Carbon Supported MoO2 Spheres Boosting Ultra-Stable Lithium Storage with High Volumetric Density

Chunli Wang,Lianshan Sun*,Bingbing Tian*,Yong Cheng*,and Limin Wang*

As important ingredients in lithium-ion battery,the Coulombic efficiency and power density greatly impact the electrochemical performances.Although recent literatures have reported nano-porous materials to enhance the specific capacities,intrinsic drawbacks such as poor initial Coulombic efficiency and low volumetric capacity could not be avoided.Herein,we propose a strategy to prepare carbon supported MoO2spheres used for lithium-ion battery with high volumetric capacity density.A high initial Coulombic efficiency of 76.5% is obtained due to limited solid electrolyte interface film formed on the exposed surface.Meantime,the sample with an optimal carbon content and a proper structural strength reveals a higher reversible capacity of 956 mA h g-1than the theoretical capacity of crystalline MoO2(838 mA h g-1)and a high capacity retention ratio of 96.4% after 100 cycles at 0.5 A g-1.And an effective compaction capacity density(under 5 MPa)of 670 mA h cm-3of the spheres proves its potential value in practical applications.

Keywords

high volumetric density,lithium-ion battery,MoO2spheres,optimal carbon content

1.Introduction

Lithium-ion batteries(LIBs)with high energy density are a key technology for addressing the rapid development of its practical applications,such as electric vehicles and mobile electronics.[1-3]Recently,in order to replace graphite(with a low theoretical capacity of 372 mA h g-1),developing new electrode materials with high energy density and stable cycle performance has become main goals,such as transition metal oxides,Si-or Sn-based metal alloys and related composites.[4-11]

Among all the various candidates, molybdenum dioxide(MoO2)associated with multiple valence states,high electrochemical activity toward lithium and low electrical resistivity and high density has attracted extensive interest.[12-15]For instance,Shon et al.demonstrated a mesoporous MoO2with abnormal Li-storage sites exhibiting a discharge capacity of 1814 mA h g-1,which is more than twice its theoretical value(838 mA h g-1).[16]More than that,in order to increase the cycling stability of MoO2, various considerable researches focused on MoO2/carbon hybrids with enhanced electrochemical performance for LIBs are carried out,such as MoO2/graphene composites,[17-19]MoO2/C core-shell spheres,[20]carbon-coated MoO2composites,[21,22]MoO2/C hollow spheres.[23,24]However,largely exposed surface of nanoparticles continuously consumes the electrolyte to form SEI layer via irreversible side reactions during the lithium insertion/extraction process,resulting in lower Coulombic efficiency.[15,25-27]Low volumetric energy densities are accompanied usually due to high specific surface areas.It is difficult to prepare a material with nanostructure and a desired volumetric energy density, and there are rare articles concerning it so far.

Herein,we provide an ideal model of carbon supported MoO2spheres to gain LIBs with high Coulombic efficiency and high volumetric density via regulating the ratios of MoO2and carbon.As a typical heteropoly acid,phosphomolybdic acid could rapidly complex with dimethyl imidazole(DI)under room temperature.By adjusting the surfactant amount(PVP)and temperature,the Mo-dimethyl imidazole(Mo-DI)precursors with in situ N and P doping were obtained through hydrothermal synthesis.After heat treatment at high temperatures,the sphere morphology basically remained.Owing to the uniform distribution of Mo,C,N,O,and P atoms in the structure,the crystallization of aggregate MoO2is hindered by the non-metallic element.Crystalline MoO2were formed on the surface of the sphere with the continuous oxidative decomposing of non-metallic components.Thus,non-aggregated MoO2with assigned carbon content can be obtained by adjusting the annealing conditions,endowing a superior capacity and rate capability.

2.Results and Discussion

Figure 1a displays the scheme for preparing Mo-DI precursors with one-pot hydrothermal synthesis.As a regular ligand in the synthesis of metal-organic complex,dimethylimidazole has a strong coordination ability to complex with oxygen metal functional groups,especially in an acidic condition.[28]And the desired Mo-DI precursors were prepared via adjusting the hydrothermal temperature.As shown in Figure 1b,the short strip precursors produced at 100°C sticked together.When elevating the hydrothermal temperature to 120 and 140°C,incomplete spherical precursors were generated with a large difference of the grain sizes(Figure 1c,d).Finally,ultra-round Mo-DI spheres with diameters of 200 nm-1 μm were prepared at 180 °C(Figure 1e,f)and their structures were proved by the TEM(Figure 1g).To get a better insight of the surface composition of Mo-DI spheres,the X-ray photoelectron spectroscopy(XPS)studies were performed.As shown in the survey spectrum(Figure S1a),different peaks observed are assigned to C 1s,N 1s,O 1s,Mo 3d,and P 2p.The high-resolution XPS spectra of Mo 3d(Figure S1b)of the Mo-DI precursor reveal a dominant Mo6+.

