Theoretical and Experimental Sets of Choice Anode/Cathode Architectonics for High-Performance Full-Scale LIB Built-up Models

Highlights Modulation of 3D super-scalable hierarchal anode/cathode models as choice architectonics into a full-scale LIB design. The scalable architectures dynamically provide effective diffusion gateways to guarantee excellent specific LIB performance. The DFT theoretical surface–surface electronic and charge map analyses confirmed the superiority of choice anode/cathode architectonics in full-scale LIB built-up models. Electronic supplementary material The online version of this article (10.1007/s40820-019-0315-8) contains supplementary material, which is available to authorized users.

(N:P)Cap value is used in order to optimal trade-off between the better safety (oversizing of negative electrode capacity, and then (N:P)Cap capacity ratio = >1:1). The optimum specific energy may be obtained at equal capacities of negative and positive electrode, and then (N:P)Cap capacity ratio can be =1:1) for proposed stacked LiFePO4//TiO2 pouch LIB-model.
The slurries were casted onto aluminium foil (10 µm thickness) for LFPO@C cathodes and copper foil (8 µm thickness) for TiO2 anodes and then dried in a vacuum oven at 80 °C for 12 h. The dried thick film electrode was pressed between twin rollers to enhance its packing density, reduce the porosity of the film and ensure intimate contact of the active material and the current collector. A microporous polymer separator is supplied from Celgard 2400TM membrane, Hoechst Celanese Corporation, Charlotte, North Carolina, USA).

Fig. S1
a Illustration of a CR2032-type coin cell assembly. b Schematic design of formulation of FRTO@C (anode) and VST(i)@C (cathode) electrodes designated in coin-cell CR2032type full-LIB To prepare 2032-coin cells, circular electrodes with diameters of 16 mm were used for Li foil and working electrodes. A separator with 20mm diameters was punched for further use. Crimper machine for the CR20XX series coin cells utilized to press our 2032-coin cells inside the glove box under Ar. The designated VST(i)@C//FRTO@C cathode//anode 2032-full-cell LIBs designated for electrochemical measurements (Fig. S1). Moreover, full-scale VST(i)@C//FRTO@C cathode//anode stacked layers pouch LIB-model are designed for further use. The prepared batteries were left for 24 h prior to be tested in order to guarantee total intake of the electrolyte solution by electrodes. Galvanostatic charge/discharge characteristic were measured using multichannel battery system (LAND CT2001A, Wuhan, China). Cyclic voltammetry (CV) measurements of the cells were tested using (CHI 660c electrochemical workstation). Electrochemical impedance spectroscopy (EIS) were performed using (Zennium/ZAHNER-Elektrik GmbH & CoKG, controlled by Thales Z-3.0 softwarefrequency range from 0.1 Hz to 1 MHz). All the electrochemical measurements were done at room temperature (30 °C ).

