In Situ Fabricated Non-Flammable Quasi-Solid Electrolytes for Li-Metal Batteries.

Lithium metal batteries (LMBs) are viewed as one of the most promising high energy density battery systems, but their practical application is hindered by significant fire hazards and fast performance degradation due to the lack of a safe and compatible configuration. Herein, nonflammable quasi-solid electrolytes (NQSEs) are designed and fabricated by using the in situ polymerization method, in which 1,3,2-dioxathiolan-2,2-oxide is used as both initiator to trigger the in situ polymerization of solvents and interphase formation agent to construct robust interface layers to protect the electrodes, and triethyl phosphate as a fire-retardant agent. The NQSEs show a high ionic conductivity of 0.38 mS cm-1 at room temperature and enable intimate solid-electrolyte interphases, and demonstrate excellent performance with stable plating/striping of Li metal anode, and high voltage (4.5 V) and high temperature (>60 °C) survivability. The findings provide an effective strategy to build high-temperature, high-energy density, and safe quasi-solid LMBs.

Achieving Practical High-Energy-Density Lithium-Metal Batteries by a Dual-Anion Regulated Electrolyte.

Lithium-metal batteries (LMBs) using lithium-metal anodes and high-voltage cathodes have been deemed as one of the most promising high-energy-density battery technology. However, its practical application is largely hindered by the notorious dendrite growth of lithium-metal anodes, the fast structure degradation of the cathode, and insufficient electrode-electrolyte interphase kinetics. Here, a dual-anion regulated electrolyte is developed for LMBs using lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) and lithium difluoro(bisoxalato)phosphate (LiDFBOP) as anion regulators. The incorporation of TFSI- in the solvation sheath reduces the desolvation energy of Li+ , and DFBOP- promotes the formation of highly ion-conductive and sustainable inorganic-rich interphases on the electrodes. Significantly enhanced performance is demonstrated on Li||LiNi0.83 Co0.11 Mn0.06 O2 pouch cells, with 84.6% capacity retention after 150 cycles in 6.0 Ah pouch cells and an ultrahigh rate capability up to 5 C in 2.0 Ah pouch cells. Furthermore, a pouch cell with an ultralarge capacity of 39.0 Ah is fabricated and achieves an ultrahigh energy density of 521.3 Wh kg-1 . The findings provide a facile electrolyte design strategy for promoting the practical utilization of high-energy-density LMBs.

Formation of LiF-rich Cathode-Electrolyte Interphase by Electrolyte Reduction.

The capacity of transition metal oxide cathode for Li-ion batteries can be further enhanced by increasing the charging potential. However, these high voltage cathodes suffer from fast capacity decay because the large volume change of cathode breaks the active materials and cathode-electrolyte interphase (CEI), resulting in electrolyte penetration into broken active materials and continuous side reactions between cathode and electrolytes. Herein, a robust LiF-rich CEI was formed by potentiostatic reduction of fluorinated electrolyte at a low potential of 1.7 V. By taking LiCoO2 as a model cathode, we demonstrate that the LiF-rich CEI maintains the structural integrity and suppresses electrolyte penetration at a high cut-off potential of 4.6 V. The LiCoO2 with LiF-rich CEI exhibited a capacity of 198 mAh g-1 at 0.5C and an enhanced capacity retention of 63.5 % over 400 cycles as compared to the LiF-free LiCoO2 with only 17.4 % of capacity retention.

A nitroaromatic cathode with an ultrahigh energy density based on six-electron reaction per nitro group for lithium batteries.

Organic electrode materials have emerged as promising alternatives to conventional inorganic materials because of their structural diversity and environmental friendliness feature. However, their low energy densities, limited by the single-electron reaction per active group, have plagued the practical applications. Here, we report a nitroaromatic cathode that performs a six-electron reaction per nitro group, drastically improving the specific capacity and energy density compared with the organic electrodes based on single-electron reactions. Based on such a reaction mechanism, the organic cathode of 1,5-dinitronaphthalene demonstrates an ultrahigh specific capacity of 1,338 mAh⋅g-1 and energy density of 3,273 Wh⋅kg-1, which surpass all existing organic cathodes. The reaction path was verified as a conversion from nitro to amino groups. Our findings open up a pathway, in terms of battery chemistry, for ultrahigh-energy-density Li-organic batteries.