Figure 1.a)Scheme of the synthesis process of Mo-DI spheres.SEM images of Mo-DI precursors produced with hydrothermal synthesis under b)100°C,c)120 °C,d)140 °C,e)and f)180 °C.g)TEM image of Mo-DI spheres obtained at 180 °C for 5 h.

To explore a proper annealing condition,the differential scanning calorimetry(DSC)and thermogravimetric(TG)measurement of the Mo-DI precursor was characterized under Ar atmosphere.An obvious heat absorption peak due to phase transformation from MoO2to Mo2C is found around 750°C(Figure 3c and Figure S2),and the continuous attenuation of the weight percentage before 750°C reveals a possibility to adjust the ratio of MoO2and carbon with the annealing temperature.[29,30]For comparison,three annealing temperature of 600,650,and 700°C were performed accordingly.The obtained carbon supported MoO2spheres are named as CMAS-600,CMAS-650,and CMAS-700.After annealing for 2 h,little morphology changes on CMAS-600(Figure 2a)proves the thermostability of the precursor.For CMAS-650 and CMAS-700,there is something formed on their surfaces(Figure 2b and c).Combining the TEM detection,the morphology differences of the three products can be observed clearly.Compared with the smooth surface of CMAS-600(Figure 2d),some flocculent bumps are observed on the surface of CMAS-650(Figure 2e).While for CMAS-700,the floc almost covers the whole sphere(Figure 2f).The high-resolution TEM(HETEM)images reveal a detailed structure of the CMAS-650(Figure S3)and obvious lattice fringes with interplanar spacings around 0.24 nm existing in the floc(Figure 2h),which is corresponding to the(-2 0 2)planes of monoclinic MoO2.[31]In addition,as shown in Figure 2g,the elements of C,N,O,P,and Mo are distributed uniformly on the CMAS-650 by energy dispersive spectrometer.

Figure 2.SEM and TEM images of a,d)CMAS-600,b,e)CMAS-650,and c,f)CMAS-700.g)Images of EDS mapping of CMAS-650.h)HRTEM image of the floc on the surface of CMAS-650.

The crystallinities of the annealed products were characterized by X-ray diffractometer(XRD).As shown in Figure 3a,there is no obvious crystalline peak in the pattern of Mo-DI precursors.When annealed at 600 °C,an obvious special peak of amorphous carbon at 26°is observed,while there are no other bulges appeared,indicating MoO2with a poor crystallinity.When increased to 650 and 700°C,there are visible diffraction characteristic peaks due to the formation of crystalline MoO2on the surface,which can be indexed to the monoclinic phase of MoO2(PDF#32-0671).[31-33]The surface electronic state of the final products was demonstrated by XPS.The peaks of P 2p,C 1s,Mo 3d,N 1s,and O 1s can be clearly seen(Figure S4).The Mo 3d peak was further examined by high-resolution XPS in Figure 3b.The Mo 3d5/2/Mo 3d3/2peaks of CMAS-600 are centered at 228.5/232.2 eV with a spin energy separation of 3.7 eV,which indicate the Mo4+state of MoO2.The characteristic peak of Mo6+3d3/2at 235.4 eV is attributed to the surface oxidation of MoO2in air.[31,33]It is noteworthy that the Mo4+3d5/2/Mo4+3d3/2peaks have no significant changes even the temperature rises up.The contents of MoO2in the composites were calculated according to Equation S1,and a high content with 76.4,80.2,and 87.1 wt.% of MoO2for CMAS-600,CMAS-650,and CMAS-700 composites are obtained,respectively.As shown in Figure 3d,the carbon in the final products is consumed out with the temperature elevating,and MoO2is separated out on the sphere surface in a membrane formation rather than particle agglomeration.This novel phenomenon reveals that the carbon supported MoO2sphere with homogeneous composition can be regarded as an ideal model to research the effects of carbon content and crystallinity of the active materials on the electrochemical properties of metal-oxide/carbon composite for LIBs.And there must be a critical state where the amorphous MoO2begins to transform into crystalline MoO2.In this work,CMAS-650 can be considered as the target product generated at the critical condition.

