Journal of Hleetoanalytical Chemistry 934 (2023) 117296 Contents wala at SleneeDiret Journal of Electroanalytical Chemistry journal homepage: www.e! wvier.com/locate/jelechem Mitigation of cation mixing of LiNiO2-based cathode materials by Li-doping £ for high-performing lithium-ion battery Yali Wen, Lina Shen, Yuling Chen, Qun Zhou, Jie Wang, Juan Wu, Junwei Zheng” cote f Chenin Cheri egering a Maer Scee, Sachow Univer, Ss 21512, Cnt ARTICLE INFO ABSTRACT Keywords dong LR? donde ‘Swe eolton Srneast etet tein bates 1. Introduetion “To develop high-performing nickel-rich materials has become the urgent target for researchers to meet the requicement of the lithium. ion batteries with higher power and energy density (> 350 Whkg™"), prolonged lifetime (> 1000 cycles), and affordable cost for electric Vehicles [1-4], Some matured materials are believed to be promising ‘as cathode materials of lithium-ion batteries for the next generation [5.6] LINIOg would, in principle, be an attractive cathode material st ofthe material (7,8) © nicke-rc metal ions to enhance the sta ple, in the eommere Sr fm NiO, doped wth wanton ‘tthe cyral arr For exam valle LiMn sCo.Os WME, te TT Gorespending eur ‘ma are son sca (Q ae, jwshongened en Den neps//do.or/10.1016/jelechem,2028.117296 Introduction ofthe Go?* and Mo"* Tons into the LiNIO,-based frame- work could effectively stabilize the layered structure [9-13]. However, the doped Min'* with valent charge higher than Ni? would inevitably, Increase the proportion of the Ni®” ions inthe layered materials, ue to the principle ofthe charge neutralization. The similar ionic radi of 'Ni?"(0.069 nm) and Li” ions (0.076 nm) could lead to the occupation ‘of Nijons at the Li sites, Moreover, te Ni?” from the nickel plane (3a) als tend so migrate to the L sites to form strongly linear antiferromag- netic NI?*=07-Ni?~ superexchange interaction to reduce the mag. netic frustration ofthe structure (14). The degree of cation disorder ‘would become intensified as the content ofthe Ni?* in the TM slabs are increased, or as the materials experience the electrochemical cycling (15). The Li” /Ni?* cation disorder would cause high intabil lity by structural deterioration, cause the blocks of Li~ diffusion, gen- erate the spinel or rock-salt phases, and induce the formation of microcracks (16,17). Those would severely deteriorate the inherent electrochemistry properties of the nickel-rich eathode materials, such as charge/discharge capacities, the rate capability, eycling stability, and thermal stability “The endeavor has been progressed to regulate cation disorder in the layered LiNiO,-bared materials, including optimization of synthesis Received 21 Jonvary 2023; Received in revised form 22 February 2023; Accepted 26 February 2028 ‘Available online 1 larch 2023 | 1572.6657/0 2025 Elsevier BY. Al ights reserve,Wen erat conditions [18-21] and multi-element doping (22-26). In a study of ‘synthetic control of LiNigMng C0920, Wang et al. revealed that the sintering temperature is crucial tothe kinetics of cationic ordering of the materials, the thermodynamics and kinetics of the synthetic reactions need to be precisely controlled through tuning the tempers ture to minimize the eation mixing and avoid the L/0 loss (271. The introduction of transition metal ions without unpaired spins at the valence state can sereen the Ni2"-O-NI2" superexchange interaction ‘and relieve the Li" /Ni2" cation disorder. Thus, the doped Co” fons ‘can efficiently regulate the cation ordering for te layered Ni-rich cath ‘de materials, as in the cases of LINi (C09 1gAlo os (NCA) and NCM. B11, although the Co-free nicke-rch materials are highly desirable ‘due to the limited Go sources in nature [28}, To reduce the proportion of the Ni?" ions in the as prepared cathode materials by doping ofthe ‘elements with low valence state would be an alternative approach to relieve the Li”/N?* cation mixing (29,20). For example, the doping fof the Zn?" ions in NCA could induce the transformation of Ni®* to N2™ to meet the charge balance requirement of the materials (91). Nevertheless, the more feasible ways for controlling the Li* /Ni?