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Compared with commercial lithium batteries with liquid electrolytes, all‐solid‐state lithium batteries (ASSLBs) possess the advantages of higher safety, better electrochemical stability, higher energy density, and longer cycle life; therefore, ASSLBs have been identified as promising candidates for next‐generation safe and stable high‐energy‐storage devices. The design and fabrication of solid‐state electrolytes (SSEs) are vital for the future commercialization of ASSLBs. Among various SSEs, solid polymer composite electrolytes (SPCEs) consisting of inorganic nanofillers and polymer matrix have shown great application prospects in the practice of ASSLBs. The incorporation of inorganic nanofillers into the polymer matrix has been considered as a crucial method to achieve high ionic conductivity for SPCE. In this review, the mechanisms of Li+ transport variation caused by incorporating inorganic nanofillers into the polymer matrix are discussed in detail. On the basis of the recent progress, the respective contributions of polymer chains, passive ceramic nanofillers, and active ceramic nanofillers in affecting the Li+ transport process of SPCE are reviewed systematically. The inherent relationship between the morphological characteristics of inorganic nanofillers and the ionic conductivity of the resultant SPCE is discussed. Finally, the challenges and future perspectives for developing high‐performance SPCE are put forward. This review aims to provide possible strategies for the further improvement of ionic conductivity in inorganic nanoscale filler‐reinforced SPCE and highlight their inspiration for future research directions.

Mn-based layered oxides are very attractive as cathodes for potassium-ion batteries (PIBs) due to their low-cost and environmentally friendly precursors. Their transfer to practical application, however, is inhibited by some issues including consecutive phase transitions, sluggish K+ deintercalation/intercalation, and serious capacity loss. Herein, Mg-Ni co-substituted K1/2Mn5/6Mg1/12Ni1/12O2 is designed as a promising cathode material for PIBs, with suppressed phase transitions that occurred in K1/2MnO2 and improved K+ storage performance. Part of Mg2+ and Ni2+ occupies the K+ layer, playing the role of a "nailed pillar", which restrains metal oxide layer gliding during the K+ (de)intercalation. The "Mg-Ni pinning effect" not only suppresses the phase transitions but also reduces the cell volume variation, leading to the improved cycle performance. Moreover, K1/2Mn5/6Mg1/12Ni1/12O2 has low activation barrier energy for K+ diffusion and high electron conductivity as demonstrated by first-principles calculations, resulting in better rate capability. In addition, K1/2Mn5/6Mg1/12Ni1/12O2 also delivers a higher reversible capacity owing to the participation of the Ni element in electrochemical reactions and the pseudocapacitive contribution. This study provides a basic understanding of structural evolution in layered Mn-based oxides and broadens the strategic design of cathode materials for PIBs.

O3-type NaCrO2 is attracting increasing attention as potential cathode material for sodium-ion batteries (SIBs). Bare NaCrO2 is usually synthesized by a solid-state reaction and suffers from serious capacity decay and poor power capability. Modification by coating is an effective method to improve the electrochemical properties, but it inevitably reduces the energy density. To avoid the decrease of energy density and optimize the electrochemical performance, a specific route, i.e., a freeze-drying-assisted sol-gel method, has been adopted to synthesize bare NaCrO2 in this work. Three-phase coexistence during charging is confirmed for the first time, which contributes to delaying the disappearance of the O3 phase and then improving the structural reversibility, resulting in superior cycle stability (∼50% capacity retention after 3000 cycles at 5C). Meanwhile, as-synthesized NaCrO2 delivers an outstanding rate capability (82.1 mAh g-1 at 50C), which is attributed to the fast Na+ diffusivity and high electronic conductivity proved by density functional theory (DFT) calculations. It is worth mentioning that NaCrO2 also exhibits excellent electrochemical properties when used as a cathode for potassium-ion batteries (PIBs). This work provides new perspectives on the structural evolution of NaCrO2, and the results are expected to contribute to the development of SIBs and PIBs.

Practical application of lithium metal anodes in high-energy rechargeable batteries is impeded by the issue of Li dendrite growth. Herein, an exceptional hydrophobic MAF-6 material is utilized to modify polypropylene (PP) separator to yield a superorganophilic MAF-6/PP composite separator. Owing to a combination of superorganophilicity with three-dimensional ordered porosity, the MAF-6/PP achieves a Li ion transference number of 0.78. Homogeneous and dense Li plating behaviors are present in cells with MAF-6/PP which can afford uniform Li ion flux. The MAF-6/PP enables Li|Cu cells to run steadily for over 350 cycles at 0.5 mA cm−2-1 mAh cm−2 with an average coulombic efficiency (CE) of 98.8%, symmetric Li|Li cells to work stably for 2200 h without short-circuit at 0.5 mA cm−2-1 mAh cm−2, and Li|LiFePO4 cells to retain a reversible capacity of 102.4 mAh g−1 after 1500 cycles at 1C with a capacity retention of 73.2% and a CE of 99.9%.

All-solid-state lithium batteries (ASSLB) are promising candidates for next-generation energy storage devices. Nevertheless, the large-scale commercial application of high energy density ASSLB with the polymer electrolyte still faces challenges. In this study, a thin solid polymer composite electrolyte (SPCE) is prepared through a facile and cost-effective strategy with an infiltration of thermoplastic polyurethane (TPU), lithium salt (LiTFSI or LiFSI), and halloysite nanotubes (HNTs) in a porous framework of polyethylene separator (PE) (TPU–HNTs–LiTFSI–PE or TPU–HNTs–LiFSI–PE). The composition, electrochemical performance, and especially the effect of anions (TFSI− and FSI−) on cycling performance are investigated. The results reveal that the flexible TPU–HNTs–LiTFSI–PE and TPU–HNTs–LiFSI–PE with a thickness of 34 μm exhibit wide electrochemical windows of 4.9 and 5.1 V (vs. Li+/Li) at 60 ℃, respectively. Reduction in FSI− tends to form more LiF and sulfur compounds at the interface between TPU–HNTs–LiFSI–PE and Li metal anode, thus enhancing the interfacial stability. As a result, cell composed of TPU–HNTs–LiFSI–PE exhibits a smaller increase in interfacial resistance of solid electrolyte interphase (SEI) with a distinct decrease in charge-transfer resistance during cycling. Li|Li symmetric cell with TPU–HNTs–LiFSI–PE could keep its stable overpotential profile for nearly 1300 h with a low hysteresis of approximately 39 mV at a current density of 0.1 mA cm−2, while a sudden voltage rise with internal cell impedance-surge signals was observed within 600 h for cell composed of TPU–HNTs–LiTFSI–PE. The initial capacities of NCM|TPU–HNTs–LiTFSI–PE|Li and NCM|TPU–HNTs–LiFSI–PE|Li cells were 149 and 114 mAh g−1, with capacity retention rates of 83.52% and 89.99% after 300 cycles at 0.5 C, respectively. This study provides a valuable guideline for designing flexible SPCE, which shows great application prospect in the practice of ASSLB.

