Commercial LiFePO4 Research Articles

Long-term stable Li metal anode enabled by strengthened and protected lithiophilic LiZn alloys

Li metal are regarded as one of the most promising anodes for next-generation rechargeable batteries. The continuous growth of Li dendrites, however, remains a big challenge for the practical application of Li metal anodes. Herein, an artificial solid-electrolyte interphase layer composed of lithiophilic LiZn alloys under the protection and strengthening of polymer-like [LiNBH]n chains with high Li ion conductivity is built to develop long-term dendrite-free Li metal anodes. The lithiophilic LiZn alloys, acting as homogeneous nucleation sites, effectively reduce the nucleation barrier for Li plating and hence promote uniform Li plating and stripping process. Simultaneously, the homogeneous layer of polymer-like [LiNBH]n chains with high Li ion conductivity that are uniformly built inside of LiZn alloys and on the surface of LiZn alloys facilitates Li diffusion down into LiZn alloys and simultaneously alleviate the volume change of LiZn alloys during long-term Li plating and stripping process. Impressively, the thus-fabricated anode delivers an ultralong lifespan of 1200 h at 5 mA cm−2 with a fixed capacity of 5 mA h cm−2. By pairing with commercial LiFePO4 cathode, the thus-assembled full cell exhibits a specific capacity of 133 mA h g−1, corresponding to a capacity retention of 88%, at 1 C after 400 cycles.

High-capacity, high-rate, and dendrite-free lithium metal anodes based on a 3D mixed electronic-ionic conductive and lithiophilic scaffold

Lithium metal anode possesses a high theoretical capacity and the lowest redox potential, while the severe growth of Li dendrite prevents its practical application. Herein, we prepared a structure of Li3P nanosheets and Ni nanoparticles decorated on Ni foam (NF) as a three-dimensional (3D) scaffold for dendrite-free Li metal anodes (Li-Li3P/Ni@Ni foam anodes, shortened as L-LPNNF) using a facile melting method. The Li3P nanosheets exhibit excellent Li-ion conductivity as well as superior lithiophilicity, and the 3D nickel scaffold provides sufficient electron conductivity and ensures structure stability. Therefore, symmetric cells assembled by L-LPNNF possess lowered voltage hysteresis and improved long cycle stability (a voltage hysteresis of 104.2 mV after 500 cycles at a high current density of 20 mA cm−2 with a high capacity of 10 mA h cm−2), compared with the cells assembled with Li foil or Li-NF anodes. Furthermore, the full cells with paired L-LPNNF anodes and commercial LiFePO4 cathodes suggest a specific capacity of 124.6 mA h g−1 and capacity retention of 90.8% after 180 cycles with the Coulombic efficiency (CE) of ∼100% at a current rate of 1 C. This work provides a potentially scalable option for preparing a mixed electronic-ionic conductive and lithiophilic scaffold for dendrite-free Li anodes at high current densities.

V-substituted pyrochlore-type polyantimonic acid for highly enhanced lithium-ion storage

Pyrochlore-structured polyantimonic acid (PAA) is a potential high-capacity electrode material, but its innately poor electroconductivity (∼10−10 S/cm) seriously impairs its electrochemical reversibility for lithium-ion storage. Herein, we report design and synthesis of a novel V-substituted PAA (PAA-V), where V5+ are introduced to partially replace Sb5+. Owing to identical valence and close ionic radius relative to Sb5+, the V5+ cation can constitute the covalent VO6 octahedra framework without changing the pyrochlore crystal structure of PAA. As a result, the V5+-substitution is capable to modulate the electronic structure of PAA with significantly improved electrical conductivity (∼10−6 S/cm for PAA-V) and meanwhile decreases the size of crystals with reduced diffusion length for Li+-ions. With varying the ratio of V5+-substitution, the PAA-V with optimized substitution molar ratio (18%) exhibits the best lithium-ion storage performance, delivering a long cycling life with high reversible capacity (731 mAh/g after 1200 cycles at 1 A/g) and outstanding rate capability (279 mAh/g at 15 A/g). More importantly, by pairing the PAA-V as anode and commercial LiFePO4 as cathode, the full cell with a limited negative/positive capacity ratio of 1.2 exhibits decent cycling stability at 1 C after 150 cycles with 85.5% capacity retention.

