Enhancing the Rate Capability and Cycling Stability of Na0.67Mn0

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C: Energy Conversion and Storage; Energy and Charge Transport

Enhancing the Rate Capability and Cycling Stability of Na Mn Fe Co O2 through a Synergy of Zr Doping and ZrO Coating 0.67

0.7

0.2

0.1

4+

2

Weijin Kong, Huibo Wang, Yanwu Zhai, Limei Sun, and Xiangfeng Liu J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.8b08742 • Publication Date (Web): 23 Oct 2018 Downloaded from http://pubs.acs.org on October 26, 2018

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The Journal of Physical Chemistry

Enhancing the Rate Capability and Cycling Stability of Na0.67Mn0.7Fe0.2Co0.1O2 through a Synergy of Zr4+ Doping and ZrO2 Coating Weijin Kong ab$, Huibo Wang a$, Yanwu Zhai a, Limei Sunc* and Xiangfeng Liua* a

College of Materials Science and Opto-Electronic Technology & CAS Center for Excellence in

Topological Quantum Computation, University of Chinese Academy of Sciences, Beijing 100049, P. R. China

b

College of Mechanical and Electronic Engineering, Shandong University of Science and Technology, Qingdao 266590, P. R. China

c Department

of Nuclear Physics, China Institute of Atomic Energy, Beijing 102413, China

$ The

two authors contribute to this work equally.

*Corresponding Author: [email protected]. (X.L.) Tel. +86 10 8825 6840 [email protected] (L.S.) Tel. +86 10 6935 8741

ACS Paragon Plus Environment

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Abstract Sodium-ion batteries (SIBs) have aroused great interest as large scale energy storage devices due to the abundant Na resource. But the lack of high performance cathode materials is still a big challenge for the practical application of SIBs. Herein, the synergic modification

of

Zr4+

doping

and

ZrO2

coating

on

P2-structure

Na0.67Mn0.7Fe0.2Co0.1O2(MFC) has been achieved by a facile Zr(OC4H9)4-mediated sol-gel method. The rate capability and cycling stability are simultaneously enhanced, and their synergetic mechanism is revealed. The enhancement of the rate capability is largely attributed to the expansion of the interlayer spacing and the enlargement of Na-O bond length, which decreases Na+ migration barrier and the electrostatic attraction between Na and O. This facilitates Na ions intercalation/extraction and enhances the rate capability. The improvement of the cycling stability is firstly attributed to the protection of ZrO2 coating, which reduces the side reactions between the electrode and electrolyte and benefits to the stability of the layered structure. In addition, the doping of Zr4+ also reduces the bond length of TM-O/O-O and increases their bonding energy, which further enhances the layered structure stability. Last but not least, the relative content of Mn3+ is also mitigated which alleviates Jahn-Teller distortion and further enhances the structure stability. In situ X-ray diffraction is also performed to probe the structure evolution of ZrO2@MFC during the sodiation/desodiation. The proposed synergetic strategy is also suitable to modify other cathode materials.


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1. Introduction Over the past few decades, Li-ion batteries(LIBS) have been widely used in portable electronics devices1-3. However, the limitation of Li source and the increasing demand result in the high cost of LIBs. Recently, sodium-ion batteries (SIBs) have attracted much attention as new chemical power sources for large scale energy storage because of the abundant Na sources and the similar storage mechanism to the counterpart of LIBs4-14. The lack of high performance cathode materials for SIBs is still a big challenge. Some cathode materials for sodium-ion batteries such as phosphates, layered transition oxide materials, and hexacyanoferrate analogues have been reported5,

15-21.

But the overall

electrochemical performances of the cathode materials still can not meet the requirements22-23. The strategy of elements doping (Li24, B25, Mg26, Cu27, Ti28, Co29, Ni, Zn30, Al31-32 et ac) have been extensively applied to

improve their electrochemical

performances. In addition, surface coating is another important strategy. For examples, the coatings of the cathode surfaces by carbon33, Al2O3

34and

graphene32 have been

reported to reduce the side reactions between electrode and electrolyte, which improves the structure stability and cycling performance. However, the strategy to achieve the simultaneous enhancement of the cathode materials in rate capability and cycling stability for SIBs is still highly desired. Herein, we propose a synergetic strategy of Zr4+ doping and ZrO2 coating to simultaneously

enhance

the

rate

capability

and

cycling

stability

of

Na0.67Mn0.7Fe0.2Co0.1O2 as a cathode material for SIBs and the synergetic modification



mechanism of the integrated Zr4+ doping and ZrO2 coating has been unraveled.