Low-cost, high-activity, non-precious metal electrocatalysts are needed to enhance the bifunctional oxygen activities of rechargeable Zn-Air batteries. In this study, a Fe-enriched FeNi3 inter-metallic nanoparticle/nitrogen-doped carbon (Fe-enriched-FeNi3/NC) electrocatalyst was designed and prepared using a facile method based on plasma engineering. The excess Fe-ions in the Fe-enriched FeNi3 nanoparticles led to a high degree of lattice distortion that produced abundant oxygen-active sites. The electrocatalyst exhibited excellent oxygen evolution reaction (OER) activity as well as favorable oxygen reduction reaction (ORR) activity in an alkaline electrolyte. In addition, the electrocatalyst revealed a lower potential difference (ΔE = 0.80 V vs. RHE) in a bifunctional oxygen reaction compared to that of the benchmark 20 wt% Pt/C + Ir/C (ΔE = 0.84 V vs. RHE), and most of the reported FeNi3 alloy-doped carbon catalysts. Based on DFT calculations, the lattice distortion in Fe-enriched-FeNi3/NC promoted a higher density of active electrons around the Fermi level. Owing to its great bifunctional oxygen activities, Fe-enriched FeNi3/NC was applied as an ORR/OER catalyst in the air cathode in a homemade zinc-air battery and exhibited an excellent discharge–charge voltage gap (0.89 V), peak power density (89 mW/cm2), and high specific capacity of 734 mAh/g at 20 mA/cm2, which outperformed the benchmark 20 wt% Pt/C + Ir/C electrocatalyst. In summary, this research provides a novel strategy to enhance the OER/ORR activities of transition metal-based alloys through lattice distortion defects. In addition, it provides a new pathway for achieving noble metal-free air cathode materials for the next generation Zn-air battery.

Designing a novel anode material with suitable elemental composition and bonding structure for improving the limited capacity and poor lithium-ion conductivity of lithium-ion batteries (LIBs) is still challenging. Here, guided by first-principles calculations, we report a higher crystal symmetric, cation-disordered zinc blende Zn0.5Ge0.5P anode material with high-capacity and high-rate capability owing to superior electron and lithium-ion transport compared to the parent allotrope chalcopyrite ZnGeP2. The Zn0.5Ge0.5P anode exhibits a large specific capacity of 1435 mA h g−1 with a high initial Coulombic efficiency of 92%. An amorphization–conversion–alloying reaction mechanism is proposed based on ex situ characterizations including X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. During lithiation, the material phase-changes through Li3P, LiZnGe, β-Li2ZnGe, and α-Li2ZnGe intermediates that provide suitable transport channels for fast diffusion of lithium ions. During delithiation, LiZn, Li15Ge4, and Li3P nanoparticles reassemble into Zn0.5Ge0.5P. A Zn0.5Ge0.5P–TiC–C composite with finer particle size and enhanced electronic conductivity exhibits an initial specific capacity of 1076 mA h g−1 and a capacity retention of 92.6% after 500 cycles.

Anatase TiO2 is considered as a promising anode material for sodium-ion batteries, but the inherent semiconductor properties and the sluggish Na+ diffusion kinetics limit its further development. To overcome these inherent drawbacks, heterojunction TiO2@TiOF2 constructed with two-dimensional nanosheets is prepared by the hydrothermal method. When heterojunction TiO2@TiOF2 is used as a sodium ion battery material, a stable cycling performance of up to 10 000 cycles can be achieved at a high current density of 5000 mA g−1, probably due to the heterojunction structure, the exposed (0 0 1) facet of TiO2 and the in situ formed NaF protective layer. Density functional theory (DFT) calculations further reveal that the heterostructure TiO2@TiOF2 nanosheets possess better electrical conductivity and lower formation energies of Na+ ions than those of the separated TiO2 and TiOF2. This work offers a new strategy to design novel heterojunction structures for the electrochemical sodium storage.

Mn-based layered oxides, as potential cathodes for potassium-ion batteries (PIBs), face major challenges such as consecutive phase transition, serious capacity loss, and sluggish K+ transport kinetics. Herein, Co–Mg co-substituted K0.45Co1/12Mg1/12Mn5/6O2 is designed as a promising cathode material for PIBs to conquer the above issues in this work. Co3+–Mg2+ ions occupying the Mn3+ sites are confirmed to effectively alleviate the Jahn–Teller distortion induced by Mn3+ ions. P3-K0.45Co1/12Mg1/12Mn5/6O2 exhibits highly reversible single-phase structural evolution during the K+ deintercalation/intercalation. In contrast, the pristine K0.45MnO2 electrode experiences incompletely reversible structural variation from a P′3 to P3 phase. The increase of structural stability in the Co–Mg co-substituted sample is the main reason leading to improved cycling stability. Moreover, K0.45Co1/12Mg1/12Mn5/6O2 delivers better rate capability resulting from faster K+ diffusion compared to K0.45MnO2. Therefore, Co–Mg co-substitution is an effective strategy to enhance the structural stability and electrochemical properties of Mn-based layered oxides in PIBs.