* dis: ‘ordering in the nickel-rich materials are sil desirable. Herein, we report the regulation of the Li /NI** disorder by the incorporation of the excessive Li" fons in the LiNiO,-based cathodes. femonstrated that with a proper amount of Lidoping, the materials exhibit greatly enhanced bulk robustness and electro- ‘chemical behaviors. The synergistic effect of the Lidoping on the st bility in terms of crystal structure and electrochemical stability Is further highlighted for the Mn co-doped LiNio,-based materials 2, Experimental section 2.1, Symhetie method of materials Lithium hydroxide and Ni(OH). spherical precursor were mixed by ‘mortar with differen Li/Ni molar rato, then ground evenly and suf ciently. The solid mixture was presintered 5 b at 480 °C, followed by 16 h at 730 °C in an 0, atmosphere to ensure full reaction. Subse. ‘quently, the resultant powders were then collected after washing, fi tering, and drying at 80 °C overnight. Eventually, an action was taken to reconstruct the surface structure ofthe obiained samples by heating them at 730 C for 10 b, For the synthesis of Li; ,;NiO, the nominal ratios between 11H and Ni(OH)2 are set to Be 1.05:1, 1.11:1, 1.22:1 and 1.93:1, The asprepared samples were defined as ENO-1.05, LNO-1.11, LNO-1.22 and LNO-1.33, respectively. The Li Mn co-doped LiNIO>-based materials (Li ,NigsaMngoi03) were ‘obtained through the above process by employing the Ni(OH), spheres doped with Mn-containing (1 mol) gel as the precursor, defined as ENOM-1.05, LNOM-1.11, LNOM-1,22 and LNOM-1.33, 22, Materials charactristions ‘The actual compositions ofthe synthetic samples were measured ‘with ICP-OFS. The crystalline structure features ofthe as-synthesized powders were determined by using an X-ray diffraction (XRD, Rigak MiniFlex 600) with a Gu Ke radiation over the range of 10-90". The ‘obtained data were refined by using Rietveld method on GSAS sof ‘ware. The scanning electron microscope (SEM) operated at 20 kV ‘as used to observe the morphology of the as-synthesized powders. Xray photoelectron spectroscopy (XPS) was employed to determine the elemental oxidation states on the surface of the as-prepared samples Jour! of Ecroanbrce! Chany 994 (2028) 117295 123, Blectrochemical measurements ‘The slurry of cathode was formed on an Al foil and then dried at 120°C for 12 h, and the mass loading of active materials in the thin electrode is ca. 2.0 mg cm, The homogeneous slutry consisted of 80% Liy NiO, (Li, +sNig Mg 910s) powders, 10% acetylene black and. 1036 polyvinylidene fluoride (PVD). All the electrochemical tests ‘were conducted by assembling coin haf-cells (CR2032), which were assembled in an Ar-filled glovebox with water and oxygen content less than 0.1 ppm. The galvanostatic charge-discharge measurements and rate capability were recorded on a LAND CT2001A battery test system Jn the potential window from 3.0 to 4.3 V. For BIS measurements all cells were tested with a frequency range of 0.01-100 kz on PARSTAT. 2273 electrochemical workstation system (Princeton Applied Research, AMETEK, America) with amplitude of 5 mV. In adeition, to identify the structural evolution and phase transition ofthe cathode materials, sia XRD measurement war carried out at a cutoff voltage of 2BASV. 3. Results and discussion 3.1, Structural characterization of Li, .NiOs ‘The actual compositions ofthe as prepared LINIOx-based materials ‘were determined with ICP-OFS analysis (Table $1). The Li/Ni ation the final products is lower than that designed values in the stating mixed materials ue othe evaporation ofthe i soureat high temper ature For example, che starting mixed materials with a Li/Ni ratio of 1.05 produces a product with a Li/Ni ratio of 0.99, close to thes chemisuy of LINO, The excesive Li source would result {9 an increase of the Li content inthe Fnal products with formula of Li NiO,, Nevertheless, all the XRD patterns fr the Lidoping samples exhibit the characteristic peeks that an be wel clase asthe typical layered structure (w.NaFEO,) of dhe RSin space group (ig. 1a). The alts of the (006)/1.02) and (018)/(110) peaks (Fs. 1b) shaw ds tint splicing in the range of 37-39 and 64-86 respectively, ndieat ing the welldefined layered structure of the materials. Furthermore, the influence of excessive Li with respect to the erjtal structure is noticable. As depieted in the selected segments (18-19.5) of the XRD pattems of all the povtders in Fig. Ie, with increasing ofthe Li content, the (003) diction peak ofthe materials slighty shits towards lower direction angle, fom 1874" for LNO-L.0S 10 18,72' for INO-1.33, indicating the expansion ofthe interlayer spacing inthe exystal lace. Rietveld refinements were Further performed £9 verify the alteration of the rytal lates, the results are shown in Fig. 15, andthe lattice parameters and unit ell volume V (bated on [Sin pase) ae listed in Table 1- As ean be seen the latice parameter atand c increase withthe L content. For example, the ltice parameter ao the materials increases from 2.87672 A for LNO-1.05 t0 2.87922 A for LNO-1.33, with an alteration of 0.09%, while the lattice parameter € correspondingly expands from 14.19826 Ato 14.21281 A, with an iteration of 0.10% resulting i latice volume expansion and elong: tion ofthe inveslayer. The evolution af the ltie parameters with the 1 content may be atributed to that the Li” fons with larger fonie radius (aj ~ 076 A 1h = 0.56 A) re doped into the wansion metal slabs. A comparison ofthe *Li MAS NMI spectra of LNO-1,05 and LNO.