Full Lithium-ion Battery Research Articles

Molecular Engineering Chemical Pre-lithiation Reagent with Low Redox Potential for Graphite Anode Enables High Coulombic Efficiency.

Graphite (Gr) is a low-cost and high-stability anode for lithium-ion batteries (LIBs). However, Gr anode exhibits an obstinate drawback of low initial Coulombic efficiency (ICE), owing to the active lithium loss for the solid electrolyte interphase (SEI) layer. Herein, a straightforward and effective chemical pre-lithiation strategy is proposed to compensate for the lithium loss. A molecular engineering phenanthrene-based lithium-arene complex (Ph-based LAC) reagent is designed by density functional theory (DFT) calculations. The engineering Ph-based reagent enhances the stability of the π-electron system and the electron-donating capacity, resulting in a reduced redox potential to facilitate lithium transfer. The electrochemical distinct of the Ph-based reagent is illustrated, the prelithiation process in a low Li-insertion platform, and the lithiation degree is controllable with the dipping time (ICE = 102%, 3min). Notably, a denser and homogeneous SEI layer has pre-formed to enhance the Li+ transport and interface stability. Moreover, the lithium-ion full batteries assemble with LiFePO4 and NCM811 cathode, which exhibits high ICE (96.5% and 90.3%) and energy density (310 and 333Whkg-1). These findings present a facile and controllable pre-lithiation strategy to compensate for the lithium of LIBs, providing new valuable insights into the design and optimization of battery manufacture.

Copper-doping enhanced electrochemical performance of cobalt embedded nitrogen-doped porous carbon dodecahedra in lithium-ion half/full batteries

The creation of negative electrode materials that have quick redox kinetics, reduced volumetric expansion, and a high reversible specific capacity is the linchpin to the advancement of lithium-ion batteries. Here, we prepared copper-doping cobalt-embedded nitrogen-doped porous carbon (CoCu@NC) by calcining copper-modified ZIF-67. The unique hollow structure presents a fast ionic diffusion channel and good structural stability. Density functional theory (DFT) calculation testifies that Cu-doping can regulate the electronic structure of the CoCu@NC surface as well as enhance lithium ions adsorption capacity on nitrogen sites. Furthermore, the presence of N and Cu could generate more defects, thereby achieving rapid storage reaction kinetics of lithium ions. Benefiting from the cooperative effect between Co and Cu double-doped at NC, strain and stress are alleviated during lithium-ion intercalation/deintercalation processes, thus improving cycling stability and performance. Therefore, CoCu@NC shows a superior capacity of 1155.10 mAh g−1 at a current density of 0.5 A g−1, and good stability with 310.90 mAh g−1 at 10 A g−1 after 600 cycles. The assembled LiCoO2//CoCu@NC-7 lithium-ion full battery can achieve a discharge-specific capacity at 3 A g−1 for 182.60 mAh g−1 after 500 cycles.

Superior electrochemical performances of Lithium vanadium oxide with coconut shell-based porous carbon as the anode of the aqueous Li ion battery

Carbon materials, as the skeleton structure of electrode materials, are composited with lithium-ion anode materials, which not only increase the electrical conductivity of the materials, but also enhance the electrochemical performance of the electrode materials. In this paper, LiV3O8@C composites were prepared by using coconut shell-based porous carbon to structurally modulate aqueous lithium-ion anode materials. And three composites with different structures and sizes were successfully synthesized by hydrothermal method, hydrothermal stirring method and improved solid-phase method. After XRD and SEM analyses, it was found that all three composites maintained the monoclinic crystal system structure of LiV3O8, and the materials prepared by the hydrothermal method showed a smooth layer structure, while the materials prepared by the hydrothermal stirring method and the solid-phase method showed nanorods with different sizes. The prepared anode materials and LiFePO4 cathode materials were assembled into an aqueous lithium-ion full battery, and were subjected to charge/discharge tests, cyclic voltammetry and electrochemical impedance spectroscopy. The results indicate that the electrochemical performances of the three composites are significantly improved compared with the pure LiV3O8. Specifically, the discharge capacities of the two groups of nanorod-like composites were 112.2 mAh/g and 85.5 mAh/g at a rate of 0.2 C, which were improved by as much as two times compared with the pure LiV3O8. However, the composite material with layered structure not only reaches an initial discharge specific capacity of 148.39 mAh/g, which is 2.7 times higher than that of the pure LiV3O8, but also effectively slows down the dissolution effect of LiV3O8 by compositing with the carbon material, and at the same time, it shows excellent rate performance.