Table S1
Mass fraction of individual components used in the pouch full-cell
Field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) of power hierarchy VST-(i-vii)@C cathodes and FRTO@C anodes were used to investigate the details of the structure. The morphologies of our samples were investigated by Field emission-type Scanning electron microscope FE-SEM (Jeol JSM-Model 7000F, JEOL Ltd) at 20 kV. This SEM is equipped with a Schottky (thermal type) field emission electron gun. Analysis material was fixed onto the FE-SEM stage using carbon tape before insertion into the FE-SEM chamber. The ion sputter (Hitachi E-1030) was used to deposit thin-layered Pt films on electrodes at 25 °C (Figs. 1 and S4-S9, Scheme 2).
High-resolution transmission electron microscopy (HRTEM) images, electron diffraction (ED), scanning transmission electron microscopy (STEM) of power hierarchy VST-(i-vii)@C cathodes and FRTO@C anodes were performed at atomic-level imaging, structural and chemical analysis field emission-type TEM (JEM-ARM200F), as shown in Fig. 2 accelerating voltage can be adjusted to 80, 120, or 200 kV, depending on the specimen material and the purpose of observation. Energy-dispersive X-ray spectroscopy (STEM-EDS) was carried out during TEM measurements with high-resolution elemental mapping for of power hierarchy VST-(i-vii)@C cathodes and FRTO@C anodes to investigate the chemical contents of the nanostructures by using a 200 kV TEM (JEOL 2100F, JEOL Ltd) field emission-type transmission electron gun microscope. The samples were dispersed in ethanol solution using an ultrasonic radiation, and then dropped on a copper mesh and vacuum dried for 20 min prior to inserting the samples into the HR-TEM and STEM-EDS columns. Prior to microscopic investigation and analysis, the sample powders were dispersed in ethanol solution by means of ultrasonic-radiation, then one drop is added to copper mesh surface and vacuum dried for 20 min before used in HR-TEM and STEM-EDS columns.
The surface properties of VST@C and FRTO fabrics were estimated by N2 adsorptiondesorption isotherms at 77 K using a BELSORP36 analyzer (JP. BEL Co., Ltd.). The samples were thermally treated at 200 °C for at least 6 h under N2 atmosphere. The specific surface area (SBET) was calculated using the Brunauer-Emmett-Teller (BET) method with multipoint adsorption data from the linear section of the N2 adsorption isotherm. The pore size distribution was determined using nonlocal DFT (NLDFT). Figure 2i that type IV isotherm with an H2 hysteresis loop is dominant for all tested VST-(i-vii) samples, which confirms its mesoporous structure. Figure 2j shows the pore size distribution curves with calculated pore diameter of our tested samples.  -(iii, iv, v, vi, and vii) morphologies affected surface parameters of electrodes.
The weight content loss of power hierarchy VST-(i-vii)@C cathodes were determined from the weight loss curve measured under simulated air atmosphere on thermo-gravimetric and differential scanning calorimetry (TG/DSC) instrument TG/DSC-60 (Shimadzu, Japan) with a heating rate of 10 °C min -1 .
X-ray photoelectron spectroscopy (XPS) analysis (0-1400eV) of power hierarchy VST-(ivii)@C cathodes and FRTO@C anodes was conducted on a PHI Quantera SXM (ULVAC-PHI) instrument (Perkin-Elmer Co., USA) equipped with Al Kα radiation as an X-ray source for excitation (1.5×0.1 mm 2 , 15 kV, 50 W) under a pressure of 4×10 −8 Pa. Raman spectroscopy (HR Micro Raman spectrometer, Horiba, Jobin Yvon) was conducted using an Ar ion laser at 633 nm. A charge coupled device (CCD) camera detection system and the LabSpec-3.01C software package were used for data acquisition and analysis, respectively.
Raman spectroscopy of power hierarchy VST-(i-vii)@C cathodes and FRTO@C anodes was pplied to determine the chemical structures of both anode and cathode in full-scale LIBs. To ensure the accuracy and precision of the Raman spectra, 10 scans of 5 s from (500-2000 cm −1 ) were recorded. The chemical compositions of power hierarchy VST-(i-vii)@C cathodes and FRTO@C anodes were analyzed by Fourier transform infrared spectroscopy (ATR-FTIR, Spectrum 100, Perkin-Elme, Inc., USA) (Figs. S11-S14).
Density functional theory (DFT) and electrostatic potential and electron maps (ESP-EM) of power hierarchy VST-(i-vii)@C cathodes and FRTO@C anodes can be studied according to DMol3 of BIOVIA Dassault systems. The Perdew-Burke-Ernzerhof (PBE) formalism was also used for exchange-correlation energy function [43]. DFT was applied to determine the electrostatic potential (ESP) distribution along the TiO2@C, and LiFePO4@C (anode and cathode) electrode surfaces designated in closely-packed flower agave rosettes (FRTO) and in vertical-star-tower (VST) building blocks. The ESP sowed the Coulomb interaction per unit charge of active site at position in space. 3D modeling objects were recorder according to the physical quantitative survey at each single isosurface point as shown from the representative surface electron/charge map (EM). Typically, the electron densities along isosurfaces were colored according to ESP intensities (ESPI) of the crystal lattice of super-scalable hierarchal models of FRTO anode and VST cathode, in which the surface charges of lattice would be mapped "so called contour". The 3D slab and super-scalable hierarchal models of FRTO anode and VST cathode was constructed according to multiple atomic building block layers. ESP was investigated over the range of −0.06 to +0.6 eV as shown in recorded designs (Scheme 2), , and VST-(vii) buildings during the hydrothermal treatment, respectively. This phenomenon can be attributed to several reasons. For instance, H3PO4 releases PO4 3anions that produces FeH2PO4 as the first nucleation seed. Meanwhile, the OHactive ions released from the addition of Et/EG can coordinate and build frameworks with Fe 3+ .