2. Experimental 2.1 Materials synthesis Na0.67Mn0.7Fe0.2Co0.1O2 (bareMFC) sample was synthesized using a sol-gel method. The stoichiometric ratio of sodium acetate (3% excess), manganese acetate, iron nitrate and cobalt acetate were dissolved into the mixed solution of citric acid (CA) and ethylene glycol (EG). The mixed solution was dried at 150℃ overnight to obtain a dried porous gel after being aged at 80℃ for 5 hours. Finally, the dried gels were grinded into powder and presinterred at 500℃ for 5 h, and then they were calcined at 900 ℃ for 12 h in air. The sample of [email protected] (ZrO2@MFC) was also synthesized by a sol-gel method. In a typical process, the stoichiometric ratio of sodium acetate (3% excess), manganese acetate, iron nitrate and cobalt acetate were dissolved into the mixed solution of CA and EG. Then a stoichiometric amount of Zr(OC4H9)4 was dissolved in 20ml ethanol and then the solution was added to the above CA/EG mixed solution. Zr4+ and ZrO2 content was set at mass ratios of Zr(OC4H9 )4 /Na0.67Mn0.7Fe0.2Co0.1O2 = 1.5%.

The drying and calcination process is similar to that of

Na0.67Mn0.7Fe0.2Co0.1O2. All of the chemicals above were purchased from China National Medicines Corp. Ltd and used without any further purification. 2.2 Material characterization The crystal structures of the cathode materials were characterized using X-ray diffractometer (XRD, smartlab, CuKα) in the 2θ range of 10°−70° with a step width of


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0.01° and a scan rate of 10°/min. A high-resolution transmission electron microscope (HRTEM, Tecnai G2 F20 S-TWIN, 200 kV) was used to observe the particle shape and morphology of the samples. And the surface element compositions and valences were characterized by an X-ray photo-electronic spectrometer (XPS, Thermo Scientific ESCALAB 250Xi) using nonmonochromated Al Kα X-ray radiation as the excitation source. 2.3 Electrochemical measurements Electrochemical performance tests were carried out using coin cells (R2025) and a metal sodium plate as the counter electrode, 1.0 M NaClO4 in propylene carbonate (PC) as the electrolyte and the glass fiber GF/D (Whatman) as the separator. The active material was mixed with super P carbon and poly(vinylidene fluoride) (PVDF) (mass ratio is 75 : 15 : 10) in N-methylpyrrolidinone (NMP) to form the composite electrode. The loaded mass of the active material on the electrode is about 2.5mg. The slurry was uniformly pasted on an Al foil then dried overnight at 120℃ in a vacuum drying box. The sodium-ion batteries were made in a glove-box filled with Ar gas. Galvanostatic charge-discharge tests were performed in the voltage range of 1.5–4.2 V versus Na+ /Na using an automatic galvanostat (NEWARE) at various current densities, The Cyclic voltammetry (CV) measurements and the Potentiostatic Intermittent Titration Technique (PITT) were performed on an electrochemical work-station (PGSTAT302N, Autolab).

3. Results and discussion 3.1 Structural characterization



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The X-ray diffraction (XRD) patterns and the results of the Rietveld refinement for the as-synthesized bare MFC and ZrO2@MFC are shown in Fig. 1 (a).

As for bare

MFC all the diffraction peaks in the patterns clearly exhibit P2-type structure with the space group of P63/mmc (no. 194). In contrast, ZrO2@MFC has some small peaks labeled by asterisk besides the peaks of P2-type phase, which can be ascribed to ZrO2. As shown in Fig. 1 (b), the (002) peak of ZrO2@ MFC shows a left shift, which corresponds to the increase of the lattice parameter c. The XRD patterns were further refined using Rietveld method as shown in Fig. 1 (c) and

Fig. 1 (d). The fitting factor Rp for the two

samples are 3.63 and 3.18%, respectively, indicating that the refinement results are acceptable. And the ICP data of the bare MFC and ZrO2@MFC cathode materials are as shown in Table S1. The refined crystallographic parameters of the samples are shown in Table 1 and the atoms occupancy information of the samples from reitveld refinement are depicted in Table S2-S3. As shown in Table 1, the interlayer spacing d of ZrO2@MFC is 3.5593 Å much larger than that of bare MFC (3.4102 Å), indicating that part of Zr4+ dope into the host. The expansion of the interlayer spacing d can lower the resistance of Na+ diffusion during charge/discharge process. In addition, the thickness of TMO2 (TM = transition metal) for ZrO2@MFC is thinner than bare MFC, and the length of TM-O/O-O bond of ZrO2@MFC is shorter than that of bare MFC, which is favorable to the stability of the layered structure. In other words, the shortening of TM-O and O-O bonds means a stronger bonding energy, which enhance the structural stability of the layered cathode material35. It should be noted that Na-O bond length of ZrO2@MFC becomes longer in


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compared to bare MFC. This reduces the electrostatic attraction between Na and O, and facilitates Na+ intercalation/extraction. The crystal structure of each sample is constructed based on the refined results as shown in Fig. 1 (e) and (f), respectively.

