Binder-free Lithium-ion Battery Research Articles

Three-Dimensional Self-Supported Ge Anode for Advanced Lithium-Ion Batteries.

Three-dimensional (3D) self-supported Ge anode is one of the promising candidates to replace the traditional graphite anode material for high-performance binder-free lithium-ion batteries (LIBs). The enlarged surface area and the shortened ions/electrons transporting distance of the 3D electrode would greatly facilitate the rapid transfer of abundant lithium ions during cycling, thus achieve enhanced energy and power density during cycling. Cycle stability of the 3D self-supported Ge electrode would be improved due to the obtained enough space could effectively accommodate the large volume expansion of the Ge anode. In this review, we first describe the electrochemical properties and Li ions storage mechanism of Ge anode. Moreover, the recent advances in the 3D self-supported Ge anode architectures design are majorly illustrated and discussed. Challenges and prospects of the 3D self-supported Ge electrode are finally provided, which shed light on ways to design more reliable 3D Ge-based electrodes in energy storage systems.

Ex-Situ Studies of Hydraulic Pressure Effect on the Electrochemical, Structural and Morphological Properties of Nickel-Rich NMC

The development of industry and technology, as well as the Earth's growing population, is forcing an ever-increasing demand for energy and raw materials. In tandem with this demand, efficient energy storage is also necessary and equally important. One of the most attractive forms of energy storage, has proven to be electrochemical cells, which allow the conversion of chemical reaction energy into electricity. The most promising cell type turned out to be lithium-ion batteries, and this was due to the attractive properties of lithium, which have the high negative standard potential (about -3 V) and high specific capacity (3860 Ah kg-1) 1. The majority of commercial lithium-ion batteries (LIB) are manufactured using roll-to-roll (R2R) wet processing technology (i.e., the slurry method), where active battery powder, conductive carbon powder and inactive binding agent are mixed in a organic solvent , cast onto metallic current collectors and then dried 2. Up next, the electrode layers undergo a calendaring process in which they are compressed. It is important to clarify the effect of hydraulic pressure on the properties of electrode materials and correlate this relationship to its type and characteristics. An inadequate selection of hydraulic pressure conditions can adversely affect the properties of the active battery material, leading to grain cracking and thus the capacity drop. The phenomenon of cracking of nickel-rich NMC secondary particles is considered to be the one of the critical causes that deteriorate the long-term cyclic stability of the NMC cathode in lithium-ion batteries 2,3.In this study various methods are applied to observe and understand the electrode properties that accompany grain fracture and electrode preparation conditions. Morphological changes that occur before and after the electrode calendaring and further the cell’s operation can be examined by scanning electron microscopy (SEM). This technique can be used as a tool to gather information about the composition of cathode materials while tracking a realistically operating battery 3. Another analysis technique is the ex-situ Raman spectroscopy, which allows us to gather detailed information on the local properties of the electrode material. It provides details on phase transitions and the causes of capacity loss over successive battery cycles 4. The information about grain size, crystallographic parameters and the phases present in the sample, can be gathered by X-ray diffraction (XRD). In this research all these methods will be employed to identify possible defects present in electrode materials before and after cycling with regard to applied hydraulic pressure during electrode preparation. We will determine the most suitable hydraulic pressure conditions and correlate our results with initial material morphology and crystallographic structure as well as the electrochemical response. A detailed data analysis will be reported at the conference. Funding for this work was provided by the National Science Center in Poland under the Sonata BIS 11 program (No. UMO-2021/42/E/ST5/00390). A. Czerwiński. Akumulatory, baterie, ogniwa. (2005). Kirsch, D. J. et al. Scalable Dry Processing of Binder-Free Lithium-Ion Battery Electrodes Enabled by Holey Graphene. ACS Appl Energy Mater 2, 2990–2997 (2019). Cheng, X. et al. Real-Time Observation of Chemomechanical Breakdown in a Layered Nickel-Rich Oxide Cathode Realized by in Situ Scanning Electron Microscopy. ACS Energy Lett 6, 1703–1710 (2021). Flores, E., Novák, P. & Berg, E. J. In situ and Operando Raman spectroscopy of layered transition metal oxides for Li-ion battery cathodes. Front Energy Res 6, (2018).

