Optimization of Layered Cathode Materials for Lithium-Ion Batteries
"> Figure 1
<p>Schematic figure of a Li-ion battery. LiCoO<sub>2</sub> is used as a cathode and graphite as an anode.</p> "> Figure 2
<p>Schematic representation of the energy diagram vs. density of states for Li<sub>x</sub>Ni<sub>1/3</sub>Mn<sub>1/3</sub>Co<sub>1/3</sub>O<sub>2</sub> at different charge states. The Fermi level of the cathode material is represented for three state of charge. (<b>a</b>) Full discharge; (<b>b</b>) half discharge; (<b>c</b>) full charge.</p> "> Figure 3
<p>Ternary phase diagram of the mixed transition-metal oxides LiNi<sub>w</sub>Mn<sub>y</sub>Co<sub>z</sub>O<sub>2</sub> (<span class="html-italic">w</span> + <span class="html-italic">y</span> + <span class="html-italic">z</span> = 1) formed by the LiCoO<sub>2</sub>-LiNiO<sub>2</sub>-LiMnO<sub>2</sub> solid solutions. The compounds studied in this work are marked in red. The samples are noted (<span class="html-italic">w’y’z’</span>) where <span class="html-italic">w</span><span class="html-italic">’</span> = 10<span class="html-italic">w</span>, <span class="html-italic">y’ =</span> 10<span class="html-italic">y</span> and <span class="html-italic">z’ =</span> 10<span class="html-italic">z</span>.</p> "> Figure 4
<p>HRTEM images of LiNi<sub>0.55</sub>Co<sub>0.45</sub>O<sub>2</sub> layered powders with different particle sizes: ca. 100–150 nm (<b>a</b>) and 1.5–2.0 µm (<b>b</b>) and discharge profiles as a function of C-rate for Li//LiNi<sub>0.55</sub>Co<sub>0.45</sub>O<sub>2</sub> coin-type cells with two cathode materials of 100 nm and 2 µm particle size. The good crystallinity of powders is shown by the electron diffraction diagram (inset); (<b>c</b>) discharge curves for 100–150 nm; (<b>d</b>) discharge curves for 1.5–2.0 µm.</p> "> Figure 5
<p>SEM images of NMC samples: (<b>a</b>) 333; (<b>b</b>) 442; and (<b>c</b>) 532 compounds prepared by solid-state reaction at 850 °C in air.</p> "> Figure 6
<p>Rietveld refinement patterns of NMC samples: (<b>a</b>) 333; (<b>b</b>) 442; (<b>c</b>) 532 synthesized by solid-state reaction. The cross marks show observed XRD intensities and the solid line (red) represents calculated intensities. The curve at the bottom (blue) is the difference between the calculated and observed intensities on the same scale.</p> "> Figure 7
<p>Typical discharge profiles of different Li//NMC cells with cathodes synthesized by the solid-state reaction route at 850 °C. The electrochemical test were carried out at discharge rate C/5 in the voltage window 2.8–4.6 V vs. Li<sup>0</sup>/Li<sup>+</sup>.</p> "> Figure 8
<p>Discharge profiles vs. specific capacity of the Li//LiNi<sub>0.4</sub>Mn<sub>0.4</sub>Co<sub>0.2</sub>O<sub>2</sub> cells between 2.5 and 4.4 V at various C-rates. The inset shows the rate capability of the 442 compound.</p> "> Figure 9
<p>SEM (<b>a</b>) and HRTEM (<b>b</b>) images of Li<sub>1.04</sub>Ni<sub>0.32</sub>Mn<sub>0.32</sub>Co<sub>0.32</sub>O<sub>2</sub> powders synthesized the co-precipitation method from hydroxide precursor assisted by ammonium and sodium hydroxides.</p> "> Figure 10
<p>Electrochemical performance of Li<sub>1+x</sub>(NMC)<sub>1-x</sub>O<sub>2</sub> electrode materials as a function of synthetic parameters. The specific capacity of the Li cells is plotted for different C-rates.</p> "> Figure 11