Figure 1. (a) The XRD patterns;(b) The XRD patterns (002) peak from 15o to 17o (c) and (d) is the refinement results of materials : bare MFC and ZrO2@MFC, respectively; Refined crystal structure of (e) bare MFC and (f)ZrO2@MFC. *represents the phase of ZrO2.



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Table 1 The refined crystallographic parameters of the cathode materials. Samples

MFC

ZrO2@MFC

a/Å c/Å V(Å3) d (Å) Na-O(Å) TMO2(Å) O-O(Å) TM-O(Å) Rp (%)

2.9035 (3) 11.1921 (4) 81.71(2) 3.4102 2.3911 2.18585 2.7546 2.0011 3.63

2.908 (4) 11.2154 (5) 82.14(6) 3.5593 2.4466 2.0484 2.6485 1.9667 3.18

Fig. 2 SEM images at the same magnifications for the samples. (a) bare MFC and; (b) ZrO2@ MFC.


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Figure 3 (a) HRTEM images and (b) the SAED pattern of the area marked in the red circle of bare MFC sample ;(c) HRTEM images and (d) the SAED pattern of the area marked in the red circle of [email protected] sample.

Fig. 2 show the SEM images of the two samples. SEM images of the two samples indicate that the samples have a similar plate-like morphology with a thickness of about 300-400 nm. Fig. 3 show the HRTEM images of the two samples. For the sample of ZrO2@MFC a non-uniform layer of ZrO2 formed on the surface as shown in Fig. 3 (c). EDS mapping was further to confirm the coating layer as shown in Fig. S1. The selected area electron diffraction patterns of MFC and ZrO2@MFC are shown in Fig. 3 (b) and (d), respectively. As shown in Fig. 3 (d) there are some diffraction spots of ZrO2 in ZrO2@MFC, which is in well agreement with the analysis of XRD.



Figure 4 XPS patterns of the cathode samples (a) Mn; (b)Fe;(c)Co;(d)Zr

The X-ray photoelectron spectroscopy (XPS) was used to analyze the surface oxidation states of the two cathode materials. The main peak of Mn 2p3/2 is divided into two peaks at 641.0 and 642.3 eV as shown in Fig. 4 (a), which indicated the existence of Mn3+ and Mn4+. The ratio of the Mn3+ and Mn4+ was further analyzed. The results indicated that Mn3+/Mn4+ is 0.66 and 0.62 for MFC and ZrO2@MFC, respectively. This means that the ralative content of Mn3+ is reduced in ZrO2@MFC. Mn3+ is one main cause of Jahn-Teller distortion, and the reduction of Mn3+/Mn4+ in ZrO2@MFC is favorable to the structure stability. As shown in Fig. 4 (b), the peak at around 710.6 eV can be ascribed to Fe 2p3/2 indicating the presence of Fe3+. The peak of Co 2p3/2 (Fig. 4 c) at about 780 eV indicating the existence of the Co3+. The peak at about 181.1 Ev (Fig.


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4 d) confirms the existence of Zr4+36-38, which is in consistence with the tetravalent electronic state of Zr in ZrO2 layer. 3.2 Results and discussion of electrochemical properties

Figure 5 The CV curves of as-prepared cathodes with the scan rate of 0.1mV/s: (a) bare MFC ; (b) ZrO2@MFC.

Fig. 5 shows the cyclic voltamogram curves of the bare MFC and ZrO2@MFC cathode material vs Na cells in the voltage range of 1.5−4.2 V with a scan rate of 0.1 mVs

−1,

which reveal three current pulse peaks at 2.389, 3.25, 3.542V in the anodic

sweep and further indicate a reversible sodium insertion-deinsertion process. In bare MFC cathode material, the redox reaction couple of the Mn4+/Mn3+, Fe4+/Fe3+ and Co4+/Co3+ are located at the 2.389V/1.99V, 3.25V/3.08V, 3.542V/3.46V, respectively39-43. ∆V are 0.399, 0.17 and 0.082V, respectively. In contrast, as for ZrO2@MFC cathode material, the redox reaction couple of the Mn4+/Mn3+, Fe4+/Fe3+ and Co4+/Co3+ are located at the 2.32V/2.02V, 3.07/2.98V, 3.49V/3.44V, respectively. ∆V are 0.3, 0.09 and 0.05V, respectively. The results show that the polarization for ZrO2@MFC cathode is greatly reduced and the charge/discharge reversibility is improved.



