Isoregic Thienylene‐Phenylene Polymers: The Effects of Structural Variation and Application to Photovoltaic Devices

Isoregic conjugated polymers composed of thiophene and dialkoxybenzene units were designed to harvest incident light in the mid‐visible energy range (band gap of 2.1 eV). Poly(1,4‐bis(2‐thienyl)‐2,5‐diheptoxybenzene) (PBTB(OC₇H₁₅)₂) and poly(1,4‐bis(2‐thienyl)‐2,5‐didodecyloxybenzene) (PBTB(OC₁₂H₂₅)₂) have shown significant photovoltaic performance as an electron donor when used in tandem with the electron acceptor [6, 6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) in bulk hetero‐junction photovoltaic devices. Photovoltaic devices incorporating PBTB(OC₇H₁₅)₂ and PCBM have shown AM1.5 efficiencies of ～0.6% with a short circuit current density of 2.5 mA/cm², an open circuit voltage of 0.74 V, and a fill factor of 0.32. Incident Photon‐to‐Current Efficiency (IPCE) of the device was found to be ca. 16% at 410 nm. In order to examine the relationship between the molecular structure of the polymers and their electronic energy levels, and to correlate this with photovoltaic performance, optoelectronic and electrochemical results are discussed in relation to the I‐V characteristics of the devices. Additionally, a computer‐aided simulation is used to gain further insight into the effect of polymer structure on the energetic relationships in the bulk heterojunction devices.     

An Above‐Room‐Temperature Ferroelectric Organo–Metal Halide Perovskite: (3‐Pyrrolinium)(CdCl3)

Hybrid organo–metal halide perovskite materials, such as CH₃NH₃PbI₃, have been shown to be some of the most competitive candidates for absorber materials in photovoltaic (PV) applications. However, their potential has not been completely developed, because a photovoltaic effect with an anomalously large voltage can be achieved only in a ferroelectric phase, while these materials are probably ferroelectric only at temperatures below 180 K. A new hexagonal stacking perovskite‐type complex (3‐pyrrolinium)(CdCl₃) exhibits above‐room‐temperature ferroelectricity with a Curie temperature T_c=316 K and a spontaneous polarization P_s=5.1 μC cm^?2. The material also exhibits antiparallel 180° domains which are related to the anomalous photovoltaic effect. The open‐circuit photovoltage for a 1 mm‐thick bulky crystal reaches 32 V. This finding could provide a new approach to develop solar cells based on organo–metal halide perovskites in photovoltaic research.     

Novel narrow‐band‐gap conjugated copolymers containing phenothiazine‐arylcyanovinyl units for organic photovoltaic cell applications

A series of novel narrow‐band‐gap copolymers ( P1 ‐ P12 ) composed of alkyl‐substituted fluorene (FO) units and six analogous mono‐ and bis(2‐aryl‐2‐cyanovinyl)‐10‐hexylphenothiazine monomers ( M1 ‐ M6 ) were synthesized by a palladium‐catalyzed Suzuki coupling reaction with two different feed in ratios of FO to M1 ‐ M6 (molar ratio = 3:1 and 1:1). The absorption spectra of polymers P1 ‐ P12 exhibited broad peaks located in the UV and visible regions from 400 to 800 nm with optical band gaps at 1.55–2.10 eV, which fit near the wavelength of the maximum solar photon reflux. Electrochemical experiments displayed that the reversible p‐ and n‐doping processes of copolymers were partially reversible, and the proper HOMO/LUMO levels enabled a high photovoltaic open‐circuit voltage. As blended with [6,6]‐phenyl C₆₁ butyric acid methyl ester (PCBM) as an electron acceptor in bulk heterojunction photovoltaic devices, narrow‐band‐gap polymers P1 ‐ P12 as electron donors showed significant photovoltaic performance which varied with the intramolecular donor‐acceptor interaction and their mixing ratios to PCBM. Under 100 mW/cm² of AM 1.5 white‐light illumination, the device of copolymer P12 produced the highest preliminary result having an open‐circuit voltage of 0.64 V, a short‐circuit current of 2.70 mA/cm², a fill factor of 0.29, and an energy conversion efficiency of 0.51%. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4285–4304, 2008     