- 1.11 ig. 2) might be an adaitional eue ofthe Li doping, anew band appears at ~1000 ppm for LNO-1.11, along with the major band at 325 ppm. The appearance of two bands for LNO-1-11 is due tothe relaxation time dlference of the Li ions at 3a and 3b sites (2532-34), The excessive Li” fons in LNO-1.11 occupying the Ni sites ‘would expand the interlayer space. Moreover, the ineprated Intensity rato ofthe (003) and (104) peaks reflects the degree of cation mixing and the refined data is Shown in Toble | [35]. The ratio ineeases from 1.30 to 1.32, 1.42¥. Wen erat ano Heroanayiel Chery 4 (2028) 117296 Wo i SN Lt ud ba AN | Fig 1. (a) XRD paterns ofthe asprepared samples; () Magnified area of (006)/(102) and (018)/(110) peak; (6) Magnified area of (003) peak ‘Table 1 ‘Structare parameters ofthe as:prepared samples fom Rietveld refinement ‘Sspies aie parartes Covi wp AS CMa Later no) NORA) a © wa or) ‘and 1.45, for LNO-1.11, LNO-1.22 and LNO-1.93, respectively. The results implies thatthe Li-doping may effectively alleviate the disorder degree of Li” /Ni?*. To interpret the phenomenon, two aspects have to bee considered: () the Li* ions preferentially occupy the 3e sites, @ large quaataty of Li” ions existe in the Li slabs would prevent Ni?" ions migrating from the TM sites to Li sites; (i) the incorporation of ‘excess Li” ions into the TM slabs could lead to less Ni?” ions formed in the TM slabs in order to meet the requirement of charge neutrality. Consequently, alleviation of the degree of Lit /Ni?™ disorder would ‘occur in the presence of excess Li” ions inthe period of synthesis ‘As shown in Fig. 2, XPS spectra of the Li, -,NiO; Samples was fur ‘ther employed to verify the alleviation ofthe Li/Ni cation disordering by the Lisdoping, The Ni 2p spectra are mainly consisted of NI 2p,,2 and Ni 2paz peaks. The Ni 2py region could be well assigned to ‘two characteristic species located st 583.4 eV and 584.6 eV, corre- sponding to Ni?" and NP *, respectively. The variation in the content ‘of Ni could be estimated from the ratio ofthe peak areas for Ni?" and Ni". The ratio of the NP*/NE* gradually increases with an increasement of Li* ions content. The increased value of the Ni?*/ [Ni ratio would be the clue that the excess Li~ fons may be doped Ino the transition metal siabs during ealcination, resulting in that in the presence ofthe doped Li* ions, more Ni* ions have to be formed in the transition mecal slabs to maintain the charge neutrality (36). A similar variation trend was also observed in the Li 1 s XPS spectra Gig. 85) of the samples, The characteristic peak can be fitted into two peaks, assigned to Liz0 species (~54 eV) and Li" (0¢x< 1) species (~53 eV). The intensity of the Li?” peak representing the ‘coordinated Li” ions increases with the Li content, confirming the ‘doping of the Li* fons in the bulk struture ofthe materials. ‘The morphologies ofthe Liy NiO, materials are revealed by the ‘SEM images shown in Fig. 48. The influence of lithium content on the precursor and as-prepared samples i barely visible. The precursors ‘are spherically shaped. For all the as-prepared samples, the primary particles are well developed with clean and smooth suface, indicating that the as-prepered samples are well crystallized after calcination. ‘The secondary particles of the samples still maintain the spherical shape, with average size of ~11 yan in diameter. Tha is, the incorpo ration of" ions would have no perceptible effect on the surface mor- phologies of the Li, . IO materials. 4.2 Flectrochemical properties of Li NOs ‘To evaluate the effect of excessive Li content as the stabilizer in Us -,NIO, samples, the cyeling performance was investigated in the coin cells using Li metal as anode between 3.0 and 4.3 V. As foremen- tioned, the Liloping into the transition metal slabs may lead to two Possible consequences: (i) The requirement of the charge neutrality leads to the reduced content of Ni?