Figure 6(a) Rate capabilities test at different current densities (1C = 200 mAh g-1); Charge and discharge curves at different rate : (b) bare MFC ; (c) ZrO2@MFC

Fig. 6(a) and Fig. 6 (b), Fig. 6 (c), show the rate capabilities and charge and discharge curves of the bare MFC and ZrO2@MFC at different current densities (1C = 200 mAh g-1) in the voltage range of 1.5–4.2 V. From Fig. 6(a), we can see that the rate


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capability of ZrO2@MFC cathode material is much better than bare MFC. As is shown in Fig. 6(b), the discharge capacity for bare MFC is 158, 145, 138, 122, 101, 80, 47, 41 and 38 mAh g-1 at 0.05, 0.1, 0.2, 0.5, 1, 2, 5, 8 and 10C, respectively. In contrast, for ZrO2@MFC the corresponding capacity is increased to 171, 162, 145, 140, 123, 104, 75, 58 and 45 mAh g-1 at 0.05, 0.1, 0.2, 0.5, 1, 2, 5, 8 and 10C were shown in Fig. 6(c), respectively. The enhancement of the rate capability can be largely attributed to the expansion of the interlayer spacing and Na-O bond length, which reduces the Na+ migration barrier and enhances the rate capability.



Figure 7 Cycling performance of cathodes at different current densities and corresponding charge and discharge profiles: (a) cycling performance at 0.1C; (b) cycling charge and discharge profiles of bare MFC ; (c) cycling charge and discharge profiles of ZrO2@MFC; (d) cycling performance at 1C; (e) cycling charge and discharge profiles of bare MFC ; (f) cycling charge and discharge profiles of ZrO2@MFC.

In order to clearly evaluate the cyclic stability of the cathode materials, and explain the synergic effect of Zr doping and ZrO2 coating on the stability, the cyclic capacities of


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the electrodes were tested at 0.1C and 1C (1C = 200mAh/g-1), respectively, as shown in Fig. 7(a) and (b). The capacity retention at 0.1C for bare MFC and ZrO2@MFC is 82 and 89%, respectively. At a high current density of 1C, they are 69% and 84 %, respectively. The results indicate that ZrO2@MFC shows a much better cycling stability than bare MFC particularly at a high current density. The performance of ZrO2@MFC are also better than some previously reported P2-type cathode materials (Table S4). The improvement of the cycling stability can be firstly attributed to the protection of ZrO2 coating. The layer of ZrO2 can reduce the side effects between the electrode and electrolyte, which stabilize the layered structure. In addition, doping of Zr4+ also reduces the bond length of TM-O/O-O and increase the bonding energy, which further enhances the stability of the layered structure44. This is also in agreement with the their bonding energy. △Hf298K(Zr-O) (760 kJmol-1) is larger than△Hf298K(Fe-O, 409 kJmol-1),

△Hf298K(Mn-O, 402 kJmol-1) or △Hf298K(Co-O, 368 kJmol-1).



Figure 8 The relationship of the transition current (I) depending on the titration time (t) at different discharge potentials. (a) bare MFC, (b) ZrO2@MFC, and (c) the comparison of the estimated diffusion coefficient.

Potentiostatic Intermittent Titration Technique (PITT) was used to test Na+ diffusion ability. The Na-ion diffusion coefficients can be calculated by the following equation : 𝐃=

𝒅𝒍𝒏(𝑰) 𝒅𝒕

𝟒𝑳𝟐

𝒆𝒙𝒑 𝝅𝟐 , where the L is the characteristic diffusion length, the I is the titration


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current, the D is the diffusion coefficient. The

𝒅𝒍𝒏(𝑰) 𝒅𝒕

is the slope of the linear regions of

the ln(I) vs. the t plots, which can be obtained from the relationship of the transition current (I) depending on time (t), as shown in Fig. 8(a) and (b) . The calculated Na-ion diffusion coefficients are shown in Fig. 8 (c) and ZrO2@MFC has a larger Na-ion diffusion coefficient than bare MFC. This is also in accordance with the improved rate capability as well as the enlargement of d spacing and Na-O bond length.