Mechanical properties of heterogeneous, porous LiFePO4 cathodes obtained using statistical nanoindentation and micromechanical simulations

Among cathode materials for Li-ion batteries, LiFePO4 (LFP) is one of the most relevant for commercial batteries in electric vehicle applications. In this work, the Young’s modulus and the indentation hardness of a commercial composite LiFePO4 cathode are measured using statistical nanoindentation. The influence of the surface roughness, a substrate effect, as well as particle size effect and densification on the measurement are discussed in detail. A focus lies on the analysis of the mechanical properties of the porous secondary LiFePO4 particles and the porosity dependence of the Young’s modulus. The measurements are validated via finite element simulations on reconstructed real microstructures. It was found that the mechanical properties of the secondary LiFePO4 particles are significantly lower than those of bulk LiFePO4 and a porosity dependence of the Young’s modulus was established. The experimental Young’s modulus of the porous LiFePO4 is 47.3GPa and the indentation hardness is 2.5GPa. For porous ceramics such as these, this results in an estimation of the yield strength of 1.5GPa.

High-yield synthesis of ultrathin silicon nanosheets by physical grinding enables robust lithium-ion storage

Ultra-thin two-dimensional (2D) silicon nanosheets (SiNSs) have potential applications in electronic, energy storage, and energy conversion devices owing to their unique properties. However, high-yield and large-scale manufacturing of high-quality ultra-thin 2D SiNSs remains a great challenge. This report describes a simple, high-yield (>98%), and large-scale method for preparing ultra-thin 2D SiNSs. The developed approach improves the yield of SiNSs (thickness < 5 nm) by controlling the interaction force between the Si ingot and the abrasive grains during the diamond wire grinding process. The ultra-thin SiNSs deliver enhanced tap density and a limited variable solid electrolyte interphase growth interface. A dynamic chemical vapor deposition technique is carried out to increase the uniformity of the carbon coating on the ultra-thin SiNSs. Lithium-ion batteries employing SiNS-carbon composite anodes exhibit ultra-high initial Coulombic efficiency (88.1%) at a high Si content (79%). The full battery constructed with the fabricated SiNS-carbon composite anode and a commercial LiFePO4 cathode exhibits strong stability (1C over 600 cycles with a capacity retention rate > 80%). The results presented herein confirm the significant potential applicability of the developed method for synthesizing ultra-thin SiNSs with carbon coatings.

A lithiophilic hyperbranched polymer-decorated three-dimensional carbon skeleton boosting highly reversible lithium metal anode

The short cycling lifespan and serious safety issues caused by the crazy growth of dendrites, have severely restricted the practical application of Li metal anodes (LMAs) in high energy density batteries. Here, a three-dimensional (3D) porous conductive framework enriched with lithiophilic functional groups is proposed for stabilizing Li metal anodes, which is fabricated by coating hyperbranched polyol (HP) on the carbon fiber cloth (CFC) through a simple esterification reaction. The abundant lithiophilic groups distributed on HP can disperse the Li ion flow and guide the uniform nucleation of Li. The 3D porous skeleton not only promotes ion diffusion and electron transport but also provides adequate space for Li storage. Symmetrical battery configurated with CFC@HP-Li hybrid anode demonstrates stable cycling over 800 h with low voltage hysteresis at a current density of 2 mA cm−2. With a commercial LiFePO4 (LFP) cathode, the CFC@HP-Li//LFP full battery can realize a high capacity retention rate of 88.9% and a stable Coulombic efficiency (CE) close to 100% after 500 cycles at 2 C. The CFC@HP-Li anode, which is constructed by a modification of LMAs using the targeted lithiophilic coating, provides a promising strategy for the exploration of high-performance Li metal batteries (LMBs).

A Free-Standing α-MoO3/MXene Composite Anode for High-Performance Lithium Storage.

Replacing the commercial graphite anode in Li-ion batteries with pseudocapacitor materials is an effective way to obtain high-performance energy storage devices. α-MoO3 is an attractive pseudocapacitor electrode material due to its theoretical capacity of 1117 mAh g−1. Nevertheless, its low conductivity greatly limits its electrochemical performance. MXene is often used as a 2D conductive substrate and flexible framework for the development of a non-binder electrode because of its unparalleled electronic conductivity and excellent mechanical flexibility. Herein, a free-standing α-MoO3/MXene composite anode with a high specific capacity and an outstanding rate capability was prepared using a green and simple method. The resultant α-MoO3/MXene composite electrode combines the advantages of each of the two components and possesses improved Li+ diffusion kinetics. In particular, this α-MoO3/MXene free-standing electrode exhibited a high Li+ storage capacity (1008 mAh g−1 at 0.1 A g−1) and an outstanding rate capability (172 mAh g−1 at 10 A g−1), as well as a much extended cycling stability (500 cycles at 0.5 A g−1). Furthermore, a full cell was fabricated using commercial LiFePO4 as the cathode, which displayed a high Li+ storage capacity of 160 mAh g−1 with an outstanding rate performance (48 mAh g−1 at 1 A g−1). We believe that our research reveals new possibilities for the development of an advanced free-standing electrode from pseudocapacitive materials for high-performance Li-ion storage.

