Amorphous/Crystalline Heterostructured Nanomaterials: An Emerging Platform for Electrochemical Energy Storage

Abstract

With the expanding adoption of large-scale energy storage systems and electrical devices, batteries and supercapacitors are encountering growing demands and challenges related to their energy storage capability. Amorphous/crystalline heterostructured nanomaterials (AC-HNMs) have emerged as promising electrode materials to address these needs. AC-HNMs leverage synergistic interactions between their amorphous and crystalline phases, along with abundant interface effects, which enhance capacity output and accelerate mass and charge transfer dynamics in electrochemical energy storage (EES) devices. Motivated by these elements, this review provides a comprehensive overview of synthesis strategies and advanced EES applications explored in current research on AC-HNMs. It begins with a summary of various synthesis strategies of AC-HNMs. Diverse EES devices of AC-HNMs, such as metal-ion batteries, metal-air batteries, lithium-sulfur batteries, and supercapacitors, are thoroughly elucidated, with particular focus on the underlying structure-activity relationship among amorphous/crystalline heterostructure, electrochemical performance, and mechanism. Finally, challenges and perspectives for AC-HNMs are proposed to offer insights that may guide their continued development and optimization.

Keywords: amorphous/crystalline heterostructure; electrochemical energy storage; interface effects; synergistic interactions.

Figure 1

Comparison of the properties of crystalline nanomaterials, amorphous nanomaterials, and AC‐HNMs.

Figure 2

Schedule of representative results for AC‐HNMs in energy storage devices from 2016 to 2024.^{[ 45} , ⁴⁶ , ⁴⁷ , ⁴⁸ , ⁴⁹ , ⁵⁰ , ⁵¹ , ⁵² , ⁵³ , ⁵⁴ , ⁵⁵ , ^{56 ]} Copyright 2016, Wiley‐VCH; Copyright 2017, Wiley‐VCH; Copyright 2018, The Royal Society of Chemistry; Copyright 2019, Springer Nature; Copyright 2019, American Chemical Society; Copyright 2020, Wiley‐VCH; Copyright 2021, The Royal Society of Chemistry; Copyright 2021, Wiley‐VCH; Copyright 2022, Elsevier; Copyright 2016, Wiley‐VCH; Copyright 2023, Elsevier; Copyright 2024, American Chemical Society.

Figure 3

Schematic illustration of AC‐HNMs for various EES applications.

Figure 4

A) Schematic illustration of the synthesis of amorphous SnO₂‐encapsulated crystalline Cu heterostructures. TEM images of B) hemicapsule Cu@SnO₂, C) yolk–shell Cu@SnO₂, and D) core–shell Cu@SnO₂ nanostructures. (B–D) Inset: schematic illustration of three types of heterostructures. Reproduced with permission.^{[ 60 ]} Copyright 2022, Wiley‐VCH. E) Schematic of synchronous synthesis process for amorphous/crystalline heterostructure nanomaterials. F) HRTEM image of crystalline Ag/amorphous NiCoMo oxides. Reproduced with permission.^{[ 71 ]} Copyright 2021, Wiley‐VCH. G) Schematic illustration of the preparation of Zn–VO _x –Co 2D ultrathin nanosheets. Reproduced with permission.^{[ 73 ]} Copyright 2022, Elsevier B.V. H) Synthesis procedure and I) atomic‐resolution HAADF‐STEM image of a/c‐RuO₂. Reproduced with permission.^{[ 74 ]} Copyright 2021, Wiley‐VCH.