Figure 9 (a) In situ XRD patterns collected during the cyclic voltammograms of ZrO2@MFC with the scan rate of 0.2 mV/s. (b) The point corresponding to test the in situ XRD patterns on the CV curves.

In situ XRD was further performed to investigate the structure evolution of ZrO2@MFC during the sodiation/desodiation as shown in Fig. 9(a). Each XRD pattern corresponds to each point from “Ao” to “END” on the cyclic voltammograms curve as shown in Fig. 9(b). As shown in Fig. 9, the four peaks of (002), (004), (100) and (102) all show a similar shift. As we all known, the shift of the peak of (002) and (004) reflect the change of the lattice parameter c, and the transformation of the peak of (100) and (102) reveal the change of the lattice parameter a and b45-48. From Fig. 9, we can see that the structural change of the cathode material is also a reversible process. In addition, there



are no undesired peaks beyond the P2-type structure during charge/discharge process, which further indicates the stability of the layered structure of ZrO2@MFC.

4. Conclusions A synergetic modification strategy, which combines the advantages of Zr4+ doping and ZrO2 coating, has been proposed to simultaneously enhance the rate capability and cycling stability of Na0.67Mn0.7Fe0.2Co0.1O2 as a cathode material for SIBs. The synergetic modification mechanism of Zr4+ doping and ZrO2 coating has been unraveled. The expansion of the interlayer spacing and Na-O bond length induced by Zr4+ doping lowers Na+ migration barrier and facilitates electronic conductivity and Na+ diffusion, which enhances the rate capability. Moreover, the doping of Zr4+ also shrinks TM-O/O-O bonds and the thickness of TMO2 slabs which increases their bonding energy and enhances the layered structure stability. In addition, the ratio of Mn3+/Mn4+ is also decreased benefiting to the structure stability. Last but no least, ZrO2 coating mitigates the side reactions between the electrode and electrolyte, which also largely improves the layered structure stability and cycling stability.

ASSOCIATED CONTENT Supporting Information ICP data, atoms occupancy of Na0.67Mn0.7Fe0.2Co0.1O2 and [email protected] and performance comparisons with other P2-type cathode materials. This material is available free of charge via the internet at http://pubs.acs.org.

AUTHOR INFORMATION ACS Paragon Plus Environment

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*Corresponding

Author: [email protected] University of Chinese Academy of Sciences,

Beijing 100049,

China. Tel. +86 10 8825 6840

Acknowledgements This work was supported by National Natural Science Foundation of China (Grant 11575192 and 11675267), the Scientific Instrument Developing Project (Grant No.ZDKYYQ20170001),

the

International

Partnership

Program

(Grant

No.

211211KYSB20170060), the Strategic Priority Research Program (Grant No. XDB28000000), and “Hundred Talents Project” of the Chinese Academy of Sciences, and Natural Science Foundation of Beijing Municipality (Grant No. 2182082) .

Reference (1) Palomares, V.; Casas-Cabanas, M.; Castillo-Martínez, E.; Han, M. H.; Rojo, T. Update on Na-based battery materials. A growing research path. Energy Environ. Sci. 2013, 6 (8), 2312-2337. (2) Yoon, C. S.; Kim, U.-H.; Park, G.-T.; Kim, S. J.; Kim, K.-H.; Kim, J.; Sun, Y.-K., Self-Passivation of a Linio2 Cathode for a Lithium-Ion Battery through Zr Doping. ACS Energy Lett. 2018, 3, 1634-1639. (3) Park, K.-J.; Choi, M.-J.; Maglia, F.; Kim, S.-J.; Kim, K.-H.; Yoon, C. S.; Sun, Y.-K., High-Capacity Concentration Gradient Li[Ni0.865Co0.120Al0.015]O2 Cathode for Lithium-Ion Batteries. Adv. Energy Mater. 2018, 8, 1703612. (4) Pan, H.; Hu, Y.-S.; Chen, L. Room-temperature stationary sodium-ion batteries for large-scale electric energy storage. Energy Environ. Sci. 2013, 6 (8), 2338-2360. (5) Han, M. H.; Gonzalo, E.; Casas-Cabanas, M.; Rojo, T. Structural evolution and electrochemistry of monoclinic NaNiO2 upon the first cycling process. J. Power Sources. 2014, 258, 266-271. (6) Palomares, V.; Serras, P.; Villaluenga, I.; Hueso, K. B.; Carretero-González, J.; Rojo, T. Na-ion batteries, recent advances and present challenges to become low cost energy storage systems. Energy Environ. Sci. 2012, 5 (3), 5884-5901. (7) Zhu, Z.; Li, H.; Liang, J.; Tao, Z.; Chen, J. The disodium salt of 2,5-dihydroxy-1,4-benzoquinone as anode material for rechargeable sodium ion batteries. Chem. Commun. 2015, 51 (8), 1446-1448. (8) Hwang, J. Y.; Myung, S. T.; Sun, Y. K. Sodium-ion batteries: present and future. Chem. Soc. Rev. 46 (12), 3529-3614.