<p>(<b>a</b>) TG/DTA profile for the precursor of NMC synthesized by the co-precipitation technique using metal acetates as raw materials and succinic acid as a polymeric agent with a chelate to metal ion molar ratio <span class="html-italic">R</span> = 0.5 (<b>a</b>) and <span class="html-italic">R</span> = 2 (<b>b</b>). With <span class="html-italic">R</span> = 2, the combustion temperature is lowered to 342 °C.</p> "> Figure 12
<p>(<b>a</b>) Rietveld refinement patterns of NMC synthesized at <span class="html-italic">R</span> = 2 via wet chemical method (<span class="html-italic">R</span><sub>p</sub> = 9.8%). The plus marks show observed X-ray diffraction intensities and the solid line (in red on the web version) represents calculated intensities. The curve at the bottom (in blue on the web version) is the difference between the calculated and observed intensities on the same scale; (<b>b</b>) The concentration of Ni(3<span class="html-italic">b</span>) defects (site-exchange rate of the Li<sup>+</sup>/Ni<sup>2+</sup> cation mixing) as a function of the <span class="html-italic">R</span> parameter for the symmetric NMC compounds.</p> "> Figure 13
<p>(<b>a</b>,<b>b</b>) SEM images of NMC synthesized at <span class="html-italic">R</span> = 2 via wet chemical method at different magnifications; (<b>c</b>) HRTEM image showing the fringe system corresponding to the spacing between (003) lattice planes in the <math display="inline"> <semantics> <mrow> <mi>R</mi> <mover accent="true"> <mn>3</mn> <mo stretchy="true">¯</mo> </mover> <mi>m</mi> </mrow> </semantics> </math> space group.</p> "> Figure 14
<p>Initial discharge profiles of synthesized NMC sample sintered at 900 °C for 15 h, synthesized with chelate to metal ion ratio at 0.5 ≤ <span class="html-italic">R</span> ≤ 3.0.</p> "> Figure 15
<p>Peukert plots showing the difference in the electrochemical performance of LiNi<sub>1/3</sub>Mn<sub>1/3</sub>Co<sub>1/3</sub>O<sub>2</sub> electrodes synthesized using wet-chemical method assisted by oxalic and tartaric acid.</p> "> Figure 16
<p>Initial capacity loss of LiNi<sub>1/3</sub>Mn<sub>1/3</sub>Co<sub>1/3</sub>O<sub>2</sub> electrodes cycled at C/20 as a function of the annealing temperature.</p> "> Figure 17
<p>(<b>a</b>–<b>c</b>) TEM images of individual LiNi<sub>0.33+<span class="html-italic">δ</span></sub>Mn<sub>0.33+<span class="html-italic">δ</span></sub>Co<sub>0.33-2<span class="html-italic">δ</span></sub>O<sub>2</sub> nanoparticles with <span class="html-italic">δ</span> = 0.025, 0.05, and 0.075, respectively; (<b>d</b>) HRTEM image of a nanoparticle (<span class="html-italic">δ</span> = 0.025) showing lattice fringes consistent with the interspacing of the (003) planes of the <math display="inline"> <semantics> <mrow> <mi>R</mi> <mover accent="true"> <mn>3</mn> <mo stretchy="true">¯</mo> </mover> <mi>m</mi> </mrow> </semantics> </math> layered structure.</p> "> Figure 18
<p>Evolution of the strain (<<span class="html-italic">e</span><sup>2</sup>>)<sup>1/2</sup> with the deviation from stoichiometry <span class="html-italic">δ</span> in LiNi<sub>0.33+<span class="html-italic">δ</span></sub>Mn<sub>0.33+<span class="html-italic">δ</span></sub>Co<sub>0.33-2<span class="html-italic">δ</span></sub>O<sub>2</sub> samples synthesized by the sol-gel method.</p> "> Figure 19