Exploiting the Bulk Photovoltaic Effect in a 2D Trilayered Hybrid Ferroelectric for Highly Sensitive Polarized Light Detection

Polarized light detection is attracting increasing attention for its wide applications ranging from optical switches to high‐resolution photodetectors. Two‐dimensional (2D) hybrid perovskite‐type ferroelectrics combining inherent light polarization dependence of bulk photovoltaic effect (BPVE) with excellent semiconducting performance present significant possibilities. Now, the BPVE‐driven highly sensitive polarized light detection in a 2D trilayered hybrid perovskite ferroelectric, (allyammonium)₂(ethylammonium)₂Pb₃Br₁₀ ( 1 ), is presented. It shows a superior BPVE with near‐band gap photovoltage of ca. 2.5 V and high on/off switching ratio of current (ca. 10⁴). Driven by the superior BPVE, 1 exhibits highly sensitive polarized light detection with a polarization ratio as high as ca. 15, which is far more beyond than those of structural anisotropy‐based monocomponent devices. This is the first realization of BPVE‐driven polarized light detection in hybrid perovskite ferroelectrics.     

New Conjugated Molecules with Two and Three Dithienyldiketopyrrolopyrrole (DPP) Moieties Substituted at meta Positions of Benzene toward p‐ and n‐Type Organic Photovoltaic Materials

Two conjugated molecules, TADPP3 and TADPP2‐TT , are reported, in which three and two dithienyldiketopyrrolopyrrole (DPP) moieties, respectively, are substituted at the meta positions of benzene. Based on cyclic voltammetry and absorption data, TADPP3 and TADPP2‐TT possess similar HOMO and LUMO energies of about ?5.2 and ?3.4 eV, respectively. Thin films of TADPP3 and TADPP2‐TT exhibit p‐type semiconducting behavior with hole mobilities of 2.36×10^?3 and 3.76×10^?4 cm² V^?1 s^?1 after thermal annealing. Molecules TADPP3 and TADPP2‐TT were utilized as p‐type photovoltaic materials to fabricate organic solar cells after blending with phenyl C₇₁ butyric acid methyl ester ( PC₇₁BM ) and phenyl C₆₁ butyric acid methyl ester ( PC₆₁BM ). The relatively low J_SC and fill factor values can be attributed to poor film morphologies based on AFM and XRD studies. A solar cell with a thin film of TADPP3 with PC₇₁BM in a weight ratio of 1:2 exhibits a high open‐circuit voltage (V_OC) of 0.99 V and a power conversion efficiency (PCE) of 2.47 %. Interestingly, TADPP3 can also be employed as an n‐type photovoltaic material. The blended thin film of TADPP3 with P3HT in a weight ratio of 1:2 gave a high V_OC of 1.11 V and a PCE of 1.08 % after thermal annealing.     

Synthesis and photovoltaic properties of two‐dimensional D‐A copolymers with conjugated side chains

Four novel two‐dimensional (2D) donor–acceptor (D‐A) type copolymers with different conjugated side chains, P1 , P2 , P3 , and P4 (see Fig. 1 ), are designed and synthesized for the application as donor materials in polymer solar cells (PSCs). To the best of our knowledge, there were few reports to systematically study such 2D polymers with D‐A type main chains in this area. The optical energy band gaps are about 2.0 eV for P1 – P3 and 1.67 eV for P4 . PSC devices using P1 – P4 as donor and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester as acceptor in a weight ratio of 1:3 were fabricated and characterized to investigate the photovoltaic properties of the polymers. Under AM 1.5 G, 100 mA/cm² illumination, a high open‐circuit voltage (V_oc) of 0.9 V was recorded for P3 ‐based device due to its low HOMO level, and moderate fill factor was obtained with the best value of 58.6% for P4 ‐based device, which may mainly be the result of the high hole mobility of the polymers (up to 1.82 × 10^?3 cm²/V s). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Significantly improved photovoltaic performances of the dithiophene‐benzothiadiazole‐alt‐fluorene copolymers by incorporating carbazole units in fluorene moiety