2017,


Page 20 of 23

(9) Cao, C.; Liu, W.; Tan, L.; Liao, X.; Li, L. Sodium-ion batteries using ion exchange membranes as electrolytes and separators. Chem. Commun. 2013, 49 (100), 11740-11742. (10) Liu, Y.; Liu, X.; Wang, T.; Fan, L.-Z.; Jiao, L. Research and application progress on key materials for sodium-ion batteries. Sustainable Energy. Fuels. 2017, 1 (5), 986-1006. (11) Guo, S.; Yi, J.; Sun, Y.; Zhou, H. Recent advances in titanium-based electrode materials for stationary sodium-ion batteries. Energy Environ. Sci. 2016, 9 (10), 2978-3006. (12) Shi, L.; Zhao, T. Recent advances in inorganic 2D materials and their applications in lithium and sodium batteries. J. Mater. Chem. A. 2017, 5 (8), 3735-3758. (13) Di Lecce, D.; Campanella, D.; Hassoun, J., Insight on the Enhanced Reversibility of a Multimetal Layered Oxide for Sodium-Ion Battery. The J.Phy. Chem. C. 2018. (DOI: 10.1021/acs.jpcc.8b07596) (14) Wang, K.; Yan, P.; Sui, M., Phase Transition Induced Cracking Plaguing Layered Cathode for Sodium-Ion Battery. Nano Energy. 2018, 54, 148-155. (15) Wang, L.; Wang, J.; Zhang, X.; Ren, Y.; Zuo, P.; Yin, G.; Wang, J. Unravelling the origin of irreversible capacity loss in NaNiO2 for high voltage sodium ion batteries. Nano Energy. 2017, 34, 215-223. (16) Manikandan, P.; Ramasubramonian, D.; Shaijumon, M. M. Layered P2-type Na 0.5 Ni 0.25 Mn 0.75 O 2 as a high performance cathode material for sodium-ion batteries. Electrochim. Acta. 2016, 206, 199-206. (17) Guo, H.; Wang, Y.; Han, W.; Yu, Z.; Qi, X.; Sun, K.; Hu, Y.-S.; Liu, Y.; Chen, D.; Chen, L. Na-deficient O3-type cathode material Na0.8[Ni0.3Co0.2Ti0.5]O2 for room-temperature sodium-ion batteries. Electrochim. Acta. 2015, 158, 258-263. (18) Li, Y.; Yang, Z.; Xu, S.; Mu, L.; Gu, L.; Hu, Y. S.; Li, H.; Chen, L. Air-Stable Copper-Based P2-Na7/9Cu2/9Fe1/9Mn2/3O2 as a New Positive Electrode Material for Sodium-Ion Batteries. Adv. Sci.

2015,

2 (6), 1500031. (19) Hasa, I.; Dou, X.; Buchholz, D.; Shao-Horn, Y.; Hassoun, J.; Passerini, S.; Scrosati, B. A sodium-ion battery exploiting layered oxide cathode, graphite anode and glyme-based electrolyte. J. Power Sources. 2016, 310, 26-31. (20) Hasa, I.; Passerini, S.; Hassoun, J. Toward high energy density cathode materials for sodium-ion batteries: investigating the beneficial effect of aluminum doping on the P2-type structure. J. Mater. Chem. A. 2017, 5 (9), 4467-4477. (21) Ortiz-Vitoriano, N.; Drewett, N. E.; Gonzalo, E.; Rojo, T. High performance manganese-based layered oxide cathodes: overcoming the challenges of sodium ion batteries. Energy. Environ Sci. 2017, 10 (5), 1051-1074. (22) Su, D.; Zhang, J.; Dou, S.; Wang, G. Polypyrrole hollow nanospheres: stable cathode materials for sodium-ion batteries. Chem.commun. 2015, 51 (89), 16092-16095. (23) Song, W.; Ji, X.; Wu, Z.; Zhu, Y.; Li, F.; Yao, Y.; Banks, C. E. Multifunctional dual Na3V2(PO4)2F3cathode for both lithium-ion and sodium-ion batteries. RSC. Adv. 2014, 4 (22), 11375-11383..