A hybrid flexible N-doped candle-soot carbon nanofibers for binder-free lithium-ion battery anode

This work demonstrates a unique fractal-like candle soot-derived carbon nanoparticles (CSC) decorated onto nitrogen-doped carbon nanofibers (CSC@N-CNFs) by a one-step electrospinning process as a self-standing flexible anode for lithium-ion battery (LIB). The CSC nanoparticles exhibit a short-range ordered structure with large interlayer spacing for enhanced Li ion storage. In addition, the N-CNFs provide flexibility and stability to prevent volume expansion during electrochemical reactions. The synergistic impact of the hybrid structure provides the flexible anode with a high initial discharge capacity of 1030 mAh/g at 0.1C with an outstanding coulombic efficiency of ∼100% at 30C (5 A/g). The enhanced performance is due to the increased electrical conductivity from N-doping from CNFs, the hard carbon morphology of CSC nanoparticles, the 3D interconnected nanofiber framework, and the binder-free flexible nature.

Cobalt Oxide Arrays Anchored to Copper Foam as Efficient Binder-free Anode for Lithium Ion Batteries.

The development of lithium-ion batteries with simplified assembling steps and fast charge capability is crucial for current battery applications. In this study, we propose a simple in-situ strategy for the construction of high-dispersive cobalt oxide (CoO) nanoneedle arrays, which grow vertically on a copper foam substrate. It is demonstrated that this nanoneedle CoO electrodes provide abundant electrochemical surface area. The resulting CoO arrays directly act as binder-free anodes in lithium-ion batteries with the copper foam functioning as the current collector. The highly-dispersed feature of the nanoneedle arrays enhances the effectiveness of active materials, leading to outstanding rate capability and superior long-term cycling stability. These impressive electrochemical properties are attributed to the highly-dispersed self-standing nanoarrays, the advantages of binder-free constituent, and the high exposed surface area of the copper foam substrate compared to copper foil, which enrich active surface area and facilitate charge transfer. The proposed approach to prepare binder-free lithium-ion battery anodes streamlines the electrode fabrication steps and holds significant promise for the future development of the battery industry.

Novel self-supporting multilevel-3D porous NiO nanowires with metal-organic gel coating via “like dissolves like” to trigger high-performance binder-free lithium-ion batteries

In this work, we put forward a concept of novel self-supporting multilevel-3D porous NiO nanowires and successfully synthesize them to be used as binder-free electrode for lithium-ion batteries (LIBs). According to the “like dissolves like” rule, Zr-based metal-organic gel (Zr-MOG) with the same organic ligand of the precursor of NiO is in situ coated on the surface of novel multilevel-3D porous nanowires, which not only effectively stabilizes the multilevel-3D porous network structure, but also adheres the electrode material to the surface of the Cu foil effectively and prevents electrode pulverization or shedding due to its own viscosity without adding binder (PVDF) in the process of fabricating electrode. Contact angle analysis illustrates Zr-MOG possesses potential to provide cementation power. Through theoretical simulation, the binding energy of NiO@Zr-MOG is lower than NiO, demonstrating the superiority to occur the redox reaction. The novel self-supporting multilevel-3D porous NiO nanowires coated by Zr-MOG possess superior electrochemical performance of LIBs (the specific capacity reached 1816.3 mAh g −1 at the current density of 100 mA g −1 , remained at 1318.7 mAh g −1 after 150 cycles). This work will provide a new perspective for the fabrication of high-performance binder-free LIB electrodes. • Put forward the concept of novel multilevel-3D porous nanowires. • Binder-free lithium-ion battery anode by “like dissolves like” coating. • The superiority of NiO@Zr-MOG was demonstrated by theoretical simulation. • The fabrication method is applicable to other transition metal oxides.

Facile synthesis and simulation of MnO2 nanoflakes on vertically aligned carbon nanotubes, as a high-performance electrode for Li-ion battery and supercapacitor

This study reports the successful fabrication of high-performance flexible binder-free lithium-ion battery anode and supercapacitor based on the synthesis of 3D hierarchical MnO2 nanoflakes (NFs) on vertically aligned carbon nanotubes (VACNTs) grown upon stainless steel (SS). The experimental results revealed that the prepared electrodes were well served as supercapacitors with a tremendous specific capacitance of MnO2 NFs VACNT/SS 1131 F/g at 0.25 A/g in 0.5 mol.L−1 Na2SO4, 518.8% more than VACNT/SS (218 F/g). Compared to other MnO2 NFs/CNT composites, as-fabricated binder-free MnO2 NFs/VACNTs electrode achieves outstanding performance with high initial discharge and charge capacities of 2438 and 1289 mAhg−1 at a current density of 250 mAg−1, respectively. The fabricated anode anode further demonstrates an extraordinarily high reversible capacity of 803.2 mAhg−1 with columbic efficiency of 98.4% at a current density of 250 mAg−1 over 150 charge/discharge runs. Compared to pure VACNTs electrode, the MnO2/VACNTs has significantly improved cycling stability and lithium storage capability, making this nanocomposite a promising anode for LIBs. Meanwhile, the electrochemical behavior of MnO2 NFs/VACNTs anode was evaluated using a numerical simulation approach. The simulation findings results showed excellent consistency between numerical and experimental results.