Transition metal oxides have high specific capacity as anode materials for lithium-ion battery. But aggregation of particles and volume expansion during lithiation/delithiation restrict their application. In this work, a three-dimensional hierarchical Ca3Co4O9 hollow fiber network assembled by nanosheets is prepared by a electrospinning combining with heat treatment method to overcome these issues and to boost its lithium storage performance. As-synthesized sample possesses excellent cyclic stability (578.6 mA h g−1 at 200 mA g−1 after 500 cycles) and rate performance (293.5 mA h g−1 at 5000 mA g−1), much better than those of commercial Co3O4. Furthermore, the fast kinetics of the three-dimensional Ca3Co4O9 hollow fiber network is also confirmed by the variable scan rates CV tests and the EIS measurements, which is dedicated to the specific hierarchical hollow fiber network structure that provides shorter ion transport distances and higher electrical conductivity. This work supplies a universal approach to improve the electrochemical performance of transition metal oxides for lithium ion batteries.

Zinc-air battery is one of the most promising next-generation energy conversion and storage systems. Green and low-cost catalysts with high oxygen reduction reaction (ORR) catalytic activity are desired to meet the requirements of Zinc-air batteries. Herein, poly-active centric Co3O4-CeO2/Co-N-C (ketjenblack carbon) catalysts were prepared by a facile method. The Co3O4 and CeO2 nanoparticles are uniformly anchored on the surface of Co and N doped carbon support. The half-wave potential of Co3O4-CeO2/Co-N-C in the rotating disk electrode testing is close to that of Pt/C. The Zn-air battery using Co3O4-CeO2/Co-N-C as the cathode catalyst can provide a high specific capacity of 728 mA h g−1 at 20 mA cm−2 and maintain a stable discharge voltage. The remarkable catalytic performance is mainly attributed to the synergistic effect among Co3O4, CeO2 and Co-N-C, the outstanding electrical conductivity and the large surface area. Benefitting from the high catalytic activity, environmental friendliness and the facile synthesis process, Co3O4-CeO2/Co-N-C catalyst lends itself well to a great prospect in the application of metal-air batteries.

Construction of three-dimensional (3D) composite lithium metal anodes (LMAs) based on Li melt-infusion into a 3D porous scaffold has been demonstrated to be effective for solving the issue of the considerable relative volume change of LMAs during Li plating/stripping. However, little attention has been paid to controllable regulation of the structure and interface of 3D composite LMAs. In this study, 3D composite LMAs, namely Li–AuLi3@CF electrodes, are firstly fabricated by infusion of molten Li into carbon fiber (CF) paper modified with nanoporous gold (NPG) which is converted to AuLi3 after infusion. We herein demonstrate a synergistic structure and interface engineering strategy realized by a simple and effective pre-stripping protocol to initially expose a portion of the 3D AuLi3@CF scaffold to create “PS-Li-AuLi3@CF” electrodes, which greatly boosted the electrochemical performance. Symmetrical Li|Li cells with PS-Li-AuLi3@CF electrodes show an overpotential of 111 ​mV after cycling at a current density of 0.5 ​mA ​cm−2 for 1800 ​h. Additionally, Li|LiFePO4 (LFP) and Li|sulfurized polyacrylonitrile (SPAN) full cells with PS-Li-AuLi3@CF electrodes exhibit a high capacity retention of 96.1% with a Coulombic efficiency (CE) of 99.2% after 1000 cycles at 5C, and a capacity retention of 70.6% with a CE of 99.8% after 1000 cycles at 2C, respectively. This work provides a simple and highly effective method for engineering the structure and interface of 3D composite LMAs to boost their electrochemical performance for high-energy-density rechargeable lithium metal batteries (LMBs).

Alloy anode with good reversibility of lithium plating/stripping and long cycling stability is considered as promising anode materials. Here, Cu–Sn alloy is used as the substrate for Li deposition to induce the most densely packed arrangement of Li atoms, thus presenting high lithiophilicity and improving Li plating behaviors. The LiFePO4-based full cell with the as-prepared dendrite-free Li metal anode retained at 85 mAh g−1 with a high coulombic efficiency of 99.5% after 300 cycles, presenting a capacity retention of 79.4%. This strategy provides a new perspective to structure dendrite-free Li anode for the next-generation high-energy density batteries.

As one of the most promising next-generation safe and green energy storage technologies, aqueous Zn-ion batteries have attracted considerable attention in recent years. However, their working mechanism is still controversial. Also, their performance needs to be further improved to meet the requirement of widespread applications. Herein, we developed a nanoflower-like MnO2/C composite with two-electron reaction pathway for use as a cathode material in aqueous Zn-ion batteries. Benefiting from the large specific surface area of the nanoflower-like structure, high conductivity of the carbon materials and the low crystallinity of birnessite-type MnO2, the Zn-ion battery using MnO2/C as the cathode material could carry out a deep and fast reaction via the Mn4+/Mn2+ two-electron pathway. At 300 mA g−1, the battery could retain a high specific capacity of 279.7 mA h g−1 after 300 cycles. The second electronic reaction process of Mn3+/Mn2+ could also work at a high current density. A high initial discharge capacity of more than 200 mA h g−1 was achieved at a high current density of 2000 mA g−1. A two-electron working mechanism of the layered-MnO2 cathode material is proposed. Due to the advantages of high capacity, high rate performance and good stability, the MnO2/C composite is a promising cathode material for aqueous Zn-ion batteries, which holds potential for applications in electric vehicles and grid energy storage.

Composite solid-state electrolytes (CSEs) that integrate the merits of different components are considered to be promising candidates for next-generation high-energy density lithium metal batteries. Herein, we have successfully designed a flexible CSE membrane consisting of the ceramic conducting Li1.3Al0.3Ti1.7(PO4)3 (LATP) filler, polyethylene oxide (PEO) matrix, and 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (BMP-TFSI) ionic liquid. In particular, the addition of ionic liquid (BMP-TFSI) can not only decrease the interface impedance between the polymer and LATP ceramic fillers and improve the ionic conductivity, but also prevent the adverse reaction between Ti4+ in LATP and Li metal and further enhance the interface stability. Benefitting from the synergistic effect of organic–inorganic hybrids, the obtained composite electrolyte membrane achieves an excellent ionic conductivity of 2.42 × 10−4 S cm−1 at 30 °C and a wide electrochemical stability window of 5 V (vs. Li+/Li). Moreover, the CSE membrane exhibits outstanding Li dendrite suppression capability, which is proved by galvanostatic Li plating/stripping tests for 1000 h. Assembled with this solid electrolyte membrane and a commercial LiFePO4 cathode, all-solid-state lithium metal batteries demonstrate superior rate capability and outstanding cycling stability at both 30 and 45 °C. These results demonstrate that such a flexible composite electrolyte is a promising alternative electrolyte for practical high-energy density all-solid-state batteries.