Figure 3.a)XRD patterns of Mo-DI precursor,CMAS-600,CMAS-650,and CMAS-700,respectively.b)High-resolution XPS patterns of Mo 3d of CMAS-600,CMAS-650,and CMAS-700.c)TG and DSC curves of Mo-DI precusors under Ar and air atmospheres.d)Flowchart of the evolution process of MoO2/C composite under different annealed temperatures.

To address the effects of carbon substrate and crystallinity of MoO2on the electrochemical performance for LIBs,cyclic voltammetry(CV)is utilized to investigate the Li+intercalation/deintercalation behavior of the samples at a scan rate of 0.1 mV s-1over the range of 0.01-3 V.As depicted in Figure 4a,for the carbon rich CMAS-600,there is an obvious dislocation between the first and the following curves,especially in the reduction sweep process.In the first cycle,a wide reduction peak is found around 2.0 V,which is attributed to the phase transition of MoO2from orthorhombic to monoclinic phase due to Li+insertion.[23,34]An irreversible reduction peak at 0.37 V corresponds to the irreversible reduction of electrolyte and the formation of a solid electrolyte interphase(SEI) film,while it disappears in the following cycles.[4,15]Then,the voltage decreases to 0.01 V,associated with a conversion reaction of Mo with Li.[23]The subsequent cycles with obvious redox peaks are located at 1.29/1.38 V,which is attributed to the phase transitions in partially lithiated LixMoO2(0≤x≤0.98),and the continuous degenerative areas indicate the instability of CMAS-600 during Li+intercalation and deintercalation process.[35]Figure 4b shows a couple of redox peaks at 1.18/1.48 V attributed to the phase transition of MoO2from orthorhombic to monoclinic and an irreversible reduction peak at 0.36 V due to the formation of SEI film in the first cycle of CMAS-650.Meanwhile,an evident reduction peak at 0.12 V reveals the reversible formation of Li2O,which yields an additional capacity.The overlap curves in the following cycles indicate a high reversibility and stability.Compared to the other two electrodes,typical CV curves of CMAS-700(Figure 4c)possess the same couple of redox peaks with different locations,while the area of the closed curves reveals a low capacity ascribed to the excessive crystallization of MoO2on the surface.[12,36]To confirm the Li+intercalation/deintercalation behavior during the cycle process,CV curves of CMAS-650 after 90 cycles at 0.1 A g-1were also measured(Figure 4d,Figure S5),a couple redox peaks at 0.13/0.14 V are found,which have only a little shift with their initial locations(Figure 4b)and the reduction peaks around 0.1-0.18 V can be seen clearly due to the conversion reaction.Moreover,the high reversibility of CMAS-650 is proved by the overlap curves once again,indicating a lower series resistance than the other two samples due to its high inherent electric conductivity.[35]Electrochemical impedance spectroscopy(EIS)analyses are carried out to research the electrode kinetics of CMASs(Figure S6).The small semicircles formed in the high frequency region represent the interfacial electrode characteristics;CMAS-650 exhibits a lower series resistance than the other two samples due to its high inherent electric conductivity.

Figure 4.The CV curves of a)the CMAS-600 electrode,b)the CMAS-650 electrode,c)the CMAS-700 electrode and d)the CMAS-650 electrode after 90 cycles,measuring at 0.1 mV s-1.