Soluble Organic Cathodes Enable Long Cycle Life, High Rate, and Wide-Temperature Lithium-Ion Batteries.

Organic electrode materials free of rare transition metal elements are promising for sustainable, cost-effective, and environmentally benign battery chemistries. However, severe shuttling effect caused by the dissolution of active materials in liquid electrolytes results in fast capacity decay, limiting their practical applications. Here, using a gel polymer electrolyte (GPE) that is in situ formed on Nafion-coated separators, the shuttle reaction of organic electrodes is eliminated while maintaining the electrochemical performance. The synergy of physical confinement by GPE with tunable polymer structure and charge repulsion of the Nafion-coated separator substantially prevents the soluble organic electrode materials with different molecular sizes from shuttling. A soluble small-molecule organic electrode material of 1,3,5-tri(9,10-anthraquinonyl)benzene demonstrates exceptional electrochemical performance with an ultra-long cycle life of 10 000 cycles, excellent rate capability of 203 mAh g-1 at 100 C, and a wide working temperature range from -70 to 100 °C based on the solid-liquid conversion chemistry, which outperforms all previously reported organic cathode materials. The shielding capability of GPE can be designed and tailored toward organic electrodes with different molecular sizes, thus providing a universal resolution to the shuttling effect that all soluble electrode materials suffer.

Interfacial Design for a 4.6 V High-Voltage Single-Crystalline LiCoO2 Cathode.

Single-crystalline cathode materials have attracted intensive interest in offering greater capacity retention than their polycrystalline counterparts by reducing material surfaces and phase boundaries. However, the single-crystalline LiCoO2 suffers severe structural instability and capacity fading when charged to high voltages (4.6 V) due to Co element dissolution and O loss, crack formation, and subsequent electrolyte penetration. Herein, by forming a robust cathode electrolyte interphase (CEI) in an all-fluorinated electrolyte, reversible planar gliding along the (003) plane in a single-crystalline LiCoO2 cathode is protected due to the prevention of element dissolution and electrolyte penetration. The robust CEI effectively controls the performance fading issue of the single-crystalline cathode at a high operating voltage of 4.6 V, providing new insights for improved electrolyte design of high-energy-density battery cathode materials.

A poorly soluble organic electrode material for high energy density lithium primary batteries based on a multi-electron reduction.

Here we report an organic cathode material with poor solubility for lithium primary batteries, i.e. indeno[3,2-b]fluorene-6,12-dione. Each carbonyl group experiences a four-electron reduction to a methylene group, resulting in a high energy density of 1392 W h kg-1, which is among the best results for organic electrode materials.

Storage Mechanism of Alkali Metal Ions in the Hard Carbon Anode: an Electrochemical Viewpoint.

The storage mechanisms of Li, Na, and K in hard carbon anodes are investigated through systematically exploring their electrochemical behaviors. Two charge/discharge voltage regions are observed for all the Li, Na, and K storage, a slope at a high voltage, and a plateau in a low-voltage range. Considerably different behaviors are revealed by the galvanostatic intermittent titration technique and electrochemical impedance spectroscopy measurements, and accordingly different storage mechanisms are proposed. The sloping region is mainly attributed to the adsorption at defects/heteroatoms for all the Li, Na, and K storage. In the plateau region, pore filling contributes very little to Li storage but much to Na and K storage. Furthermore, significant effects of ionic sizes on the storage behavior in hard carbons are revealed by the electrochemical performance from Li to Na to K. These findings not only offer a fundamental understanding of storage mechanisms of alkali metal ions in hard carbons but also help develop and design innovative electrode materials for low-cost and large-scale energy storage systems.