<p>Peukert plots for Li//LiNi<sub>0.33+<span class="html-italic">δ</span></sub>Mn<sub>0.33+<span class="html-italic">δ</span></sub>Co<sub>0.33-2<span class="html-italic">δ</span></sub>O<sub>2</sub> cells.</p> "> Figure 20
<p>HRTEM images of Li-rich cathode materials <span class="html-italic">y</span>Li<sub>2</sub>MnO<sub>3</sub>•(1 − <span class="html-italic">y</span>)(LiNi<sub>0.5</sub>Mn<sub>0.5</sub>O<sub>2</sub>). (<b>a</b>) <span class="html-italic">y</span> = 0.0 (LiNi<sub>0.5</sub>Mn<sub>0.5</sub>O<sub>2</sub>); (<b>b</b>) <span class="html-italic">y</span> = 0.3 (Li<sub>1.134</sub>Ni<sub>0.3</sub>Mn<sub>0.566</sub>O<sub>2</sub>); (<b>c</b>) <span class="html-italic">y</span> = 0.5 (Li<sub>1.2</sub>Ni<sub>0.2</sub>Mn<sub>0.6</sub>O<sub>2</sub>); (<b>d</b>) image magnification for Li<sub>1.2</sub>Ni<sub>0.2</sub>Mn<sub>0.6</sub>O<sub>2</sub> showing the hexagonal shape of nanoparticles.</p> "> Figure 21
<p>Charge–discharge profiles of Li//Li(Ni<sub>x</sub>Li<sub>(1/3-2x/3)</sub>Mn<sub>(2/3-x/3)</sub>)O<sub>2</sub> coin cells: (<b>a</b>) LiNi<sub>0.5</sub>Mn<sub>0.5</sub>O<sub>2</sub>; (<b>b</b>) Li<sub>1.134</sub>Ni<sub>0.3</sub>Mn<sub>0.556</sub>O<sub>2</sub>; and (<b>c</b>) Li<sub>1.2</sub>Ni<sub>0.2</sub>Mn<sub>0.6</sub>O<sub>2</sub>. Cycles were carried out at C/10 rate (30 mA·g<sup>−1</sup>) in the potential range 2.0–4.8 V vs. Li<sup>0</sup>/Li<sup>+</sup>.</p> "> Figure 22
<p>The first charge–discharge profile of a Li//Li<sub>1.2</sub>Ni<sub>0.2</sub>Mn<sub>0.6</sub>O<sub>2</sub> cell cycled at C/10, showing the mechanism of the activation of Li<sub>2</sub>MnO<sub>3</sub> and LiNi<sub>0.5</sub>Mn<sub>0.5</sub>O<sub>2</sub> components.</p> "> Figure 23
<p>Cyclic performance of Li//Li(Ni<sub>x</sub>Li<sub>(1/3-2x/3)</sub>Mn<sub>(2/3-x/3)</sub>)O<sub>2</sub> electrodes at C/10.</p> ">
Abstract
:1. Introduction
2. Experimental
2.1. Synthesis Procedures
2.2. Characterizations
2.3. Electrochemical Tests
3. Results and Discussion
3.1. The Effect of Particle Size
3.2. The Effect of Cationic Mixing
3.3. Adjustment of the Li/M Ratio
3.4. Effect of the Chelating Agent
3.5. Effect of the Synthesis Recipe
3.6. Effect of Small Deviation of Co Content
3.7. Layered-Layered Integrated Materials
4. Concluding Remarks
Acknowledgments
Author Contributions
Conflicts of Interest
References
- Julien, C.M.; Mauger, A.; Vijh, A.; Zaghib, K. Lithium Batteries: Science and Technology; Springer: Heidelberg, Germany, 2015; p. 630. [Google Scholar]
- Julien, C.M.; Mauger, A.; Zaghib, K.; Groult, H. Comparative issues of cathode materials for Li-ion batteries. Inorganics 2014, 2, 132–154. [Google Scholar] [CrossRef]
- Zaghib, K.; Mauger, A.; Groult, H.; Goodenough, J.B.; Julien, C.M. Advanced electrode of high-power Li-ion batteries. Materials 2013, 6, 1028–1049. [Google Scholar] [CrossRef]
- Fergus, J.W. Recent developments in cathode materials for lithium ion batteries. J. Power Sources 2010, 195, 939–954. [Google Scholar] [CrossRef]
- Mauger, A.; Julien, C.M. Nanoscience supporting the research on the negative electrodes of Li-ion batteries. Nanomaterials 2015, 5, 2279–2301. [Google Scholar] [CrossRef]
- Vediappan, K.; Guerfi, A.; Gariépy, V.; Demopoulos, G.P.; Hovington, P.; Trottier, J.; Mauger, A.; Zaghib, K.; Julien, C.M. Stirring effect in hydrothermal synthesis of C-LiFePO4. J. Power Sources 2014, 266, 99–106. [Google Scholar] [CrossRef]
