Sb Doped O3 Hom Na0.9Ni0.5Mn0.3Ti0.2O2 Cathode Khoom Rau Na-ion roj teeb

KONG Guoqiang, LENG Mingzhe, ZHOU Zhanrong, XIA Chi, SHEN Xiaofang. Sb Doped O3 Hom Na0.9Ni0.5Mn0.3Ti0.2O2 Cathode Khoom siv rau Na-ion roj teeb[J]. Phau ntawv Journal of Inorganic Materials, 2023, 38(6): 656-662.

Abstract

Lub voj voog ruaj khov thiab lub peev xwm tshwj xeeb ntawm cov khoom siv cathode rau cov roj teeb sodium ion ua lub luag haujlwm tseem ceeb hauv kev ua tiav lawv daim ntawv thov dav. Raws li lub tswv yim ntawm kev qhia cov heteroelements tshwj xeeb los txhim kho cov qauv kev ruaj ntseg thiab lub peev xwm tshwj xeeb ntawm cov ntaub ntawv cathode, O{{0}}Na0.9Ni0.5-xMn 0.3Ti0.2SbxO2 (NMTSbx, x{{10}}, 0.02, {{20 }}.04, 0. }}.9Ni0.5Mn{{50}}.3Ti0.2O2 cov ntaub ntawv cathode tau tshawb xyuas. Cov txiaj ntsig tau pom tau hais tias cov electrostatic repulsion quab yuam ntawm oxygen atoms hauv cov txheej txheem hlau hloov pauv tau txo qis tom qab Sb doping, thaum lub lattice spacing nthuav dav, uas yog qhov zoo rau deintercalation ntawm Na ntxiv. Lub caij no, lub zog hluav taws xob delocalization tshwm sim los ntawm Sb doping txo lub zog ntawm tag nrho cov kab ke, ua rau cov qauv ruaj khov, zoo dua rau kev them nyiaj cyclic thiab tawm. Kev ntsuam xyuas electrochemical qhia tau hais tias thawj zaug tso tawm muaj peev xwm ntawm undoped NMTSb0 yog 122.8 mAh·g−1 ntawm 1C (240 mA·g−1), thiab lub peev xwm tuav tau tsuas yog 41.5 feem pua ​​tom qab 200 cycles. Tab sis thawj zaug tso tawm muaj peev xwm ntawm doped NMTSb0.04 yog 135.2 mAh·g-1 ntawm 1C, thiab lub peev xwm tuav tau txog li 70 feem pua ​​tom qab 200 cycles. Txoj kev tshawb no qhia tau hais tias Sb doped O3 hom Na0.9Ni0.5Mn0.3Ti0.2O2 cov khoom siv cathode tuaj yeem txhim kho qhov kev tso tawm tshwj xeeb thiab muaj peev xwm tuav tau ntawm sodium ion roj teeb. Peb cov txiaj ntsig tau qhia tias Sb doping lub tswv yim yuav yog ib txoj hauv kev muaj txiaj ntsig rau kev npaj cov roj teeb sodium ion ruaj khov.

Ntsiab lus:Sib doping; O3 yam; cov khoom siv cathode; Cov txheej txheem txheej txheem; dav voltage; Na-ion roj teeb

Txij li thaum kev lag luam ntawm lithium-ion roj teeb, lawv tau siv dav hauv cov khoom siv hluav taws xob portable, hluav taws xob tsheb thiab hluav taws xob hluav taws xob khaws cia, thiab lwm yam. Txawm li cas los xij, cov peev txheej tsawg thiab tsis sib xws ntawm lithium yog ib qho tseem ceeb txwv txoj kev loj hlob ntawm lithium-ion roj teeb. . Nyob rau tib lub sijhawm, sodium reserves muaj ntau thiab nthuav dav, thiab tseem ceeb tshaj, vim qhov zoo sib xws ntawm cov khoom siv tshuaj ntawm lithium thiab sodium, lub hauv paus ntsiab lus ua haujlwm ntawm sodium-ion roj teeb yog ze rau ntawm lithium-ion roj teeb. Yog li ntawd, daim ntawv thov ntawm sodium-ion roj teeb nyob rau hauv lub teb ntawm loj-scale zog cia tau txais kev saib xyuas zoo.