Characteristics and electrochemical performances of silicon/carbon nanofiber/graphene composite films as anode materials for binder-free lithium-ion batteries

We report the interfacial study of a silicon/carbon nanofiber/graphene composite as a potentially high-performance anode for rechargeable lithium-ion batteries (LIBs). Silicon nanoparticle (Si)/carbon nanofiber (CNF)/reduced graphene oxide (rGO) composite films were prepared by simple physical filtration and an environmentally-friendly thermal reduction treatment. The films were used as high-performance anode materials for self-supporting, binder-free LIBs. Reducing graphene oxide improves the electron conductivity and adjusts to the volume change during repeated charge/discharge processes. CNFs can help maintain the structural stability and prevent the peeling off of silicon nanoparticles from the electrodes. When the fabricated Si/CNF/rGO composites were used as anodes of LIBs, the initial specific capacity was measured to be 1894.54 mAh/g at a current density of 0.1 A/g. After 100 cycles, the reversible specific capacity was maintained at 964.68 mAh/g, and the coulombic efficiency could reach 93.8% at the same current density. The Si/CNF/rGO composite electrode exhibited a higher specific capacity and cycle stability than an Si/rGO composite electrode. The Si/CNF/rGO composite films can effectively accommodate and buffer changes in the volume of silicon nanoparticles, form a stable solid–electrolyte interface, improve the conductivity of the electrode, and provide a fast and efficient channel for electron and ion transport.

Hollow multi-nanochannel carbon nanofiber/MoS2 nanoflower composites as binder-free lithium-ion battery anodes with high capacity and ultralong-cycle life at large current density

The electrode materials with high pseudocapacitance can enhance the rate capability and cycling stability of lithium-ion storage devices. Herein, we fabricated MoS2 nanoflowers with ultra-large interlayer spacing on N-doped hollow multi- nanochannel carbon nanofibers (F2-MoS2/NHMCFs) as freestanding binder-free anodes for lithium-ion batteries (LIBs). The ultra-large interlayer spacing (0.78∼1.11 nm) of MoS2 nanoflowers can not only reduce the internal resistance, but also increase accessible active surface area, which ensures the fast Li+ intercalation and deintercalation. The NHMCFs with hollow and multi-nanochannel structure can accommodate the large internal strain and volume change during lithiation/delithiation process, it is beneficial to improving the cycling stability of LIBs. Benefiting from the above combined structure merits, the F2-MoS2/NHMCFs electrodes deliver a high rate capability 832 mA h g−1 at 10 A g−1 and ultralong cycling stability with 99.29 and 91.60 % capacity retention at 10 A g−1 after 1000 and 2000 cycles, respectively. It is one of the largest capacities and best cycling stability at 10 A g−1 ever reported to date, indicating the freestanding F2-MoS2/NHMCFs electrodes have potential applications in high power density LIBs.

Design of quadruple-layered metal oxides/nitrogen, oxygen-doped carbon nanotube arrays as binder-free electrodes for flexible lithium-ion batteries

Designing flexibly binder-free metal oxide electrodes, which could effectively alleviate the mechanical stress and maintain the structural integrity during the lithiation/delithiation process, is still a major challenge. Here we report a facile strategy for successfully synthesizing free-standing quadruple-layered metal oxides/nitrogen, oxygen-doped carbon nanotube array electrodes. In the quadruple-layered structure, metal oxides are protected by carbon layer to minimize the direct exposure to the electrolyte and accommodate the huge volume change during cycling, and thus form the solid-electrolyte interface layer. Besides that, the abundant oxygen and nitrogen-containing functional groups of carbon layer shows a strong interaction with metal oxides to prevent the electrode pulverization during charging and discharging. Meanwhile, carbon layer is introduced to facilitate the stable and fast electrons mobility. As a result, the as-prepared quadruple-layered electrodes show excellent electrochemical performance in terms of high reversible capacity, good rate capability, and stable cyclability. This work may pave the way for the construction of flexible binder-free lithium ion batteries with superior lithium storage properties.