- Hovington, P.; Lagacé, M.; Guerfi, A.; Bouchard, P.; Mauger, A.; Julien, C.M.; Armand, M.; Zaghib, K. New lithium metal polymer solid state battery for an ultrahigh energy: Nano C-LiFePO4 versus nano Li1.2V3O8. Nano Lett. 2015, 15, 2671–2678. [Google Scholar] [CrossRef] [PubMed]
- Liu, Z.; Yu, A.; Lee, J.Y. Synthesis and characterization of LiNi1-x-yCoxMnyO2 as the cathode materials of secondary lithium batteries. J. Power Sources 1999, 81–82, 416–419. [Google Scholar] [CrossRef]
- Ohzuku, T.; Makimura, Y. Layered lithium insertion material of LiCo1/3Ni1/3Mn1/3O2 for lithium-ion batteries. Chem. Mater. 2001, 30, 642–643. [Google Scholar] [CrossRef]
- MacNeil, D.D.; Lu, Z.; Dahn, J.R. Structure and electrochemistry of Li(NixCo1-2xMnx)O2 (0 ≤ x ≤ 1/2). J. Electrochem. Soc. 2002, 149, A1332–A1336. [Google Scholar] [CrossRef]
- Yabuuchi, N.; Ohzuku, T. Novel lithium insertion material of Li(Co1/3Ni1/3Mn1/3)O2 for advanced lithium-ion batteries. J. Power Sources 2003, 119, 171–174. [Google Scholar] [CrossRef]
- Belharouak, I.; Sun, Y.K.; Liu, J.; Amine, K. Li(Ni1/3Co1/3Mn1/3)O2 as a suitable cathode for high power applications. J. Power Sources 2003, 123, 247–252. [Google Scholar] [CrossRef]
- Zhang, X.; Mauger, A.; Lu, Q.; Groult, H.; Perrigaud, L.; Gendron, F.; Julien, C.M. Synthesis and characterization of LiNi1/3Mn1/3Co1/3O2 by wet-chemical method. Electrochim. Acta 2010, 55, 6440–6449. [Google Scholar] [CrossRef]
- Shaju, K.M.; Subba Rao, G.V.; Chowdari, B.V.R. Performance of layered Li(Ni1/3Co1/3Mn1/3)O2 as cathode for Li-ion batteries. Electrochim. Acta 2002, 48, 145–151. [Google Scholar] [CrossRef]
- Kim, J.M.; Chung, H.T. The first cycle characteristics of Li(Ni1/3Mn1/3Co1/3)O2 charged up to 4.7 V. Electrochim. Acta 2004, 49, 937–944. [Google Scholar] [CrossRef]
- Goodenough, J.B.; Kim, Y. Challenges for rechargeable Li batteries. Chem. Mater. 2010, 22, 587–603. [Google Scholar] [CrossRef]
- Song, C.H.; Stephan, A.M.; Kim, A.; Nahm, K.S. Influence of solvents on the structural and electrochemical properties of Li(Li0.2Ni0.1Co0.2Mn0.5)O2 prepared by a solvothermal reaction method. J. Electrochem. Soc. 2006, 153, A390–A395. [Google Scholar] [CrossRef]
- Julien, C.; El-Farh, L.; Rangan, S.; Massot, M. Studies of LiNi0.6Co0.4O2 cathode material prepared by the citric acid-assisted sol-gel method for lithium batteries. J. Sol-Gel Sci. Technol. 1999, 15, 63–72. [Google Scholar] [CrossRef]
- Julien, C.; Letranchant, C.; Rangan, S.; Lemal, M.; Ziolkiewicz, S.; Castro-Garcia, S.; El-Farh, L.; Benkaddour, M. Layered LiNi0.5Co0.5O2 cathode materials grown by soft-chemistry via various solution methods. Mater. Sci. Eng. B 2000, 76, 145–155. [Google Scholar] [CrossRef]
- El-Farh, L.; Massot, M.; Lemal, M.; Julien, C. Physical properties and electrochemical features of lithium nickel-cobalt oxide cathode materials prepared at moderate temperature. J. Electroceram. 1999, 3, 425–432. [Google Scholar] [CrossRef]
- Julien, C.; Nazri, G.A.; Rougier, A. Electrochemical performances of layered LiM1-yM’yO2 (M = Ni, Co; M′ = Mg, Al, B) oxides in lithium batteries. Solid State Ion. 2000, 135, 121–130. [Google Scholar] [CrossRef]