Towards practical Li-ion full batteries with glass anodes

Vanadium (V)-based glasses have recently garnered considerable attention as promising anode materials for lithium-ion batteries (LIBs) due to their abundance of Li+ storage sites, neglectable volume expansion upon lithiation/delithiation, and facile preparation. However, the inherently low electronic conductivity and relatively low energy density of V-based glass anodes hinder its application in full LIBs. In this work, we tackled this challenge by optimizing the chemical composition of the V-based glass anode to achieve high-performance half and full cells. We investigated the impact of partially substituting B2O3 for P2O5 in 50V2O5-(50-x)P2O5-xB2O3 (mol%) (VPB) glass series on its structure and electrochemical performances. The glass with 30 mol% B2O3 (VPB30 glass) was found to deliver the highest electronic conductivity, an enhanced reversible capacity of 470 mA h g−1 at 1 A g−1 after 500 cycles, and an excellent rate capability. The optimized performances were ascribed to the boosted lithium-ion diffusivity and the increased lithium storage sites. We assembled a full cell by coupling a VPB30 glass anode with a LiCoO2 cathode to test its cycling performance. The VPB30//LiCoO2 cell exhibits the required power density, and hence, high practicality. Our work implied the practical application of glass anodes in high-performance LIBs.

Flexible free-standing Fe-CoP-NAs/CC nanoarrays for high-performance full lithium-ion batteries

In this study, a flexible, free-standing Fe-doped CoP nanoarrays electrode for superior lithium-ion storage has been successfully fabricated. The electrode combines the advantages of a Fe-doping and a flexible carbon cloth (CC) support, resulting in a high specific capacity (1356 mAh/g at 0.2 A/g) and excellent cycling stability (1138 mAh/g after 100 cycles). The cyclic voltammetry (CV) curves at different scan rates investigate the outstanding lithium storage behavior of Fe-CoP-NAs/CC which indicates a combined influence of diffusion behavior and capacitance behavior on the electrochemical process. The galvanostatic intermittent titration technique (GITT) analyzes the diffusion kinetics of Li+ which indicates the fast diffusion kinetics in the Fe-CoP/NAs/CC anode. The assembled Fe-CoP-NAs/CC//LiFePO4 battery exhibits a remarkable capacity of 325.2 mAh/g even at 5 A/g. And the battery also has good cycle stability, and still provides 498.1 mAh/g specific capacity after 200 cycles. Moreover, the Fe-CoP-NAs/CC//LiFePO4 soft-pack battery can continuously power the LEDs when it is bent at various angles which demonstrates its potential for use in wearable devices.

MXene-reinforced Sb@C nanocomposites with synergizing spatial confinement architecture enabled ultra-stable and fast lithium ion storage