Amine-Wetting-Enabled Dendrite-Free Potassium Metal Anode.

Considered as an imperative alternative to the commercial LiFePO4 battery, the potassium metal battery possesses great potential in grid-scale energy storage systems due to the low cost, low standard redox potential, and high abundance of potassium. The potassium dendrite growth, large volume change, and unstable solid electrolyte interphase (SEI) on the potassium metal anode have, however, hindered its applications. Although conductive scaffolds coupling with potassium metal have been widely proposed to address the above issues, it remains challenging to fabricate a uniform composite with uncompromised capacity. Herein, we propose a facile and efficient strategy to construct dendrite-free and practical carbon-based potassium composite anodes via amine functionalization of the carbon scaffolds that enables fast molten potassium infusion within several seconds. On the basis of experiments and theoretical calculations, we show that highly potassiophilic amine groups immediately transform carbon scaffolds from nonwetting to wetting to postassium. Our carbon-cloth-based potassium composite anode (K@CC) can accommodate volume fluctuation, provide abundant nucleation sites, and lower the local current density, achieving nondendritic morphology with a stable SEI. The fabricated K0.7Mn0.7Ni0.3O2|K@CC full cell displays excellent rate capability and an ultralong lifespan over 8000 cycles (68.5% retention) at a high current of 1 A g-1.

Dynamic phase transition behavior of a LiMn0.5Fe0.5PO4 olivine cathode material for lithium-ion batteries revealed through in-situ X-ray techniques

LiMn0.5Fe0.5PO4 has attracted great interest due to its good electrochemical performance and higher operating voltages. This has led to a greater than 30 percent higher energy density than for commercial LiFePO4 olivine cathodes. Understanding the phase transition behaviors and kinetics of this material will help researchers to design and develop next generation cathodes for Li-ion batteries. In this study, we investigated non-equilibrium phase transition behaviors in a LiMn0.5Fe0.5PO4 cathode material during charge–discharge processes by varying current rates (C-rates) using synchrotron in-situ X-ray techniques. These methods included wide angle X-ray scattering (in-situ WAXS) and X-ray absorption spectroscopy (in-situ XAS). The WAXS spectra indicate that the phase transition of LiMn0.5Fe0.5PO4 material at slow C-rates is induced by a two-phase reaction. In contrast, at a high C-rate (5C), the formation of an intermediate phase upon discharge is clearly observed. Concurrently, the oxidation numbers of the redox reactions of Fe2+/Fe3+ and Mn2+/Mn3+ were evaluated using in-situ XAS. This combination of synchrotron in-situ X-ray techniques gives clear insights into the non-equilibrium phase transition behavior of a LiMn0.5Fe0.5PO4 cathode material. This new understanding will be useful for further developments of this highly promising cathode material for practical commercialization.

Dendrites‐Free Lithium Metal Anode Enabled by Synergistic Surface Structural Engineering

AbstractLithium (Li) metal with high specific capacity and low redox potential is widely considered as a potential anode for lithium‐ion batteries (LIBs) with high energy density. However, the catastrophic dendrites growth, “dead Li” formation, and surface passivation hinder its practical application. Herein, a selective artificial solid electrolyte interphase (SEI) layer (Li2Sx, x = 1, 2) protection strategy is adopted, where the tip sites passivation and the uniform Li nucleation in grooves are well combined, which enables reversible Li stripping/plating with high storage capacity and robust electrode framework. The grooves derived patterned array Li with selective Li2Sx artificial SEI (LS@A‐Li) exhibit over 1800 h cycling life at 1.0 mA cm–2/1.0 mAh cm–2 and over 600 h even under 5.0 mA cm–2/10.0 mAh cm–2. The application feasibility of such LS@A‐Li is also confirmed by coupling with commercial LiFePO4 and LiNi0.5Co0.2Mn0.3O2 (NCM523) in the full batteries. This work paves way for the large‐scale application of Li metal anode in lithium‐metal batteries with a facile and efficient fabrication process.