* ions, which can moderate the degree of mixing of Li~ and Ni®* and maintain the ordering structure of the materials; (i) Correspondingly, the increasing content of Ni fons may contribute more reversible capacity during the electrocher- Jeal eyeling process. The initial discharge capacity at 0.1 (1c = 200 mA g~") shown in Fig. 3a is heavily dependent om lithium content of the materials. For example, INO-1.33 dolivers the highest Alischarge capacity (232.9 mAh g~*) in the Fist cycle, followed by 1NO-1.22 (228.7 mAh g~'), LNO-L.11 (215.6 mAh g~"), and LNO- 1.05 (208.3 mAh g~"). The corresponding initial coulombic efficien les are 84.1386, 84.22%, 86.25%, and 88.31% for LNO-1.08, LNO- 1.11, LNO-1.22, and LNO-1.33, respectively. As expected, the Lidop- Jing fesults in mote Ni" fons available for the electrochemical reac: tions, providing higher charge and discharge capacities. Due to that the samples would possess similar surface or electrode/lectrolyte Interface property, the increased inial coulombic efficiency with fncreasing ofthe Li content, on the other hand, might be ascribed to the alleviation of the electrochemieally induced Li/Ni cation disorder lng by the Liloping during the rst charge/discharge cycle. AS the L- doping results in les proportion of Ni*~ ions in the bulk structure, during the charge process less Li vacancies could be occupied by theWen erat aa of roan Chery 904 (2023) 117208 a 6 A Smal | a, | is | Ee 3 iW i i} } | #/ > i A e ep ang nee <¥ Boning Fare /< e a f i FN z if i Boning nee LNO-1.22 > INO. 1.33=1NO-L.05. That i, a proper amount of the Lixloping can stabi lize the LINiOp-based crystal structure as in the case of LNO-1.11, hile excess of the Lisdoping (LNO-1,22 and LNO-1.33) would have detrimental effect, contributing tothe severe structural collapse during the electrochemical eycling ofthe materials As aforementioned, the Lidoping would result in enlargement of the crystal lattice ofthe Li ,,NiO, cathodes, therefore, it is expected that the Lisdoped materials could exhibie superior rate capability. Fig. Sa and b depict the rate capabilites of the electrode cathodes, Which indicate that the rate performance of the LNO-1.11, INO: 1,22, and LNO-1,33 eathodes is far superior to Uhat of the INO-1.05- counterpart. The capacity retention of the Liy NiO, electrodes at 5C Is 29.44% for LNO-1.05, 56.12% for LNO-1.11, 34.29% for LNO- 1,22, and 30.27% for LNO-1.33, relative to the discharge capacities of those materials at 0.1G, respectively. Again, INO-1.11 exhibits the mast excellent rate performance among the elecirodes. The deterio rated rate performance of LNO-1.22 and LNO-1.39 might be related to ther less stable erysal structure during continous eyeing at differ ‘ent rates, although those two materials possess larger exystal lattice ‘than LNO-1.11. Partial collapse of the erystal structure would lead t0 obstacle to the fast Li” diffusion in the bulk structure of the LNO- 1,22 and LNO-1.33 materials Voltage V Hig. 4. CV curves of (a) LNO-L05;(b) LNO-L:11; (6) LNO-1.22;(@) LNO-.83. Fig. 6 displays the FIS spectra at different eyeling stages for all Li. .NiO2 cathode materials to verify the above point. The impedance Spectra ofall the electrode materials after eycling show that all the electrodes posses similar resistance ofthe SEI film (R,), reflected by the semiciele inthe high-frequency region. On the other hand, the charge transfer resistance (R,) continuously increases during cycling ‘The data obtained by fitting the EIS spectra with the equivalent circuit ig. 68), a listed in Table 2, indicate thatthe variation of Re stongly connected with the 1i content of the materials, The Rx of LNO-1.05 electrode increases rapidly from 190.3 2 at the 25th cycle to 630.1 0 up to 100 cycles. The rest electrodes exhibit relatively lower increments in Rz during the same period of cycling, from 146.2 8 to 344.2 9 for LNO-1.11, 1635 9 to 431.8 @ for LNO-1.22, and 205.0 0 to 578.6 0 for LNO-1.33, respectively. The data is consistent withthe rate performance of the Li; +;NiOz cathodes. Evidently, the partial steuetural degradation of the crystal lattice of LNO-1.22 and INO-1.33 occurring during cycling might undermine the interfacial property of the materials inthe electrochemical proces. 3.3. Synergistic effect of doped Li" ions with co-dapant of another element Although the Lisdoping could inhibit stuctural instability of the LINIO,-based materials to provide better eyclability and rate eapabil ity further enhancement in the performance during the charging-dis charging cycling is necessary from the perspective of practical application. Considering that transitional metal ions are widelyWen erat Jour! of Eecroanbic! Chonan 994 (2023) 117295 . in £ fis i. i i 2w. i. os 6 two * i tno2 E ». yee Nanber ae ig. 5. (a) Rate perfomance of LINO-1.05,1NO-1.1,1NOW.22, and LNOLL. 