Antimony (Sb) is recognized as a potential anode material for lithium-ion batteries due to its high theoretical capacity and adequate working potential. However, its application is hindered by the significant volume expansion during lithiation and low intrinsic conductivity, leading to considerable capacity fading and reduced rate capability. Herein, a unique MXene-reinforced Sb@C (MSC) nanocomposite is constructed via in-situ growing Sb-MOF over the conductive MXene substrate, followed by annealing. MXene substrate and MOF-derived carbon layer coupling effectively creates a continuous and conductive framework, encapsulating Sb nanoparticles. This unique architecture mitigates volume expansion, prevents particle aggregation, and enhances interfacial charge transfer, significantly improving the lithium storage performance of the MSC nanocomposite over its Sb@C (SC) counterpart. The MSC nanocomposite achieves a high capacity of 625 mAh g−1 at 100 mA g−1, superior rate capability of 305 mAh g−1 at 10 A g−1, as well as excellent cycling stability with a capacity retention of 84.4 % over 2000 continuous cycles. Additionally, a lithium-ion full batteries with MSC anode and LiFePO4 cathode demonstrates a capacity of 168.9 mAh g−1 at 100 mA g−1 and a maximum energy density of 381.2 Wh kg−1 based on the cathode mass, illustrating its promising potential for constructing high-performance lithium ion batteries.

Investigation on the Application of Microporous Current Collector in Ultra-Fast Lithium-Ion Full Battery

Investigation on the Application of Microporous Current Collector in Ultra-Fast Lithium-Ion Full Battery

In-situ differential electrochemical mass spectrometry study on the effects of negative/positive ratios on gas evolution in lithium-ion full batteries

In-situ differential electrochemical mass spectrometry study on the effects of negative/positive ratios on gas evolution in lithium-ion full batteries

Layered titanium phosphate nanosheets with water in salt electrolyte toward high-voltage aqueous full lithium-ion batteries

A high voltage aqueous full lithium-ion battery using novel Ti(HPO4)2·H2O as the anode material with excellent stability.

Construction of core-shell TiNb2O7/Li4Ti5O12 composites with improved lithium storage for lithium-ion batteries

In this study, the (TiNb2O7) TNO and modified (Li4Ti5O12) LTO composites with the core–shell (CS) structures have been designed and prepared by the spry-dried method. In the structural composite, the modified LTO core can stabilize the dimensional stability with excellent rate capability, and the TNO shell can offer a larger capacity, leading to high-performance anode materials. Our results indicate that the CS composites without the TNO nanoparticles (NPs) aggregation reveal a more negligible electrochemical polarization (EP) with improved kinetics than traditional composites. The optimal TNO content in the CS composite is 30 wt%, which can show a larger capacity than that of bare LTO, with the C-rate ranging between 17.5 and 3500 mA g−1. It delivers a capacity of 164.9 mA h g−1 at 1050 mA g−1, higher than bare LTO (157.6 mA h g−1) and traditional composite (154.6 mA h g−1). Furthermore, the full lithium-ion battery (LIB) is fabricated using the CS composite as the anode and LiNi0.5Mn1.5O4 (LNMO) as the cathode. The designed LIB shows an improved energy density of 122.0 W h kg−1 with remarkable cycling stability.

Binding SnO2 Nanoparticles with MoS2 Nanosheets Toward Highly Reversible and Cycle‐Stable Lithium/Sodium Storage

SnO2, with its high theoretical capacity, abundant resources, and environmental friendliness, is widely regarded as a potential anode material for lithium‐ion batteries (LIBs). Nevertheless, the coarsening of the Sn nanoparticles impedes the reconversion back to SnO2, resulting in low coulombic efficiency and rapid capacity decay. In this study, we fabricated a heterostructure by combining SnO2 nanoparticles with MoS2 nanosheets via plasma‐assisted milling. The heterostructure consists of in‐situ exfoliated MoS2 nanosheets predominantly in 1 T phase, which tightly encase the SnO2 nanoparticles through strong bonding. This configuration effectively mitigates the volume change and particle aggregation upon cycling. Moreover, the strong affinity of Mo, which is the lithiation product of MoS2, toward Sn plays a pivotal role in inhibiting the coarsening of Sn nanograins, thus enhancing the reversibility of Sn to SnO2 upon cycling. Consequently, the SnO2/MoS2 heterostructure exhibits superb performance as an anode material for LIBs, demonstrating high capacity, rapid rate capability, and extended lifespan. Specifically, discharged/charged at a rate of 0.2 A g−1 for 300 cycles, it achieves a remarkable reversible capacity of 1173.4 mAh g−1. Even cycled at high rates of 1.0 and 5.0 A g−1 for 800 cycles, it still retains high reversible capacities of 1005.3 and 768.8 mAh g−1, respectively. Moreover, the heterostructure exhibits outstanding electrochemical performance in both full LIBs and sodium‐ion batteries.