3D cubic framework of fluoride perovskite SEI inducing uniform lithium deposition for air-stable and dendrite-free lithium metal anodes

High-capacity lithium metal batteries have attracted wide attention as the next-generation energy storage systems. However, lithium dendrite caused by uneven deposition is a primary obstacle that hinders practical application of lithium metal batteries. In this work, fluoride perovskite with 3D octahedron framework, is first utilized as artificial solid electrolyte interface (SEI) to induce uniform lithium deposition for air-stable and dendrite-free lithium metal anode. The stable perovskite KNiF3 protective layer separates lithium metal from air and electrolyte, not only increases the stability of Li metal electrode, but also improves the interface contact and Li ion conduction. As evidenced theoretically and experimentally, lithium ions can migrate through the space in 3D cubic framework of perovskite with a low energy barrier, achieving fast ions migration and homogeneous deposition. The symmetric cells protected by KNiF3 SEI deliver stable cycling over 3000 h at a high capacity of 4 mAh cm−2. Coupled with commercial LiFePO4 cathodes (LFP, 13.3 mg cm−2), LFP||Li-KNiF3 batteries show promoted cycling stability and rate capability, much better than the bare Li. This work uncovers the transport mechanism of Li+ within KNiF3 SEI, and provides an avenue to air-stable and dendrite-free lithium metal anodes.

The effect of removing the native passivation film on the electrochemical performance of lithium metal electrodes

Lithium metal is accepted as the promising anode for next-generation Li batteries such as solid-state, Li–S, and Li-air batteries, etc. Besides, it is commonly employed as the reference electrodes for evaluating the electrode materials of Li-ion batteries (LIBs) in a half-cell. However, native passivation film (NPF), which is inevitable on the surface, can change the topography and surface composition distribution, and thus deteriorate the performance stability of lithium metal electrodes. Unfortunately, these effects are always neglected during the evaluation of anode or cathode materials of LIBs. Here, we conduct a comprehensive study on the effects of NPF on the electrochemical performance of lithium metal electrodes. After the removal of NPF by polishing, both the interfacial impedance and electrode overpotential are significantly decreased, with a more homogeneous lithium deposition during the charge/discharge process. When it is employed as the reference electrode for characterizing the commercial LiFePO4 or graphite materials in a coin cell, the consistency of the results is remarkably improved. This work not only provides an insight for the interfacial electrochemistry of lithium metal electrodes, but also helps characterize electrode materials in a reliable way.

SnO2/Bi2O3/NF heterojunction with ordered macro/meso-pore structure as an advanced binder-free anode for lithium ion batteries

So far, the high theoretical specific capacity metal oxide is considered as a promising anode material for lithium-ion batteries (LIBs). Unfortunately, the intrinsic poor conductivity and structural stability of metal oxide, the huge volume expansion during the cycling cause serious capacity fading and unstable cycle. Here, the three-dimensional (3D) ordered inverse opal (IO) heterojunction structure of SnO2/Bi2O3 on commercial nickel foam (NF) were fabricated. When used as a binder-free anode material for LIBs, the initial discharge specific capacity and charge specific capacity of the IOs electrode were 1229 mA h g−1 and 1098 mA h g−1. The SnO2/Bi2O3/NF IOs exhibited excellent electrochemical activity and delivered a discharge capacity about 493 mA h g−1 after 500 cycles at the current density of 1000 mA g−1, the Coulomb efficiency (CE) had been maintained at around 100%, which was much more than the control groups of SnO2/NF IOs (247 mA h g−1) and Bi2O3/NF IOs (124 mA h g−1). Furthermore, the prepared was successfully assembled with commercial LiFePO4 to a full cell that displayed stable capacity about 101.2 mA h g−1 at the current density of 100 mA g−1 after 100 cycles. The excellent performance of SnO2/Bi2O3/NF IOs is due to that the 3D interconnected macroporous and mesoporous structures can shorten the transmission path of ions/electrons and buffer volume expansion. In addition, the heterojunction structure with obvious lattice defects can effectively promote the contact between electrode material and electrolyte. The strategy in this study lights on the illuminating design of 3D inverse opal heterostructure binder-free anode, and the obtained product has a great potential as the anode material applied in next-generation LIBs.