Macroporous Cu(OH)2 nanorod network fabricated directly on Cu foil as binder-free Lithium-ion battery anode with ultrahigh capacity

Metal-hydroxide based materials have attracted much attention as electrode materials for electrochemical energy storage and conversion owing to their unique large interlayer spacing, enhanced active surface area and robustness that can result in high electrochemical performance. Here, we report on the synthesis of a macroporous Cu(OH)2 nanorod network via single-step surface chemical oxidation and demonstrate its impressive Li ion battery (LIB) performance as a binder-free anode material. The Cu(OH)2 nanorod network anode delivers an ultrahigh reversible discharge capacity of 2145 mAhg−1 at a current density of 0.1 Ag−1 in the first cycle that then stabilizes at 1472 mAhg−1 in the subsequent cycles. The excellent rate performance at the ultrahigh current rates of 1.0 and 2.0 Ag−1 with a Coulombic efficiency of 99% was obtained. The electrode exhibits the capacity of 506 mAhg−1 even after 100 cycles which is higher than the conventional carbonaceous materials. Our experimental findings and scalable synthesis approach can be useful for developing other free-standing binder-free transition metal hydroxide materials that can be directly used as battery electrodes and catalysts.

Hierarchical urchin-like Fe2O3 structures grown directly on Ti foils for binder-free lithium-ion batteries with fast charging/discharging properties

Hierarchical urchin-like Fe2O3 structures were grown on conductive Ti foil with robust adhesion via a facile two-step solvothermal method and subsequent annealing, and directly used as a binder-free lithium-ion battery anode Benefitting by the unique structural features, the resultant Fe2O3 hierarchical structures exhibited excellent electrochemical performance with remarkable specific capacities at a serious of current rates 1–5 A g−1 and good cycling stability for excellently reversible lithium storage. The enhanced electrochemical performance demonstrates their promise for use as integrated binder-free electrodes in lithium-ion batteries. Using this additive/binder-free electrode, a discharge capacity as high as 581.2 mAh g−1 at a current density of 5 A g−1 was achieved after 1000 cycles. Importantly, the facile and effective strategy developed in this study can be extended to other metal oxides for various applications.

Electrospun vanadium sulfide / carbon hybrid fibers obtained via one-step thermal sulfidation for use as lithium-ion battery electrodes

Many metal sulfides present a layered structure with large interlayer space and a high theoretical capacity for lithium-ion battery applications. Compared to other transition metal dichalcogenides, vanadium sulfides remain little explored. Vanadium sulfides are commonly obtained by hydrothermal synthesis, which requires further post-processing and coating with binder and carbon additives. Here, we introduce a route to obtain free-standing vanadium sulfide fiber mats with in-built carbon. The combination of electrospinning and thermal sulfidation with H2S produces homogeneous vanadium sulfide particles embedded in carbon fibers that provide electrical conductivity and mechanical resistance for the electrode. The fibers were tested as a binder-free lithium-ion battery cathode within different potential ranges to evaluate insertion and conversion mechanisms and contributions to the overall capacity. Between 1.2 V and 3.5 V vs. Li/Li+, lithium intercalation provides a specific capacity up to 138 mAh∙g−1 at 0.01 A g−1 with good rate handling. When operating in a larger potential range between 0.1 V and 3.0 V vs. Li/Li+, the contribution by conversion reactions increases the capacity to 790 mAh∙g−1, but there is a fast capacity fading.

Scalable Dry Processing of Binder-Free Lithium-Ion Battery Electrodes Enabled by Holey Graphene

To address the multitude of issues that accompany wet electrode fabrication techniques, composite lithium-ion battery (LIB) electrodes composed of solely active components (active battery material and conductive additive) are fabricated using a scalable and eco-friendly dry processing method known as dry pressing. To accomplish this, a nanoporous carbon allotrope (i.e., holey graphene or hG) acts as the compressible and conductive matrix to accommodate incompressible cathode and anode battery powders. The inherent nanoporosity facilitates the escape of trapped gases upon compression, enabling the successful formation of binderless and solventless composite electrodes independent of selected active battery powder, fabrication pressure, or pressing time. Dry pressed LIB electrodes fabricated with different processing parameters (e.g., hydraulic pressure, pressing time) are evaluated structurally and electrochemically using a model cathode material (lithium iron phosphate, LFP) in order to demonstrate the po...