Page 21 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(24) Li, Z.-Y.; Zhang, J.; Gao, R.; Zhang, H.; Zheng, L.; Hu, Z.; Liu, X. Li-Substituted Co-Free Layered P2/O3 Biphasic Na0.67Mn0.55Ni0.25Ti0.2–xLixO2 as High-Rate-Capability Cathode Materials for Sodium Ion Batteries. The J. Phy. Chem. C. 2016, 120 (17), 9007-9016. (25) Vaalma, C.; Buchholz, D.; Passerini, S. Beneficial effect of boron in layered sodium-ion cathode materials – The example of Na2/3B0.11Mn0.89O2. J.Power Sources. 2017, 364, 33-40. (26) Hou, H.; Gan, B.; Gong, Y.; Chen, N.; Sun, C. P2-Type Na0.67Ni0.23Mg0.1Mn0.67O2 as a High-Performance Cathode for a Sodium-Ion Battery. Inorg. Chem. 2016, 55 (17), 9033-9037. (27) Ramasamy, H. V.; Kaliyappan, K.; Thangavel, R.; Aravindan, V.; Kang, K.; Kim, D. U.; Park, Y.; Sun, X.; Lee, Y.-S. Cu-doped P2-Na0.5Ni0.33Mn0.67O2 encapsulated with MgO as a novel high voltage cathode with enhanced Na-storage properties. J. Mater. Chem. A. 2017, 5 (18), 8408-8415. (28) Sun, X.; Jin, Y.; Zhang, C.-Y.; Wen, J.-W.; Shao, Y.; Zang, Y.; Chen, C.-H. Na[Ni0.4Fe0.2Mn0.4−xTix]O2: a cathode of high capacity and superior cyclability for Na-ion batteries. J. Mater. Chem. A. 2014, 2 (41), 17268-17271. (29) Li, Z. Y.; Zhang, J.; Gao, R.; Zhang, H.; Hu, Z.; Liu, X. Unveiling the Role of Co in Improving the High-Rate Capability and Cycling Performance of Layered Na0.7Mn0.7Ni0.3-xCoxO2 Cathode Materials for Sodium-Ion Batteries. ACS Appl. Mater. Interfaces. 2016, 8 (24), 15439-15448. (30) Kumakura, S.; Tahara, Y.; Sato, S.; Kubota, K.; Komaba, S. P′2-Na2/3Mn0.9Me0.1O2 (Me = Mg, Ti, Co, Ni, Cu, and Zn): Correlation between Orthorhombic Distortion and Electrochemical Property. Chem. Mater. 2017, 29 (21), 8958-8962. (31) Pang, W.-L.; Zhang, X.-H.; Guo, J.-Z.; Li, J.-Y.; Yan, X.; Hou, B.-H.; Guan, H.-Y.; Wu, X.-L. P2-type Na 2/3Mn1-xAlxO2

cathode material for sodium-ion batteries: Al-doped enhanced electrochemical properties

and studies on the electrode kinetics. J. Power Sources. 2017, 356, 80-88. (32) Zhang, X. H.; Pang, W. L.; Wan, F.; Guo, J. Z.; Lu, H. Y.; Li, J. Y.; Xing, Y. M.; Zhang, J. P.; Wu, X. L. P2-Na2/3Ni1/3Mn5/9Al1/9O2 Microparticles as Superior Cathode Material for Sodium-Ion Batteries: Enhanced Properties and Mechanisam via Graphene Connection. ACS appl. mater. Interfaces. 2016, 8 (32), 20650-20659. (33) Li, M.; Xiao, X.; Fan, X.; Huang, X.; Liu, Y.; Chen, L. Carbon coated sodium-titanate nanotube as an advanced intercalation anode material for sodium-ion batteries. J. Alloys and Compounds

2017, 712,

365-372. (34) Liu, Y.; Fang, X.; Zhang, A.; Shen, C.; Liu, Q.; Enaya, H. A.; Zhou, C. Layered P2-Na2/3[Ni 1/3 Mn2/3]O2 as high-voltage cathode for sodium-ion batteries: The capacity decay mechanism and Al2O3 surface modification. Nano Energy. 2016, 27, 27-34. (35) Li, Z.-Y.; Gao, R.; Zhang, J.; Zhang, X.; Hu, Z.; Liu, X. New insights into designing high-rate performance cathode materials for sodium ion batteries by enlarging the slab-spacing of the Na-ion diffusion layer. J. Mater. Chem. A. 2016, 4 (9), 3453-3461. (36) Bespalov, I.; Datler, M.; Buhr, S.; Drachsel, W.; Rupprechter, G.; Suchorski, Y. Initial stages of oxide formation on the Zr surface at low oxygen pressure: An in situ FIM and XPS study. Ultramicroscopy.



