Spectroscopic Characterization of Mn1+ Low Oxidation State in Prussian Blue-Based Battery Anodes.

Stabilization of ions in exotic oxidation states is beneficial for the development of new materials for green energy technologies. Exotic Mn1+ was proposed to play a role in the function of sodium-based Prussian blue analogues (PBA) batteries, a highly sought-out technology for industrial energy storage. Here, we report the detailed electronic structure characterization of uncharged and charged sodium-based manganese hexacyanomanganate anodes via Mn K-edge X-ray absorption spectroscopy (XAS), Kß nonresonant X-ray emission (XES), and resonant inelastic X-ray scattering (RIXS). The latter allowed us to obtain site-selective XANES information about two distinct Mn centers. The obtained spectroscopic data represent the first electronic structure characterization of low-spin Mn1+ using hard X-ray RIXS and XES and allowed us to confirm its role in anode reduction. Our experimental approach can be expanded to analysis of analogues with other 3d transition metals broadening the application of exotic ionic states in materials engineering.

Monovalent manganese based anodes and co-solvent electrolyte for stable low-cost high-rate sodium-ion batteries.

The demand of sustainable power supply requires high-performance cost-effective energy storage technologies. Here we report a high-rate long-life low-cost sodium-ion battery full-cell system by innovating both the anode and the electrolyte. The redox couple of manganese(I/II) in Prussian blue analogs enables a high-rate and stable anode. Soft X-ray absorption spectroscopy and resonant inelastic X-ray scattering provide direct evidence suggesting the existence of monovalent manganese in the charged anode. There is a strong hybridization between cyano ligands and manganese-3d states, which benefits the electronic property for improving rate performance. Additionally, we employ an organic-aqueous cosolvent electrolyte to solve the long-standing solubility issue of Prussian blue analogs. A full-cell sodium-ion battery with low-cost Prussian blue analogs in both electrodes and co-solvent electrolyte retains 95% of its initial discharge capacity after 1000 cycles at 1C and 95% depth of discharge. The revealed manganese(I/II) redox couple inspires conceptual innovations of batteries based on atypical oxidation states.

Full open-framework batteries for stationary energy storage.

New types of energy storage are needed in conjunction with the deployment of renewable energy sources and their integration with the electrical grid. We have recently introduced a family of cathodes involving the reversible insertion of cations into materials with the Prussian Blue open-framework crystal structure. Here we report a newly developed manganese hexacyanomanganate open-framework anode that has the same crystal structure. By combining it with the previously reported copper hexacyanoferrate cathode we demonstrate a safe, fast, inexpensive, long-cycle life aqueous electrolyte battery, which involves the insertion of sodium ions. This high rate, high efficiency cell shows a 96.7% round trip energy efficiency when cycled at a 5C rate and an 84.2% energy efficiency at a 50C rate. There is no measurable capacity loss after 1,000 deep-discharge cycles. Bulk quantities of the electrode materials can be produced by a room temperature chemical synthesis from earth-abundant precursors.

Highly reversible open framework nanoscale electrodes for divalent ion batteries.

The reversible insertion of monovalent ions such as lithium into electrode materials has enabled the development of rechargeable batteries with high energy density. Reversible insertion of divalent ions such as magnesium would allow the creation of new battery chemistries that are potentially safer and cheaper than lithium-based batteries. Here we report that nanomaterials in the Prussian Blue family of open framework materials, such as nickel hexacyanoferrate, allow for the reversible insertion of aqueous alkaline earth divalent ions, including Mg(2+), Ca(2+), Sr(2+), and Ba(2+). We show unprecedented long cycle life and high rate performance for divalent ion insertion. Our results represent a step forward and pave the way for future development in divalent batteries.

A high-rate and long cycle life aqueous electrolyte battery for grid-scale energy storage.

New types of energy storage are needed in conjunction with the deployment of solar, wind and other volatile renewable energy sources and their integration with the electric grid. No existing energy storage technology can economically provide the power, cycle life and energy efficiency needed to respond to the costly short-term transients that arise from renewables and other aspects of grid operation. Here we demonstrate a new type of safe, fast, inexpensive, long-life aqueous electrolyte battery, which relies on the insertion of potassium ions into a copper hexacyanoferrate cathode and a novel activated carbon/polypyrrole hybrid anode. The cathode reacts rapidly with very little hysteresis. The hybrid anode uses an electrochemically active additive to tune its potential. This high-rate, high-efficiency cell has a 95% round-trip energy efficiency when cycled at a 5C rate, and a 79% energy efficiency at 50C. It also has zero-capacity loss after 1,000 deep-discharge cycles.

Chemical intercalation of zerovalent metals into 2D layered Bi2Se3 nanoribbons.

We have developed a chemical method to intercalate a variety of zerovalent metal atoms into two-dimensional (2D) layered Bi(2)Se(3) chalcogenide nanoribbons. We use a chemical reaction, such as a disproportionation redox reaction, to generate dilute zerovalent metal atoms in a refluxing solution, which intercalate into the layered Bi(2)Se(3) structure. The zerovalent nature of the intercalant allows superstoichiometric intercalation of metal atoms such as Ag, Au, Co, Cu, Fe, In, Ni, and Sn. We foresee the impact of this methodology in establishing novel fundamental physical behaviors and in possible energy applications.

High-density chemical intercalation of zero-valent copper into Bi2Se3 nanoribbons.

A major goal of intercalation chemistry is to intercalate high densities of guest species without disrupting the host lattice. Many intercalant concentrations, however, are limited by the charge of the guest species. Here we have developed a general solution-based chemical method for intercalating extraordinarily high densities of zero-valent copper metal into layered Bi(2)Se(3) nanoribbons. Up to 60 atom % copper (Cu(7.5)Bi(2)Se(3)) can be intercalated with no disruption to the host lattice using a solution disproportionation redox reaction.