Cov khoom siv cathode rau cov roj teeb sodium-ion feem ntau suav nrog kev hloov pauv hlau txheej oxides, polyanionic compounds, thiab Prussian xiav analogues. Ntawm lawv, txheej txheej oxide NaxTMO2 (TM hais txog kev hloov pauv hlau, 0

Ntawm ntau yam O{{0}} hom NaxTMO2 cov ntaub ntawv uas tau tshaj tawm, NaxTMO2 muaj Ni thiab Mn tau nyiam ntau vim nws cov peev txheej Ni / Mn ntau thiab muaj peev xwm cia siab. Piv txwv li, O3-type NaNi0.5Mn0.5O2 muaj peev xwm thim rov qab siab (133mAh g−1). Kev ua tau zoo ntawm tus nqi (30C, 40mAh g−1) thiab lub neej voj voog ntev (70 feem pua ​​​​cov peev txheej tshwj xeeb tuav tom qab 500 Lub voj voog ntawm 3.75C). Txawm li cas los xij, tseem muaj qee qhov teeb meem txwv tsis pub nws txoj kev loj hlob ntxiv, xws li kev ua haujlwm tsis txaus ntseeg, kev hloov pauv theem nyuaj thaum lub sij hawm them nqi thiab tawm, thiab lub peev xwm nrawm nrawm tshwj xeeb tshaj yog nyob rau high voltages ntawm 4.1-4.5 V. Cov kev tshawb fawb tsis ntev los no tau pom tias ib nrab doping ntawm lwm cov ntsiab lus. tuaj yeem txhim kho qhov thim rov qab ntawm theem kev hloov pauv. Piv txwv li, Ti-doped Na0.9Ni0.4Mn0.4Ti0.2O2 muaj kev hloov pauv ntau dua O3-P3 theem hloov ntawm 2.5 thiab 4.2 V, muaj peev xwm ntau dua (197 mAh g{{39} }), thiab kev ua haujlwm ruaj khov dua. Fe-doped NaFe0.2Mn0.4Ni0.4O2 muaj lub peev xwm thim rov qab siab (165 mAh g-1) thiab hloov pauv theem ruaj khov (87 feem pua ​​​​muaj peev xwm tuav tau tom qab 200 cycles) nyob rau hauv thaj tsam ntawm 4.0-4 .3 V.

Tsis tas li ntawd, Sb5 ntxiv rau doping tuaj yeem txhim kho lub voj voog ruaj khov thiab ua haujlwm voltage ntawm cov khoom siv cathode. Txhawm rau kom tau txais cov qauv khoom ruaj khov dua thiab kev ua tau zoo tshaj plaws nyob rau hauv qhov dav dav voltage ntau rau O3- hom txheej txheej oxides. Hauv txoj kev tshawb no, Sb5 plus tau hloov ib nrab rau Ni2 ntxiv rau hauv Na0.9Ni0.5Mn0.3Ti0.2O2 (NMT) los ntawm cov khoom yooj yim- lub xeev txoj kev los kawm txog cov nyhuv ntawm Sb doping ntawm cov electrochemical kev ua tau zoo ntawm txheej oxides thiab kev hloov pauv ntawm O3-P3 theem hloov nyob rau hauv ntau qhov hluav taws xob ntau.

1 Kev sim txoj kev

1.1 Kev npaj khoom siv

Na{{0}}.9Ni0.5-xMn0.3Ti{{10}}.2SbxO2 (NMTSbx, x{{9} }}, 0.02, 0.04, 0.06) cov ntaub ntawv tau npaj los ntawm cov txheej txheem txheej txheem. Cov kauj ruam tshwj xeeb yog raws li hauv qab no: sib tov Na2CO3, NiO, Sb2O5, MnO2, thiab TiO2 nyob rau hauv qhov sib piv stoichiometric piv, thiab ntxiv ib qho ntxiv 5 feem pua ​​mole feem ntawm Na2CO3 nyob rau hauv kev txiav txim siab ntawm volatility ntawm Na ntawm qhov kub thiab txias. Sib tov nws tusyees nrog ib tug agate mortar thiab siv lub tshuab ntsiav tshuaj los ua ib tug nyias disc ntawm ϕ16 mm. Kev kho cua sov ntawm 950 degree hauv huab cua ob zaug, txhua lub sijhawm rau 12 teev. Cov txheej txheem tib yam tau siv los npaj NMTSb0 yam tsis muaj Sb2O5 pib cov khoom, thiab tag nrho cov qauv tau muab khaws cia rau hauv lub hnab looj tes rau yav tom ntej.