S3 Mechanistic Formation of Anode/Cathode Architectonics
The key components that control the super-scalable model include the OHamount, which can change the reaction kinetics and influence the nucleation and growth pathways of LFPO crystals as well as the formation of the VST configuration in a block/stacked or open morphology. The high EG concentration (i.e., 100%) facilitates the spread and diffusion of OHions in the vessel and subsequently transforms the EG into a directing orientation agent for reducing the interaction surface potential, which may lead to the arrangement of a highrise mixed-complex building in a tip-to-tip configuration along an axial center at its core to occupy the framework geometry in multiple directions. The intensive c-axis orientation of superstructured surfaces lead to block/stacked building blocks on each floor (layer) of the most complex 3D-hierarchical VST (vii) structure. OHions are quantitatively added to the LFPO composition domain by increasing the Et/EG ratio up to (Et, 100%), which changes the densely compact building with full 3D open wings and the directions of the VST modulate superstructure VST(i). The addition of 100% EG to the mixture synthesis domains will significantly change the open grooves, convex-up planar needle wings, and well-oriented VST-(i) tower projection to VST-(vii) fully stacked coverage flanks at the in-out-plane of the upper zone surface of open-, multi-directional tower wings ( Fig. 1a-i). Among all VST superstar-towers, the VTS-(i) design can be considered a free manifold nucleation of LFPO crystals in well-designed orientations.
Another key factor in the formation of the VST-(i) to VST-(vii) designs is the time-dependent, drop-wise insertion of OH -(i.e., Et/EG mixture), which is dominated by a well-controlled layer-by-layer growth fabrication. The slow kinetic-binding rate mode of species can provide a sufficient relaxation time to define the formation of the open-space building blocks in specific 3D hierarchy and multi-orientations, such as VST-(i), compared with the formation time rate of unorganized and condensed structure VST-(vii) blocks.
In general, chemically controlling the addition of high EG amounts in composition domains can increase the number of VST block layers and cover the outer entrances, vacancies, grooves, and wings of the entire building block, thereby diminishing all possible freemovement electron, gateways, and diffusion pathways (Figs. S4-S9). The drop-wise addition of H2O2 to TiO(SO4) also contributes to the formation of a flower sphere-like vase with solitary succulents and feathery prickly spines. The time-dependent treatment also leads to the formulation of agave rosettes with fleshy needle-ended branches ( Fig. 1j-k).

S11 Thermal Stability of Vertical-star-tower Blocks of VST Cathodes
The effect of super-scale hierarchal VST@C cathode with open-end vestibule corridors of VST-(i) and (ii), and with floor-on-floor building blocks VST-( iii, iv, v, vi and vii) morphologies on the thermal stability of cathode electrode was investigated by using thermogravimetric analysis TG and differential thermal analysis (DTA) measurements. Thermal stability of super-scale hierarchal VST@C cathode and loss in carbon content of VST-(i, ii, iii, iv, v, vi and vii)@C composites were investigated through thermo-gravimetric and differential scanning calorimetry (TG/DSC) method using TG-60 (Shimadzu, Japan) instrument under a continuous flow of air with a heating rate of 5 °C min −1 from 20 to 900 °C as shown in Fig. S9.  (ii), and with floor-on-floor building blocks VST-( iii, iv, v, vi and vii) morphologies were found. The first insignificant weight loss or heat transfer region below 350 °C , is basically produced by releasing of absorbed water and chemisorbed crystal water (desorption of water). The second region from 350 to 550 °C showed significant changes. These thermal effects in weight loss or heat transfer of present samples become significant. It is important to note that carbon coated samples may lead to offer high significant weight loss or heat transfer in the super-scale frameworks indicated the endothermic effects, which are mainly due to pyrolysis of the non-polymeric organic compounds such as glucose (c-sources) as shell-dressers of cathodic VST@C samples. The third weight loss or heat transfer region above 600 °C showed an insignificant change of weight loss or heat transfer due to the stability of crystal structures and atomic-scale frameworks of VST@C samples even when the treated temperature is further increased to 900 °C . At above 600 °C , exothermic or endothermic peaks are not not discovered in DSC curves and the mass of the sample is not changed, indicating that the oxidization reactions of VST-(i-vii)@C cathode composites were terminated.
This finding of TG /DTA measurement offer key clues on the fabrication of stable electrodes in full-scale LIBs as follows: (i) The appropriate calcination temperature to form stable organic-inorganic frameworks is 600 °C ;