Tunable reaction potentials in open framework nanoparticle battery electrodes for grid-scale energy storage.

The electrical energy grid has a growing need for energy storage to address short-term transients, frequency regulation, and load leveling. Though electrochemical energy storage devices such as batteries offer an attractive solution, current commercial battery technology cannot provide adequate power, and cycle life, and energy efficiency at a sufficiently low cost. Copper hexacyanoferrate and nickel hexacyanoferrate, two open framework materials with the Prussian Blue structure, were recently shown to offer ultralong cycle life and high-rate performance when operated as battery electrodes in safe, inexpensive aqueous sodium ion and potassium ion electrolytes. In this report, we demonstrate that the reaction potential of copper-nickel alloy hexacyanoferrate nanoparticles may be tuned by controlling the ratio of copper to nickel in these materials. X-ray diffraction, TEM energy dispersive X-ray spectroscopy, and galvanostatic electrochemical cycling of copper-nickel hexacyanoferrate reveal that copper and nickel form a fully miscible solution at particular sites in the framework without perturbing the structure. This allows copper-nickel hexacyanoferrate to reversibly intercalate sodium and potassium ions for over 2000 cycles with capacity retentions of 100% and 91%, respectively. The ability to precisely tune the reaction potential of copper-nickel hexacyanoferrate without sacrificing cycle life will allow the development of full cells that utilize the entire electrochemical stability window of aqueous sodium and potassium ion electrolytes.

A desalination battery.

Water desalination is an important approach to provide fresh water around the world, although its high energy consumption, and thus high cost, call for new, efficient technology. Here, we demonstrate the novel concept of a "desalination battery", which operates by performing cycles in reverse on our previously reported mixing entropy battery. Rather than generating electricity from salinity differences, as in mixing entropy batteries, desalination batteries use an electrical energy input to extract sodium and chloride ions from seawater and to generate fresh water. The desalination battery is comprised by a Na(2-x)Mn(5)O(10) nanorod positive electrode and Ag/AgCl negative electrode. Here, we demonstrate an energy consumption of 0.29 Wh l(-1) for the removal of 25% salt using this novel desalination battery, which is promising when compared to reverse osmosis (~ 0.2 Wh l(-1)), the most efficient technique presently available.

Nickel hexacyanoferrate nanoparticle electrodes for aqueous sodium and potassium ion batteries.

The electrical power grid faces a growing need for large-scale energy storage over a wide range of time scales due to costly short-term transients, frequency regulation, and load balancing. The durability, high power, energy efficiency, and low cost needed for grid-scale storage pose substantial challenges for conventional battery technology. (1, 2) Here, we demonstrate insertion/extraction of sodium and potassium ions in a low-strain nickel hexacyanoferrate electrode material for at least five thousand deep cycles at high current densities in inexpensive aqueous electrolytes. Its open-framework structure allows retention of 66% of the initial capacity even at a very high (41.7C) rate. At low current densities, its round trip energy efficiency reaches 99%. This low-cost material is readily synthesized in bulk quantities. The long cycle life, high power, good energy efficiency, safety, and inexpensive production method make nickel hexacyanoferrate an attractive candidate for use in large-scale batteries to support the electrical grid.

Copper hexacyanoferrate battery electrodes with long cycle life and high power.

Short-term transients, including those related to wind and solar sources, present challenges to the electrical grid. Stationary energy storage systems that can operate for many cycles, at high power, with high round-trip energy efficiency, and at low cost are required. Existing energy storage technologies cannot satisfy these requirements. Here we show that crystalline nanoparticles of copper hexacyanoferrate, which has an ultra-low strain open framework structure, can be operated as a battery electrode in inexpensive aqueous electrolytes. After 40,000 deep discharge cycles at a 17 C rate, 83% of the original capacity of copper hexacyanoferrate is retained. Even at a very high cycling rate of 83 C, two thirds of its maximum discharge capacity is observed. At modest current densities, round-trip energy efficiencies of 99% can be achieved. The low-cost, scalable, room-temperature co-precipitation synthesis and excellent electrode performance of copper hexacyanoferrate make it attractive for large-scale energy storage systems.

Hippocampal-dependent learning requires a functional circadian system.

Decades of studies have shown that eliminating circadian rhythms of mammals does not compromise their health or longevity in the laboratory in any obvious way. These observations have raised questions about the functional significance of the mammalian circadian system, but have been difficult to address for lack of an appropriate animal model. Surgical ablation of the suprachiasmatic nucleus (SCN) and clock gene knockouts eliminate rhythms, but also damage adjacent brain regions or cause developmental effects that may impair cognitive or other physiological functions. We developed a method that avoids these problems and eliminates rhythms by noninvasive means in Siberian hamsters (Phodopus sungorus). The present study evaluated cognitive function in arrhythmic animals by using a hippocampal-dependent learning task. Control hamsters exhibited normal circadian modulation of performance in a delayed novel-object recognition task. By contrast, arrhythmic animals could not discriminate a novel object from a familiar one only 20 or 60 min after training. Memory performance was not related to prior sleep history as sleep manipulations had no effect on performance. The GABA antagonist pentylenetetrazol restored learning without restoring circadian rhythms. We conclude that the circadian system is involved in memory function in a manner that is independent of sleep. Circadian influence on learning may be exerted via cyclic GABA output from the SCN to target sites involved in learning. Arrhythmic hamsters may have failed to perform this task because of chronic inhibitory signaling from the SCN that interfered with the plastic mechanisms that encode learning in the hippocampus.