Figure 5

A) Schematic illustration of the synthesis process for 3D CoBO _x /NiSe. Reproduced with permission.^{[ 87 ]} Copyright 2023, Wiley‐VCH. B) High‐magnification HAADF‐STEM images of Ni–B_i/meso‐Ir heterostructures; C,D) Enlarged image and corresponding FFT from the area “1” of (B). E,F) Enlarged image and corresponding fast Fourier transform (FFT) from the area “2” of (B). Reproduced with permission.^{[ 70 ]} Copyright 2021, Wiley‐VCH. G) TEM images of a‐Rh(OH)₃/NiTe, inset shows SAED patterns of amorphous Rh(OH)₃. H) HRTEM images of a‐Rh(OH)₃/NiTe. Reproduced with permission.^{[ 89 ]} Copyright 2022, Elsevier. I) Schematic illustration of the synthesis process of CC/NiCo₂O₄@NiCo‐P. Reproduced with permission.^{[ 91 ]} Copyright 2022, The Royal Society of Chemistry. TEM patterns and FFT patterns of J) 1cPt/aRu, K) 3cPt/aRu, and L) 5cPt/aRu. Reproduced with permission.^{[ 93 ]} Copyright 2023, American Chemical Society.

Figure 6

A) Pressure‐induced transformation of crystalline Cu₁₂Sb₄S₁₃ to the nested order–disorder framework (NOF) structure. B) The single crystal XRD images. Reproduced with permission.^{[ 96 ]} Copyright 2022, Springer Nature. C) Schematic of the amorphous/crystalline interfaces via fluorine surface doping in cobalt boride. D) HRTEM image of the F‐Co₂B. Reproduced with permission.^{[ 97 ]} Copyright 2019, The Royal Society of Chemistry. E) Schematic illustration of the synthetic process of Ni‐ZIF/Ni‐B@NF. F) XRD patterns of all the samples. G) HRTEM images of Ni‐ZIF/Ni‐B‐4. Reproduced with permission.^{[ 100 ]} Copyright 2019, Wiley‐VCH. H) Schematic of the synthesis of the Ni _x Fe_{1− x} ‐AHNA nanowire array. I–K) HRTEM images of Ni _x Fe_{1− x} ‐AHNA, the inset of (I) is the SAED pattern, the images (J,K) are enlarged views of the selected area in (I). Reproduced with permission.^{[ 104 ]} Copyright 2020, The Royal Society of Chemistry.

Figure 7

A) Schematic illustration of the synthesis of amorphous/crystalline Ru nanosheets. B) TEM image, and C) HRTEM image of amorphous/crystalline Ru nanosheets. Reproduced with permission.^{[ 62 ]} Copyright 2021, Wiley‐VCH. D) Schematic illustration of the synthesis of Co_{1− x} SnO_{3− y} ‐Fe_z‐A/C. E) HRTEM image of Co_{1− x} SnO_{3− y} ‐Fe _z ‐A/C, and the corresponding FFT patterns of the selected regions marked by the F) blue and G) yellow squares, respectively. Reproduced with permission.^{[ 106 ]} Copyright 2023, American Chemical Society. H) The spherical aberration‐corrected HAADF‐STEM image and I) SAED pattern of the a‐PdCu nanosheets. J) The spherical aberration‐corrected HAADF‐STEM images of a‐PdCu after aging for 14 days. K) XRD patterns of a‐PdCu samples being aged for 0 day and 14 days. Reproduced with permission.^{[ 107 ]} Copyright 2019, Oxford University Press.

Figure 8

A) Schematic Illustration of montmorillonite montmorillonite‐derived Si (M‐Si). B) Crystal model of montmorillonite. C) XRD patterns of montmorillonite and M‐Si samples at different reduction times. D) TEM image of M‐Si‐4. E) HRTEM image with clear lattice fringes and SAED pattern (inset) of M‐Si‐4. F) Cycling stability of different Si samples at 0.2 C. Reproduced with permission.^{[ 117 ]} Copyright 2024, American Chemical Society. G) Schematic diagram of the multiple functions of Co–B nanoflakes in the ZCO/Co–B hybrid electrode. H) Rate performance of ZCO/Co–B and ZCO electrodes. Reproduced with permission.^{[ 118 ]} Copyright 2019, Wiley‐VCH. I) HRTEM image of order–disorder VO‐6 structure. J) The schematic diagram of the Li‐ion diffusion path of VO‐6. Reproduced with permission.^{[ 115 ]} Copyright 2024, Elsevier.