S12 Chemical Structure of Vertical-star-tower Blocks of VST Cathodes
The chemical compositions and stability of atomic-scale framework structures of the superscale hierarchal VST@C cathodes synthesized with open-end vestibule corridors of VST-(i) and (ii), and with floor-on-floor building blocks VST-(iii, iv, v, vi and vii) morphologies were investigated by Fourier transform infrared spectroscopy, FTIR. FTIR analysis may shed lights of the effect of the morphological shapes in the composition domains of anisotropic, heterogeneous composites. Fourier transform infrared (FT-IR) spectra were performed for VST@C samples as shown in Fig. S10. FT-IR spectra of VST@C exhibit a peak at 578 cm −1 , small intense peak around 1440 cm −1 and peak at 3250 cm −1 that attributed to Fe−O, P−C and C=H2 stretching vibrations, respectively, in our samples. Also, strong band centered at 1090 cm −1 is ascribed to −CPO3 group tetrahedral stretching vibration. Moreover, the weak peak at 1536 cm −1 is due to C=H2 bending vibration. Therefore, FT-IR result ensure the present of FeP framework. The C-shell dressed the VST exhibit characteristic peaks (Fig. S10, star marks), which indicate the organic-inorganic binding during the formation of the VST@C hierarchy. The FTIR spectra at 1615 and 1718 cm -1 suggests the existence of C=O stretching. It is important to note that FTIR showed no significant change in the peak signals with changes in the VST morphological VST-(i)-to-(vii) shapes. This finding indicates the stability of chemical compositions and stability of atomic-scale framework structures of the super-scale hierarchal VST@C cathodes synthesized with open-end vestibule corridors of VST-(i) and (ii), and with floor-on-floor building blocks VST-(iii, iv, v, vi and vii) morphologies

S13 Chemical Bonding and Composition of Vertical-star-tower Blocks of VST Cathodes
Raman spectroscopy is a powerful tool allows revealing of surface composition and chemical bonding along anisotropic and heterogeneous multi-components. Raman spectroscopy results for all VST@C composites are shown in Fig. S11. The bands at 640.0 and 939.6 cm −1 indicate the symmetric mode of Fe3O4 and PO4 3− groups in VST@C composites. Two peaks at 1350.73 and 1582.45 cm −1 are shown, attributing to D and G bands of carbon bonding in VST@C, respectively. The C-D-peak matched with disordered carbon binding of highly defective graphite. In turn, the C-G-peak is related to (graphite, in-plane vibrations with E2g symmetry). Therefore, according to Raman and FTIR analysis, the finding confirms the thin-loading of carbon shell wrapped surface of VST@C. The carbon shell is cross-linked via C=C, C=N, C=O bonds to the LiFePO4 frameworks.
Together, first, this Raman spectroscopic finding indicates the stable molecular binding of Cshell bumps wrapped inorganic LFPO frameworks and spatial distributions of carbon dots along the LFPO chemical compositions without dislocation or disturbance in the atomic-scale crystalline framework structures of the super-scale hierarchal VST@C cathodes and FRTO@ C anodes. Second, there is no significant change in D and G bands of the carbon-type bonding along LiFePO4 frameworks with 3D super-scalable model structures that synthesized with confinement open-end vestibule corridors of VST-(i) and (ii), and with dense stacking of layer-to-layer building blocks VST-( iii, iv, v, vi and vii) morphologies. Third, the prominent binding pairs between carbon and inorganic frameworks of TiO2 anode and LiFePO4 cathode may attain the super-scale molecular dimensionality and directionality along laterally, vertically, and longitudinally convex-up planar tubular pipes and grooves and at in-out-plane of the upper zone surfaces of TiO2 anode and LiFePO4 cathode designated in FRTO agave rosettes and vertical super-star-building block towers, respectively. Finally, the dynamic electron movements along super-scalable architectures, and anisotropic heterogeneity components would provide surface with effective diffusion gateways for excellent specific capacities, facile charge-discharge rates, high-energy-density, and long-timescale stability LIBs.

S14 Surface Binding Energy and Exposure Active-surface Sites in the Chemical Components
X-ray photoelectron spectrometry (XPS) shows evidence of the composition domains, oxidation states of active sites and binding surface energy along exposure top-zone surface sites of heterogeneous composite superstructures of TiO2@C anode, and LiFePO4@C cathode. To explore the oxidation states of metal and non-metal globule components of superscale models of TiO2@C// LiFePO4@C (anode//cathode) compositions, we carried out extensive surface sensitive information on the VST(i)@C and FRTO@C samples using continuously irradiation to X-ray beam during XPS analyses as shown in Figs. S12-A(a-e) and B(a-c).