Scalable synthesis of high-performance Si/CNTs/C anodes for lithium-ion batteries based on recycling of silicon cutting waste

Si is expected to replace graphite anode materials in the next generation of high-energy–density lithium-ion batteries due to its high specific capacity and abundant resources. However, the poor electrical conductivity and the huge volume expansion during the lithiation and delithiation process hindering its further commercial application. In this work, silicon cutting waste（SCW）generated in the photovoltaic industry was recycled as raw material, and a slurry containing Si after sanding(S-Si) was obtained in the sanding machine, carbon nanotubes (CNTs) and polyvinylpyrrolidone (PVP) were added to the slurry, mixed homogeneously and then spray-dried and granulated, after high-temperature carbonization, Si/CNTs/C composite with high vibrational density, homogeneous particle size and excellent electrochemistry were obtained. The nano-sized Si can accommodate the volume expansion during the cycling process, and the CNTs are interspersed in the composite to construct a conductive network, thus enhancing the electronic conductivity of the composite. The as-synthesized Si/CNTs/C composite exhibited a residual capacity of more than 1000 mAh·g−1 after 500 cycles at a current of 1 A·g−1 and a capacity of 878 mAh·g−1 even at 10 A·g−1. Notably, full lithium-ion batteries with a Si/CNTs/C anode and LiFePO4 cathode delivered a stable capacity of 130 mAh·g−1 with an ICE of 88.1 %. Our work provides reference solutions for the recycling of waste materials in the photovoltaic industry as well as the preparation of low-cost, high-performance Si/C anodes for lithium-ion batteries.

Revealing the key role of MnSiO3 in boosting the lithium storage performance of bamboo-derived anode materials

Carbon/manganese oxide hybrid materials, as potential candidates for lithium-ion battery anode materials, have attracted extensive attention due to their abundant resources and simple preparation. However, poor rate performance, weak cycle stability, and relatively high cost still limit their further development as commercial materials for next-generation Li-ion batteries. Herein, a novel carbon/manganese oxide hybrid material was fabricated from low-cost carbonized bamboo leaves and manganese nitrate for the lithium-ion battery anode. Interestingly, an additional MnSiO3 component found in this hybrid material is able to increase the material's intrinsic conductivity for improving the charge transfer as well as to enhance the Li+ diffusion ability for accelerating the reaction kinetics. Thus, the rate capability and cycle performance of the prepared hybrid material with additional MnSiO3 have been significantly improved by 18.4 and 52.6 %, respectively, compared to hybrid material without the MnSiO3 component. Moreover, the cycle performance of this hybrid material is also superior to that of many similar carbon/silicate and carbon/manganese oxide hybrid materials. Thanks to the excellent electrochemical performance, our hybrid material has also been successfully fabricated into a lithium-ion full battery, which displays considerable energy storage performance and good practical application ability.

A long service life silicon-doped laser-etched polyimide anode materials for high-rate lithium-ion battery