To exploit an effective way to improve polymeric photovoltaic performance, a series of dithiophene‐benzothiadiazole‐alt‐fluorene copolymers containing carbazole groups at C‐9 positions of the alternating fluorene units (PFO‐FCz‐DBT) were synthesized and characterized. The effect of the carbazole groups on the optophysical, electrochemical, and photovoltaic properties of these copolymers was investigated. By comparison, this type of copolymers with carbazole units exhibited significantly improved photovoltaic properties than poly(2,7‐(9,9‐dioctyl‐fluorene)‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole) (PFO‐DBT) in the bulk heterojunction solar cells. A maximum power‐conversion efficiency (PCE) of 2.41% and a highest short‐circuit current density (J_sc) of 9.68 mA cm^?2 were obtained for the PFO‐FCz‐DBT30, which are about two times higher than the corresponding levels for the PFO‐DBT30. This work demonstrated that introducing a hole‐transporting carbazole unit into copolymer is a simple and effective method to improve the J_sc and PCE. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

An Ultrastable Anode for Long‐Life Room‐Temperature Sodium‐Ion Batteries

Sodium‐ion batteries are important alternative energy storage devices that have recently come again into focus for the development of large‐scale energy storage devices because sodium is an abundant and low‐cost material. However, the development of electrode materials with long‐term stability has remained a great challenge. A novel negative‐electrode material, a P2‐type layered oxide with the chemical composition Na_2/3Co_1/3Ti_2/3O₂, exhibits outstanding cycle stability (ca. 84.84 % capacity retention for 3000 cycles, very small decrease in the volume (0.046 %) after 500 cycles), good rate capability (ca. 41 % capacity retention at a discharge/charge rate of 10 C), and a usable reversible capacity of about 90 mAh g^?1 with a safe average storage voltage of approximately 0.7 V in the sodium half‐cell. This P2‐type layered oxide is a promising anode material for sodium‐ion batteries with a long cycle life and should greatly promote the development of room‐temperature sodium‐ion batteries.     

Synthesis and properties of polythiophene derivatives containing triphenylamine moiety and their photovoltaic applications

A series of novel soluble polythiophene derivatives containing triphenylamine moiety were synthesized by Grignard metathesis (GRIM) method. The structures of the polymers were characterized and their physical properties were investigated. High molecular weight (M_n up to 25,800 g/mol) and thermostable polymers were obtained. The absorption spectra demonstrated that the absorption wavelength of the polymers could be tuned dramatically by introducing thiophene units in the main chain of the polymers. Photoluminescence spectra indicated that there was intramolecular energy transfer from the side chain to the main chain, and the maximum emission was red‐shifted gradually with the increase of thiophene units in the main chain. Cyclic voltammetry displayed that the polymers possessed relatively high oxidation potential, which promised good air stability and high open circuit voltage for photovoltaic cells application. Finally, bulk heterojunction photovoltaic devices were fabricated by using the polymers as donors and (6,6)‐phenyl C₆₁‐butyric acid methyl ester (PCBM) as acceptor. The maximal open circuit voltage of the photovoltaic cells reached 0.71–0.87 V and the power conversion efficiencies of the devices were measured between 0.014% and 0.45% under white light at 100 mW/cm². © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3970–3984, 2008     

New selenophene‐based low‐band gap conjugated polymers for organic photovoltaics

Low‐band gap selenophene‐based polymers were synthesized. Their optoelectronic and photovoltaic properties and space‐charge limited currents were compared with those of the related thiophene‐based polymers. The band gaps of the Se‐based derivatives were approximately 0.05–0.12 eV lower than those of their thiophene counterparts. Organic photovoltaic (OPV) devices based on the blends of these polymers and 1‐(3‐methoxycarbonyl)propyl‐1‐phenyl‐[6,6]‐C₇₁ (PC₇₁BM) were fabricated, and the maximum power conversion efficiency of the OPV device based on PSPSBT and PC₇₁BM was 3.1%—with a short‐circuit current density (J_sc) of 9.3 mA cm^?2, an open‐circuit voltage (V_oc) of 0.79 V, and a fill factor of 0.42—under AM 1.5 G illumination (100 mW cm^?2). © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4550–4557     