Upcycling of photovoltaic silicon waste into ultrahigh areal-loaded silicon nanowire electrodes through electrothermal shock

Upcycling of photovoltaic silicon (Si) waste to produce high-energy-density energy storage materials represents an effective way to achieve carbon neutrality. However, at present, photovoltaic Si waste (WSi) can only be suitable for degraded utilization because WSi recycling processes are limited by deep oxidation, entrainment of trace impurities, and structural reconstruction difficulties. Here, we propose an electrothermal shock method to convert photovoltaic WSi directly into ultrahigh areal-loaded (4.02 mg cm−2) silicon nanowire (SiNW) electrodes. High-gradient thermal fields (∼104 K s−1) are produced to drive the formation and deposition of gaseous Si molecules using the easy oxidation characteristics of the WSi powder. Carbon fiber cloth is used as both a heater and an in-situ growth substrate for the SiNWs to construct SiNW-carbon cloth self-supporting electrode (SiNWs@CC) structures. When used as a binder-free anode for lithium-ion batteries, it exhibits ultra-high areal capacity (3.2 mAh cm−2 for 600 cycles, capacity retention rate >83%) and long-cycle stability (1706.2 mAh g−1 at 1 A g−1 after 1800 cycles). A full battery assembled using a commercial LiFePO4 cathode also demonstrates stable cycling performance (>91.2% initial capacity maintained at 0.5 C for 250 cycles). Such an upcycling strategy will help to promote environmentally friendly, economical, and sustainable development of the photovoltaic and energy storage industries.

Interfacial covalent bonding enables transition metal phosphide superior lithium storage performance

High theoretical capacity and moderate redox potential enable transition metal phosphide (TMP) sparkle under a spotlight as viable anode materials for lithium-ion batteries (LIBs). However, TMP suffers from severe voltage hysteresis and poor reversibility due to the breaking and formation of TM-P and Li-P bonds during lithiation/delithiation processes, resulting in significant energy dissipation and rapid capacity decay. Besides, traditional thermal phosphorization involves generation of toxic PH3, which contradicts green chemistry concept. Herein, Ni2P@C composite is successfully achieved under plasma activation with Ni MOF-74 and red phosphide as the starting materials. The monodispersed Ni2P nanoparticles are uniformly anchored within carbon matrix through covalent chemical bonding of C-O-Ni and C-P. Systematic experimental analysis and theoretical calculation indicates that such efficient interfacial chemical linkage could weaken TM-P bonds and bridge the gap between Ni2P nanoparticles and carbon matrix, thus promoting the conversion reversibility during charge/discharge reactions. Benefited from the unique structure, voltage hysteresis of Ni2P@C is significantly suppressed, the reversible lithium storage capacity and cycling stability is greatly enhanced. By employing Ni2P@C and commercial LiFePO4 as anode and cathode, the full LIBs delivers a high reversible capacity of 0.6 mAh cm−2 after 300 cycles at 1.7 mA cm−2. This strategy is expected to shed more light on interfacial chemical linkage towards rational design of advanced materials for LIBs.

(Fe, Ni)-Zif-8 Derived Sp2-C-Rich Carbon as Surface Coating for Enhancing Commercial Lifepo4 Performance

(Fe, Ni)-Zif-8 Derived Sp2-C-Rich Carbon as Surface Coating for Enhancing Commercial Lifepo4 Performance

Few layered graphene wrapped Sn4P3 with high initial coulombic efficiency and cyclic stability for reversible Li+ storage

To enhance the rate capability and cyclic stability, we develop few layered graphene wrapped nanocrystalline/amorphous Sn4P3 (named as Sn4P3@FLG) by ball milling. The high energy output of vibrational ball milling enables tight contact of Sn4P3 with FLG via POC bonding as well as compact structure with a high tap density of 4.5 g cm−3. The constraint of FLG not only enhances kinetics of electron and Li+ transfer, but also relieves the volume variation and particle aggregation of Sn4P3 during the lithiation/delithiation process. Therefore, Sn4P3@FLG exhibits superior rate and cyclic performance when evaluated as anode material for lithium-ion batteries. At 0.1 A g−1, it delivers a high reversible capacity of 1077.6 mA h g−1 with a high coulombic efficiency of 89.0% in the first cycle. Even at 1 A g−1, it still retains 929.6 mA h g−1 after 830 cycles. Furthermore, when matched with commercial LiFePO4 cathode in a full cell, it delivers a reversible capacity of 778.0 mA h g−1, with a coulombic efficiency of 79.4%. Considering the high tap density of 4.5 g cm−3, the volumetric capacity of Sn4P3@FLG can be as high as 3500 A h dm−3. Therefore, Sn4P3@FLG can be a promising anode material for high performance lithium-ion batteries.