Fig. S12
A XPS survey spectrum of the prepared VST(i)@C. B XPS survey spectrum of the prepared FRTO@C Figure S12-A illustrates the XPS peaks at 711.2 and 530.9 eV are the binding energies (Bes) related to Fe 2p and O 1s, respectively. The Fe-BE domain is markedly related to its oxidation state (Fe 2+ ). Some other oxidation states of Fe-domains couldn't be observed via XPS analysis. In addition, the P 2p, Li 1s, and C 1s peaks are shown at 133.4, 55.8, and 284.9 eV, respectively, attributable to the formation of orthorhombic olivine-type LiFePO4 structure with homogenous molecular phase formation along LiFePO4@C cathode surfaces.
The XPS analysis of FRTO@C was carried out and surface states of the samples were revealed, as shown in Fig. S12B. XPS peaks show evidence of the existence of C 1s, O 1s, and Ti 2p surface states with formation of super-scale TiO2@C anode or FTRO@C hierarchy.
Nano-Micro Letters S15/S27 The binding energy of Ti 2p exhibits two peaks at 468 and 462 eV which are related to present of Ti 2p1/2 and Ti 2p3/2 stated. The observed peak at 534 eV can be attributed to O 1s state. The overall peaks of Ti 2p1/2, Ti 2p3/2, and O 1s indicate the formulation of TiO2 phases. Finally, C 1s surface state exhibits two peaks at 288.5 and 284.2 eV owing to sp 2 C=O and C-C/C-O bonds, indication the successful formation of homogeneous rutile TiO2 phase in multi-composite TiO2@C anode phase.
Together, both the XPS and XRD results ensured that VST@C and FRTO@C composites are consisted of anisotropic multi-reactive components oriented in crystal structures of olivine LiFePO4@C (VST@C) and rutile TiO2@C (FRTO@C); respectively. The multi-functional surface composites are probably responsible for the efficient electrochemical performance of both electrodes in design of power hierarchy LIBs built-up sets for maintaining high Li + iondiffusivity, facile electron transfer, and excellent charge-discharge rates, high-energy-density with long-period of timescale reusability of LIBs.

S15 Electrochemical Performance of Half-cell FRTO@C Anode
Fig. S13 a The charge-discharge voltage profiles of first and multi-cycles up to 200 cycles-at current rate 1C of half-cell FRTO@C anode (2032 coin-type half-cell tests with a Li counter electrode). b Long term cycling performance (stability) and Coulombic efficiency for half-cell FRTO@C, at rate of 1C up to 200 cycles, and in voltage range 1-3V at room temperature. c Rate capability performance over a range of 1-3V among half-cell FRTO@C anode at various current rates from 0.1 to 20 C. All electrochemical measurements for FRTO@C halfcell anode were operated at room temperature.