Tuning photovoltaic performance of 9,9‐dioctylfluorene‐alt‐5,7‐bis(thiophen‐2‐yl)‐2,3‐biphenylthieno[3,4‐b]pyrazine copolymeric derivatives by attaching additional donor units in pendant phenyl ring

A class of the 9,9‐dioctylfluorene‐alt‐5,7‐bis(thiophen‐2‐yl)‐2,3‐biphenylthieno [3,4‐b]pyrazine copolymeric derivatives (PFO‐3ThPz‐D) attaching additional donor (D) units in the pendant phenyl ring with a D‐A D structure was synthesized and investigated, where the additional D unit is a substituent group of fluorene, carbazole, and triphenylamine (Tpa). Their photovoltaic properties were significantly tuned by these pending donor units. Among these copolymers, the PFO‐3ThPz‐Tpa exhibited the best photovoltaic properties in the bulk heterojunction polymeric solar cells (BHJ‐PSC). The maximum power conversion efficiency (PCE) of 2.09% and the highest circuit current density (J_sc) of 7.91 mA/cm² were obtained in the cell using a blend of PFO‐3ThPz‐Tpa and PC₆₀BM (1:3, w/w) as active layer, which are 2.5 and 1.8 times higher than those corresponding levels in the other cell using the parent PFO‐3ThPz‐Ph copolymer instead of PFO‐3ThPz‐Tpa as donor, respectively. While PC₆₀BM was replaced by PC₇₀BM, the PFO‐3ThPz‐Tpa‐based BHJ‐PSC exhibited better photovoltaic properties with PCE of 3.08% and J_sc of 10.3 mA/cm². This work demonstrated that attaching donor units into the D‐A‐based copolymeric side‐chain is a simple and effective method to improve the photovoltaic properties for the resulting copolymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Visualizing Phase Segregation in Mixed‐Halide Perovskite Single Crystals

Mixed organolead halide perovskites (MOHPs), CH₃NH₃Pb(Br_xI_1?x)₃, have been shown to undergo phase segregation into iodide‐rich domains under illumination, which presents a major challenge to their development for photovoltaic and light‐emitting devices. Recent work suggested that phase‐segregated domains are localized at crystal boundaries, driving investigations into the role of edge structure and the growth of larger crystals with reduced surface area. Herein, a method for growing large (30×30×1 μm³) monocrystalline MAPb(Br_xI_1?x)₃ single crystals is presented. The direct visualization of the growth of nanocluster‐like I‐rich domains throughout the entire crystal revealed that grain boundaries are not required for this transformation. Narrowband fluorescence imaging and time‐resolved spectroscopy provided new insight into the nature of the phase‐segregated domains and the collective impact on the optoelectronic properties.     

Naphtho[2,1‐b:3,4‐b′]dithiophene‐based Bulk Heterojunction Solar Cells: How Molecular Structure Influences Nanoscale Morphology and Photovoltaic Properties

Organic bulk heterojunction photovoltaic devices based on a series of three naphtho[2,1‐b:3,4‐b′]dithiophene (NDT) derivatives blended with phenyl‐C₇₁‐butyric acid methyl ester were studied. These three derivatives, which have NDT units with various thiophene‐chain lengths, were employed as the donor polymers. The influence of their molecular structures on the correlation between their solar‐cell performances and their degree of crystallization was assessed. The grazing‐incidence angle X‐ray diffraction and atomic force microscopy results showed that the three derivatives exhibit three distinct nanoscale morphologies. We correlated these morphologies with the device physics by determining the J–V characteristics and the hole and electron mobilities of the devices. On the basis of our results, we propose new rules for the design of future generations of NDT‐based polymers for use in bulk heterojunction solar cells.     