33 i the volage range between 3.0 and 4.3 V (0 Camespondig discharge capac tention diferent ater elatve ote ape a 1G a ==] "Tb 5 <= Sis eee ce a 5 om. 5 a. 7 a ss aff ia SS} oid : =e ria via Fig. 6. Nyt plot after diferent cyl for (2) LNO-.05; (6) INO-1.115 (¢)1NO-.22; (8) 1NO-.39. ‘employed as the dopants to boost the crystal structure of the layered nickeltich cathodes, in this ease, we select Mn as the co-dopant to investigate the synergistic effect of the dual doping (Li, Ma) strategy in the layered LIN(O,-based materials. Mn element with fixed content was introduced into the Liy NiO, materials with varied Li contents to form the LNOM-1,05, LNOMC1,11, LNOML-1.22, and LNOM-1.33 mate ‘The analysis of the XRD patterns of those Li/Ma co-doped LINIO,-based materials presented in Fig. 75, which indicates that the Mn-o-doping would lead to serious cation disordering, due co that the valent charge of the incorporated Mn** is higher than that of Ni, and the formation of the Ni?" ions in equivalent quantity is nec essary to maintain the charge neutralization. The koo3)/Lo4 ratio for INOM-1.05 is 1.20, which is even lower than that of LNO-1.05 (1.30). ‘Te Loo/Ia oo Fat is increased as the Li content in the materials isural of Berean! Chaney 934 (2023) 117298 ‘table2 eo a mu) a) re Re N@ me ‘increased, indicating that the Li-doping would efficiently alleviate the degree of Li" /Ni** disorder in the L/Man co-doped cathode materials. ‘This is verified by the Ni 2p XPS spectra shown in Fig. 8S, clarifying that the Ni content in the materials is decreased with increasing of the Li content. As we discussed in Fig. 2, benefited from the Li-dop- ing strategy, the less formation of Ni?” ions could be achieved in the TM slabs of Li . IO, materials, The tendency is maintained in the Li/ Ma co-doped cathode materials owe tothe synergistic effect of doped 1 fons and Mn‘ ions, despite more NiF~ ions existed in the co- doped material relative to that in Li ..NiO, cathodes. For example, the incorporation of Li* ions is conducive tothe alleviation of Li*/ Ni?" disorder, whereas the Mn** ions would induce serious cation ‘mixing in the cathode materials as documented in literature (12). AS depicted in the Fig. 85, the fitting data manifest that the content of [Ni** fons experience 2 great drop from 27.75% for LNOM-1.05 to 1931% for LNOM-1.33, The results clearly demonstrate thatthe Li- doping can effectively regulate the level ofthe the cation mixing of the cathodes with co-doped elements ‘The charge/discharge curves upon the initial cycling process of the ENOM-1.05, LNOM-I.11, LNOM-1,22, and LNOM-1.33 materials are depicted in Fig. 7a, As expected, LNOM-I.05 only delivers discharge capacity of 191.1 mAh g~* with an intial coulombic efficiency of 78.68% because ofthe serious catlon mixing, with the incorporation of Li" ions, the discharge capacity is increased to 225.1 mAh g~ for INOM-1.11, 223.3 mAh g~! for INOM-1.22, and 221.7 mAh g7? for LNOM-1.33, accompanied with the coulombic efficiency of 82.96%, 85.2695, and 84.77%6, respectively. The results indicating that the Li-doping can mitigate the Li" /Ni2" cation mixing, which exhibits great impact on the reversible capacity and coulombic efficiency of the materials. To provide further proof forthe synergistic effect of the Li/ Ma dual doping strategy, the comparison in the long-term cyelabilites for LNO-1.05, LNO-1.11, LNOM-1,05, LNOM-1.11 at OSC are pre sented in Fig. 7B, As can be seen, the increased capacity retention could be achieved from 31.88% for LNO-1,05 to 58.89% for LNOM- 1105 after 200 eyeles, probably due to that the co-doping effect of “Mn can significantly boost the crystal structure stability ofthe mater als during eyeling. With evident Lidoping, LNOM-1.11 can provide a capacity retention of 71.11%, which is much higher than that of LNO-1.11 (57.625), implying the synergistic effect of dual doping (i, Ma) strategy on the eyelie properties of the materials. The effect of Li-modified and 1i/Ma co-doping strategy i further highlighted in Fig. 98 and Table 83, To further gain insight into the combined roe ofthe dual doping of 1 and Mn in the performance of the materials, the SEM images of the 1NO-1.05, LNO-L11, and LNOMC1.11 cathode particles obtained before and after 100 cycles at room temperature were measured. As shown in Fig. 10S, compared with the pristine cathodes, the secondary particles ofthe cycled