GPa, mechanical strength greater than 85 MPa, and energy density up to 3 mWh/kg for the total combined system including electrodes, current collector, Kevlar or fiberglass, and electrolyte matrix. Furthermore, findings from in-situ mechano-electro-chemical tests indicate simultaneous mechanical and electrochemical functionality with invariant and stable supercapacitor performance maintained throughout the elastic regime.

Here we demonstrate the broad capability to exploit interactions at different length scales in 2D materials to prepare macroscopic functional materials containing hybrid black phosphorus/graphene (BP/G) heterostructured building blocks. First, heterostructured 2D building blocks are self-assembled during co-exfoliation in the solution phase based on electrostatic attraction of different 2D materials. Second, electrophoretic deposition is used as a tool to assemble these building blocks into macroscopic films containing these self-assembled 2D heterostructures. Characterization of deposits formed using this technique elucidates the presence of stacked and sandwiched 2D heterostructures, and zeta potential measurements confirm the mechanistic interactions driving this assembly. Building on the exceptional sodium alloying capacity of BP, these materials were demonstrated as superior binder-free and additive-free anodes for sodium batteries with specific discharge capacity of 2365 mA h gP-1 and long stable cycling duration. This study demonstrates how controllable co-processing of 2D materials can enable material control for stacking and building block assembly relevant to broad future applications of 2D materials.

We report the first demonstration of potassium ion cointercalation into graphitic carbon electrodes including both natural graphite and multi-layered graphene in both diglyme and monoglyme based electrolytes. Contrary to conventional desolvation-based intercalation of potassium, we demonstrate excellent capacity retention of ∼80% at rates up to 10 A g−1 (30 second charge), with 95% capacity retention over 1000 cycles, and up to 100 mA h g−1 capacity. Raman and X-ray diffraction following 1000 cycles demonstrates no signature of defects, damage, or change to graphitic crystallinity compared to uncycled pristine materials that is attributed to weak ion–lattice interactions due to the solvated guest K ions. In situ Raman spectroscopy highlights the sequential formation of a stage 4, 3, 2, and 1 graphite intercalation compound (GIC) that occurs without the signature of dilute staging. In a charged stage 1 compound, we observe lattice expansion from 0.335 nm to 1.16 nm and measure the work function to be ∼3.4 eV. Overall, this system overcomes rate and durability bottlenecks that limit current K-ion battery electrodes, and gives promise to cointercalation for durable, fast, and low-cost storage systems.

We demonstrate a room-temperature sodium sulfur battery based on a confining microporous carbon template derived from sucrose that delivers a reversible capacity over 700 mAh/gS at 0.1C rates, maintaining 370 mAh/gS at 10 times higher rates of 1C. Cycling at 1C rates reveals retention of over 300 mAh/gS capacity across 1500 cycles with Coulombic efficiency >98% due to microporous sulfur confinement and stability of the sodium metal anode in a glyme-based electrolyte. We show sucrose to be an ideal platform to develop microporous carbon capable of mitigating electrode–electrolyte reactivity and loss of soluble intermediate discharge products. In a manner parallel to the low-cost materials of the traditional sodium beta battery, our work demonstrates the combination of table sugar, sulfur, and sodium, all of which are cheap and earth abundant, for a high-performance stable room-temperature sodium sulfur battery.

The effectiveness of using catalyst nanoparticles to reduce the overpotential and energy efficiency of lithium-oxygen (or lithium-air) batteries (LOBs) is usually attributed to the inherent catalytic properties of individual nanoparticles. Here, we demonstrate that the morphology of the catalyst layer is equally important in maintaining integrity of the catalyst coating during product formation in LOBs. We demonstrate this by comparing the performance of smooth, conformal coated Mn2O3 catalyst nanoparticles prepared by electric field-assisted deposition, and more irregular coatings using conventional film assembly techniques both on three-dimensional mesh substrates. Smooth coatings lead to an improved overpotential of 50 mV during oxygen reduction and 130 mV during oxygen evolution in addition to a nearly 2X improvement in durability compared to the more irregular films. In situ electrochemical impedance spectroscopy combined with imaging studies elucidates a mechanism of morphology-directed deactivation of catalyst layers during charging and discharging that must be overcome at practical electrode scales to achieve cell-level performance targets in LOBs.

A key parameter in the operation of an electrochemical double-layer capacitor is the voltage window, which dictates the device energy density and power density. Here we demonstrate experimental evidence that π-π stacking at a carbon-ionic liquid interface can modify the operation voltage of a supercapacitor device by up to 30%, and this can be recovered by steric hindrance at the electrode-electrolyte interface introduced by poly(ethylene oxide) polymer electrolyte additives. This observation is supported by Raman spectroscopy, electrochemical impedance spectroscopy, and differential scanning calorimetry that each independently elucidates the signature of π-π stacking between imidazole groups in the ionic liquid and the carbon surface and the role this plays to lower the energy barrier for charge transfer at the electrode-electrolyte interface. This effect is further observed universally across two separate ionic liquid electrolyte systems and is validated by control experiments showing an invariant electrochemical window in the absence of a carbon-ionic liquid electrode-electrolyte interface. As interfacial or noncovalent interactions are usually neglected in the mechanistic picture of double-layer capacitors, this work highlights the importance of understanding chemical properties at supercapacitor interfaces to engineer voltage and energy capability.

Strain engineering has been a critical aspect of device design in semiconductor manufacturing for the past decade, but remains relatively unexplored for other applications, such as energy storage. Using mechanical strain as an input parameter to modulate electrochemical potentials of metal oxides opens new opportunities intersecting fields of electrochemistry and mechanics. Here we demonstrate that less than 0.1% strain on a Ni-Ti-O based metal-oxide formed on superelastic shape memory NiTi alloys leads to anodic and cathodic peak potential shifts by up to ~30 mV in an electrochemical cell. Moreover, using the superelastic properties of NiTi to enable strain recovery also recovers the electrochemical potential of the metal oxide, providing mechanistic evidence of strain-modified electrochemistry. These results indicate that mechanical energy can be coupled with electrochemical systems to efficiently design and optimize a new class of strain-modulated energy storage materials.