Figure 9

A) Schematic diagram illustrating the synthesis of a‐VO _x /V₂C heterostructures. B) Rate capability of a‐VO _x /V₂C. Reproduced with permission.^{[ 126 ]} Copyright 2021, Wiley‐VCH. C) Differential charge density distributions (various perspectives) and cross‐sectional contours of Na atoms adsorbed on model surfaces or interfaces in W–P clusters, WSe₂, and W–P/WSe₂. Reproduced with permission.^{[ 127 ]} Copyright 2024, Elsevier. D) Integrated CV curves at 0.25 mV s⁻¹, E) reversible discharge profiles at 0.25 A g⁻¹, and F) rate capability and cycling stability of the MoO₂ electrodes. Reproduced with permission.^{[ 55 ]} Copyright 2023, Elsevier.

Figure 10

A) Schematic of the fabrication of SA‐VO₂. B) Rate performance of SA‐VO₂ and VO₂ at different current densities. Reproduced with permission.^{[ 134 ]} Copyright 2020, Wiley‐VCH. C) A structural model of possible adsorption sites with K⁺ adsorption energy on a‐Bi₂S₃/c‐Bi₂O₃ and c‐Bi₂S₃/c‐Bi₂O₃. G) Comparison of the energy barrier of K⁺ diffusion in a‐Bi₂S₃/c‐Bi₂O₃ and c‐Bi₂S₃/c‐Bi₂O₃. E) Comparison results of initial coulombic efficiency (ICE), initial discharged capacity (IDC), highest current rate (HCR), low‐rate specific capacity (SCL), high‐rate specific capacity (SCH), and the proportion of capacitance contribution (PCC) with a‐Bi₂S₃/c‐Bi₂O₃, c‐Bi₂S₃/c‐Bi₂O₃, and c‐Bi₂O₃. Reproduced with permission.^{[ 132 ]} Copyright 2024, The Royal Society of Chemistry. F) K adsorption energy of A‐Re₂Te₅, A/C‐Re₂Te₅, and C‐Re₂Te₅. G) Charge density difference of A/C‐Re₂Te₅. H) Work function and formation process of the built‐in electric field of A‐Re₂Te₅, A/C‐Re₂Te₅, and C‐Re₂Te₅. Energy barriers for K diffusion in I) A‐Re₂Te₅, J) A/C‐Re₂Te₅, and K) C‐Re₂Te₅. Reproduced with permission.^{[ 133 ]} Copyright 2024, Wiley‐VCH.

Figure 11

A) Schematic of the fabrication of ZnVOH@CC. B) TEM images of ZnVOH@CC. Reproduced with permission. C) Amorphous and crystalline domains heterostructure in ZnVOH@CC. Reproduced with permission.^{[ 141 ]} Copyright 2024, Elsevier. The energy barriers to Zn²⁺ diffusion along different pathways. D) Amorphous–crystalline structure, E) crystalline structure, and F) amorphous structure. Insets show the diffusion path. Reproduced with permission.^{[ 54 ]} Copyright 2023, Wiley‐VCH. G) HRTEM image and H) IFFT of Mn₃O₄‐A. I) Ex situ XRD, the ex situ XPS during the (dis)charging of Mn₃O₄‐A cathode at a current density of 0.5 A g⁻¹. Reproduced with permission.^{[ 53 ]} Copyright 2022, Elsevier.