1.2 Roj teeb sib dhos

Cov khoom siv nquag NMTSbx, acetylene dub thiab polyvinylidene fluoride (PVDF) tau hnyav ntawm qhov sib piv ntawm 7: 2: 1, thiab qhov tsim nyog ntawm N-methylpyrrolidone (NMP) tau ntxiv rau kev zom kom tau txais ib qho sib xyaw slurry. Cov slurry tau coated rau saum npoo ntawm aluminium ntawv ci, thiab qhov chaw thauj khoom ntawm cov khoom siv hauv electrode yog li 2.5 mg cm -2. Nqus-qhuav ntawm 80 degree rau 12 h, thiab ces txiav mus rau hauv me me discs ntawm ϕ12 mm nrog ib tug microtome raws li zoo electrode. CR2032 khawm hlwb tau sib sau ua ke hauv lub hnab looj tes uas muaj cov roj Ar (qhov ntim feem ntawm cov dej thiab cov pa oxygen tau qis dua 1 × 10-6). Ntawm lawv, lub txee electrode yog hlau sodium daim ntawv, lub separator yog iav fiber, thiab cov electrolyte yog 1 mol L-1 NaClO4 dibutyl carbonate ntxiv rau fluoroethylene carbonate tov (ntim piv 1: 1).

1.3 Cov yam ntxwv ntawm cov khoom siv thiab kev sim

X-ray diffraction (XRD) spectrum ntawm tus qauv tau sim siv MiniFlex 600 (Rigaku, Nyiv, Cu K ), thiab cov qauv siv lead ua tau ua kom zoo ntxiv los ntawm Rietveld los ntawm kev txheeb xyuas cov qauv (GSAS ntxiv rau EXPGUI ). Lub microscopic morphology thiab particle loj ntawm cov qauv tau soj ntsuam los ntawm JSM-7610F (JEOL, Nyiv) scanning electron microscope (SEM) thiab JEOL JEM-2100F high-resolution transmission electron microscope (HRTEM). X-ray photoelectron spectroscopy (XPS) ntawm lub xeev valence ntawm cov ntsiab lus tau sim ntawm Escalab250xi spectrometer siv AlK achromatic X-ray qhov chaw. Cov molar piv ntawm txhua lub ntsiab lus hauv cov qauv tau txheeb xyuas los ntawm inductively coupled plasma optical emission spectrometer (ICP-AES, iCAP 6300). Kev ntsuas hluav taws xob thiab kev tso tawm tau ua nyob rau hauv chav tsev kub uas siv Land CT2001A roj teeb ntsuas qhov nruab nrab ntawm 2.0 thiab 4.2 V, thiab cov electrochemical impedance spectroscopy (EIS) ntawm cov electrodes tau ntsuas siv CHI660E electrochemical workstation (CH Instruments).

2 Cov txiaj ntsig thiab kev sib tham

2.1 Cov yam ntxwv ntawm NMTSbx

Cov ntsiab lus muaj pes tsawg leeg ntawm tag nrho cov qauv raug txiav txim los ntawm ICP-AES, thiab cov txiaj ntsig tau qhia hauv Table S1. Tsis pub dhau qhov kev ntsuas qhov yuam kev, qhov tseeb cov ntsiab lus ntawm txhua cov hlau ion yog qhov tseem ceeb raws li kev tsim qauv. Hauv XRD spectrum ntawm daim duab 1(a), tag nrho cov qauv muaj O3-hom hexagonal -NaFeO2 qauv (chaw pab pawg R-3m), zoo ib yam nrog NaNi 0.5Mn{{ 9}}.5O2 (JCPDS 54-0887). Nws tau pom tias qhov kev taw qhia ntawm Sb rau hauv NMT lattice tsis hloov cov qauv ntawm cov khoom siv. Cov txheej txheem ntawm kev npaj high-nickel txheej oxide cathodes los ntawm cov txheej txheem solid-state yuav inevitably tsim ib tug me me ntawm residual inactive NiO Cheebtsam, thiab cov ntaub ntawv qhia tau hais tias qhov cuam tshuam ntawm ib tug npaum li cas ntawm NiO rau roj teeb kev ua tau zoo yog negligible. Hauv daim duab 1(b), qhov sib txawv peaks ntawm NMTSb0.02, NMTSb{{20}}.04, thiab NMTSb{{28 }}.06 hloov mus rau cov ces kaum loj, thiab lwm yam ncov pib tshwm hauv NMTSb0.06. Raws li kev sib npaug Bragg (nλ=2dsinθ), qhov nruab nrab ntawm cov hmoov nplej yog ntsuas zoo. qhov twg n yog qhov kev txiav txim ntawm diffraction, d yog qhov nruab nrab thickness (nm) ntawm cov nplej ntawm cov qauv perpendicular mus rau cov kev taw qhia ntawm lub siv lead ua dav hlau, θ yog lub diffraction lub kaum sab xis sib haum mus rau lub zog diffraction ncov, thiab λ yog X-ray. wavelength (nm). Cov txiaj ntsig siv lead ua dav hlau pom tau tias cov nplej loj ntawm cov qauv txo qis tom qab Sb doping, uas cuam tshuam rau qhov sib txawv ntawm ionic vojvoog ntawm Sb (0.06 nm) thiab Ni (0.069 nm). Raws li Vegard's theorem, qhov no kuj txhais tau hais tias muaj kev daws teeb meem zoo tshwm sim thaum tsim NMTSbx.

