1、Lithium Ion Battery 1. Theoretical and Experimental Sets of Choice Anode/Cathode Architectonics for HighPerformance FullScale LIB Builtup Models 2. Electrostatic Selfassembly of 0D2D SnO2 Quantum Dots/Ti3C2Tx MXene Hybrids as Anode for LithiumIon Batteries 3. Cobalt Sulfide Confined in NDoped Porous
2、 Branched Carbon Nanotubes for LithiumIon Batteries 4. NanogeneratorBased SelfCharging Energy Storage Devices 5. MetalOleate ComplexDerived Bimetallic Oxides Nanoparticles Encapsulated in 3D Graphene Networks as Anodes for Efficient Lithium Storage with Pseudocapacitance 6. CoralLike YolkShellStruct
3、ured Nickel Oxide/Carbon Composite Microspheres for HighPerformance LiIon Storage Anodes 7. Bi Nanoparticles Anchored in N-Doped Porous Carbon as Anode of High Energy Density Lithium Ion Battery 8. MetalOrganic Framework-Assisted Synthesis of Compact Fe2O3 Nanotubes in Co3O4 Host with Enhanced Lithi
4、um Storage Properties 9. The Surface Coating of Commercial LiFePO4 by Utilizing ZIF-8 for High Electrochemical Performance Lithium Ion Battery Vol.:(0123456789)1 3Theoretical andExperimental Sets ofChoice Anode/Cathode Architectonics forHighPerformance FullScale LIB Builtup ModelsH.Khalifa1,4, S.A.E
5、lSafty1*, A.Reda1, M.A.Shenashen1, M.M.Selim2, A.Elmarakbi3, H.A.Metawa4 * S. A. ElSafty, sherif.elsaftynims.go.jp1 National Institute forMaterials Science (NIMS), Sengen 121, Tsukuba, Ibaraki3050047, Japan2 Department ofMathematics, AlAflaj College ofScience andHuman Studies, Prince Sattam Bin Abdu
6、laziz University, AlAflaj71011912, SaudiArabia3 Department ofMechanical andConstruction Engineering, Faculty ofEngineering andEnvironment, Northumbria University, NewcastleuponTyneNE18ST, UK4 Department ofPhysics, Faculty ofScience, Damanhur University, Damanhur, EgyptHIGHLIGHTS Modulation of 3D sup
7、erscalable hierarchal anode/cathode models as choice architectonics into a fullscale LIB design. The scalable architectures dynamically provide effective diffusion gateways to guarantee excellent specific LIB performance. The DFT theoretical surfacesurface electronic and charge map analyses confirme
8、d the superiority of choice anode/cathode architectonics in fullscale LIB builtup models.ABSTRACT To control the power hierarchy design of lithiumion battery (LIB) builtup sets for electric vehicles (EVs), we offer intensive theoretical and experimental sets of choice anode/cathode architectonics th
9、at can be modulated in fullscale LIB builtup models. As primary structural tectonics, heterogeneous composite superstructures of fullcellLIB (anode/cathode) electrodes were designed in closely packed flower agave rosettes TiO2C (FRTOC anode) and verticalstartower LiFePO4C (VSTC cathode) building blo
10、cks to regulate the electron/ion movement in the threedimensional axes and orientation pathways. The superpower hierarchy surfaces and multidirectional orientation components may create isosurface potential electrodes with mobile electron movements, intoout interplay electron dominances, and electro
11、n/charge cloud distributions. This study is the first to evaluate the hotkeys of choice anode/cathode architectonics to assemble different LIBelectrode platforms with highmobility electron/ion flows and highperformance capacity functionalities. Density functional theory calculation revealed that the
12、 FRTOC anode and VST(i)C cathode architectonics are a superior choice for the configuration of fullscale LIB builtup models. The integrated FRTOC/VST(i)C fullscale LIB retains a huge discharge capacity ( 94.2%), an average Coulombic efficiency of 99.85% after 2000 cycles at 1C, and a high energy den
13、sity of 127Whkg1, thereby satisfying scaleup commercial EV requirements.KEYWORDS Lithiumion battery; 3D superscalable hierarchal anode/cathode models; Density functional theory; Anode/cathode architectonics; Electric vehicle applicationsSuper-scalable LIB modelsElectrolyteLi+Li+Li+Li+Li+Li+Li+Li+Li+
14、Li+Li+Li+Li+Li+Cu- foilAl- foilAnodeCathodeSeparatorHigh-energy density127 Wh kg1VSTC (Cathode)open-end vestibulesblock/stacked cuboids5 nm5 nm ISSN 23116706eISSN 21505551 CN 312103/TBARTICLECite asNanoMicro Lett. (2019) 11:84 Received: 12 July 2019 Accepted: 10 September 2019 The Author(s) 2019http
15、s:/doi.org/10.1007/s4082001903158 NanoMicro Lett. (2019) 11:84 84 Page 2 of 23https:/doi.org/10.1007/s4082001903158 The authors1 IntroductionIn response to the growing demand for an assortment of highenergy storage systems, energy sources, and environmentally clean and sustainable energy, rechargeab
16、le lithiumion batteries (LIBs) have become predominant electrochemical storage materials for modern transport systems and electronic devices, such as laptops, electronic gadgets, camcorders, and smartphones. Although LIB builtup sets are of particular interests for EVs, LIBs still have some limitati
17、ons associated with their economic cost and inherent risks 14. Therefore, numerous attempts have been made to improve the performance of rechargeable LIBs and increase their energy density, rates, and life cycle. These limitations have also necessitated the efficient utilization of green energy to m