Effects of Oriented Surface Dipole on Photoconversion Efficiency in an Alkane/Lipid‐Hybrid‐Bilayer‐Based Photovoltaic Model System

When a phospholipid monolayer containing a zinc‐coordinated porphyrin species formed atop a self‐assembled monolayer of heptadecafluoro‐1‐decanethiol (CF₃(CF₂)₇(CH₂)₂SH) is subjected to photoelectrochemical current generation, a significant modulation effect is observed. Compared with devices that contain similar photoactive lipid monolayers but formed on 1‐dodecanethiol SAMs, these fluorinated hybrid bilayers produce a >60 % increase in cathodic currents and a similar decrease in anodic currents. Photovoltages recorded from these hybrid bilayers are found to vary in the same fashion. The modulation of photovoltaic responses in these hybrid‐bilayer‐based devices is explained by the opposite surface dipoles associated with the thiols employed in this study, which in one case (fluorothiol) increase and in another (alkanethiol) decrease the work function of the underlying gold substrates. A similar trend of photovoltage/photocurrent modulation is also observed if fullerene is used as the photoagent in these devices. Our results reveal the intricacy of orientated surface dipole in influencing the photovoltaic processes, and its subtle interplay with other factors related to the photoagents, such as their location and orientation within the organic matrix.     

The use of sublimable chlorotricarbonyl bis(phenylimino)acenaphthene rhenium(I) complexes as photosensitizers in bulk-heterojunction photovoltaic devices

A series of sublimable substituted chlorotricarbonyl bis(phenylimino)acenaphthene rhenium(I) complexes was synthesized and used in the fabrication of photovoltaic devices. The hole and electron carrier mobilities of these complexes are in the order of 10⁻³ to 10⁻⁴ cm² V⁻¹ s⁻¹. Heterojunction devices with CuPc/complex/C₆₀ (CuPc = copper phthalocyanine) as the active layer and bulk heterojunction devices with complex:C₆₀ as the active layer were fabricated. The rhenium complexes function as photosensitizer in the devices, and exhibit optical absorption in the region between 500 and 550 nm within which other components in the device do not absorb. Other devices with hole transport materials, exciton blocking materials, and different active layer thickness were also fabricated. Variation of substitution groups in the ligand did not show significant difference in device performance. The best power conversion efficiency of the devices was measured to be 1.29% under illumination of AM1.5 simulated solar light.     

Centimeter-Size Single Crystals of Halide Perovskite Photoferroelectric Solid Solution with Ultrahigh Pyroelectricity Boosted Photodetection

Photoferroelectrics, especially emerging halide perovskite ferroelectrics, have motivated tremendous interests owing to their fascinating bulk photovoltaic effect (BPVE) and cross-coupled functionalities. However, solid solutions of halide perovskite photoferroelectrics with controllable structure and enhanced performance are scarcely explored. Herein, through mixing cage cation, a homogeneous halide perovskite photoferroelectric PA₂FA_xMA_1−xPb₂Br₇ solid solution (PA, FA and MA are CH₃CH₂CH₂NH₃⁺, NH₂CHNH₂⁺ and CH₃NH₃⁺, 0≤x≤1) has been developed, which demonstrates tunable Curie temperature in a wide range of 263–323 K and excellent optoelectrical features. As the component adjusted to x=0.7, the bulk crystal demonstrates ultrahigh pyroelectric coefficient up to 1.48 μC cm⁻² K⁻¹ around room temperature. Strikingly, benefiting from the light-induced pyroelectricity and remarkable BPVE, a self-powered and sensitive photodetector based solid solution crystals with boosted responsivity and detectivity over than 1300 % has been achieved. This pioneering work sheds light on the exploration of photoferroelectric solid solutions towards high-performance photoelectronic devices.     

Solution‐Processed Bulk Heterojunction Photovoltaic Cells from Gradient π‐Conjugated Thienylene Vinylene Dendrimers