Fig. 1 Survey (a) and enlarged (b) XRD patterns of NMTSbx (x=0, 0.02, 0.04, 0.06)

Daim duab 2(a, b) qhia txog XRD Rietveld cov qauv ua kom zoo ntawm NMTSb0 thiab NMTSb0.04, thiab cov ntsiab lus ntawm lattice tsis muaj nyob hauv Table S2. Nws tuaj yeem pom tau tias cov lattice parameters ntawm NMTSb{{10}}}04 (a=b=0.2979{{20} }} nm) raug txo me ntsis piv nrog cov thawj NMTSb0 (a{11}}b=0.29812 nm). Qhov no kuj yog vim qhov tseeb tias lub vojvoog ionic ntawm Sb ({27}}.06 nm) yog me dua li ntawm Ni (0.069 nm), uas zoo ib yam nrog XRD tsom xam. Lub c (c{18}}.608391 nm) ntawm NMTSb0.04 tau nce ntxiv piv nrog cov NMTSb0 (c=1.600487 nm). Qhov laj thawj tseem ceeb yog vim li cas lub lattice parameter a / b yog rhiab rau qhov kev hloov ntawm (Ni / Mn / Ti / Sb)-O daim ntawv cog lus ntev ntawm cov txheej txheem basal dav hlau, thiab kev koom ua ke ntawm Sb ua kom luv luv ntawm daim ntawv cog lus ntev. Qhov no ua rau lub electrostatic repulsion ntawm oxygen atoms nyob rau hauv tas li ntawd mus hloov hlau txheej (Ni/Mn/Ti/Sb) ua loj, ua rau muaj kev nce nyob rau hauv c. Ntxiv mus, tom qab kev xam, c/a ntawm NMTSb0 thiab NMTSb0.04 tsis hloov ntau, lawv yog 5.36 thiab 5.39 feem, ob qho tib si tau ntau dua 4.99, qhia tias cov qauv doped khaws cov txheej txheem zoo.

Fig. 2 Rietveld refinement XRD qauv ntawm NMTSb0 (a) thiab NMTSb0.04(b)

Daim duab 3 qhia cov duab SEM ntawm NMTSb0 thiab NMTSb0.04. Ob qho khoom lag luam yog tsim los ntawm ntau tus micro-nano-scale nyias discs nrog cov tuab tuab thiab cov npoo ntshiab. Tshwj xeeb tshaj yog tom qab Sb doping, flake nto yog smoother, thiab tsis muaj hexagonal flake qauv nrog ntse npoo thiab fab. Xaiv-chaw EDS lub ntsiab lus tsom xam ntawm NMTSb0.04 qhia tau hais tias Na, O, Ni, Ti, Mn, thiab Sb cov ntsiab lus raug faib sib npaug hauv cov qauv, uas tseem ua pov thawj tias Sb cov ntsiab lus tau ua tiav tiav rau hauv qhov tseeb. Structure of NMTSb0.