Zero-waste: Carbon and SiO2 composite materials from the solid residue of the hydrothermal liquefaction of anaerobic digestion digestate for Li-ion batteries

Hydrothermal liquefaction (HTL) of wet biomass waste (e.g., from anaerobic digestion (AD) digestate) is an efficient technology to produce bio-crude, a hydrocarbon based renewable fuel. However, the solid waste by-product has limited use and could be an environmental nuisance if not managed appropriately. Herein, we demonstrate a sustainable way of transforming the solid residue generated through HTL of AD of sugarcane bagasse digestate into potential electrodes for lithium-ion battery (LIB). Briefly, the solid residue from the HTL process was converted into hard carbon (HC@WA) or converted through KOH activation to a carbon with a higher specific surface area carbon material (HC@AA). The structural and morphological characterizations confirm the encapsulation of SiO2 nanoparticles in the carbon matrix to form composite materials. When employed as anode materials in LIB, HC@WA and HC@AA achieve specific capacities of 452 mAh/g and 319 mAh/g respectively, and with long term cycling stability. The practical feasibility of the electrode materials was assessed by fabricating full cells with commercial LiFePO4 (LFP) cathode material. The full cells delivered good specific capacities and cycling stabilities, confirming the potential of the composite materials as electrodes for LiB. Thus, the solid residue after HTL of AD digestate could be one of the sustainable sources to develop materials for energy storage systems, thereby paving the way towards zero-waste and clean energy for a circular economy.

Unleash the Capacity Potential of LiFePO4 through Rocking‐Chair Coordination Chemistry

AbstractThere is still a considerable gap between the actual and theoretical capacities of the commercial cathode material LiFePO4 (LFP) for lithium‐ion batteries (LIBs). Here, a new strategy to release the full capacity of LFP through the rocking‐chair coordination chemistry is reported. Specifically, the zinc acetate‐diethanolamine complex (Zn(OAc)2·DEA) is used as a functional binder for the LFP cathode, where the N atom of DEA can coordinate with Zn2+, Fe2+, or Fe3+. The bond strength sequence is Fe3+–N &gt; Zn2+–N &gt; Fe2+–N, which makes the N atom swing between Fe3+ on the surface of FePO4 in the charged state and Zn2+ of Zn(OAc)2 in the discharged state. Density functional theory simulations reveal that the adsorption of DEA reduces the surface bandgap and the energy barriers of Li+ diffusion along the [010] direction of LFP, which promotes electronic conduction and Li+ diffusion, respectively. The Zn(OAc)2·DEA‐based LFP electrode achieves a high capacity of 169 mAh g−1 at 0.2C, which approaches the theoretical value of 170 mAh g−1. The electrode also has excellent cycling performance, showing a low capacity decay rate of 0.03% per cycle over 1500 cycles at 5C.

Constructing Robust Cross-Linked Binder Networks for Silicon Anodes with Improved Lithium Storage Performance.

Despite the high specific capacity of silicon as a promising anode material for the next-generation high-capacity Li-ion batteries (LIBs), its practical applications are impeded by the rapid capacity decay during cycling. To tackle the issue, herein, a binder-grafting strategy is proposed to construct a covalently cross-linked binder [carboxymethyl cellulose/phytic acid (CMC/PA)], which builds a robust branched network with more contact points, allowing stronger bonds with Si nanoparticles by hydrogen bonding. Benefitting from the enhanced mechanical reliability, the resulting Si-CMC/PA electrodes exhibit a high reversible capacity with improved long-term cycling stability. Moreover, an assembled full cell consisting of the as-obtained Si-CMC/PA anode and commercial LiFePO4 cathode also exhibits excellent cycling performance (120.4 mA h g-1 at 1 C for over 100 cycles with 88.4% capacity retention). In situ transmission electron microscopy was employed to visualize the binding effect of CMC/PA, which, unlike the conventional CMC binder, can effectively prevent the lithiated Si anodes from cracking. Furthermore, the combined ex situ microscopy and X-ray photoelectron spectroscopy analysis unveils the origin of the superior Li-ion storage performance of the Si-CMC/PA electrode, which arises from its excellent structural integrity and the stabilized solid-electrolyte interphase films during cycling. This work presents a facile and efficient binder-engineering strategy for significantly improving the performance of Si anodes for next-generation LIBs.