The construction of a lithiophilic phase on the surface of a current collector with a lithiophobic nature is an effective method to suppress Li dendrite growth by reducing the overpotential for Li nucleation and inducing the growth of homogeneous Li nuclei to obtain high-performance lithium metal anodes (LMAs). Nevertheless, the structural regulation of the lithiophilic phase and the underlying mechanism of lithiophilicity have been overlooked in previous studies. In this study, we designed a triporous, nanoporous AuLi3 (NPAuLi3) nanosheet-modified Ni foam (NF) (NPAuLi3@NF) composite current collector for use in LMAs. First principle calculations revealed that the lithiophilicity of the AuLi3 phase originates from the strong electronic interaction between the Au and Li atoms. The morphological characterization demonstrated that the as-designed NPAuLi3@NF current collector not only guided homogeneous Li nucleation and growth during the Li plating process, but also induced uniform Li removal during the Li stripping process, which effectively suppressed Li dendrite growth and formation of dead Li, leading to a boosted electrochemical performance in LMAs. The symmetric Li|Li cells with the NPAuLi3@NF-based LMAs could run stably for 1990 and 1420 h without cell failure at current densities of 1 and 2 mA cm−2 with a capacity of 2 mA h cm−2, respectively, and the Li@NPAuLi3@NF|LFP full cells showed an excellent capacity retention of 83.8% with a coulombic efficiency of 99.8% at 5C after 1000 cycles, and a good rate capability. This work provides insight into the design of the composition and structure of the lithiophilic phase on the surface of the current collector skeleton to obtain high-performance LMAs.

The short life span of lithium metal anodes (LMAs) due to dendrite growth and low coulombic efficiency (CE) has been regarded as the bottleneck in developing next-generation high-energy-density lithium metal based secondary batteries. Employing three-dimensional (3D) current collectors is one approach to reduce the effective current density and delay dendrite growth. Commercial Ni foam, in spite of its high electronic conductivity and 3D topology, has not been considered for this application due to its low specific surface area and lithiophobic nature. In this study, we develop a surface engineering strategy to uniformly coat lithiophilic AuLi3 particles on Ni foam skeletons through lithiation of electrodeposited gold nanoparticles. In comparison with the bare Ni foam, the AuLi3@Ni foam is more lithiophilic, significantly lowering the nucleation energy barrier and enhancing the uniformity for Li deposition. Such a structure results in effective suppression of Li dendrite growth in the void space of the foam. As a result, the AuLi3@Ni foam current collector based LMAs can run for 740 h without cell failure in a symmetric cell. Furthermore, the Li-AuLi3@Ni foam|LiFePO4 full cell shows an excellent capacity retention of 43.8% with a high CE of 99.2% at 1C for 500 cycles. This work further illustrates the critical importance of surface lithiophilicity in guiding lithium cycling and suggests engineering the skeleton surface of commercial metal foam current collectors is important to improve 3D structured LMAs.

The NiS2 nanosheet array on Ni foil (NiS2/NF) was prepared using an in situ growth strategy and sulfidation method and was used as the cathode of lithium sulfur battery. The unique nanostructure of the NiS2 nanosheet array can provide abundant active sites for the adsorption and chemical action of polysulfides. Compared with the sulfur powder coated pure NF (pure NF-S) for lithium sulfur battery, the sulfur powder coated NiS2/NF (NiS2/NF-S) electrode exhibits superior electrochemical performance. Specifically, the NiS2/NF-S delivered a high reversible capacity of 1007.5 mAh g−1 at a current density of 0.1 C (1 C= 1675 mA g−1) and kept 74.5% of the initial capacity at 1.0 C after 200 cycles, indicating the great promise of NiS2/NF-S as the cathode of lithium sulfur battery. In addition, the NiS2/NF-S electrode also showed satisfactory electrochemical performance when used as the cathode for sodium sulfur battery.

Cu2P7-black P-MWCNT (CuP5/MWCNT) is prepared by a facile mechanical milling method. When used as anodes for Li/Na-ion batteries, the composite delivers high comprehensive performances: initial Coulombic efficiency up to 90/84%, 1455/1170 mA h g−1 after 200 cycles, and 960/580 mA h g−1 at 5 A g−1 for Li/Na-ion batteries, respectively. The performances can be attributed to the hybridized strategy of two-dimension layered structure of Cu2P7, black P, and one-dimension multiwall carbon nanotubes. The former offers a fast transport channel for Li/Na-ions and the latter provides for fast transport of electrons and accommodates the volume variation during cycling. In addition, the synergistic effect among different phases also leads to enhanced performance. The integrated strategy of one-dimensional and two-dimensional advantages can excite more research interest in the energy-storage field.

The metal-air battery is a form of renewable energy generation technology that produces energy electrochemically and can address energy concerns in the near future. However, state-of-the-art Pt electrocatalysts often suffer from agglomeration or detachment from carbon supports under prolonged operation, eventually limiting the long-term utilization of metal-air batteries. In this work, Pt nanoparticles were deposited on sulfur-doped nanocarbon to increase its stability. We first synthesized sulfur-doped (S-doped) and pristine carbon as support materials via a plasma process, and thereafter loaded platinum (Pt) nanoparticles onto the S-doped and pristine carbon matrix. From a sintering test at 600 °C, the Pt nanoparticles supported on pristine carbon increased from 2.4 to 5.2 nm; meanwhile, the average size of Pt NPs supported on S-doped carbon only increased from 2.2 to 2.51 nm. From the electrochemical analyses, the mass activity of Pt on pristine and S-doped carbon supports decreased by 25% and 10%, respectively, after 1500 cycles. The results proposed that the sulfide C–S–C bond provided a strong platinum-S-doped carbon support interaction between the support materials and the loaded Pt nanoparticles. Thus, S-doped carbon supports can serve as a stabilizer of Pt nanoparticles to enhance their durability in the application of metal-air batteries and other electrochemical devices.