Fig. 3 SEM images thiab EDS mappings of NMTSb0 (a, b) and NMTSb0.04 (c, d)

Cov microstructures ntawm NMTSb{{0}} thiab NMTSb0.04 tau soj ntsuam ntxiv los ntawm HRTEM, thiab cov txiaj ntsig tau pom hauv daim duab S1. Nyob rau hauv daim duab S1(a, c), cov hais ua ntej thiab tom qab Sb doping yog txuas los yog superimposed, thiab macroscopically tshwm sim raws li ib daim ntawv zoo li los yog kwv yees li ib ncig los yog polygonal qauv. HRTEM cov duab ntawm daim duab S1(b, d) qhia lub lattice fringes ntawm cov khoom, thiab cov lattice spacings ntawm NMTSb{{10}} thiab NMTSb0.04 yog 0.238 thiab 0.237 nm, feem. Ob leeg sib haum mus rau (101) siv lead ua dav hlau, thiab cov nyhuv ntawm doping Sb ntawm lub lattice spacing yog ua raws li XRD tsom xam. Cov insets ntawm daim duab S1(b, d) yog cov chaw ntawm cheeb tsam xaiv electron diffraction qauv (SEAD) ntawm NMTSb0 thiab NMTSb0.04, uas ua pov thawj tias cov tau NMTSb0 thiab NMTSb0.04 muaj crystallinity zoo.

X-ray photoelectron spectroscopy (XPS) ntawm daim duab S2 qhia cov txiaj ntsig ntawm oxidation xeev ntawm Mn, Ni, Ti, thiab Sb cov ntsiab lus hauv NMTSb0 thiab NMTSb0.04. Hauv daim duab S2(a), ob lub ncov tseem ceeb ntawm NMTSb0 ntawm 877 thiab 850 eV sib haum rau Ni2p1/2 thiab Ni2p3/2, raws li, thiab ob qho tib si yog Ni2 ntxiv rau hauv cov qauv. Lub zog khi lub ncov ntawm 858.2 eV yog lub ncov siab tshaj plaws hauv Ni keeb. Lub Ni2p1/2 ntawm NMTSb0.04 faib ua ob lub ncov, qhia tias kev taw qhia ntawm Sb rau hauv NMTSb0 lattice tuaj yeem txo cov xov tooj ntawm cov hluav taws xob sab nraud ncig Ni, ua rau muaj zog electron delocalization nyhuv. Cov hlau hloov pauv muaj ntau dua delocalized d orbitals, uas tuaj yeem txhim kho cov hlau-hlau sib cuam tshuam ntawm MO6 sab sib koom octahedra hauv cov txheej txheem txheej, yog li inhibiting lub cev qhuav dej ntawm MO6 octahedrons thiab alleviating sab kev cuam tshuam ntawm lattice oxygen thiab electrolyte. Thaum lub sij hawm tus nqi-tso tawm, cov qauv ntawm cov txheej txheem oxide khoom yuav ruaj khov, qhia tias muaj zog electron delocalization muaj txiaj ntsig zoo rau cov qauv kev ruaj ntseg ntawm NMTSb0.04. Rau Mn keeb, Mn2p3/2 ncov ntawm 642 eV thiab Mn2p1/2 ncov ntawm 652 eV hauv daim duab S2(b) qhia tias muaj Mn nyob rau hauv lub plus 4 valence xeev nyob rau hauv ob qho tib si NMTSb0 thiab NMTSb{ {84}} 04. Mn2p3/2 ncov ntawm 643eV tuaj yeem sib phim nrog Mn3 ntxiv rau ncov. Lub octahedral configuration ntawm Mn3 ntxiv yuav deformed, uas yog tshwm sim los ntawm qhiav-Taylor distortion. Kev tawg ntawm Mn lub caij yuav ua rau muaj peev xwm poob sai sai, thaum Ti hauv NMTSb0.04 hloov ib feem ntawm Mn, thiab qhov txo qis ntawm Mn cov ntsiab lus tseem tuaj yeem ua kom ruaj khov ntawm cov qauv txheej txheem ntawm cov khoom, yog li inhibiting qhov poob sai ntawm cov roj teeb muaj peev xwm tshwm sim. los ntawm Ginger-Taylor nyhuv. Qhov sib khi lub zog peaks ntawm Ti2p1/2 thiab Ti2p3/2 ntawm 457.3 thiab 453.1 eV rau NMTSb0 hauv daim duab S2(c) sib raug rau qhov ruaj khov ntxiv rau 4 valence xeev ntawm Ti. Thaum Ti2p1/2 thiab Ti2p3/2 peaks ntawm 454.1 thiab 463.9 eV ntawm NMTSb0.04 sib raug rau Ti hauv lub plus 3 valence xeev. Los ntawm qhov kev xav ntawm tus nqi them, qhov no feem ntau yog vim qhov txo qis ntawm Ti tom qab kev taw qhia ntawm high-valence Sb5 ntxiv. Thaum lub sij hawm tus nqi-tso tawm cov tshuaj tiv thaiv, Ti4 ntxiv rau muaj nyob rau hauv ib tug ruaj khov daim ntawv, uas tau soj ntsuam nyob rau hauv lub cyclic voltammetry (CV) nkhaus ntawm NMTSb0.04, raws li qhia nyob rau hauv daim duab 4. Qhov no kuj qhia tau hais tias lub hauv paus ntawm lub roj teeb muaj peev xwm tsis muaj dab tsi. ua nrog Ti4 plus / Ti3 plus redox khub. Tsis tas li ntawd, qhov khi lub zog peaks ntawm NMTSb0.04 ntawm 529–536 eV hauv daim duab S2(d) paub meej tias muaj Sb.