Figure 12

A) Optimized structures of amorphous SiO₂ and MoO₂@SiO₂. B) Electronic density of states (DOS) for amorphous SiO₂ and MoO₂@SiO₂. C) Optimized structures and D) adsorption energy diagrams for LiO₂ adsorbed on amorphous SiO₂ and MoO₂@SiO₂. Reproduced with permission.^{[ 157 ]} Copyright 2023, Wiley‐VCH. E) Discharge curves of LOBs with NiS/NiPO cathodes at 200 mA g⁻¹. F) Discharge/charge profiles of LOBs with NiS/NiPO cathodes at 200 mA g⁻¹ with a cut‐off capacity of 1000 mAh g⁻¹. Reproduced with permission.^{[ 158 ]} Copyright 2023, Wiley‐VCH. Surface model with intermediates: G) AMO, H) ACMO, and I) CMO. J) Bond distance of three types of Mn─O bonds. L) Gibbs free energy diagram at 0 V. Reproduced with permission.^{[ 165 ]} Copyright 2022, Wiley‐VCH. M) Schematic of ZABs configuration. O) Polarization and power density curves of Co_{1− x} SnO_{3− y} ‐Fe_0.021‐A/C compared with Pt/C + IrO₂ catalyst. P) Cyclic stability of ZABs at 5 mA cm⁻². Reproduced with permission.^{[ 106 ]} Copyright 2023, American Chemical Society.

Figure 13

A) Atomic scale crystalline–amorphous MoO₃ heterostructure. B) Preparation process of c–a‐MoO₃. C) Optimized atomic configuration images for Li₂S₆ adsorption on a‐MoO₃ and c‐MoO₃. D) Calculated binding energies for various lithium polysulfide molecules on a‐MoO₃ and c‐MoO₃. E) Free energy evolution for conversion from S₈ to Li₂S on a‐MoO₃ and c‐MoO₃, respectively. Reproduced with permission.^{[ 175 ]} Copyright 2024, Elsevier. F) HRTEM image with insets showing the FFT patterns of the selected areas. G) AC‐HAADF‐STEM image of A/T‐Nb₂O₅. H) Calculated geometries of A‐Nb₂O₅ and T‐Nb₂O₅, as well as A/T‐Nb₂O₅ heterostructure, with differences in electron density. I) Optimized configuration of the Li₂S₆ adsorption on the surface of A‐Nb₂O₅ and T‐Nb₂O₅. J) Geometrical configurations and K) energy profiles of Li⁺ diffusion on A‐Nb₂O₅ and T‐Nb₂O₅ surfaces. L) Rate performances of the S‐A/T‐Nb₂O₅//Li‐A/T‐Nb₂O₅ full cell. Reproduced with permission.^{[ 51 ]} Copyright 2021, The Royal Society of Chemistry. M) Schematic illustration of the LiPS trapping and conversion process on the MoS₃–Ti₃C₂T _x heterostructures. N) Cycling performance and O) rate performances of MoS₃–S, Ti₃C₂T _x –S, and MoS₃–Ti₃C₂T _x –S cathodes. Reproduced with permission.^{[ 177 ]} Copyright 2021, Elsevier.

Figure 14

A) Illustration of a single ASV‐FO nanorod with exposed (110) surface plane and (1‐10) cross‐section plane. B) Atomic configurations of the selected area in the dashed box in (A). C) Ragone plots of the solid‐state ASV‐FO//V‐CO ASC. Reproduced with permission.^{[ 190 ]} Copyright 2018, Elsevier. D) The TDOS plots of NiCo₂O₄, NiCo‐P, and NiCo₂O₄@NiCo‐P. E) Adsorption energy of OH⁻ on NiCo₂O₄, NiCo‐P, and NiCo₂O₄@NiCo‐P. F) Schematic illustration of the HSC device. Reproduced with permission.^{[ 91 ]} Copyright 2022, The Royal Society of Chemistry. G) TEM images and SAED patterns of NiMoO₄@Co–B. H,I) Energy band schematic of the Mott–Schottky heterojunction of the NiMoO₄@Co–B before and after contacting. Ec: conduction band; Ev: valence band; Ef: Fermi level; Eg: bandgap; U: work function. Reproduced with permission.^{[ 44 ]} Copyright 2023, Elsevier. J) Charge/discharge schematic diagram of VO _x @N‐MXene HSs. K) Ragone plots of sodium‐ion hybrid capacitor device and reported literature. L) Cycling stability of the device at 1 A g⁻¹. Reproduced with permission.^{[ 194 ]} Copyright 2024, Wiley‐VCH.