Tungsten oxide nanorod architectures as 3D anodes in binder-free lithium-ion batteries.

Tungsten oxide nanorods were synthesized using a template assisted process. A polycarbonate membrane (pore diameter 100 nm) was vacuum infiltrated by an aqueous solution of ammonium paratungstate ((NH4)10H2W12O42·xH2O) and yielded crystalline 3D oriented WO3 nanorod arrays after template etching and calcination. By coating the nanorod arrays with carbon, a binder-free 3D WO3/C composite electrode could be fabricated, allowing capacities up to 1149, 811, 699, 559 and 253 mA h g-1 for cycles 1, 2, 20, 50 and 200 as well as a coulombic efficiency of around 99%. Moreover, as prepared WO3 nanorod structures without that specific type of carbon coating deliver capacities in a range of 200-250 mA h g-1 after 20 cycles. Finally, a full cell lithium ion battery system is fabricated. It consists of LiCoO2 nanoparticles as cathode and binder-free carbon coated 3D WO3 composite material as anode. Pre-lithiation of this 3D WO3/C composite material as pre-conditioning before full cell assembly leads to a cell capacity of almost twice of that without pre-lithiation. Discharge capacities of 111, 91, 41 and 23 mA h g-1 can be obtained for cycles 2, 20, 100 and 200 with a coulombic efficiency of around 99% in the case of the pre-lithiated 3D WO3/C composite anode.

Facile synthesis of mesoporous NiCo2O4 nanoneedle arrays on three dimensional graphene thin film grown on Ni foam for a high-performance binder-free lithium-ion battery anode

Mesoporous NiCo2O4 nanoneedle arrays on graphene film grown directly on a three-dimensional Ni foam have been fabricated by a facile hydrothermal method, accompanied by annealing under air atmosphere. The BET specific surface area of NiCo2O4@graphene film@Ni foam is as high as 47.65 m2 g−1. The porous composites served as a binder-free anode material for lithium-ion batteries display an excellent and stable electrochemical performance with high specific capacities of 1232 mAh g−1 at the current density of 500 mA g−1 over 100 cycles and 1493 mAh g−1 at the current density of 1500 mA g−1 after 230 cycles with Coulombic efficiency higher than 97%. Moreover, a fairly high rate capacity of 586 mAh g−1 retained even at a high current density of 8000 mA g−1. The outstanding electrochemical performance should be attributed to synergetic effect of NiCo2O4 nanoneedle arrays with mesoporous nature and high specific area as well as graphene substrate supporting, which can accommodate the volume variation during the electrochemical reactions and facilitate the ion and electron transmission.

Nanosized CoO Loaded on Copper Foam for High-Performance, Binder-Free Lithium-Ion Batteries

The synthesis of nanosized CoO anodes with unique morphologies via a hydrothermal method is investigated. By adjusting the pH values of reaction solutions, nanoflakes (CoO-NFs) and nanoflowers (CoO-FLs) are successfully located on copper foam. Compared with CoO-FLs, CoO-NFs as anodes for lithium ion batteries present ameliorated lithium storage properties, such as good rate capability, excellent cycling stability, and large reversible capacity. The initial discharge capacity is 1470 mA h g−1, while the reversible capacity is maintained at 1776 m Ah g−1 after 80 cycles at a current density of 100 mA h g−1. The excellent electrochemical performance is ascribed to enough free space and enhanced conductivity, which play crucial roles in facilitating electron transport during repetitive Li+ intercalation and extraction reaction as well as buffering the volume expansion.

WS2 nanoplates embedded in graphitic carbon nanotubes with excellent electrochemical performance for lithium and sodium storage

WS2 has been considered as a promising anode material due to its high lithium storage capacity as well as fascinating physical properties. However, the insufficient electrical and ionic conductivities deteriorate the rate performance of the batteries. Herein, we report a simple synthetic approach towards graphene-WS2 hybrids by rolling graphene into a hollow nanotube in which WS2 nanoplates are encapsulated. This new electrode design strategy facilitates the fabrication of integrated and binder-free lithium ion battery and sodium ion battery electrodes by combining electrospinning and chemical vapor deposition (CVD) methods. Benefiting from their confined growth and the interconnected in-situ graphitic carbon coating nanocable web, the WS2@G with nano-level WS2 dispersion not only provides an efficiently conductive and electrolyte accessible framework, but effectively alleviates the volume change during the cycling, enabling a mechanically robust binder-free electrode along with the outstanding electrochemical Li+ and Na+ storage properties.