S16 Influence of Super-Hierarchal Shaped VST Cathodes on LIB Performance
To explore the effect of uniformly-ordered LFPO@C cathode that has morphologically vertical star tower VST@C structures and designated with flexible, multiple building blocks and units at high-end tower roofs on the LIB performance, we studied the non-uniform LFPO@C cathode in the electrochemical reaction of half-cell cathodes. First, we have fabricated non-uniformly morphological LiFePO4 cathode via simple hydrothermal treatment, as follows: A mixture of Lithium acetate dihydrate (CH3COOLi· 2H2O), iron III nitrate nonhydrate (Fe(NO3)3· 9H2O), phosphoric acid (H3PO4) and Et/EG mixture ratios (100%:0) was inserted one-pot in time-independent treatment process at 170 °C for 12 h. The non-uniform or notcontrolled LFPO materials were calcined in a muffle furnace under Ar at 450 °C for 6 h. In addition the not-controlled LFPO@C materials and LFPO@C electrode were fabricated according the typical procedures used for VST@ cathode electrodes, respectively, see the experimental section. FE-SEM micrographs show non-uniformly LFPO@C morphological structures, as seen in Fig. S14a, b.
To study the effect of cathode structure ordering and hierarchy on the electrochemical performance of half-cell cathode LIBs, we used non-controlled LiFePO4@C cathode morphology and VST-(i)@C hierarchy half-cell cathode LIB models, as shown in Fig. S14c. Figure S14c presented the typical 1 st cycle charge-discharge voltage profiles of structurally not-controlled LiFePO4@C and hierarchy controlled VST-(i)@C half-cell cathodes at different current rates 0.1 C, 1 C, and 10 C designated in 2032 coin-type half-cell tests with a Li counter electrode between 2.0 and 4.3 V. The VST-(i)@C exhibits an excellent discharge capacity at C-rates ranging from 0.1 to 10 C compared with the structurally non-controlled LiFePO4@C half-cells. The superior long-term cycling performance and stability of the current VST(i)@C cathodes are presented in Fig. S14d. VST-(i)@C retains 99.5% of its 1stcycle capacity after 100 cycles at 0.1 C. Meanwhile, non-controlled structure LiFePO4@C retains 75% of its initial capacities after 100 cycles at 0.1 C, respectively. The VST-(i)@C half-cell cathode does not demonstrate any capacity fading over 100 cycles at a rate of 0.1 C, which indicates the hotkeys of the open-star tower VST-(i)@C hierarchy in high electrochemical reversibility during the lithiation/delithiation process. The hierarchal directions of VST-(i)@C cathode in the lateral, vertical (axial), and longitudinal axes, offering bowl-shaped ridges/alcoves, extensive convex-up planar needles arranged in a tip-to-tip configuration, and carved trenches in the flanks result in the predominance of high-mobility electron/ion flows and the enhancement of surface potential compared with the non-uniform LiFePO4@C cathode (Fig. S14).
The rate capability of VST(i)@C (controlled) and generally non-uniform LiFePO4@C structure cathodes was evaluated at different rates (0.1, 0.2, 0.5, 1, 2, and 5 C then back to 0.1 C and 10 C and then back to 1 and 20 C, with 10 cycles at each rate at room temperature (Fig.  S14e). The reversible discharge capacity of controlled VST@C and non-controlled LFPO@C cathodes has retained 66 and 8.4% of its initial capacities, respectively, at a rate of 20 C over 100 cycles. In other words, the specific capacity usually decreases as the C-rate increases for all tested cathodes. VST-(i)@C cathode shows a superior rate performance at a rate of 20 C and after 100 cycles while poor rate capability observed for non-controlled LFPO@C structure. The excellent electrochemical performance, high capacity at high rate capability, and long cycle life of VST-(i)@C cathode may be ascribed to its hierarchy regular morphology and 3D superstructure composite with single, upper-top-capped pyramidal prism headings at the end-zone incidents of the multi-directional wing scales. The capping prismbase shapes have clear apex, edge, and vertex-ended surfaces, which play important roles in achieving a high volumetric energy density, excellent rate capability, and Li-ion diffusion throughout all dimensions and loops of the VST-(i)@C cathode.

Fig. S14 a, b
Low and high-resolution FE-SEM images of LiFePO4@C cathode material without control the structure. c The first cycle charge-discharge voltage profiles of structurally non-controlled LiFePO4@C and controlled hierarchy VST-(i)@C half-cell cathodes at different current rates 0.1 C, 1 C, and 10 C designated in (2032 coin-type half-cell tests with a Li counter electrode). d Cycling performance (stability) for structurally non-controlled LiFePO4@C and hierarchally-controlled VST-(i)@C half-cell cathodes, at rate of 0.1 C for 100 cycles. e Rate capability performance for structurally non-controlled LiFePO4@C and hierarchally-controlled VST-(i)@C half-cell cathodes from 0.1 to 20 C. All electrochemical measurements were operated a within voltage range of 2.0-4.3 V, at room temperature.
In this regard, Fig. S14c-e confirmed the remarkable advantages of VST-(i)@C, leading to its superb retention performance, excellent rate capability, and high cycling stability. The superior choice of VST-(i)@C-cathode architectonics merits the following: (i) Rapid electron movement and Li+-diffusion kinetics at interfaces during the lithiation/delithiation process; (ii) Excellent electronic contact, and high electronic conductivity, as well as its ability to reduce the Li + -ions diffusion path, and to facilitate the transport of electrons; (iii) 3D hierarchical super-scale building blocks with multi-diffusive meso/macro open sites; (iv) Open-multi-direction, scalable mosaic towers, which comprise a mass of curved, prismed room grooves; (v) Corridor tunnels and evoke a crop of bowels, with each kernel cavity representing individual cave spaces for facilitating diffusion mobility and ensuring the accommodation of Li+ ions during charge/discharge process.
Given its outstanding electrochemical performance, VST-(i)@C is considered as one of potential candidates for meeting the high-power and high-energy requirements of LIBs and EV applications.