Silicon (Si)-based materials emerge as promising anode materials owing to their theoretical capacity as high as 4200 mAh g−1. However, when Si-based materials are assembled into battery anode sheets, they face the dilemmas of severe volume expansion and poor electric conductivity. In this study, three-dimensional (3D) layered porous Si‑carbon (C) composites are designed and fabricated from a polyimide (PI) precursor through cyclization polymerization and laser etching. SiC particles are dispersed in the porous network structure, which reduces the volume expansion of the anode during charging and discharging, so that the electrode has good cycle life and specific capacity. The laser-etched Si-doped polyimide (L-Si-PI) anode achieves 1332 mAh g−1 capacity in the first discharge and a high capacity of 1057 mAh g−1 after 1500 cycles at 0.2 A g−1 for half lithium-ion batteries (LIBs). When the L-Si-PI is employed for full LIBs, it exhibits a specific capacity of 142 mAh g−1 at 0.1C with 800 cycles working life. And kinetic analysis reveals a diffusion-controlled lithium storage mechanism in the composite. In a word, such rational nanostructure design and multi-component synergic interaction system has a good application prospect in the field of LIB research.

Amorphous FePO4/reduced graphene oxide composite prepared from jarosite residue and its application as a novel anode material for lithium-ion batteries

Rational utilization of jarosite residue is significantly important from the view of environmental protection and resource recycling. Herein, we report a facile preparation of porous amorphous FePO4/reduced graphene oxide (rGO) composite by utilizing the iron resource in jarosite residue with a selective chemical precipitation method, and demonstrate its great potential as a high-performance anode material of lithium-ion batteries (LIBs). The FePO4/rGO composite exhibits superior cyclic performance (812.7 mA h g−1 over 300 cycles at 500 mA g−1) and high-rate capability (335.2 mA h g−1 even at a high current density of 10 A g−1) in a half cell. More importantly, the full LIB assembled with FePO4/rGO anode and commercial Li(Ni0.5Co0.2Mn0.3)O2 (NCM523) cathode still delivers a high and stable capacity of 674.9/528.7 mA h g−1 upon 100/300 cycles at 200/500 mA g−1, indicating the great potential of this FePO4/rGO composite as a new anode material with high lithium storage performance. This work proposes a simple, feasible, and cost-effective strategy for the high-valued utilization of jarosite residue and provides a reference for the design and development of FePO4-based anode materials for LIBs.

Cr-doped LiNi0.5Mn1.5O4 derived from bimetallic Ni/Mn metal-organic framework as high-performance cathode for lithium-ion batteries

Metal-organic frameworks (MOFs) have potential applications in the field of electrochemical energy storage due to their unique characteristics, such as structural diversity, tolerability, and chemical homogeneity. LiNi0.5Mn1.5O4 (LNMO) is a great cathode material due to its wide working voltage, high energy density, and excellent rate capability. In this study, bimetallic Ni/Mn-MOFs and Cr-doped Ni/Mn-MOFs have been prepared by solvothermal reaction, which can be used as the precursor for the synthesis of pristine and Cr-doped LNMOs. The results indicate that the MOF-derived LNMO has better electrochemical behavior than the sample obtained from the conventional co-precipitation route. The resulting MOF-derived LNMO exhibits a high specific capacity (SC, 132.4 mAh/g at 0.2C), good rate ability (116.5 mAh/g at 10C), and remarkable long-cycle performance (80.1 % capacity retention for 200 cycles at 4C). More significantly, the full lithium-ion batteries (LIBs) incorporated with the MOF-derived LNMO as a cathode and Li4Ti5O12 (LTO) as an anode exhibit superior energy storage properties. This finding provides an efficient strategy for preparing high-performance LNMO cathode materials.

Reversible multi-electron redox chemistry of organic salt as anode for high-performance Li-ion/dual-ion batteries

Organic electrode materials are attracting increasing attention for rechargeable secondary batteries because of their low cost, high capacity, nontoxic and environmentally friendly. Herein, we report an excellent anode of a novel organic hexalithium salt of mellitic acid (Li6C12O12) for lithium-ion battery (LIB)/dual-ion battery (DIB). A combination of electrochemical and spectroscopic studies verifies a reversible coordination reaction mechanism based on carboxylic carbonyl and Li+ ions. Li6C12O12 delivers large reversible capacities of 730 mA h g−1 at 0.21 A/g and 372 mA h g−1 even at 2 A/g. Furthermore, the Li6C12O12 electrode enables LiFePO4//Li6C12O12 full LIB and graphite//Li6C12O12 full DIB to exhibit high capacity and good cycling stability. This work presents a new perspective on designing and tailoring organic electrode materials to build high-performance lithium-ion batteries/dual-ion batteries.