Multilayer Zn-doped SnO2 hollow nanospheres encapsulated in covalently interconnected three-dimensional graphene foams for high performance lithium-ion batteries

Multilayer Zn-doped SnO2 nanospheres are successfully synthesized by using Sn/Zn bimetal-organic nanoparticles as precursor. These multilayer spheres are found to be very suitable for solving the critical volume expansion problem and mass transfer property due to its high surface area, small crystal size and hollow structure, which is critical for high capacity metal oxide electrodes for lithium-ion batteries. Moreover, the covalently interconnected three-dimensional graphene foams encapsulated these multilayer spheres are successfully obtained through self-assembly effect and chemical cross-linking of graphene oxide nanosheets. The graphene network could further greatly improve the cycling stability and rate capability of the Zn-doped SnO2 spheres electrode due to its flexible buffering matrix and high electric conduction. As a result, the graphene encapsulating multilayer Zn-doped SnO2 spheres anodes exhibit excellent rate capacity and a high reversible capacity of 446mAhg−1 even after 1000 cycles at the current density of 1Ag−1. These excellent electrochemical performances are ascribed to its large specific surface area, fast electron/ion transfer, and stable electrode structure. Furthermore, this strategy using covalently interconnected 3D graphene foams encapsulate the Zn-doped SnO2 spheres not only develops a high performance anode material with long cycle life but also holds great promise for binder-free lithium ion batteries.

Stable High-Capacity Lithium Ion Battery Anodes Produced by Supersonic Spray Deposition of Hematite Nanoparticles and Self-Healing Reduced Graphene Oxide

Hematite (Fe2O3) nanoparticles and reduced graphene oxide (rGO) were supersonically sprayed onto copper current collectors to create high-performance, binder-free lithium ion battery (LIB) electrodes. Supersonic spray deposition is rapid, low-cost, and suitable for large-scale production. Supersonic impact of rGO sheets and Fe2O3 nanoparticles on the substrate produces compacted nanocomposite films with short diffusion lengths for Li+ ions. This structure produces high reversible capacity and markedly improved capacity retention over many cycles. Decomposition of lithium oxide generated during cycling activates the solid electrolyte interface layer, contributing to high capacity retention. The optimal composition ratio of rGO to Fe2O3 was 9.1wt.%, which produced a reversible capacity of 1242mAhg−1 after N=305 cycles at a current density of 1000mAg−1 (1C).

Morphology-Tuned NiCo2O4-Coated 3D Graphene Rrchitectures As Binder-Free Electrode for Lithium Ion Battery

In recent decades, lithium ion batteries (LIBs) have been considered as the most effective and practical technology products for portable electronic devices because of their flexibility, high energy density and long lifespan. Nanostructured transition metal oxides have been intensively studied as one of the most promising candidates for LIBs because of their high theoretical capacities (500-1000 mAh g-1), good reversible conversion, and low cost. However, in general, poor cycling performance and low electrical conductivity have hindered their practical application. Recently, 3D graphene synthesized by chemical vapor deposition (CVD) method has been studied extensively and used as a binder-free electrode in energy storage devices because of its excellent electron conductivity as current collector and high stability in electrolyte, but the application of 3D graphene as free-standing electrode is still limited due to its weak mechanical strength. In this work, nanostructured NiCo2O4 is directly grown on the surface of three-dimensional graphene-coated nickel foam (3D-GNF) by a facile electrodeposition technique and subsequent annealing. The resulting NiCo2O4 possesses a distinct flower or sheet morphology tuned by potential or current variation electrodeposition, which is used as a binder-free lithium ion battery anode for the first time. Both samples exhibit high lithium storage capacity profiting from unique binder-free electrode structures. The flower-type NiCo2O4 demonstrates high reversible discharge capacity (1459 mAh g–1 at 200 mA g–1) and excellent cyclability with around 71% retention of the reversible capacity after 60 cycles, which are superior to sheet-type NiCo2O4. Such superb performance can be attributed to high volume utilization efficiency with unique morphological character, a well-preserved connection of active materials to the current collector, a short lithium ion diffusion path, and fast electrolyte transfer in binder-free NiCo2O4-coated 3D graphene structure. The simple preparation process and easily controllable morphology make binder-free NiCo2O4/3D-GNF hybrid a potential material for commercial application.