S17 Effect of C-dot Well-dressing and Content on Capacity and Cycling Stability of VST(i) Cathode
Various electrochemical experiments of VST-(i) and VST-(i)@C half-cell cathodes have been carried out to confirm the effect of well-ordered decoration and sustainable coating of C-shell dressers along superhierarchally-shaped VST cathodes in improving the kinetics of electron/Li + ion transportation during lithiation/delithiation Fig. S15. Figure S15a shows the charge/discharge cycling of the VST(i) and VST(i)@C cathodes. The built-in half-cell cathodes practically charged to 4.3 V at 0.1 C, maintained at 4.3 V for 1 h, and discharged to 2.0 V at 0.1 C. The finding indicated that the presence of well-dressing C-dot enhanced the electrochemical performance. Evidentially, the super-hierarchal VST@C cathode displayed higher storage capacity than that of the VST cathode. At the first cycle (0.1 C), the VST-(i)@C shows discharge capacity (165 mAh g −1 ), which is higher than that of VST (153.2 mAh g −1 ) (Fig. S15 a). Figure S15b shows superior capacity retention at the long-term cyclability (i.e., stability) of the VST@C-cathode, indicating that the 99.5% capacity was retained of the initial capacity after 100 cycles for the VST@C cathode (0.1 C). However, the VST cathode maintained 94% of its initial capacity. The low charge transfer resistance of the VST@C cathode may be due to high electronic conductivity and excellent electron/ion transfer kinetics during lithiation/delithiation. The continuous distribution of C-shell dressing of the few nanometres (≤ 5 nm) C-dot bump maps along the super hierarchal VST cathode significantly enhanced Li + -ion diffusion coefficient (Figs. 1b,1c,and 1k). The VST@C electrode exhibits high Li-storage capacity and excellent rate performance. The well-dressing of C-dot bump maps along active material surface ingredients may create multi-pool bowls for reactive and contiguous surface coverage of electron/Li ions during discharge/charge cycles.
Together, the dressing of C-dot bump maps along the super-hierarchal anode/cathode electrodes did not change in the atomic-scale ordering structures or disturb in atomic localizations. The C-dot shelled VST-cathode may provide: (i) 3D affordable outer surface ridges and bowls; (ii) Reduction of the binding energy surface; (iii) Enhancement of the electronic surface transport functionality, and electrical conductivity of electrode surfaces; (iv) Retention of electron/Li + ion pathways along the surface coverage without vortex surface hindrance that may be created due to the mechanical shock and atomic-scale volume expansion in single-crystal super-structures associated with frequent and continuous lithiation/delithiation cycling; (v) Protection of the electrode cuticles and building block hierarchy from degradation against the heating out created within multiple charge/discharge cycles.

Fig. S15 a
The charge-discharge voltage profiles at a current rate 0.1C of half-cell VST(i) and VST(i)@C cathodes. b Cycling performance (stability) for VST(i) and VST(i)@C cathodes in half cell 2032-coin cell with Li foil as counter electrode, at rate of 0.1 C for 100 cycles

S18 Calculating Processes of Specific Energy Density of VST-(i)@C//FRTO@C (Cathode//Anode) Full-scale LIB-model
As shown in Table S1, the mass fraction of a VST-(i)@C cathode active material in a pouch LIB cell design is approximately 44%. Then, the practical value of a specific energy density for the (LiFePO4//TiO2) VST-(i)@C//FRTO@C super-hierarchical building blocks full-scale LIB was found to be 127 Wh kg -1 . Moreover, the theoretical capacity (Qtheoretical) of a LIB cell that has been calculated by Faraday's law represented that the Q of LiFePO4 and TiO2 was found to be =170 and 335 mAh g -1 , respectively [S1-S4]. The idealized capacity ratio of LiFePO4: TiO2 = (170 Ah kg −1 /335 Ah kg −1 ) = 0.51. Table S1 shows that ~34% weight allowance for both electrode balances is considered for a practical pouch Li-ion cell components. Thus, the full scale LIB with a specific capacity of ((170 Ah)/(1kg +0.51 kg))/1.34 is about 84.0 Ah kg -1 . One can then calculate the specific energy density (i.e., theoretically) for the full-scale LiFePO4//TiO2 battery to be (1.6 V × 84 Ah kg -1 ) equal 134 Wh kg -1 . The results confirmed that the specific energy density for the VST-(i)@C//FRTO@C super-hierarchical building blocks full-scale LIB has a value of 127 Wh kg -1 (i.e., practically) and 134 Wh kg -1 (i.e., theoretically). The low value of the practical capacity compared with its theoretical value may be due to the following: 1. All the Li + -ions can't be removed from the lattice of the host cathode/anode material after lithiation/delithiation process; 2. The rest-loaded Li + along electrode coverage surfaces needs high voltage, which is mainly above the cut-off potential (i.e., it is not applicable in normal designated conditions).
Together, either theoretically or practically, the specific energy density of VST-(i)@C//FRTO@C super-hierarchical building blocks full-scale LIB offers more salutary limit than that of driving range requirement for EVs. The proposed battery system based on VST-(i)@C//FRTO@C super-hierarchical building blocks integrates the state-of-the-art developments in Li-battery technology.