- Chen, J.; Wang, S.; Whittingham, M.S. Hydrothermal synthesis of cathode materials. J. Power Sources 2007, 174, 442–448. [Google Scholar] [CrossRef]
- Zhang, X.; Jiang, W.J.; Zhu, X.P.; Mauger, A.; Lu, Q.; Julien, C.M. Aging of LiNi1/3Mn1/3Co1/3O2 cathode material upon exposure to H2O. J. Power Sources 2011, 196, 5102–5108. [Google Scholar] [CrossRef]
- Abdel-Ghany, A.; Zaghib, K.; Gendron, F.; Mauger, A.; Julien, C.M. Structural, magnetic and electrochemical properties of LiNi0.5Mn0.5O2 as positive electrode for Li-ion batteries. Electrochim. Acta 2007, 52, 4092–4100. [Google Scholar] [CrossRef]
- Yamada, A.; Chung, S.C.; Hinokuma, K. Optimized LiFePO4 for lithium battery cathode. J. Electrochem. Soc. 2001, 148, A224–A229. [Google Scholar] [CrossRef]
- Okubo, M.; Hosono, E.; Kim, J.; Enomoto, M.; Kojima, N.; Kudo, T.; Zhou, H.; Honma, I. Nanosize effect on high-rate Li-ion intercalation in LiCoO2 electrode. J. Am. Chem. Soc. 2007, 129, 7444–7452. [Google Scholar] [CrossRef] [PubMed]
- Castro-Couceiro, A.; Castro-Garcia, S.; Senaris-Rodriguez, M.A.; Soulette, F.; Julien, C. Effects of the aluminum doping on the microstructure and morphology of LiNi0.5Co0.5O2 oxides. Ionics 2002, 8, 192–200. [Google Scholar] [CrossRef]
- Brochu, F.; Guerfi, A.; Trottier, J.; Kopec, M.; Mauger, A.; Groult, H.; Julien, C.M.; Zaghib, K. Structure and electrochemistry of scaling nano C-LiFePO4 synthesized by hydrothermal route: Complexing agent effect. J. Power Sources 2012, 214, 1–6. [Google Scholar] [CrossRef]
- Lee, K.S.; Myung, S.T.; Prakash, J.; Yashiro, H.; Sun, Y.K. Optimization of microwave synthesis of Li(Ni0.4Co0.2Mn0.4)O2 as a positive electrode material for lithium batteries. Electrochim. Acta 2008, 53, 3065–3074. [Google Scholar] [CrossRef]
- Zhang, X.; Jiang, W.J.; Mauger, A.; Li, Q.; Gendron, F.; Julien, C.M. Minimization of the cation mixing in Li1+x(NMC)1-xO2 as cathode material. J. Power Sources 2010, 195, 1292–1301. [Google Scholar] [CrossRef]
- Chen, Z.; Wang, J.; Chao, D.; Baikie, T.; Bai, L.; Chen, S.; Zhao, Y.; Sum, T.C.; Lin, J.; Shen, Z. Hierarchical porous LiNi1/3Co1/3Mn1/3O2 nano-micro spherical cathode material: Minimizes cation mixing and improved Li+ mobility for enhanced electrochemical performance. Sci. Rep. 2016, 6, 25771. [Google Scholar] [CrossRef] [PubMed]
- Liao, P.Y.; Duh, J.G.; Sheen, S.R. Effect on Mn content on the microstructure and electrochemical performance of LiNi0.75-xCo0.25MnxO2 cathode materials. J. Electrochem. Soc. 2005, 152, A1695–A1700. [Google Scholar] [CrossRef]
- Kang, K.; Meng, Y.S.; Bréger, J.; Grey, C.P.; Ceder, G. Electrodes with high power and high capacity for rechargeable lithium batteries. Science 2006, 311, 977–980. [Google Scholar] [CrossRef] [PubMed]
- Oh, S.W.; Park, S.H.; Park, C.W.; Sun, Y.K. Structural and electrochemical properties of layered Li(Ni0.5Mn0.5)1-xCoxO2 positive materials synthesized by ultrasonic spray pyrolysis method. Solid State Ion. 2004, 171, 167–172. [Google Scholar] [CrossRef]
- Tran, N.; Croguenec, L.; Jordy, C.; Biensan, P.; Delmas, C. Influence of the synthesis route on the electrochemical properties of LiNi0.425Mn0.425Co0.15O2. Solid State Ion. 2005, 176, 1539–1547. [Google Scholar] [CrossRef]
- Ngala, J.K.; Chernova, N.A.; Ma, M.; Mamak, M.; Zavalij, P.Y.; Whittingham, M.S. The synthesis, characterization and electrochemical behavior of the layered LiNi0.4Mn0.4Co0.2O2 compound. J. Mater. Chem. 2004, 14, 214–220. [Google Scholar] [CrossRef]