LNO-1.05 cathode are obviously pulverized, and microcracks are observed in the particle surface of cycled LNO-1.11 cathode. While for the LNOM-1.11 cathode, the sphere-shaped mor phology is well maintained after 100 cycles. The instability of secondary particles may contribute tothe difference in capacity reten. tion diseussed above, To verify this point clearly, the cross-sectional SEM images of the three cathodes after cycling are presented in ig. 8a. Propagated microcracks are formed in che LLNO-1.05 particle, as presented in Fig. Ga, along with many holes or defect sites over the entire particle. Inthe case of LNO-1.11, the situation becomes better, LUmited amount of the microeracks and defeet sites can be observed on the cross-section of the particle. The inner structure of the LNOM-1.11 particle, on the other hand, seems to be well maintained, only a few defect sites formed inside the particle Is considered that dhe forma. tion of the defect sites might be associated with the collapse of the crystal structure as described above (Fig. 58), while the microcracks could be generated by the internal mechanical strain accumulated dur ing the electrochemical cycling which involves anisotropic volume change during repetitive Ithiation/delithiation. As aforementioned, proper amount of the doped Li" ions could serve as a stabilizer to enhance crystal structure stability of the LINIO;based cathodes. In addition to tha, the stabilizing effect of the incorporated Mn** ions are signifcandy beneficial for improving the structure stability of Vonage Capacity mah cyte Number Fig. 7. (0) inital charge/discharge profiles of L/Mn codoped LiNO based material at 0.2C; (0) Cyeling performance of LNO-I.08, LNO-1.11, LNOMCLOS andWen erat ie a 2 saagree Jour! of Eecroanbic! Chonan 994 (2023) 117295 ! | Erte As es (2) Comparison of eros-setional SEM images ofthe (21) LNO-.05, (2) LNO-.11 and (3) LNONC-1.11 cathodes after 100 cycle; ()Insit XRD patterns ‘0f (1) IN0-1.05, (2) tNO-L.11 and (b3) ENOMEL1T cathodes inthe (003) region ‘the nickel-vich metals, which has been well documented inthe litera tures (37-39). That is, both doped ions could result inthe alleviation of the structure degradation of the host LINiO, based cathodes. To understand the different behaviors in the microerack formation of the three materials, the in-situ XRD measurements were conducted dur ing the charge/discharge process. Due to that the changes in the unit ‘ell volume mainly occurs along the c-axis, the alteration of the (003) diffraction peak is particularly emphasized in this case. The results shown in Fig. Sb indicate that during the early period of charge (feom 3.98 to 4.08 V), the (003) diffraction peak slightly shifts towards the lower difrection angle, mainly corresponding to the M ‘to H2 phase conversion with the expansion of the erystal lattice. AS the voltage becomes > 4.20 V, the (003) diffraction peak undergoes a slight shift to higher angle, indicating the abrupt volume extraction ‘of the unit eell along the c-axis, The reversed volume alteration of the ‘crystal lattice takes place during the discharge process. Although the ‘end of the (003) peak shift during the charge/discharge processes is similar for LNO-1.05, LNO-1.11, and LNOM-1.1, the overall change in the dfracton angle forthe three samples is different, whichis 1.35° for LNO-1.05, 1.25" for LNO-1.11, and 1.06" for LNOM-I.11, respec: tively. That i, the LNO-1,05 material experiences the largest change {in the unit cell volume of the material during the electrochemical ‘ycles. The repetitive volume change of the unit cell during the charg ing-lischarging cycles would generate relatively large mechanical ‘rain accumulated inside the secondary grains of the materials, and ‘eventually Iead to the generation and propagation of the microcracks. ‘Therefore, the diference in the formation behaviors of the microc racks forthe three samples shown in Fg. Ba would result from the dif ferent extent of the volume evolution of the crystal lattice of the ‘cathode materials upon electrochemical cyclin. In other words, the ENOMA1.11 material with the Li/Mn co-doping possesses the best structure stability ofthe secondary grains. In addition, the generation of the mievocracks and defect sites of the secondary particle interior of the cathodes may result in the newly formed surfaces to expose tothe electrolyte. Therefore, the electrolyte ‘would further decompose on those surfaces, consequently increasing the impedance of the clectodes. AS revealed by the EIS spectra in Fig 6 the increment in the Ry