Electrolytes and Interphases in Potassium Ion Batteries.

Potassium ion batteries (PIBs) are recognized as one promising candidate for future energy storage devices due to their merits of cost-effectiveness, high-voltage, and high-power operation. Many efforts have been devoted to the development of electrode materials and the progress has been well summarized in recent review papers. However, in addition to electrode materials, electrolytes also play a key role in determining the cell performance. Here, the research progress of electrolytes in PIBs is summarized, including organic liquid electrolytes, ionic liquid electrolytes, solid-state electrolytes and aqueous electrolytes, and the engineering of the electrode/electrolyte interfaces is also thoroughly discussed. This Progress Report provides a comprehensive guidance on the design of electrolyte systems for development of high performance PIBs.

A Lithium-Organic Primary Battery.

Lithium primary batteries are still widely used in military, aerospace, medical, and civilian applications despite the omnipresence of rechargeable Li-ion batteries. However, these current primary chemistries are exclusively based on inorganic materials with high cost, low energy density or severe safety concerns. Here, a novel lithium-organic primary battery chemistry that operates through a synergetic reduction of 9,10-anthraquinone (AQ) and fluoroethylene carbonate (FEC) is reported. In FEC-presence, the equilibrium between the carbonyl and enol structures is disabled, and replaced by an irreversible process that corresponds to a large capacity along with methylene and inorganic salts (such as LiF, Li2 CO3 ) generated as products. This irreversible chemistry of AQ yields a high energy density of 1300 Wh/(kg of AQ) at a stable discharge voltage platform of 2.4 V as well as high rate capability (up to 313 mAh g-1 at a current density of 1000 mA g-1 ), wide temperature range of operation (-40 to 40 °C) and low self-discharge rate. Combined with the advantages of low toxicity, facile and diverse synthesis methods, and easy accessibility of AQ, Li-organic primary battery chemistry promises a new battery candidate for applications that requires low cost, high environmental friendliness, and high energy density.

Bismuth Nanoparticle@Carbon Composite Anodes for Ultralong Cycle Life and High-Rate Sodium-Ion Batteries.

Bismuth has emerged as a promising anode material for sodium-ion batteries (SIBs), owing to its high capacity and suitable operating potential. However, large volume changes during alloying/dealloying processes lead to poor cycling performance. Herein, bismuth nanoparticle@carbon (Bi@C) composite is prepared via a facile annealing method using a commercial coordination compound precursor of bismuth citrate. The composite has a uniform structure with Bi nanoparticles embedded within a carbon framework. The nanosized structure ensures a fast kinetics and efficient alleviation of stress/strain caused by the volume change, and the resilient and conductive carbon matrix provides an interconnected electron transportation pathway. The Bi@C composite delivers outstanding sodium-storage performance with an ultralong cycle life of 30 000 cycles at a high current density of 8 A g-1 and an excellent rate capability of 71% capacity retention at an ultrahigh current rate of 60 A g-1 . Even at a high mass loading of 11.5 mg cm-2 , a stable reversible capacity of 280 mA h g-1 can be obtained after 200 cycles. More importantly, full SIBs by pairing with a Na3 V2 (PO4 )3 cathode demonstrates superior performance. Combining the facile synthesis and the commercial precursor, the exceptional performance makes the Bi@C composite very promising for practical large-scale applications.

Room-Temperature Potassium-Sulfur Batteries Enabled by Microporous Carbon Stabilized Small-Molecule Sulfur Cathodes.