A high superior Coulombic efficiency is a crucial judgment for indicating good Li+reversibility during lithiation/delithiation process for practical applications.An inferior initial Coulombic efficiency could be ascribed to SEI film formation or undesirable side reactions.[37]And a bad Coulombic efficiency during cycling is normally attributed to structure breakage due to the substantial expansion or contraction of electrode materials,leading to continuous consumption of Li+provided by cathode in practical application.[25]As shown in Figure 5a,the charge/discharge curves in the first and 100th cycle of the electrodes at 0.5 A g-1measured between 0.01 and 3 V exhibit the characteristic lithiation/delithiation process.The cycling performances are further exhibited in Figure 5b,the CMAS-650 electrode shows a high superior discharge capacity of 918 mA h g-1and a high initial Coulombic efficiency of 76.3% .At the first several cycles,the capacity attenuation can be observed,while the discharge capacity of the CMAS-650 electrode is stable at the 6th cycle with a little decrease,the capacities of the other two electrodes get steady after 10 cycles with～25% capacity loss.It is reasonable to explain the capacity loss of CMAS-700 as structure pulverization of the crystalline MoO2layer corresponding to the reported works,[38]while why there is a similar capacity drop on the curve of CMAS-600 is confusing.After cycling 100 cycles,a high capacity 916 mA h g-1is maintained and the capacity retention ratio was around 96% .Although the CMAS-600 and CMAS-700 electrodes show an initial discharge capacity of 1177 and 907 mA h g-1,the capacity retention ratio is just 56% and 58% ,respectively.In addition,as shown in Figure 5c,d,the CMAS-650 electrode exhibits a high reversibility and stability with unified Coulombic efficiency of 99% at various current densities from 0.1 to 2 A g-1(Figure 5c).Compared to the CMAS-600 and CMAS-700 electrodes(Figure 5d),a high discharge capacity of 734.9 mA h g-1for the CMAS-650 electrode is maintained even at the current density of 2 A g-1.The cycling performance at a higher current density of 5 A g-1of the CMAS-650 electrode is shown in Figure 5e,although fluctuations of the points happen occasionally,the electrode maintains a high capacity around 456 mA h g-1and a capacity retention of 85% when cycling to 1800 cycles,which are most possibly caused by the changes of internal structure during lithiation/delithiation process.To better understand the origin of the electrochemical performance,the images of these samples after 100 cycles were captured by SEM.As shown in Figure S7a,the spherical structure of CMAS-600 is hardly found on the electrode instead of agglomerates,indicating weak structure stability.Even so,due to function of carbon matrix,CMAS-600 still keeps a capacity retention ratio of 83% after 100 cycles with respect to the discharge capacity of the 10th cycle.For CMAS-650 and CMAS-700,they partially retain the initial global morphologies(Figure S7b,c),which prove that the structure stabilities of the CMASs are different and depend on the temperature in the annealing process.Thus,owing to oversaturated crystalline MoO2existed in the structure(Figure 2f),the CMAS-700 electrode shows a lower capacity than CMAS-600.However,the exposed MoO2on the surface could react with Li+in the electrolyte directly without any obstacles during lithiation/delithiation process,together with limited SEI film formed on the electrode surface;thus,the CMAS-700 electrode owns the highest initial Coulombic efficiency.Thus,by adjusting the annealing conditions,a desired product with special structural strengths can be obtained.Here,the CMAS-650 electrode achieves a high discharge capacity of 916 mA h g-1and capacity retention ratio of 96% after cycling for 100 cycles at 0.5 A g-1and an ultra-stable cycling performance with 456 mA h g-1at 5 A g-1,which presents a superior electrochemical performance than the majority of crystalline MoO2or MoO2/C composite,especially MoO2/C with porous structures(Table S1).Meanwhile,to analyze the reasons of the excellent electrochemical performances,the CV of the CMAS-650 electrode was measured under different scan rates.As shown in Figure S8a,b,we confirm that the b-value for the CMAS-650 electrode at the Peaks 1,2,and 3 are 0.86,0.86,and 0.76,respectively,via Equation S2.Thus,the CMAS-650 electrode has a combined characteristic of diffusion and capacitive co-controlled process according to the diffusion-controlled process(i.e.,b≤0.5)and a capacitive process(i.e.,b≥1)according to the classification of b-value(i.e.,0.5＜b＜1).[39,40]In addition,the contribution of diffusion and capacitive process could be quantitatively calculated with the contribution of capacitive process around 60-82% with increasing the scan rate from 0.1 to 1 mV s-1according to the Equation S3.[39,40]

Figure 5.a)The initial and 100th charge and discharge profiles and b)the cycling performances at 0.5 A g-1.c)The charge and discharge profiles and d)rate capabilities under various current densities from 0.1 A g-1to 2 A g-1of the CMAS-600,CMAS-650 and CMAS-700 electrodes.e)The cycling performance of the CMAS-650 electrode at 5 A g-1.