for LNO-1.05 is much larger than that for LNO-1.11, Similar PIS spectral measurement for LNOM-1.11 (ig. 118) indieate that the Rj is only increased from 87.4 to 100.4, which is smaller than those of LNO-1.05 and LNO-1.11 ‘Therefore, the Li/Ma co-doping not only stabilize the structure of ers. tal lattice andthe mechanical integrity of the secondary particles, but also relieve the side reactions atthe electrode/electrolyt interface of the materials, 4. Conelusion, In summary, the Ly, NiO, materials with various Li content were fabricated by high-temperature solid-state method. With excessive Li source in the starting materials, the Lidoping,in the TM slabs could ‘occur during the growth stage of the erystal structure I has been man. ested that the Lidoping would induce the evolution in erystal struc ture of the as-synthesized materials, and alleviate the degree of Li*/ Ni?* disorder due to the charge balance of the TM slabs. The LiNiO;- based cathodes modified witha proper amount ofthe i* ions exhibit the mitigated structure degradation, ensuring acceptable cycling ste bility of the cathode materials. In addition, the expansion of the crystal tice indueed by the incorporation of Li* ions are highly beneficial for Li” diffusion, thus providing enkanced rate capability at diferent current densities. However, doping with excessive Lit ions would aggravate the structure degradation ofthe cathodes upon the electro chemical eycls. With optimized Li-doping content, discharge capacity of 215.6 mAh g~? at 0.16 was obtained for LNO-1.11 after an inital cyele, with capacity retention of 57.62% atter the long-term cycling (200 eyeles) at current density of O.5C, which is outstanding to a greater degree than 31.88% for INO-1.05, 40.0596 for LNO-1.22, and 30.45% for LNO-1.33, respectively. In the presence of Mico dopant, the synergistic effec of the Li-doping is highlighted by further enhancement inthe stability in terms of erystal structure and the inteWen erat rity of the secondary particles ofthe LiNiO,-based cathode materials, leading to less mierocreck formation and side resctions at the elec: twode/electrolyte interface, Therefore, structure regulation by the Li- ‘doping might be an efficient strategy for the design of the layered nickel-rich cathode materials and improvement of the performance ‘of the lithium-ion batteries CRediT authorship contribution statement ‘Yali Wen: Writing — original drat, Validation, Conceptualization, ‘Writing - review & editing, Methodology, Data curation, Lina Shen! Conceptualization, Writing ~ review & editing, Methodology. Yuling ‘Chen: Conceptualizaion, Supervision, Resources. Qun Zhou: Writing, ~ review & editing, Conceptualization, Supervision, Project admins tration, Jie Wang: Methodology, Conceptualization. Juan Wut Data ‘curation, Validation. Junwei Zheng: Supervision, Resources, Concep tualization, Writing ~ review & editing, Project administration, Fund: ing acquisition, Declaration of Competing Interest ‘The authors declare that they have no knovn competing financial Interests or personal relationships that could have appeared to inl ‘ence the work reported in this paper. Acknowledgements “Tis study was financially supported by the Innovation District of Miltary China (18-163-13-20-008.005-02) and the National Key R&D Program of China (2019¥FC1604605). Appendix A. Supplementary data Supplementary data to this article can be found online at ‘nupsi//doi.org/10.1016 ,jlechem.2023.117296. References 11% Kim, WME Seong. A. Mancha, Cobal‘ee,highakal lyered oxide aes for Libueien bates popes chlenges, abd perspeetis, Ber Storage Mate 34 (2021) 250-25 (ay Yi ay L9 Weh Lo ang Hang, 2-¥, Wang, 2 le, Ya a, Dal Zheng, Neen and cobs yore ated materia fot Iie on bers Energy Storage Mate. 0 (2022) 274307 (3) Haz, ev. Lay, Sheng Wang, P Rl, Yang . Ren HX, X. He baltic cathode materia: anes an het respec Ad nergy Mer 13 (Goan 2103990 HAL RCK. Rey Xn, A 25, C-¥ $5, Mangan fameworis and thir leis a ahd for htnien bate apletons a ele Eetochers ergy Rev 52021) 812-47 (51 Z than Radel, K. Hein Are, M. Zend Kuan, V. Blesnan, S ‘Rohan Sth Rar NAb ain Subramanian, Review pn! cn Oy ‘Gthode mater under hg ctf wage in Kon taser chalnges Sh eae J Hactoanal Cher 920 (2922) 116625 (6) eninge Tan K Zhang, Cao, ¥. Zheng W Tia Wang Wee Wag. ang Recent advances in cathode peltiaton addives ad thir se i ‘Hoon ttre tran. Chen 89 2021) 11558, (1 Ye fis Te, Kitch Diem F. Sauy, Ma, Goose, lane, MC aching. Brsea, Ceing peromance 2nd isons of NO, Seid ates, ACS Boegy Ltt (2021) 3000-3028 (a) Me lancny oxeAyas,P Haren, T- resis, Jen, Teron back ‘re jaumey of LINO, wend eive aerial Ange Chem a El gh $s 019) 1osse 048 (91 1 Mee Knee Sen XL, Corolle ethos interface of Ls [htagenestng IOs for iim Son aterce a review, Ady Energy Mater. 