Fig. 4 CV nkhaus ntawm NMTSb0.04 cathode khoom

2.2 Electrochemical kev ua tau zoo

Daim duab 5 qhia txog electrochemical impedance Nyquist zajlus ntawm NMTSbx. Ntawm lawv, lub semicircle nyob rau hauv nruab nrab thiab siab zaus cheeb tsam sawv cev rau tus nqi hloov pauv tsis kam (Rct) ntawm cov electrolyte thiab electrode, thiab oblique kab nyob rau hauv qis zaus cheeb tsam sawv cev rau Warburg kuj tshwm sim los ntawm diffusion ntawm sodium ions. Haum rau qhov sib npaug Circuit Court qhia tau hais tias Rct ntawm NMTSb0 thiab NMTSb0.04 yog 1185.4 thiab 761 Ω, feem. Raws li Sb doping cov ntsiab lus nce, qhov impedance ntawm cov qauv kuj txo. Thaum x=0.04, qhov impedance ntawm tus qauv mus txog qhov tsawg kawg nkaus tus nqi. Kev nce ntxiv ntawm Sb doping cov ntsiab lus ua rau muaj kev nce hauv impedance. Thaum x=0.06, qhov impedance tshaj li ntawm NMTSb0 qauv. Cov ntsiab lus doping tsim nyog tuaj yeem tau txais qhov zoo tshaj plaws hlau interlayer qhov sib nrug ntawm cov txheej txheej txheej, ua kom cov hluav taws xob thauj mus los zoo, pab txhim kho cov yam ntxwv zoo ntawm NMTSb0.04, thiab tib lub sijhawm coj mus rau hauv tus account qhov ruaj khov ntawm tag nrho cov qauv.

Daim duab 5 Electrochemical impedance spectra ntawm NMTSbx

Under the condition of current density of 1C (240 mA·g−1) and voltage range of 2.0-4.2 V, the sodium storage performance of the Na-ion battery with NMTSbx as the electrode was tested. As shown in Figure 6(a), the reversible capacities of NMTSbx (x=0, 0.02, 0.04, 0.06) samples are 122.8, 128.0, 135.2 and 103.9 mAh g−1, respectively. The difference in specific capacity is due to different doping content. The strategy of chemical element substitution can suppress the irreversible phase transition and improve the sodium ion transport kinetics. The advantages are summarized as follows: replace highly active elements with electrochemically inactive and structurally stable elements, such as preventing cation mixing by increasing the energy barrier of Ni2+ migration, and reducing the oxygen released during electrochemical cycling by strengthening metal-oxygen bonds. Doping or replacing transition metal sites can significantly inhibit the phase transition, inhibit transition metal ion migration, and improve the chemical and electrochemical stability of desodiumized materials. The specific doping content should be explored according to the type of doping element and the intrinsic structure. . On the one hand, doping with high-valent metal ions can improve the bulk conductivity of the material after the metal ions enter the interior of the lattice. When the mole fraction of doping is greater than 1% (stoichiometric ratio x>{{0}}.01), qhov kev tiv thaiv yuav txo qis sai, uas yuav muaj txiaj ntsig zoo rau kev coj ua. Ntawm qhov tod tes, cov nyiaj doping ntau dhau yuav ua rau txo qis cov ntsiab lus ntawm cov khub niam txiv redox hauv lub cev thiab cuam tshuam rau lub zog ntom ntom ntawm lub cev, thaum me ntsis doping tus nqi yuav tsis txaus los txhim kho cov qauv ntawm cov khoom siv oxide txheej. Nyob rau hauv txoj kev tshawb no, NMTSbx(x=0, 0.02, 0.04, 0.06), x yog tus stoichiometric piv, thiab cov ntsiab lus tseeb doping yog 2 feem pua, 4 feem pua ​​thiab 6 feem pua ​​los ntawm mole feem, raws.