To understand the charge storage kinetics in the CMAS-650 electrode,the lithium-ion dynamic diffusion coefficient(DLi+)was measured by using galvanostatic intermittent titration technique(GITT).[41,42]Figure 6a presents the GITT curves and the DLi+values changes of the CMAS-650 electrode during the second cycle as a function of time ranging from 0.01 to 3.0 V(vs.Li+/Li).The cell is discharged and charged by getting a trigger at 0.1 A g-1for 20 min followed by a 30 min open-circuit relaxation to allow the cell voltage to reach a near equilibrium state.This process is repeated for the whole working potential range until the final voltage lower limit(～0.01 V)and ceiling(～3.0 V)are reached.According to the Fick’s second law and the calculated DLi+values under different lithiation states range from 9.4×10-11to 1.44×10-9cm-2s-1during the discharge step and vary from 1.5×10-10to 1.4×10-9cm-2s-1during the charge step,both of which are higher than those of MoO2/C composites.In order to further reveal the application prospects of CAMS-650 as anode materials in lithium-ion batteries,which is used to assemble the anode to match with the lithium layer oxide(e.g.,LiNi0.6Co0.2Mn0.2O2)(Figure 6b).One merit of the stabilized the CAMS-650 electrode is its high capacity of around 1100 mA h g-1at 0.1 A g-1,which can reduce 3.25 times the mass amount of the anode in the battery for the same energy capacity as that of graphite(i.e.,340 mA h g-1).In this work,the capacity ratio of the anode and cathode for the designed battery is controlled around 1.1.As shown in Figure 6c,the full cell exhibited excellent rate capability and the capacity could be maintained 100% ,93% ,86% ,78% ,and 71.2% (vs.170.5 mA h g-1)with the current density of 0.1,0.3,0.5,1,and 2 C(1 C=180 mA h g-1),respectively.Moreover,when cycling at 0.3 C(Figure 6d),the battery capacity is maintained at 100.4 mA h g-1with a capacity retention of 61.2% after 100 cycles.

Figure 6.a)GITT curves and DLi+values range under different lithiation states,b)schematic illustration of the outstanding diffusion kinetics of the CMAS-650 electrode,c)the charge and discharge profiles under various current densities from 0.1 to 2 C of the NCM 622 electrodes.d)The cycling performance of the NCM 622 electrode at 0.3 C.

Owing to the optimized structure and size distribution,as a close-packed model,[43]a relative low compression density of 0.608 g cm-3of CMAS-650 can be obtained under a press of 5 MPa(Figure S9).For comparison,nanosize Si(0.245 g cm-3;Figure S10)with diameters around 50-200 nm is selected.After calculations,compaction capacity densities of nanosize Si and CMAS-650 are shown in Figure 7.Based on the theoretical capacity of 4200 mA h g-1,nanosize Si exhibits a compaction capacity density of 1028 mA h cm-3.[44-46]Correspondingly, CMAS-650 reveals a maximum compaction density of 774 mA h cm-3and an effective compaction capacity density of 670 mA h cm-3.On the basis of the above results,such high electrochemical performance and compaction capacity density of CMAS-650 can be ascribed to the following factors:i)Optimized structure and composition enables a high volume capacity density and high Coulombic efficiency;ii)a proper annealed condition ensures the product possesses a suitable content of carbon matrix and high structural strength;iii)non-aggregated MoO2proves a high electrochemical activity when they are located uniformly in the carbon matrix;and iv)the spheres with gradient distributed diameters are easy to form a dense structure.

Figure 7.Compaction capacity densities of nano-Si powder and CMAS-650 under 5 MPa press.

3.Conclusion

In summary,we demonstrate that carbon supported MoO2spheres owns an enhanced electrochemical property by a facile hydrothermal synthesis and subsequent heat treatment.And the sample reveals a discharge capacity of 956 mA h g-1at 0.5 A g-1,which is far beyond the theoretical capacity of crystalline MoO2(838 mA h g-1).Furthermore,it also shows excellent electrochemical performance in the fullbattery.The effects of the carbon content and structural strength on the high reversibility and stability were also proved in our work.Moreover,as an essential factor,the spheres with high capacity and energy density could greatly reduce the effective space in practical applications.Instead of constructing nanostructure with hierarchical pores,the optimized carbon matrix and the structure would be a new strategy for preparing anode materials with high energy densities.