Rechargeable Li-ion full batteries based on one-dimensional Li-rich Li1.13Mn0.26Ni0.61O2 cathode and nitrogen-doped carbon-coated NiO anode materials.

To meet the increasing requirements of lithium-ion batteries (LIBs) as energy sources for mobile electronic devices and electric vehicles, great efforts are being made to develop cathode and anode materials with high specific capacity and lifetime stability. Herein, we report a Li-rich one-dimensional (1D) Li1.13Mn0.26Ni0.61O2 (0.3Li2MnO3·0.7LiNiO2, LMO@LNO) cathode and a nitrogen-doped carbon-decorated NiO (NC@NiO) anode material prepared from 1D Ni(OH)2 nanowires (NWs) for application in full LIBs. The as-prepared 1D Li-rich LMO@LNO cathode displays a high discharge capacity (184.4 mA h g-1), high coulombic efficiency (73.9%), long-term cyclability, and good rate performance in comparison with pristine LiNiO2 (LNO). Moreover, the 1D NC@NiO composite anode exhibits a high discharge capacity (914.5 mA h g-1), high coulombic efficiency (76.8%), long cycling life, and better rate performance, as compared with bare NiO. A full LIB consisting of the nanostructured Li-rich LMO@LNO cathode and the NC@NiO anode delivers a high capacity of over 167.9 mA h g-1 between 4.0 and 0.1 V. These enhanced electrochemical characteristics suggest that the full LIB configuration with 1D Li-rich LMO@LNO and NC@NiO composites holds promise as a next-generation secondary battery platform.

Cr3+-Doped TiNb2O7 as an advanced anode material for high-performance lithium-ion batteries

Because of its high operating potential (ca. 1.6 V), high theoretical capacity (ca. 387 mA h/g), and safety of operation, TiNb2O7 (TNO) is a promising anode material and an excellent alternative to spinel Li4Ti5O12. To overcome the poor electrical conductivity and low Li+ ion diffusion coefficient of pure TNO, and, thereby, significantly improve its rate performance, in this study we prepared a novel Ti1–xCrxNb2O7 (x = 0.05; Cr-TNO) anode material. When evaluated for its energy storage performance, the electrochemical properties of Cr-TNO were improved relative to those of TNO, including an excellent rate capability (178.2 mA h/g at 10C) and good cycle stability (84.2 % retention after 500 cycles), due to enhanced electronic and ionic conductivities. Furthermore, we demonstrate herein the practical applications of Cr-TNO when combined with active carbon and a LiNi0.5Mn1.5O4 cathode in an asymmetric supercapacitor and a full lithium-ion battery, respectively. Both of these devices possessed pronounced cycling stability and rapid charge/discharge characteristics, reflecting the excellent electrochemical performance of Cr-TNO.

Emerging Lithiated Organic Cathode Materials for Lithium-Ion Full Batteries.

Organic electrode materials have application potential in lithium batteries owing to their high capacity, abundant resources, and structural designability. However, most reported organic cathodes are at oxidized states (namely unlithiated compounds) and thus need to couple with Li-rich anodes. In contrast, lithiated organic cathode materials could act as a Li reservoir and match with Li-free anodes such as graphite, showing great promise for practical full-battery applications. Here we summarize the synthesis, stability, and battery applications of lithiated organic cathode materials, including synthetic methods, stability against O2 and H2 O in air, and strategies to improve comprehensive electrochemical performance. Future research should be focused on new redox chemistries and the construction of full batteries with lithiated organic cathodes and commercial anodes under practical conditions. This Minireview will encourage more efforts on lithiated organic cathode materials and finally promote their commercialization.