- Tsai, Y.W.; Lee, J.F.; Liu, D.G.; Hwang, B.J. In-situ X-ray absorption spectroscopy investigations of a layered LiNi0.65Co0.25Mn0.1O2 cathode material for rechargeable lithium batteries. J. Mater. Chem. 2004, 14, 958–965. [Google Scholar] [CrossRef]
- Mauger, A.; Gendron, F.; Julien, C.M. Magnetic properties of LixNiyMnyCo1−2yO2 (0.2 ≤ 1 − 2y ≤ 0.5, 0 ≤ x ≤ 1). J. Alloys Compd. 2012, 520, 42–51. [Google Scholar] [CrossRef]
- Julien, C.M.; Ait-Salah, A.; Mauger, A.; Gendron, F. Magnetic properties of intercalation compounds as positive electrodes for Li-ion batteries. Ionics 2006, 12, 21–32. [Google Scholar] [CrossRef]
- Samarasinghab, P.; Tran-Nguyen, D.H.; Behma, M.; Wijayasinghe, A. LiNi1/3Mn1/3Co1/3O2 synthesized by the Pechini method for the positive electrode in Li-ion batteries: Material characteristics and electrochemical behaviour. Electrochim. Acta 2008, 53, 7995–8000. [Google Scholar] [CrossRef]
- Myung, S.T.; Komaba, S.; Kurihara, K.; Hosoya, K.; Kumagai, N.; Sun, Y.K.; Nakai, I.; Yonemura, M.; Kamiyama, T. Synthesis of Li((Ni0.5Mn0.5)1-xLix)O2 by emulsion drying method and impact of excess Li on structural and electrochemical properties. Chem. Mater. 2006, 18, 1658–1666. [Google Scholar] [CrossRef]
- Xu, B.; Qian, D.; Wang, Z.; Meng, Y.S. Recent progress in cathode materials research for advanced lithium ion batteries. Mater. Sci. Eng. R 2012, 73, 51–65. [Google Scholar] [CrossRef]
- Shaju, K.M.; Subba Rao, G.V.; Chowdari, B.V.R. Li-ion kinetics and polarization effect on the electrochemical performance of Li(Ni1/2Mn1/2)O2. Electrochim. Acta 2004, 49, 1565–1576. [Google Scholar] [CrossRef]
- Julien, C.; Michael, S.S.; Ziolkiewicz, S. Structural and electrochemical properties of LiNi0.3Co0.7O2 synthesized by different low-temperature techniques. Intl. J. Inorg. Mater. 1999, 1, 29–37. [Google Scholar] [CrossRef]
- Ben-Kamel, K.; Ben-Amor, G.; Amdouni, N.; Mauger, A.; Groult, H.; Julien, C.M. LiNi0.33+δMn0.33+δCo0.33–2δO2 (0.025 ≤ δ ≤ 0.075) cathode materials for Li-ion batteries: Local structure. ECS Trans. 2011, 35, 129–134. [Google Scholar]
- Ben Kamel, K.; Amdouni, N.; Trottier, J.; Zaghib, K.; Mauger, A.; Groult, H.; Julien, C.M. LiNi0.33+δMn0.33+δCo0.33–2δO2 (0.0 ≤ δ ≤ 0.075) cathode materials for Li-ion batteries: Electrochemical features. ECS Trans. 2011, 35, 135–139. [Google Scholar]
- Ye, D.L.; Wang, L.Z. Li2MnO3 based Li-rich cathode materials: Towards a better tomorrow of high energy lithium ion batteries. Mater. Technol. Adv. Perform. Mater. 2014, 29, A59–A69. [Google Scholar]
- Yu, H.; Zhou, H. High-energy cathode materials (Li2MnO3−LiMO2) for lithium-ion batteries. J. Phys. Chem. Lett. 2013, 4, 1268–1280. [Google Scholar] [CrossRef] [PubMed]
- Lu, Z.; Dahn, J.R. Structure and electrochemistry of layered Li(CrxLi(1/3-x/3)Mn(2/3-2x/3)O2. J. Electrochem. Soc. 2002, 149, A1454–A1459. [Google Scholar] [CrossRef]
- Deng, Z.; Manthiram, A. Influence of cationic substitutions on the oxygen loss and reversible capacity of lithium-rich layered oxide cathodes. J. Phys. Chem. C 2011, 115, 7097–7103. [Google Scholar] [CrossRef]