4.Experimental Section

Preparation of Carbon Supported MoO2Spheres(CMAS):Brie fly,0.5 g phosphomolybdic acid hydrate(H3PO412MoO3,Aladdin)was first dissolved in 60 mL ethanol with stirring,and then 1 g dimethylimidazole(Sigma-Aldrich)was added into the above solution.After the dimethylimidazole dissolved completely,0.2 g PVP(K30,Sigma-Aldrich)was added in the mixture and kept stirring for 10 min.Then the turbid liquid was poured into a 100 mL polytetrafluoroethylene-lined stainless high-pressure kettle and transferred in a draught drying cabinet keeping at 180°C for 5 h.The supernatant was gathered and rinsed with absolute ethyl alcohol at 7000 rpm for three times by centrifugal machine,and then dried at 70°C.The as-synthesized precursors were annealed under Ar atmosphere at 650 °C for 2 h with a temperature ramp of 5 °C min-1.The comparisons were prepared according to the same ratios under different reaction conditions.

Materials Characterization:The microstructures of the as-synthesized samples were measured by scanning electron microscopy(SEM,Hitachi S-4800).Transmission electron microscopy(TEM),high-resolution TEM(HRTEM)images and were analyzed by a FEI Tecnai G2 S-Twin instrument.Differential scanning calorimetry(DSC)and thermogravimetric(TGA)curve was carried out on a STA 449°C Jupiter(NETZSCH)thermogravimetry analyzer from ambient temperature to 800/1000 °C under air/Ar environment with a heat-up speed of 10 °C min-1.The X-ray diffraction(XRD)graphics of the products were determined by a Bruker D8 Focus power X-ray diffractometer(Cu Ka radiation).X-ray photoelectron spectroscopy(XPS)characterizations were carried out in an ESCALAB 250 instrument with 150 W Al Ka probe beam.

Electrochemical Measurements:The anode slurry for lithium-ion battery was made in N-methyl-2-pyrrolidone solvent by mixing 20 wt.% carbon black(CB),70 wt.% composite,and 10 wt.% polyvinylidene fluoride(PVDF).The positive electrode was composed of LiNi0.6Co0.2Mn0.2O2(NCM 622),CB,and PVDF with a weight ratio of 91:5:4,which were initially mixed in NMP to form a slurry,then paint on aluminized paper.The painted positive plate was baked in a vacuum drying chamber at 120°C through night and tailored into a wafer.The loading amount of the negative and positive active materials was regulated about 0.8 mg cm-2and 2.74 mg cm-2,respectively.The coin cells(CR-2025)contained Celgard 2300 separator and lithium foils.A solution of 1 M LiPF6 dissolved in ethylene carbonate and diethylene carbonate with same volume was employed as electrolyte.The charge-discharge performances were tested galvanostatically in the voltage scope of 0.01-3.0 V at incremental current densities using a programmable cell tester(LAND CT2001A)at room temperature.The cyclic voltammogram(CV)was measured with a sweep speed of 0.1 mV s-1and the potential vs.Li+/Li varying in the scope from 0.01 to 3.0 V,the electrochemical impedance spectrum tests were performed in the frequency scope from 100 kHz to 0.1 Hz,both CV and EIS were measured on a Bio-Logic VMP3 Electrochemical Workstation.The Li+dynamic diffusion coefficient(DLi+)was operated using LAND testing system,which is regarded as a reliable method to calculate the diffusion coefficient of Li+in electrodes.Assuming that a new steady-state behavior of potential can be reached at the end of each titration,according to the Fick’s second law and DLi+could be calculated from the equation DLi+=(4L2/πτ) × (ΔEs/ΔEτ)2,where L is the Li+diffusion length,assigned to the electrode thickness,τ is corresponding to the relaxation time(min),ΔEsstands for the variation of the equilibrium potential via the current impulse,and ΔEτis the transient voltage change within the pulse time τ after subtracting the IR drop.[47]

Acknowledgements

This work is financially supported by the National Natural Science Foundation of China(21975250),the National Key R&D Program of China(2017YFE0198100),the Hightech Research Key laboratory of Zhenjiang(SS2018002),and Jiangsu Post-doctoral Research Funding Program(2020Z257).

Conflict of Interest

The authors declare no conflict of interest.

Supporting Information

Supporting Information is available from the Wiley Online Library or from the author.