Potassium-sulfur (K-S) batteries are a promising alternative to lithium ion batteries for large-area energy storage applications, owing to their high capacity and inexpensiveness, but they have been seldom investigated. Here we report room-temperature K-S batteries utilizing a microporous carbon-confined small-molecule sulfur composite cathode. The synergetic effects of the strong confinement of microporous carbon matrix and the small-molecule sulfur structure can effectually eliminate the formation of soluble polysulfides and ensure a reversible capacity of 1198.3 mA h g-1 and retain 72.5% after 150 cycles with a Coulombic efficiency of ∼97%. The potassium-storage mechanism was investigated by X-ray photoelectron spectroscopy analysis and theoretical calculations. The results suggest that K2S is the final potassiation product along with the reaction of 2K + S ↔ K2S, giving a theoretical capacity of 1675 mA h g-1. Our findings not only provide an effective strategy to fabricate high-performance room-temperature K-S batteries but also offer a basic comprehension of the potassium storage mechanism of sulfur cathode materials.

Conjugated Microporous Polymers with Tunable Electronic Structure for High-Performance Potassium-Ion Batteries.

Conjugated microporous polymers (CMPs) with π-conjugated skeletons show great potential as energy storage materials due to their porous structure and tunable redox nature. However, CMPs and the structure-performance relationships have not been well explored for potassium-ion batteries (KIBs). Here, we report the structure-engineered CMP anodes with tunable electronic structures for high-performance KIBs. The results demonstrate that the electronic structure of the CMPs plays an important role in enhancing potassium storage capability, including the lowest unoccupied molecular orbital (LUMO) distribution, LUMO energy level, and band gap, which can be finely tuned by synthetic control. It was revealed that the poly(pyrene- co-benzothiadiazole) (PyBT) with optimized structure delivers a high reversible capacity of 428 mAh g-1 and shows an excellent cycling stability over 500 cycles. Our findings provide a fundamental understanding in the design of CMP anode materials for high-performance potassium-organic energy storage devices.

Marriage of an Ether-Based Electrolyte with Hard Carbon Anodes Creates Superior Sodium-Ion Batteries with High Mass Loading.

Inferior rate performance, insufficient cycle life, and low mass loading have restricted the practical application of hard carbon (HC) anodes in sodium-ion batteries (NIBs). Here, a compatible strategy is developed by matching HC anodes with an ether-based electrolyte. Systematical investigation reveals that good compatibility of the electrode-electrolyte systems forms thinner but a more sustainable solid-electrolyte interphase and delivers a higher ionic conductivity and Na+ ion diffusion coefficient than the commonly used ester-based electrolytes. Therefore, an excellent electrochemical performance is demonstrated with a long cycle life (∼196 mA h/g and 90% capacity retention after 2000 cycles at 1 A/g), a super rate capability (∼51% capacity retention at 10 A/g) at a mass loading of 1.5 mg/cm2, and a high initial Coulombic efficiency of 85.9%. More importantly, a high reversible areal capacity of 4.3 mA h/cm2 can be achieved at an ultrahigh mass loading of 17 mg/cm2, superior to all reported HC anodes. Our findings not only shed light on the design of high-performance battery systems but also promise a commercial transformation from the lab test to mass production of NIBs.

Red Phosphorus Nanoparticle@3D Interconnected Carbon Nanosheet Framework Composite for Potassium-Ion Battery Anodes.

Red phosphorus (P) has been recognized as a promising storage material for Li and Na. However, it has not been reported for K storage and the reaction mechanism remains unknown. Herein, a novel nanocomposite anode material is designed and synthesized by anchoring red P nanoparticles on a 3D carbon nanosheet framework for K-ion batteries (KIBs). The red P@CN composite demonstrates a superior electrochemical performance with a high reversible capacity of 655 mA h g-1 at 100 mA g-1 and a good rate capability remaining 323.7 mA h g-1 at 2000 mA g-1 , which outperform reported anode materials for KIBs. The transmission electron microscopy and theoretical calculation results suggest a one-electron reaction mechanism ofP + K+ + e- → KP, corresponding to a theoretical capacity of 843 mA h g-1 ,which is the highest value for anode materials investigated for KIBs. The study not only sheds light on the rational design of high performance red P anodes for KIBs but also offers a fundamental understanding of the potassium storage mechanism of red P.