18、eet the requirements of future renewable energy storage systems and promote their use in cuttingedge zeroemission transportation applications, such as plugin hybrid (PHEVs) and fully electric vehicles (EVs) 58. Since then, the growth of the international vehicle market has been stunted on account of
19、 the expensetorange ratio. Therefore, sustainable hybrid electrode materials must be manufactured with prominent electrochemical functionalities.Many studies have focused on discovering cathode materials with unique features, such as excellent structural stability, high safety, environment friendlin
20、ess, and low cost, that can replace hazardous cathode materials, including LiCoO2, LiNiO2, or LiMn2O4. Fabrication control of polyaniontype (ZO4y: Z = P, S, Si, As, Mo, W) electrode materials with unique features is still challenging. Among these positive electrode composites, phosphor, an olivinest
21、ructured LiXPO4 (X = Fe, Mn, Co, and Ni) with a theoretical capacity of approximately 170mAhg1, has received much interest as an excellent cathode candidate for LIBs 9, 10. The electrochemical behavior of LiXPO4 was first studied by Padhi etal. 9. LiFePO4 (LFPO) and LiMnPO4 (LMPO) were identified as
22、 the best candidates for newgeneration rechargeable LIBs 9, 11. These materials have similar stable cyclability and rate capability induced by their poor electronic and ionic conductivities, which can be overcome by synthesizing the hierarchical multidiffusive materials of nanosized particles, apply
23、ing coatings, and doping highly conductive materials, such as graphite or carbon 11, 12. However, these substances also showed a critical disparity. For instance, LFPO has broader commercial application compared with LMPO given its cycling stability, while LMPO shows some performance restrictions du
24、e to the powerless kinetics of electrons and the movement of Li+ ions. Moreover, a JahnTeller distortion of anisotropy can be observed in Mn3+ sites and interface strain results from the apparent discrepancy in volume between LiMnPO4 and MnPO4 1114. LFPO also has several merits, such as its outstand
25、ing structure stability, low material cost, nontoxicity, high theoretical capacitance, and thermally stable behavior at high temperatures. Therefore, LFPO is identified as one of the best cathode candidates for rechargeable LIBs 15, 16. However, LFPO cathodes have poor electronic and ionic conductiv
26、ities, poor rate capability, sluggish electrode kinetics, Li+ ion transport, Li+ ion diffusion at the LiFePO4/FePO4 interface, and low tap density 1719. These problems hinder the largescale use of LFPO in zeroemission transportation applications, such as PHEVs and EVs. To solve this problem, previou
27、s studies have enhanced the electrochemical performance of LFPO by improving its electric conductivity and accelerated the Li+ ion diffusion by reducing the particle size, inserting conductive additives, doping with supervalence metal ions, synthesizing hierarchically structured materials with multi
28、diffusive sites, and coating the LFPO composite with carbon nanoparticles to form an LFPOC composite 2027. The hierarchical structures of LFPO have been recently studied for electron enhancement/Li+ ion transportation enhancement with a high load reversible capacity and excellent rate capability 283
29、0. LFPO crystal orientation also plays an important role in improving Li+ ion kinetics during the lithiation/delithiation process, which in turn is crucial in improving the electrochemical performance of LIBs 28, 31. Therefore, additional effort must be devoted to finding the appropriate controlled
30、modulation for synthesizing LFPO hierarchical meso/macrostructured hybrid electrode materials with a desirable crystalline orientation to improve electronic/ionic conductivities, rate capability, and ionic diffusion at the interface. Meanwhile, nanotransitional metal oxides have been widely reported
31、 as promising anode materials for LIBs as these materials were studied for the first time by Tarascon etal. 32. Among these nanotransitional oxides, titanium dioxide TiO2 (TO) is one of the most attractive candidates owing to its high safety performance, low price, nontoxicity, pollutantfree charact
32、eristics, ecofriendliness, low polarization, and good cyclic stability and reversibility 33, 34.NanoMicro Lett. (2019) 11:84 Page 3 of 23 84 1 3To enhance the electrochemical behavior of power hierarchy LIB builtup sets, we offer intensive theoretical and experimental sets of choice anode/cathode ar
33、chitectonics to be modulated in fullscale LIB builtup models. As a mode of choice anode/cathode architectonics in LIB design, novel 3D modulated LIB superstructural models were built based on a LFPOC verticalstartower building block (VSTC cathode)/TiO2C flower agave rosettes (FRTOC anode) nanoarchit