9 (Goi) ro01s97 no) Kae, 7h, 7a, Bi, G. hau, ILM. Cheng A nonamabe ete feraleabghvolage (4 Vas) NEM cll wih wide temper range ff 108", tneg veo. Set 1 (2) 485-244 (01) ¥ Malar, Sek Nona Nl, Uys C- OY. oY ate, Factors acing cyeng Me of LNyCoqysAgnO2 for Honan Sei Mater Ch A (208) 8380-2358, tof roan hemiry 994 (2023) 117298 (02) 7 Xu, Fu, LW Z Fan Shen, 3 eng, Boosting the eectrocemie eloizaee of UNIO, by exe low catet of Mesoping ahd He ech, coc Act 47 2072) 140345. (0) He ha LD. Tang, YD aang, 2%. Wag. YL, 2-1 He, Yan Mo, CK ay, it. Zeng, Comprehensive undetading of L/¥ neraing Tajo ernstion meal onde, Mate. Today St (202) 365-392. (04 J aheg¥ Ye, T Ut ¥ Xi, Wang FW, F Pat AVL soding i injered nso net) onde: erotik oa, and conta, cs (Gham: Res 52 2019) 2201-2208. (5K Mabe Pl Reeves, CX, KG, CP. Grey, fsian of rete ad Iam yvamies in LggngsCon,0, (QMCBII) cathodes ding ‘eevochemiel eyeing, Chen. Mate 31 (2019) 2548-2558 (a) G5, Yoon DA Jun £7 Myung Sun, Structure stably of NO, yd Shove 12 V, AGS Energy Lae 2 017) 150-1155. (071 nc eu Harrann Bee, Jnek,Aninscemacel ey ‘nh sychessael epost iN Mae. he, A (2020) 1608-180, (08) 8 Mes, A Manohar Sythe of LINO, et moderate oxygen presse and oon Val ei, ACS Ap Mater. tteres 12 (09) Karger Weber. Goonies, A Mai i Rang, Mi. eis ondrakow ns, Breve, Lvctempeatr on exchange sth of layer io, gers wh high ordering, Cher. Mae 85 (2128) 688-557. (a0) zo, 8 Wang. 2 Zhan. Zhan, Se, Yu, sepals compute eine ne ti tery atte sey lector 8 (3020) (211 1.6 tang W- Zheng, S. hang Kav, VK Pang, 7 Gao, Adresing ction ning leer srctted eatodes fo ain bate tea view, Nano hate Se (2022). hid ogy 0 D016/ ums 2028.09 00, (2 Lit, Wit san CMe 2 Yang. LC Sun 6 Sano. M.A, ondond Lin, Sutrl and wetochese pts of Mga ldots fon he NO, atonal basen ACS App Mater Iteres 122020) (25) ¥ zhang. Li Ym, YL HM. Cheng J Che, Gaent dopng Mga AL {o alice Neh exthode mater for charge anon Hate, J PowerSource 55 (2022) 23145, (24) b Wang, © naan 1 Ba J eng Xo, AY. Rete Ka, AH, ‘Zhong CS, ¥ Yang Chem, ¥ io, Aan, Fh, F Wa, Ine ‘ole of ett tbstion tuning LZ ming in Hi layered weds, ‘hem: ate 31 (2019) 2731-2740, (251 1 lan Hen, ¥- Zn He, Wi, Weg, Yang HLM Sar eros review, Heeochen. Energy Re. § (202) 2 Wang Kou, ¥ Re, CSM Zhao, M.S. Zang, Uy A. Hug 30K Pan, YC Sun Yang KA J Ba Chen, Wang sya eel of trenton pata ap cates daring in high ner xe canoes, ‘ev ter 25 (2017) Tes715- (271A Cairo, 5. Konniaroan, Kent, 8, Mackveky,D- Aba, ML Diy DIT Major, Layered emtbode mately for lMumcion Deters: tevew of ompatational sis on LN. jC0MD,0, and UNI, 600A Ox. Che, Mater 52 (2020) 915.952 (2) CA tonnes, Ge famasSSncer, M. Over Talensna, Hh Pie, ‘onal, imrovng the sutra reversity of 0s by neorgeation of Cy ‘neseciobeml and insta ARDS J Aly. Cnpa-923 (2022) 166325, (29) R Satsyensorth, Sask, 5. Ramla, YC. Slots of Mg dopingon the pertormanc of NO, atric ceramic nanoparticles in ghee {amon cl Power Sources 71 (2007) 922-822 (0) €Xe, We Xing 7 Wes 1 Qi ¥ ig, W. Yar, Ya Thang, Bong ‘Guo, Wang is, Dost ce modfeston regulated ete renin or [isi cathode owes bested seve cey ad eye Sal, Che, og 403 (2027) 126314 (911 SE Arn, aa, A Cakraborty, Nae, Nand, 5 anata. ‘ewe Gena, Vasa, Som fle Deep © HS Ma Se, Goober, Bi. Major, Me Takiasker& Maroy, D-Rarach Boron hoped NEFeh Ng CannhgoeDy athe rats See by stuctrel Sslysis sd sate NII compustonal modeing, snd. ecvochemi petonmance, meray Storage Mater 12 (2021) 596-00? 221 stmoda Malan. Yaa H.R Urls 2 Ogu nit Nik rerton of the hem sxtacon/inion fom scab, athade lctoehny_ Art 108 2013) 34349, (93) GP. Gry, Ve, Lids MAS NM sais of etbode aati orton Sauer, So Sate Se 5 (203) 883-594 124) YX J-Zheng c Wang, M Go, Designing peincple for Nisich cathode materia with igh energy denny for practical apletions, Nano boergy 45°01) (95) 6X, We Ain, Z Wa, ¥. X,Y. Wang, ¥. ao, Guo, 8 Zhang Mly ‘blond NERich ‘ahode teil’ wit Mo ndaced pany” grown ‘ambaecured hybrid mace for highperfomnnce hii bate, ACS ‘Rot Mer iss 1 (019) 16609-16638 (36) Who, 9. Lm, SA a, Kin Song. Yo, Yin, MS Park Fae ‘Ma slacedopiag of Ni ered entode meas for Lu fon ates, [ACS App Matar Inrtee 10 2OT) 38915-38921. (971X Wang, Ih lino 3 Las Tung, AY, A novel mathod fo preparation of Sheets, Eero Ac 96 211) saint (98) 11g, Xe SH DoW Seog L-, Zar, Elecwoehemla pecomance of Nis Stag wh diferent shasta, are et. 94 2013) 80-385. e