A series of gradient π‐conjugated dendrimers and their corresponding models based on 5,5,10,10,15,15‐hexahexyltruxene moieties as nodes and oligo(thienylene vinylene) (OTVs) units with different lengths as branching arms are synthesized in good yields through Wittig–Horner reactions. All new compounds are fully characterized by ¹H and ¹³C NMR spectroscopy, elemental analysis, and MALDI‐TOF MS or ESI‐MS. Investigation of their photophysical properties reveals that the gradient dendritic scaffold not only results in a higher molar absorption coefficient and broader absorption region than those of their corresponding model compounds, but also improves the PL quantum yields relative to the corresponding OTVs. The suitable HOMO and LUMO levels as well as excellent film forming properties make these molecules potential candidates for organic solar cells. Solution‐processed bulk heterojunction solar cells using these dendrimers as donor and [6,6]‐phenyl‐C₆₁ butyric acid methyl ester as acceptor are prepared and tested. The power conversion efficiency of the devices based on G0-4-2 is 0.40 % under illumination of air mass 1.5 and 100 mW cm^?2. This is the highest record value for OTV‐based materials to date. Although the absorption band of dendrimer G0-4-2 is much narrower than that of poly(3‐hexylthienylene vinylene) (P3HTV), the efficiency of its solar cell device is almost twice that of the device based on P3HTV. This result shows clearly the advantage of gradient dendritic structures as active materials for photovoltaic cells.     

Efficient organic photovoltaic cells based on thiazolothiazole and benzodithiophene copolymers with π‐conjugated bridges

New donor–π–acceptor (D–π–A) type conjugated copolymers, poly[(4,8‐bis((2‐hexyldecyl)oxy)benzo[1,2‐b:4,5‐b′]dithiophene)‐alt‐(2,5‐bis(4‐octylthiophen‐2‐yl)thiazolo[5,4‐d]thiazole)] (PBDT‐tTz), and poly[(4,8‐bis((2‐hexyldecyl)oxy)benzo[1,2‐b:4,5‐b′]dithiophene)‐alt‐(2,5‐bis(6‐octylthieno[3,2‐b]thiophen‐2‐yl)thiazolo[5,4‐d]thiazole)] (PBDT‐ttTz) were synthesized and characterized with the aim of investigating their potential applicability to organic photovoltaic active materials. While copolymer PBDT‐tTz showed a zigzagged non‐linear structure by thiophene π‐bridges, PBDT‐ttTz had a linear molecular structure with thieno[3,2‐b]thiophene π‐bridges. The optical, electrochemical, morphological, and photovoltaic properties of PBDT‐tTz and PBDT‐ttTz were systematically investigated. Furthermore, bulk heterojunction photovoltaic devices were fabricated by using the synthesized polymers as p‐type donors and [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester as an n‐type acceptor. PBDT‐ttTz showed a high power conversion efficiency (PCE) of 5.21% as a result of the extended conjugation arising from the thienothiophene π‐bridges and enhanced molecular ordering in the film state, while PBDT‐tTz showed a relatively lower PCE of 2.92% under AM 1.5 G illumination (100 mW/cm²). © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1978–1988     

Design of a Quinoidal Thieno[3,4‐b]thiophene‐Diketopyrrolopyrrole‐Based Small Molecule as n‐Type Semiconductor

A quinoidal small‐molecule semiconductor QDPPBTT was synthesized. Organic thin‐film transistor (OTFT) devices based on QDPPBTT showed an electron mobility as high as 0.13 cm² V^?1 s^?1 and I_on/I_off ratio of 10⁶ under ambient conditions. We suggested that 2D extended π‐conjugation and quinoid‐enhancing effect had an important role in electron mobility and stability of n‐type FET devices, which might be a good strategy in designing new material systems.     

Lithium Germanate (Li2GeO3): A High‐Performance Anode Material for Lithium‐Ion Batteries

A simple, cost‐effective, and easily scalable molten salt method for the preparation of Li₂GeO₃ as a new type of high‐performance anode for lithium‐ion batteries is reported. The Li₂GeO₃ exhibits a unique porous architecture consisting of micrometer‐sized clusters (secondary particles) composed of numerous nanoparticles (primary particles) and can be used directly without further carbon coating which is a common exercise for most electrode materials. The new anode displays superior cycling stability with a retained charge capacity of 725 mAh g^?1 after 300 cycles at 50 mA g^?1. The electrode also offers excellent rate capability with a capacity recovery of 810 mAh g^?1 (94 % retention) after 35 cycles of ascending steps of current in the range of 25–800 mA g^?1 and finally back to 25 mA g^?1. This work emphasizes the importance of exploring new electrode materials without carbon coating as carbon‐coated materials demonstrate several drawbacks in full devices. Therefore, this study provides a method and a new type of anode with high reversibility and long cycle stability.