Transition metal sulfides such as Ni–Co sulfides are promising electrode materials for supercapacitors owing to their advantageous electrical conductivity. Current approaches for the synthesis of Ni–Co sulfides normally involve wet chemical sulfurization. In this work, we demonstrate a facile method for synthesizing CoxNi1-xS2 (0

Phosphides are promising anode candidates profiting from their relatively smaller voltage hysteresis which thus are promising to be high energy efficiency and power capabilities for secondary batteries, compared with the corresponding fluorides, oxides and sulfides. Herein we for the first time synthesized ternary Cu 2 P 7 /CuP 2 /graphite composite by a facile ball milling method. When initiated as anodes for Li-ion batteries, the as-synthesized ternary composite provides 1415 mA h g −1 after 100 cycles and 684 mA h g −1 at a high current density of 10 A g −1 . When initiated as anodes for Na-ion batteries, the as-synthesized ternary composite provides 1254 mA h g −1 after 100 cycles and 200 mA h g −1 at a high current density of 5 A g −1 . These electrochemical performances are comparable or even surpass the P/C, CuP 2 /C and other transition metal phosphides reported before. The enhanced performances can be attributed to the high P concentration, layered structure and small band gap of the Cu 2 P 7 phase and the heterointerface between these phases, which not only assists electron and Li-ion transportation and but also creates more active sites endowed by interfacial coupling and positive electrochemical synergistic effect. The multiphase design strategy can further excite more research interest in the energy-storage field.

Various P-Ge compounds including GeP5 and GeP3 can be easily synthesized by a direct ball milling method while GeP can not. Herein, we successfully synthesize binary-phase Ge2P3 composite which derived from layered GeP and black P. When applied as anodes for Li-ion batteries, the as-synthesized binary-phase composite delivers a large reversible capacity of 1605 mA h g−1 with a high initial Coulombic efficiency of 89%, retains 1380 mA h g−1 after 100 cycles and even achieves 920 mA h g−1 at a current density of at 5 A g−1. Also, for sodium-storage it shows a reversible capacity of 970 mA h g−1 with an initial Coulombic efficiency of 88% and retains 890 mA h g−1 after 100 cycles. The performance can be attributed to the following merits: the binary Li/Na-storage components host more Li/Na ions, the layered structure favors Li/Na-ion transportation and the abundant heterointerfaces increase the amount of active sites.

This work presents a desirable bifunctional catalyst—Co3O4 nanoparticles anchored on nitrogen-doped partially exfoliated multiwall carbon nanotubes (Co3O4/N-p-MCNTs)—for oxygen reduction reaction (...

Recently, rechargeable Zn-ion batteries (ZIBs) have attracted incremental attention as prospective energy storage devices for grid-scale applications and flexible devices, due to their low cost, environmental benignity, high safety and unique properties of the Zn metal. However, the sustained development of high-performance ZIBs is hindered by the limited availability of cathode materials. Here, for the first time, we demonstrate MoS2 with expanded inter-layer spacing (E-MoS2) can be a promising cathode candidate for rechargeable and flexible ZIBs. By X-ray diffraction (XRD) and Raman studies, a reversible Zn2+ ion intercalation/deintercalation mechanism was revealed. The E-MoS2 electrode delivers a specific capacity of 202.6 mA h g−1 at 0.1 A g−1, a desirable energy density of 148.2 Wh kg−1 and good cycle stability with a capacity retention ratio of 98.6% over 600 cycles. By using the newly-developed starch/ polyacrylamide (PAM) based polymer electrolyte with high zinc ion conductivity, a quasi-solid Zn/E-MoS2 battery was developed, which exhibits decent electrochemical performance even under various heavy deformations, holding great potential for applications in future flexible and wearable devices.

In this work, a unique artificial interface combing characteristics of both high ionic and electronic conductivities has been successfully constructed at the surface of Ni-rich LiNi0·8Co0·1Mn0·1O2 (NCM811). The ionic conductor layer is fabricated through reacting H3PO4 with the lithium residuals on the surface of NCM811 to form Li3PO4. The interface with high electronic conductivity is constructed by attaching graphene fragments to the NCM811 spherical particles. Due to the synergistic effect of the Li3PO4 coating layer and the graphene network, the modified sample (GN-LPO-NCM811) exhibits high capacity retention of 94.3% after 150 cycles at 0.5C between 3.0 and 4.3 V, while the pristine material shows a much lower retention of only 88.1%. In addition, the GN-LPO-NCM811 also presents improved cycling stability at elevated temperature of 55 °C. Even at an extremely high rate of 10C, the GN-LPO-NCM811 still remains 70% of its original capacity, while the pristine NCM811 only delivers 50% of the capacity. The stable cycling performance of GN-LPO-NCM811 is demonstrated in a full cell with graphite anode at ambient temperatures. Importantly, the thermal stability of the modified samples is also greatly enhanced. This study provides an effective method to improve the electrochemical performance of LiNi0·8Co0·1Mn0·1O2.

Nanocomposites LiMnxFe1-xPO4/C (x = 1, 5/6, 2/3, 1/2) are synthesized by a sol-gel route combined with freeze drying. Fe2+ substituted samples coated by high-ordered carbon have the same olivine structure of LiMnPO4/C but reduced cell volumes. Fe2+ substituting greatly influences magnetic characteristics of LiMnPO4/C and slight amounts of Fe2P impurity in Fe2+ doped samples are verified by magnetic tests. Fe2+ substituted samples exhibit much better electrochemical properties. Among them, LiMn1/2Fe1/2PO4/C displays the best rate capacity and cyclic stability. Its initial discharge capacity reaches 140.1 mAh g−1 and remains at 132.5 mAh g−1 after 100 cycles at 2C, remarkably higher than those of LiMnPO4/C. The superior electrochemical performances are mainly attributed to small charge-transfer impedance, fast Li+ diffusion, residual carbon and existence of Fe2P with excellent electronic conductivity.