- Muhammad, S.; Kim, H.; Kim, Y.; Kim, D.; Song, J.H.; Yoon, J.; Park, J.H.; Ahn, S.J.; Kang, S.H.; Thakeray, M.M.; et al. Evidence of reversible oxygen participation in anomalously high capacity Li- and Mn-rich cathodes for Li-ion batteries. Nano Energy 2016, 21, 172–184. [Google Scholar] [CrossRef]
- Lee, D.K.; Park, S.H.; Amine, K.; Bang, H.J.; Parakash, J.; Sun, Y.K. High capacity Li(Li0.2Ni0.2Mn0.6)O2 cathode materials via a carbonate co-precipitation method. J. Power Sources 2006, 162, 1346–1350. [Google Scholar] [CrossRef]
- Liu, Y.J.; Liu, S.B.; Wang, Y.P.; Chen, L.; Chen, X.H. Effect of MnO2 modification on electrochemical performance of LiNi0.2Li0.2Mn0.6O2 layered solid solution cathode. J. Power Sources 2013, 222, 455–460. [Google Scholar] [CrossRef]
- Zhao, Y.; Xia, M.; Hu, X.; Zhao, Z.; Wang, Y.; Lv, Z. Effects of Sn doping on the structural and electrochemical properties of Li1.2Ni0.2Mn0.6O2 Li-rich cathode materials. Electrochim. Acta 2015, 174, 1167–1174. [Google Scholar] [CrossRef]
- Lu, Z.; MacNeil, D.; Dahn, J.R. Layered cathode materials Li(NixLi(1/3–2x/3)Mn(2/3-x/3))O2 for lithium-ion batteries. Electrochem. Solid-State Lett. 2001, 4, A191–A194. [Google Scholar] [CrossRef]
- Lu, Z.; Dahn, J.R. Understanding the anomalous capacity of Li(NixLi(1/3–2x/3)Mn(2/3-x/3))O2 cells using in situ X-ray diffraction and electrochemical studies. J. Electrochem. Soc. 2002, 149, A815–A822. [Google Scholar] [CrossRef]
- Lu, Z.; Beaulieu, L.; Donaberger, R.; Thomas, C.; Dahn, J.R. Synthesis, structure, and electrochemical behavior of Li(NixLi(1/3–2x/3)Mn(2/3-x/3))O2. J. Electrochem. Soc. 2002, 149, A778–A791. [Google Scholar] [CrossRef]
- Boulineau, A.; Simonin, L.; Colin, J.-F.; Bourbon, C.; Patoux, S. First Evidence of manganese–nickel segregation and densification upon cycling in Li-rich layered oxides for lithium batteries. Nano Lett. 2013, 13, 3857–3863. [Google Scholar] [CrossRef] [PubMed]
- McCalla, E.; Rowe, A.W.; Camardese, J.; Dahn, J.R. The role of metal site vacancies in promoting Li–Mn–Ni–O layered solid solutions. Chem. Mater. 2013, 25, 2716–2721. [Google Scholar] [CrossRef]
- Yu, H.; Ishikawa, R.; So, Y.G.; Shibata, N.; Kudo, T.; Zhou, H.; Ikuhara, Y. Direct atomic-resolution observation of two phases in the Li1.2Mn0.567Ni0.166Co0.067O2 cathode material for lithium-ion batteries. Angew. Chem. Int. Ed. 2013, 52, 5969–5973. [Google Scholar] [CrossRef] [PubMed]
- Hy, S.; Felix, F.; Rick, J.; Su, W.-N.; Hwang, B.J. Direct in situ observation of Li2O evolution on Li-rich high-capacity cathode material, Li(NixLi(1/3–2x/3)Mn(2/3-x/3))O2 (0 ≤ x ≤ 0.5). J. Am. Chem. Soc. 2014, 136, 999–1007. [Google Scholar] [CrossRef] [PubMed]
- Wu, F.; Li, N.; Su, Y.; Shou, H.; Bao, L.; Yang, W.; Zhang, L.; An, R.; Chen, S. Spinel/layered heterostructured cathode material for high-capacity and high-rate Li-ion batteries. Adv. Mater. 2013, 25, 3722–3726. [Google Scholar] [CrossRef] [PubMed]
- Yu, H.; Kim, H.; Wang, Y.; He, P. High-energy ‘composite’ layered manganese-rich cathode materials via controlling Li2MnO3 phase activation for lithium-ion batteries. Phys. Chem. Chem. Phys. 2012, 14, 6584–6595. [Google Scholar] [CrossRef] [PubMed]
- Rowe, W.; Dahn, J.R. Positive Electrode Materials in the Li-Mn-Ni-O System exhibiting anomalous capacity growth during extended cycling. J. Electrochem. Soc. 2014, 161, A308–A317. [Google Scholar] [CrossRef]