Daim duab 6 Kev ua tau zoo ntawm Na-ion roj teeb nrog NMTSbx ua electrodes

(a) Them thiab tso tawm nkhaus ntawm Na-ion roj teeb nrog cov qauv ua electrodes rau thawj lub voj voog ntawm 1C; (b) Cycling kev ua tau zoo ntawm Na-ion roj teeb nrog cov qauv ua electrodes ntawm 1C rau 200 cycles; (c, d) Kev them nyiaj thiab tso tawm nkhaus ntawm Na-ion roj teeb nrog cov qauv ua electrodes rau thawj 3 lub voj voog ntawm 5C; (e) Coulombic efficiency ntawm Na-ion roj teeb nrog NMTSbx li electrodes rau 200 cycles ntawm 1C Cov duab muaj yeeb yuj muaj nyob rau ntawm lub vev xaib

Nyob rau hauv daim duab 6(a), tus nqi-kho tawm nkhaus ntawm cov qauv uas tsis tau hloov NMTSb0 pom tseeb muaj ntau qhov hluav taws xob toj siab thiab cov kauj ruam, qhia tias ntau theem hloov ntawm hexagonal mus rau monoclinic yuav tshwm sim hauv cov txheej txheem txheej. Txawm li cas los xij, thaum lub interlayer plam ntawm txoj kev hloov hlau txheej tshwm sim, tag nrho cov nqi-kho tawm nkhaus yog tus du. Peb qhov hluav taws xob platforms saum toj no 3.00 V zoo li yuav plooj. Rau NMTSb0, qhov kev them nyiaj nkhaus feem ntau muab faib ua ob ntu: ntu nqes hav ntawm 3.00-3.80 V thiab ntu ntev toj siab saum toj 3.80 V .Txawm li cas los xij, thaum Sb tau qhia, qhov pib qhov hluav taws xob ntawm lub platform ntu tau nce mus rau saum toj 4.00 V. Rau qhov kev tawm nkhaus, qhov ntev toj siab feem ntau tshwm sim hauv qhov voltage ntawm 2.50-2.75 V. Cov tsos ntawm qhov hluav taws xob toj roob hauv pes tuaj yeem raug ntaus nqi los ntawm kev hloov pauv ntawm O3 theem mus rau theem P3, thaum txoj kab nqes nqes thaum lub zog nce yog tshwm sim los ntawm cov khoom siv tshuaj tiv thaiv nrog P3 qauv. Daim duab 6(b) yog kev sib piv ntawm lub voj voog kev ua haujlwm ntawm NMTSbx (x=0, {{30}}}02, 0.0 4, 0.06) electrodes ntawm qhov ceev tam sim no ntawm 1C. Nws yog ib qho tsim nyog sau cia tias kev caij tsheb kauj vab ntawm NMTSb0.04 cov khoom siv cathode yog qhov zoo tshaj plaws, thiab kwv yees li 70 feem pua ​​​​ntawm cov peev txheej thim rov qab tuaj yeem khaws cia tom qab 2{{95} }0 cycles. Hauv qhov sib piv, lub peev xwm tshwj xeeb ntawm NMTSb{{1{{1{107}}5}}1}} electrode decays sai heev, nrog tus nqi pib ntawm 122.8 mAh g-1, uas poob rau 51 mAh g-1 tom qab 200 lub voj voog, thiab tsuas yog 41.5 feem pua ​​​​ntawm cov peev txheej tshwj xeeb tseem nyob. Nyob rau hauv daim duab 6(c, d), txawm nyob rau ntawm tus nqi siab heev ntawm 5C (1200 mA g−1), qhov tshwj xeeb muaj peev xwm tuav ntawm NMTSb0.04 electrode tseem yog 92.6 feem pua ​​(125.3 mAh g−1). Lub peev xwm tshwj xeeb ntawm NMTSb0 electrode tsuas yog 106.7 mAh·g-1, uas zoo dua rau lwm qhov tshaj tawm O3- hom txheej txheej oxides. Thawj qhov tso tawm tshwj xeeb ntawm O3-Na(Ni1/3Mn1/3Fe1/3)0.95Al0.05O2 npaj los ntawm Yan pawg ntawm tus nqi ntawm 0.1C yog 145.4 mAh·g−1. Thiab tom qab 80 lub voj voog ntawm 0.2C tus nqi, lub peev xwm thim rov qab yog 128.4 mAh·g-1. Lub O3-NaNi0.5Mn0.5O2 npaj los ntawm Guo cov kev tshawb fawb pab pawg muaj peev xwm ntawm 80 mAh·g-1 nyob rau hauv qhov voltage range ntawm 2-4 V ntawm tus nqi ntawm 2C. Daim duab 6(e) nthuav qhia Coulombic efficiency ntawm Na-ion roj teeb thaum caij tsheb kauj vab tas li ntawm 1C. Ntawm lawv, Coulombic efficiency faib ntawm NMTSb0.04 electrode yog ruaj khov thiab nyhav rau ib txoj kab ncaj nraim, yeej tswj ntawm 98 feem pua, uas kuj qhia tau hais tias nws cov txheej txheem txheej ruaj khov dua. Txawm li cas los xij, Coulombic efficiency ntawm NMTSb0 electrode fluctuated ho tom qab 140 cycles, thiab muaj ib tug loj dhia thaum nws nyob ze rau 200 cycles. Lub roj teeb sib sau ua ke nrog NMTSb0.04 tom qab 200 lub voj voog raug tshem tawm thiab ua tiav, thiab XRD spectrum ntawm daim ntawv electrode tau sim, cov txiaj ntsig tau pom hauv daim duab S3. Lub XRD diffraction peaks ntawm NMTSb0.04 ncej ncej tsis hloov pauv loj tom qab kev caij tsheb kauj vab, qhia tias qhov hloov pauv tsis hloov pauv ntawm NMTSb0.04 cathode cov khoom raug tshem tawm tom qab doping.