AP65 doped with different elements are rolled into the anode plates for Mg-air battery and higher-power seawater activated battery. The discharge and corrosion behaviour of their cross- section surfaces (CS) and rolling surfaces (RS) is systematically studied and the results show that the RS consisting of (0001) crystallographic planes have lower corrosion rates and inhibit the self- discharge at 180 mA cm−2, whereas the CS with ( 11 2 ¯ 0 ) and ( 10 1 ¯ 0 ) planes provide higher anodic efficiencies at 10 mA cm−2 and possess stronger discharge activity. Furthermore, the dissolution mechanisms of different surfaces are also elucidated based on microstructure characterization and electrochemical response.

Highlights Single-atom M-N4/N-doped carbons (M = Fe, Co) prepared as OER/ORR catalysts.Ultrasonication-assisted plasma engineering used for catalyst synthesis.Co-N4/NC outperformed benchmark commercial catalysts in practical Zn–air battery test.DFT calculations provided insights into the origin of superior ORR/OER performance. Supplementary Information The online version contains supplementary material available at 10.1007/s40820-020-00581-4, As bifunctional oxygen evolution/reduction electrocatalysts, transition-metal-based single-atom-doped nitrogen–carbon (NC) matrices are promising successors of the corresponding noble-metal-based catalysts, offering the advantages of ultrahigh atom utilization efficiency and surface active energy. However, the fabrication of such matrices (e.g., well-dispersed single-atom-doped M-N4/NCs) often requires numerous steps and tedious processes. Herein, ultrasonic plasma engineering allows direct carbonization in a precursor solution containing metal phthalocyanine and aniline. When combining with the dispersion effect of ultrasonic waves, we successfully fabricated uniform single-atom M-N4 (M = Fe, Co) carbon catalysts with a production rate as high as 10 mg min−1. The Co-N4/NC presented a bifunctional potential drop of ΔE = 0.79 V, outperforming the benchmark Pt/C-Ru/C catalyst (ΔE = 0.88 V) at the same catalyst loading. Theoretical calculations revealed that Co-N4 was the major active site with superior O2 adsorption–desorption mechanisms. In a practical Zn–air battery test, the air electrode coated with Co-N4/NC exhibited a specific capacity (762.8 mAh g−1) and power density (101.62 mW cm−2), exceeding those of Pt/C-Ru/C (700.8 mAh g−1 and 89.16 mW cm−2, respectively) at the same catalyst loading. Moreover, for Co-N4/NC, the potential difference increased from 1.16 to 1.47 V after 100 charge–discharge cycles. The proposed innovative and scalable strategy was concluded to be well suited for the fabrication of single-atom-doped carbons as promising bifunctional oxygen evolution/reduction electrocatalysts for metal–air batteries. Supplementary Information The online version contains supplementary material available at 10.1007/s40820-020-00581-4

With the increasing demand for high energy and power energy storage devices, lithium metal batteries have received widespread attention. Li metal has long been regarded as an ideal candidate for negative electrode due to its high theoretical specific capacity (3860 mAh g−1) and low redox potential (-3.04 V vs. standard hydrogen electrode). However, notorious dendrite, low coulombic efficiency (CE), fast electrolyte consumption, large volume change and formation of “dead lithium” during cycling hinder its practical applications for decades. In order to address these issues and improve the electrochemical performance and safety of lithium metal batteries, tuning the lithium deposition via structuring a host for Li metal anode has been widely recognized as an efficient method. Thus, this paper overviews the recent progress in engineering Li host structure, with the focus on different approaches and design criteria. In the end, the perspectives for boosting the practical application of Li metal negative electrode are also proposed.

Ni-rich layered oxide (LiNi0.8Co0.1Mn0.1O2) has become popular commercial cathode material for lithium ion batteries, due to its high working potential and high specific capacity. It is still a challenge, however, to maintain the structure and performance under extreme conditions, such as at high charging cutoff (≥4.5 V), high temperature (≥60 °C) and higher charge-discharge rate (≥3 C). Herein, Poly (pyrrole-co-citral nitrile) (PPC) optimized interfacial layer is designed and constructed on the surface of LiNi0.8Co0.1Mn0.1O2 by an in situ photopolymerization self-assembly technology. The sweater-like co-polymer coating provides an integral protection from side reaction, particle rupture and irreversible phase transition during cycling under the extreme conditions. Furthermore, the delocalized π bonds and cross-linked network structure of the co-polymer coating ensure the efficient and stable interface between electrolyte and electrode. This work offers a novel and useful strategy to enhance the electrochemical performance of Ni-rich cathode materials for high-energy lithium ion batteries at extreme conditions.

Lithium–sulfur battery with high theoretical capacity becomes the subject of recent attention. Its commercial progress is impeded by its poor electrical conductivity and high dissolubility of intermediate products in organic electrolyte. In the present work, we report a novel three-dimensional graphene-wrapped porous carbon (3D-G) to accommodate sulfur, which consists of outside highly stable interconnected graphene-like sheets and inner activated porous carbon. The 3D-G was synthesized from cheap polyacrylic acid cation-exchange resin, which introduces nickel ions as catalysts in the carbonization process, as a cost effective, facile and simple method. This 3D-G showed hierarchical pores: 0.7 nm micropores and macropores, providing a large specific surface area of 1375.08 m2 g−1. Benefiting from this unique structure, the 3D-G performed well as host materials to achieve a high sulfur content (75.4 wt%). Such a 3D-G@S composite exhibits capacity-fading rate as low as 0.28% per cycle over 100 cycles at 0.1 C, and good cyclability at various cycling rates (0.1–1 C).

Rechargeable lithium oxygen batteries (LOBs) are one of the most promising energy storage systems by virtue of their high energy density and environmental amiability. However, the development of LOBs is still hindered by some critical issues. Herein, 3D hexapod-shaped Co-ZIFs-thiourea/dimethyl sulfoxide (H-Co-ZIFs-S) derived Co nanoparticles embedded into nitrogen and sulfur co-doped carbon (H-Co-NSC) are developed, and then low content of ruthenium nanoparticles are decorated on the surface to obtain Ru/H-Co-NSC as efficient catalyst for LOBs. The Ru/H-Co-NSC catalysts exhibits unique structure and catalytic properties, such as accommodating the insoluble discharge product Li2O2, promoting the transportation of ions/O2, enhancing the electronic conduction, demonstrating excellent OER/ORR kinetics as well. In addition, the Ru-decorated nanoparticles could effectively suppress some side-reactions caused by the exposed carbon of H-Co-NSC in LOBs. First-principles Density functional theory (DFT) calculations reveal the cooperative effect of multiple active sites in Ru/H-Co-NSC can effectively promote the ORR/OER kinetics in LOBs. Therefore, the LOBs with Ru/H-Co-NSC cathode provide a positive catalytic capacity with low overpotential, large specific capacities, long cycle life and superior reversibility. Our work may pave the way to design more advanced catalysts for metal-air batteries with superior electrochemical performance.