- Gu, M.; Belharouak, I.; Zheng, J.; Wu, H.; Xiao, J.; Genc, A.; Amine, K.; Thevuthasan, S.; Baer, D.R.; Zhang, J.-G.; et al. Formation of the spinel phase in the layered composite cathode used in Li-ion batteries. ACS Nano 2013, 7, 760–767. [Google Scholar] [CrossRef] [PubMed]
- Song, B.; Lai, M.O.; Liu, Z.; Liu, H.; Lu, L. Graphene-based surface modification on layered Li-rich cathode for high-performance Li-ion batteries. J. Mater. Chem A 2013, 1, 9954–9965. [Google Scholar] [CrossRef]
- Song, B.; Liu, H.; Liu, Z.; Xiao, P.; Lai, M.O.; Lu, L. High rate capability caused by surface cubic spinels in Li-rich layer-structured cathodes for Li-ion batteries. Sci. Rep. 2013, 3, 3094. [Google Scholar] [CrossRef] [PubMed]
Sample | a (Å) | c (Å) | c/a | V (Å3) | L (nm) | I003/I104 | R | η (%) |
---|---|---|---|---|---|---|---|---|
550 | 2.8833(2) | 14.3251(2) | 4.948 | 119.08(9) | 59.9 | 1.197 | 0.420 | 6.70 |
4½4½1 | 2.8766(8) | 14.3005(5) | 4.971 | 118.33(2) | 65.5 | 1.209 | 0.418 | 5.31 |
532 | 2.8732(2) | 14.2684(4) | 4.966 | 102.01(2) | 61.6 | 1.252 | 0.415 | 3.34 |
442 | 2.8685(1) | 14.2655(3) | 4.973 | 101.65(1) | 64.6 | 1.425 | 0.401 | 2.97 |
333 | 2.8604(2) | 14.2376(2) | 4.977 | 100.88(2) | 72.3 | 1.456 | 0.387 | 1.56 |
334 | 2.8622(3) | 14.2455(7) | 4.977 | 116.70(2) | 63.8 | 1.450 | 0.395 | 1.77 |
¼¼½ | 2.8628(5) | 14.2259(6) | 4.981 | 116.86(6) | 62.0 | 1.452 | 0.390 | 0.70 |
Cathode | (1 − 2y) | E0,1 (V) | −K1 | E0,2 (V) | −K2 |
---|---|---|---|---|---|
550 | 0.00 | 3.737 | 3.82 | 3.869 | 3.12 |
4½4½1 | 0.10 | 3.734 | 3.75 | 3.903 | 2.98 |
442 | 0.20 | 3.731 | 3.75 | 3.955 | 2.98 |
333 | 0.33 | 3.722 | 3.71 | 3.932 | 3.00 |
334 | 0.40 | 3.717 | 3.78 | 3.921 | 3.01 |
(1 + x) | a (Å) | c (Å) | c/a | V (Å3) | L (nm) | ηR (%) | ηM (%) |
---|---|---|---|---|---|---|---|
1.02 | 2.8650(1) | 14.2252(2) | 4.975 | 101.31(2) | 59.4 | 1.98 | 1.88 |
1.04 | 2.8603(2) | 14.241(2) | 4.979 | 100.90(3) | 55.9 | 1.43 | 1.50 |
Crystal Data | R = 0.5 | R = 1.0 | R = 2.0 | R = 3.0 | R = 4.0 |
---|---|---|---|---|---|
a (Å) | 2.8680(2) | 2.8671(2) | 2.8602(1) | 2.8675(2) | 2.8684(3) |
c (Å) | 14.2588(3) | 14.2593(2) | 14.2458(2) | 14.2589(4) | 14.2619(3) |
c/a | 4.9716(4) | 4.9734(4) | 4.9807(2) | 4.9726(5) | 4.9720(6) |
V (Å 3) | 101.57(2) | 101.51(2) | 100.92(1) | 101.53(2) | 101.62(2) |
L (Å) | ≈570 | ≈540 | ≈490 | ≈550 | ≈610 |
I(003)/I(104) | 1.440 | 1.614 | 1.728 | 1.558 | 1.423 |
(I(006) + I(102))/I(101) | 0.482 | 0.427 | 0.378 | 0.438 | 0.459 |
S(MO2) (Å) | 2.126(2) | 2.120(5) | 2.109(3) | 2.123(3) | 2.126(2) |
I(LiO2) (Å) | 2.627(2) | 2.633(6) | 2.640(3) | 2.630(3) | 2.628(3) |
η (%) | 2.96 | 2.04 | 1.26 | 2.90 | 3.0 |
© 2016 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC-BY) license (http://creativecommons.org/licenses/by/4.0/).
Share and Cite
Julien, C.; Mauger, A.; Zaghib, K.; Groult, H. Optimization of Layered Cathode Materials for Lithium-Ion Batteries. Materials 2016, 9, 595. https://doi.org/10.3390/ma9070595
Julien C, Mauger A, Zaghib K, Groult H. Optimization of Layered Cathode Materials for Lithium-Ion Batteries. Materials. 2016; 9(7):595. https://doi.org/10.3390/ma9070595
Chicago/Turabian StyleJulien, Christian, Alain Mauger, Karim Zaghib, and Henri Groult. 2016. "Optimization of Layered Cathode Materials for Lithium-Ion Batteries" Materials 9, no. 7: 595. https://doi.org/10.3390/ma9070595