3 Kev xaus

Hauv kev kawm no, Na{{0}}.9Ni0.5-xMn0.3Ti{{10}}.2SbxO2 (NMTSbx, x=0, 0. Nws cov khoom yog tsim los ntawm micro-nano-scale flakes nrog cov tuab tuab thiab cov npoo ntshiab, thiab cov qoob loo txo ​​qis tom qab Sb hloov ib feem ntawm Ni. Nyob rau tib lub sijhawm, cov doping ntawm Sb ua rau muaj zog electron delocalization, uas txo lub zog ntawm tag nrho cov kab ke thiab tau txais cov qauv ruaj khov uas muaj txiaj ntsig zoo rau lub sij hawm mus sij hawm ntev-kev tawm mus. Hauv kev sim electrochemical hauv thaj tsam ntawm 2. Thaum them thiab tso tawm ntawm 1C tus nqi, qhov pib tso tawm tshwj xeeb ntawm NMTSb0.04 yog 135.2 mAh·g-1, thiab lub peev xwm tuav tau tom qab 200 cycles yog 70 feem pua. Lub peev xwm tshwj xeeb khaws cia tuaj yeem ncav cuag 92.6 feem pua ​​(125.3 mAh·g-1) ntawm 5C tus nqi.

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Cov ntaub ntawv ntxiv

Fig. S1 HRTEM cov duab ntawm NMT (a, b) thiab NMTSb0.04 (c, d) nrog inset hauv (b, d) uas qhia cov duab sib xws SEAD

Fig. S2 (a) Ni2p, (b) Mn2p, (c) Ti2p, and (d) Sb3d XPS spectra of NMTSb0 and NMTSb0.04

Fig. S3 XRD qauv ntawm NMTSb0.04as cathode khoom ntawm Na-ion roj teeb tom qab 200 cycles

Table S1 ICP-AES cov txiaj ntsig ntawm O3-NMTSbx (x=0, 0.02, 0.04, 0.06) (Stoichiometric ratio)

Table S2 Lattice parameters ntawm cov ntaub ntawv nrog NMTSb0thiab NMTSb0.04