Constructing the M-N-C (M = Fe, Co, etc.) with meso- and macroporous structures is an effective strategy for designing the high-performance catalysts towards oxygen reduction reaction (ORR). However, these structures can hardly be achieved via the pyrolysis of classic metal-organic frameworks. Herein, we prepare the CoFe nanoparticles with surface oxides dispersed in Co/Fe-N-C support via carbonizing melamine and ethylenediaminetetraacetic acid chelated with metal ions. This hybrid exhibits high proportions of meso- and macropores along with excellent ORR catalytic activity, as evidenced by the half-wave potentials of 0.91 and 0.61 V (vs. RHE) in 0.1 M KOH and 3.5 wt% NaCl, respectively. The Al/Mg-air batteries with this catalyst exhibit superior performance to those employing Pt/C, primarily derived from the enlarged pore diameters and the exposed ORR active sites substantially enhancing the air-electrode performance. Our study provides an avenue to broaden the pore sizes of M-N-C for boosting its ORR catalytic activity.

Highly efficient and low-cost nonprecious metal electrocatalysts that favor a four-electron pathway for the oxygen reduction reaction (ORR) are essential for high-performance metal–air batteries. Herein, we show an ultrasonication-assisted synthesis method to prepare Mn3O4 quantum dots (QDs, ca. 2 nm) anchored on nitrogen-doped partially exfoliated multiwall carbon nanotubes (Mn3O4 QDs/N-p-MCNTs) as a high-performance ORR catalyst. The Mn3O4 QDs/N-p-MCNTs facilitated the four-electron pathway for the ORR and exhibited sufficient catalytic activity with an onset potential of 0.850 V (vs reversible hydrogen electrode), which is only 38 mV less positive than that of Pt/C (0.888 V). In addition, the Mn3O4 QDs/N-p-MCNTs demonstrated superior stability than Pt/C in alkaline solutions. Furthermore, a Zn–air battery using the Mn3O4 QDs/N-p-MCNTs cathode catalyst successfully generated a specific capacity of 745 mA h g–1 at 10 mA cm–2 without the loss of voltage after continuous discharging for 105 h. The superior...

LiNi0.5Mn1.5O4 is a promising cathode material for high power lithium ion batteries (LIBs) for electric vehicles (EVs) and hybrid electric vehicles (HEVs). For the first time we design a tri-functional coating to improve the cycling performance of LiNi0.5Mn1.5O4. With the designed BiPO4 coating, the capacity retentions of LiNi0.5Mn1.5O4 are largely improved from 84.3% to 93.6% at 0.5 C after 50 cycles and from 80.6% to 96.2% at 10 C after 100 cycles. The tri-functional coating reduces the charge transfer resistance of LiNi0.5Mn1.5O4 cathode and plays a critical role in enhancing the electrochemical performance and lifetime. This strategy provides a new way to modify electrode materials to elevate the performance of LIBs.

High-performance energy storage devices are in urgent need due to the fast development of wearable electronics, while the challenge of achieving outstanding flexibility has not been properly addressed yet, let alone the safety, another critical issue determines their practicability. Herein, we report a quasi-solid-state aqueous rechargeable lithium-ion battery (ARLIB) based on carbon cloth substrates and PVA-LiNO3 gel polymer electrolyte (GPE). Thanks to the protective PPy coating layer on LiV3O8 and the use of solid GPE, the as-assembled ARLIB exhibits a good cycling stability of 98.7% and 79.8% capacity retention after 100 and 500 cycles, respectively. It also demonstrates exceptional flexibility to sustain various deformations including bending, squeezing, twisting and folding because of its solid-state design. Moreover, the ARLIB can be tailored into any desired shapes, and even be punched penetrative holes, exhibiting excellent safety. Thus, the creation of numerous tiny through-holes across the whole ARLIB body is testified feasible, and a designed breathability catering to the demand of comfortability in wearable devices is subsequently realized. Obviously, our study offers a promising strategy to construct flexible energy storage device with outstanding stability, flexibility, safety and breathability towards various wearable electronics.

The increasing demand for portable electronic devices and hybrid electric vehicles stimulates the development of supercapacitors as an advanced energy storage system. Here, we demonstrate a binder-free nickel hydroxide@nanoporous gold/Ni foam (Ni(OH)2@NPG/Ni foam) electrode for high-performance supercapacitors, which is prepared by a facile three-step fabrication route including electrodeposition of Au-Sn alloy on Ni foam, chemical dealloying of Sn and electrodepostion of Ni(OH)2 on NPG/Ni foam. Such Ni(OH)2@ NPG/Ni foam electrode is composed of a thin layer of conformable Ni(OH)2 nanoflakes supported on three-dimensional (3D) hierarchically porous NPG/Ni foam substrate. The resulting Ni(OH)2@NPG/Ni foam electrode can offer highways for both electron transfer and ion transport and lead to an excellent electrochemical performance with an ultrahigh specific capacitance of 3,380 F g–1 at a current density of 2 A g–1. Even when the current density was increased to 50 A g–1, it still retained a high capacitance of 1,927 F g–1. The promising performance of the Ni(OH)2@NPG/Ni foam electrode is mainly ascribed to the 3D hierarchical porosity and the highly conductive network on the NPG/Ni foam composite current collector, as well as the conformal electrodeposition of Ni(OH)2 active material on the NPG/Ni foam, which induces the formation of interconnected porosity both on the top surface and on the inner surface of the electrode. This inspiring electrochemical performance would make the as-designed electrode material become one of the most promising candidates for future electrochemical energy storage systems.