34、ecture building to guarantee their outstanding electrochemical performance and excellent rate discharge capacities over a potential range of 2.0 to 4.3V (vs. Li+/Li). Our intensive theoretical/experiment sets based on the choice VST cathode architectonics modulated LIB models indicated that VST(i)ty
35、pe architectonic with predominant cave wavy canyons and longrange space domains of crater bays, coves, rims, and ridges as 3D accommodating space vacancy of electron/charge cloud configuration may offer a forest of electron mobility, shortrange electron transport, and highdensity ion diffusion in pr
36、oximal massive craters, bays, and rims with dominatedrich surface faces and enriched upperzone sites. VST(i)C cathode architectonics having vertical/central axes connected to four lateral/longitudinal exposure wings may also offer vast and broad surface access of Li+ ion loads in the axial, lateral,
37、 and horizontal directions for the movement of ions/electrons during the charge/discharge process. The VST(i)C hierarchical structure is a potential choice anode/cathode architectonics for highperformance fullscale LIB builtup models because it shows an excellent performance as a halfcell LIB with d
38、ischarge capacities of 167.9 and 125mAhg1 at rates of 0.1 and 20 C, respectively, among all VST(ii)toVST(Vii) architectonics 4. The integration of superior choice anode/cathode architectonics in a fullLIBscale builtup set (FRTOC anode/VST(i)C cathode) configuration achieves a high longterm cycling p
39、erformance (stability) with an excellent discharge capacity retention ( 94.2%), an average Coulombic efficiency of 99.85% for 2000 cycles at a rate of 1C, and a voltage range of 0.83.5V at room temperature (Scheme1). The proposed DFT surface analysis and building blocks for a fullscale battery syste
40、m indicate the potential effect of the choice anode/cathode architectonics on highperformance fullscale LIB builtup models. The FRTOC anode/VST(i)C cathode has an outstanding energy density of 127Whkg1 that may satisfy the requirements for energy storage devices and meet the commercial requirements
41、for EV applications.2 Experimental2.1 Controlled Synthesis ofVST CathodesTo control the VST anisotropic architecture complexity, a mixture of a VST cathode, labeled VST(i), was prepared as follows. First, an aqueous solution mixture of phosphoric acid and 10mL iron (III) nitrate nonahydrate (Fe(NO3)
42、39H2O) was stirred for 1h. Second, a 12.6mL ethanol (Et):0mL ethylene glycol (EG) mixture ratio (100%:0%) was added dropwise (0.5mLmin1) to the aqueous solution mixture under continuous stirring for 1h. Third, a 10mL lithium acetate dihydrate (CH3COOLi2H2O) dissolved in MilliQwater was stirred for 1
43、h at 30C and added dropwise to multicomponent mixtures at the same rate (0.5mLmin1). The total Li/Fe/P molar ratio in the final mixture was 3:1:1. This final mixture was vigorously stirred for 6h to obtain VST(i). The other VST mixtures (iivii, where i to vii denoted the range of anisotropic degree
44、in architecture complexity) were synthesized following the same protocol but with the controlled addition of different volumes of Et/EG mixture ratios. The additive volumes of Et/EG (mL:mL) were 10.5:2.1, 8.4:4.2, 6.3:6.3, 4.2:8.4, 2.1:10.5, and 0:12.6, which correspond to Et/EG mixtures ratios of 8
45、3.33%:16.67%, 66.67%:33.33%, 50%:50%, 33.33%:66.67%, 16.67%:83.33%, and 0:100% for fabricating VST(ii), VST(iii), VST(iv), VST(v), VST(vi), and VST(vii), respectively (Fig.1). The final mixtures of VST(i), VST(ii), VST(iii), VST(iv), VST(v), VST(vi), and VST(vii) were transferred into 100mL Teflonli
46、ned stainless steel autoclaves and kept at 170C for 12h before being cooled to room temperature. The resulting solid products were centrifuged, repeatedly washed with MilliQwater and absolute ethanol, and dried overnight at 60C under a vacuum. The VST was calcined in a muffle furnace under Ar at 450
47、C for 6h. The final VST powders were labeled VST(i), VST(ii), VST(iii), VST(iv), VST(v), VST(vi), and VST(vii) architectonics and applied to cathode electrode fabrication; please see Supporting Information S1S14.2.2 Synthesis ofthe TiO2 Flower Agave Rosettes HierarchyA150mg titanoxysulfatTiO(SO4)xH2
48、O was dissolved in 2M hydrochloric acid (2molL1) in 40mL MilliQwater NanoMicro Lett. (2019) 11:84 84 Page 4 of 23https:/doi.org/10.1007/s4082001903158 The authorsand stirred for 1h. A 6mL hydrogen peroxide (H2O2) solution was added dropwise at rate 0.5mLmin1 under vigorous magnetic stirring for 2h.
49、The final FRTO mixtures were transferred into a 100mL of Teflonlined stainless steel autoclaves and maintained at 170C for 12h and cooled to room temperature. The resulting FRTO solid product was calcined in a muffle furnace under Ar at 450C for 6h. In general, the dropwise addition of H2O2 to TiO(S
50、O4) contributes to the formation of a flower spherelike vase with solitary succulents and feathery prickly spines. This timedependent treatment leads to the formulation of agave rosettes with fleshy needleended branches (Fig.1j, k). The FRTO materials were used for fabrication of the anode electrode