S19 Optimization of Full Cell (Balancing) -(N/P) Ratio
The effect of N/P ratio (N = negative anode electrode capacity; and P = positive cathode electrode capacity in mAh) on electrochemical reaction and full cell performance was studied. However, due to the differences in reversible specific capacities of negative and positive electrode, a suitable control of mass loading of both negative and positive electrodes is necessary to realize equal discharge specific capacity for both electrodes during LIB-cell operation [S6-S9]. Furthermore, to avoid risk of lithium metal plating, which is considered as a severe aging and safety-deteriorating process [S10, S11], a slight oversizing of the capacity of negative electrodes ( (N:P)Cap capacity ratio >>1-1.2: 1) is additionally required for better safety and battery life, termed as "capacity balancing" or simply "balancing" in literature [S12-S17].
To optimize a full cell (balancing) -(N/P) ratio, we apply electrochemical cell design of 3D super-scalable full-scale LiFePO4//TiO2 cathode//anode stacked layers pouch LIB-model. Thus, we rationally control the optimal trade-off between better safety (oversizing of negative electrode capacity, (N:P)Cap capacity ratio = >1:1) and optimum specific energy (equal capacities of negative and positive electrode, (N:P)Cap capacity ratio =1:1). In this study, we found that our proposed 3D super-scalable full-scale LiFePO4//TiO2 cathode//anode stacked layers pouch LIB-model is optimized mass loading with (N:P)Cap capacity ratio ≈ 1.02 -1.1:1.
We built the full-scale stacking sequence of VST-(i)@C//FRTO@C (cathode//anode) electrodes with dimensions of 35 mm (width), 55 mm (length) and ~2-2.5 mm (thickness). The weight fraction calculations of these stacked pouch cell components show that the active mass of cathode and anode are 1.96 and 0.99 g, respectively. The VST-(i)@C//FRTO@C (cathode//anode) stacked pouch LIB-model was designed used 6 layers of cathode with 10 sides loaded Al-foil (10 µm) positive collector, and 5 layers of anodes with 10 sides loaded Cu-foil (8 µm) negative collector. In order to optimize the full-scalable cell, the total electrode area of the cathode and anode in the full-cell are 150 and 143 cm 2 , respectively.

S20 Estimation of Volumetric Energy Density
On the base of electrochemical cells of stacked layers pouch full-LIB-scale built-up set and the superior choice anode/cathode architectonics LIB-models, the volumetric energy density was found to be 172 Wh L -1 . In turn, the stored energy density was found to be 6.1 Wh and its volumetric energy density ~ 381 Wh L -1 ; which is reasonable value comparing to the range of the volumetric energy density for most commercial 18650-LIBs 250-500 Wh L -1 , as produced in market trade names of Panasonic NCR18650B, and NCR18650GA for EVs [S18-S20]. Accordingly, the full cell 18,650 cylindrical design gives a real space of evidence to be used as a model for our proposed VST-(i)@C//FRTO@C material-based electrodes.

S21 Electrochemical Impedance Spectroscopy
The EIS-experiments of the structurally non-controlled LiFePO4@C sample and controlled VST(i)-non-coated and VST(i-vii)@C-coated cathode samples were examined, see Fig. S16 and Table S2.

Fig. S16
Nyquist plots at room temperature of the general structurally not-controlled LiFePO4 sample and controlled VST(i)-not-coated and VST(i-vii)@C-coated samples by ~ 5 nm Cparticles. The inset in figure is the simple equivalent circuit used to fit the impedance data.  Table S2 indicated that the VST(i)@C composite has minimum Rct and higher exchange current density (I0) than that of other cathode samples. The key facts are that hierarchallycontrolled structure and carbon coating effect play a role in the performance of half-cell cathodes. For instance, the hierarchally-controlled VST-(i)@C cathode structure is connected with four lateral/longitudinal exposure wings or vestibule corridors, offering vast active surfaces of axially, laterally, longitudinally and horizontally directional movements of ions/electrons. This structural feature leads to excellent electron/ion transfer kinetics of the VST-(i)@C cathode through the lithiation/delithiation process.