Cathode materials LiMn 0.5 Fe 0.5 PO 4 /C and LiMnPO 4 /C were synthesized by a high-energy ball-milling assisted sol-gel method. The LiMn 0.5 Fe 0.5 PO 4 consists of nanorods and nanoparticles homogeneously wrapped with highly ordering carbon. The increased Neel-temperature and decreased effective magnetic moment of LiMn 0.5 Fe 0.5 PO 4 /C revealed the microstructure differences from LiMnPO 4 /C. Meanwhile, tiny amount of ferromagnetic impurities is detected in LiMn 0.5 Fe 0.5 PO 4 /C by magnetic tests. The synergetic effects of Fe substitution and carbon coating remarkably improve rate capacity and cyclic stability of LiMn 0.5 Fe 0.5 PO 4 /C. This solid solution delivers initial discharge capacities of 128.6 mAh g −1 and 116.3 mAh g −1 and capacity retentions of 93.5% and 90.3% after 100 cycles at 1C and 2C respectively, significantly better than LiMnPO 4 /C.

Well-aligned Zn 3 P 2 nanowires-assembly bundles/Ti foil integrated anodes were for the first time successfully synthesized by a facile chemical vapor deposition. When directly applied as anodes for lithium/sodium ion batteries, they show excellent lithium/sodium storage performance especially in high-rate capability. Specifically, applied as anode material for lithium ion batteries, it showed 1100 mA h g −1 after 100 cycles and an ultrahigh rate performance with 300 mA h g −1 even at 40 A g −1 ; as anode material for sodium ion batteries, it was, for the first time, investigated and delivered a high initial specific capacity of 1120 mA h g −1 , and excellent rate capability with 280 mA h g −1 at 5 A g −1 , demonstrating that Zn 3 P 2 nanowires-assembly bundles/Ti foil integrated anodes are a promising anode candidate for lithium/sodium ion batteries. The Ex-situ XRD and HRTEM were for the first time, carried out to investigate the sodium storage mechanism of Zn 3 P 2 . Such superior lithium/sodium storage performances can be attributed to this well-aligned Zn 3 P 2 nanowires-assembly bundles structure, which not only mitigates the volume expansion of Zn 3 P 2 during cycling but also provides the direct electron transfer to ensure high-rate performances.

Lithium metal batteries (LMBs) have received extensive attention and research interest as high specific energy systems. However, the issues of Li dendrites growth in LMBs restrict their practical applications. The development of lithiophilic collectors can effectively solve the issues of Li dendrites growth. This study reports excellent lithium storage performance of lithiophilic nanosheet arrays which consist of electronic conductor Ni and ionic conductor Li2O (Ni-LONSs) on Ni foil (NF) fabricated via a simple preparation method for LMBs. The ionic conductor Li2O of the Ni-LONSs layer is lithiophilic and can induce uniform Li deposition on the Ni-LONSs collector. In addition, the nanosheet array structure of the Ni-LONSs collector is beneficial to slow down the volume change of the Li plating/stripping. In comparison with the NF collector, due to the specific nanosheet array structure of Ni-LONSs collector, the Ni-LONSs collector demonstrates excellent coulombic efficiency of 97.2% after 280 cycles (95.7% after 100 cycles of NF collector) and satisfactory cycling lifespan of 340 h (about 120 h of NF collector) at 0.5 mA cm-2with 1.0 mAh cm-2. Furthermore, the Ni-LONSs collector shows superior electrochemical performance in Ni-LONS/Li∣LiFePO4full cells. The excellent lithium storage performance of Ni-LONSs collector with mixed ionic/electronic conductor is conducive to the development and practical applications of LMBs.

Fabricating the magnesium alloy with fine grains, low dislocation density, and weak grain orientation is of crucial importance to enhance its anode performance for primary aqueous battery. However, this structure mode can hardly be realized for bulk magnesium alloy via the conventional approaches such as plastic working. Herein, we construct an AZ31 magnesium alloy with ultrafine grains (667.28 ± 291.35 nm) by using the spark plasma sintering of the alloy powder that has been treated via high-energy ball milling. This alloy exhibits weak grain orientation and its dislocation density is not increased compared to the precursor alloy. Benefiting from the unique microstructure, the modified AZ31 displays significantly more active behaviour with enhanced capacity during the discharge of Mg-air battery, as compared with the precursor AZ31 that has the grain size of 472.89 ± 154.31 μm. Furthermore, the impact of ultrafine grains on the discharge behaviour is also analysed based on microstructure characterization and electrochemical response.

Nano-sized LiFePO4·Li3V2(PO4)3/C was synthesized via a sol-gel route combining with freeze-drying. X-ray diffraction results show that this composite mainly consists of olivine LiFePO4 and monoclinic Li3V2(PO4)3 phases with small amounts of V-doped LiFePO4 and Fe-doped Li3V2(PO4)3. The magnetic properties of LiFePO4·Li3V2(PO4)3/C are significantly different from LiFePO4/C. Trace quantities of ferromagnetic impurities and Fe2P are verified in LiFePO4/C and LiFePO4·Li3V2(PO4)3/C by magnetic tests, respectively. LiFePO4·Li3V2(PO4)3/C possesses relatively better rate capacities and cyclic stabilities, especially at high charge-discharge rates. The initial discharge capacities are 136.4 and 130.0 mA h g−1 , and the capacity retentions are more than 98% after 100 cycles at 2 C and 5 C, respectively, remarkably better than those of LiFePO4/C. The excellent electrochemical performances are ascribed to the mutual doping of V3+ and Fe2+, complementary advantages of LiFePO4 and Li3V2(PO4)3 phases, the residual high-ordered carbon and Fe2P with outstanding electric conductivity in the nanocomposite.

Biomass walnut shell was used to prepare activated carbon (AC) through a carbonization treatment and an activation procedure with potassium hydroxide (KOH). AC showed hierarchical pores: 0.6 nm micropores, 2.7 nm mesopores and macropores with average diameter of 50 nm, providing a large specific surface area of 2318 m 2 g −1 . This highly porous AC was tested as a host material to encapsulate sulfur via a vapor phase infusion process. The developed AC-S electrode showed a high initial specific capacity of 1350 mAh g −1 and good capacity retention over 100 cycles at 0.1 C for lithium–sulfur battery.