2015, 159 Pt 2, 147-151. (37) Yang, H.; Qian, Z.; Zhang, G.; Nie, J.; Liu, X. The grain refinement performance of B-doped TiC on Zr-containing Al alloys. J.Alloys and Compounds. 2018, 731, 774-783. (38) Skoryna, J.; Pacanowski, S.; Marczyńska, A.; Werwiński, M.; Rogowska, A.; Wachowiak, M.; Majchrzycki, Ł.; Czajka, R.; Smardz, L. XPS valence band studies of nanocrystalline Zr Pd alloy thin films. Surface and Coatings Technology. 2016, 303, 125-130. (39) Wang, K.; Wu, Z.-G.; Zhang, T.; Deng, Y.-P.; Li, J.-T.; Guo, X.-D.; Xu, B.-B.; Zhong, B.-H. P2-type Na0.67Mn0.72Ni0.14Co0.14O2 with K + doping as new high rate performance cathode material for sodium-ion batteries. Electrochim. Acta. 2016, 216, 51-57. (40) Chu, S.; Wei, S.; Chen, Y.; Cai, R.; Liao, K.; Zhou, W.; Shao, Z. Optimal synthesis and new understanding of P2-type Na

2/3

Mn

1/2

Fe

1/4

Co

1/4

O 2 as an advanced cathode material in sodium-ion

batteries with improved cycle stability. Ceramics International. 2018, 44 (5), 5184-5192. (41) Song, X.; Zhou, X.; Deng, Y.; Nan, J.; Shu, D.; Cai, Z.; Huang, Y.; Zhang, X. Synthesis of NaxMn0.54Ni0.13Fe0.13O2 with P2-type hexagonal phase as high-performance cathode materials for sodium-ion batteries. J.Alloys and Compounds. 2018, 732, 88-94. (42) Bao, S.; Luo, S.; Wang, Z.; Wang, Q.; Hao, A.; Zhang, Y.; Wang, Y. The critical role of sodium content on structure, morphology and electrochemical performance of layered P2-type NaxNi0.167Co0.167Mn0.67O2 for sodium ion batteries. J. Power Sources. 2017, 362, 323-331. (43) Rangasamy, V. S.; Zhang, L.; Seo, J. W.; Locquet, J.-P.; Thayumanasundaram, S. Enhanced electrochemical performance of Na2/3[Mn0.55Ni0.30Co0.15]O2 positive electrode in sodium-ion batteries by functionalized multi-walled carbon nanotubes. Electrochim. Acta. 2017, 237, 29-36. (44) Li, Z.-Y.; Gao, R.; Sun, L.; Hu, Z.; Liu, X. Zr-doped P2-Na0.75Mn0.55Ni0.25Co0.05Fe0.10Zr0.05O2 as high-rate performance cathode material for sodium ion batteries. Electrochim. Acta. 2017, 223, 92-99. (45) Dose, W. M.; Sharma, N.; Pramudita, J. C.; Kimpton, J. A.; Gonzalo, E.; Han, M. H.; Rojo, T. Crystallographic Evolution of P2 Na2/3Fe0.4Mn0.6O2 Electrodes during Electrochemical Cycling. Chem. Mater. 2016, 28 (17), 6342-6354. (46) Song, J.; Gim, J.; Park, S.; Kim, J. Sodium manganese oxide electrodes accompanying self-ion exchange for lithium/sodium hybrid ion batteries. Electrochim. Acta. 2018, 261, 42-48. (47) Wang, H.; Gao, R.; Li, Z.; Sun, L.; Hu, Z.; Liu, X. Different Effects of Al Substitution for Mn or Fe on the Structure and Electrochemical Properties of Na0.67Mn0.5Fe0.5O2 as a Sodium Ion Battery Cathode Material. Inorg. Chem. 2018, 57 (9), 5249-5257. (48) Tapia-Ruiz, N.; Dose, W. M.; Sharma, N.; Chen, H.; Heath, J.; Somerville, J. W.; Maitra, U.; Islam, M. S.; Bruce, P. G. High voltage structural evolution and enhanced Na-ion diffusion in P2-Na2/3Ni1/3−xMgxMn2/3O2 (0 ≤ x ≤ 0.2) cathodes from diffraction, electrochemical and ab initio studies. Energy Environ. Sci. 2018.


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Enhancing the Rate Capability and Cycling Stability of Na0.67Mn0

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