Fabrication and Performance of High Energy Li-Ion ... - ACS Publications

Research Article www.acsami.org

Fabrication and Performance of High Energy Li-Ion Battery Based on the Spherical Li[Li0.2Ni0.16Co0.1Mn0.54]O2 Cathode and Si Anode Jing Ye,† Yi-xuan Li,† Li Zhang,‡ Xue-ping Zhang,† Min Han,† Ping He,*,† and Hao-shen Zhou*,†,§ †

Center of Energy Storage Materials and Technology, College of Engineering and Applied Sciences, National Laboratory of Solid State Microstructures, and Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, Jiangsu 210093, China ‡ Soochow University, Center of Suzhou Nanoscience and Technology, College of Physics, Optoelectronics and Energy and Collaborative Innovation, Suzhou, Jiangsu 215006, China § Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Umezono 1-1-1, Tsukuba, Ibaraki 305-8568, Japan S Supporting Information *

ABSTRACT: The cathode materials of Li-ion batteries for electric vehicles require not only a large gravimetric capacity but also a high volumetric capacity. A new Li-rich layered oxide cathode with superior capacity, Li[Li0.20Ni0.16Co0.10Mn0.54]O2 (denoted as LNCM), is synthesized from precursor, a coprecipitated spherical metal hydroxide. The preparation technology of precursor such as stirring speed, concentration of metal solution, and reaction time are regulated elaborately. The final product LNCM shows a well-ordered, hexagonallayer structure, as confirmed by Rietveld refinement of X-ray diffraction pattern. The particle size of the final product has an average diameter of about 10 μm, and the corresponding tap density is about 2.25 g cm−3. Electrochemical measurements indicate that as-prepared LNCM has great initial columbic efficiency, reversible capacity, and cycling stability, with specific discharge capacities of 278 and 201 mAh g−1 at 0.03 and 0.5 C rates, respectively. Cycling at 0.1 C, LNCM delivers a discharge capacity of 226 mAh g−1 with 95% retention capacity after 50 cycles. Si/LNCM cell is fabricated using Si submicroparticle as anode against LNCM. The cell can exhibit a specific energy of 590 Wh kg−1 based on the total weight of cathode and anode materials. KEYWORDS: lithium-ion battery, lithium-rich layered oxide, silicon anode, coprecipitation method, spherical cathode

1. INTRODUCTION

These materials can be described in two ways: for example, as a two-component “composite” structure xLi 2 MnO 3 ·(1 − x)LiMO2 (M represents transition metals) proposed by Thackeray and co-workers13−15 or as a “solid-solution” Li[LixM1−x]O2 with a homogeneous long-range order proposed by Dahn and co-workers.16−19 Both notations have the same material and have been extensively used in published literature. Although Li-rich layered transition metal oxides possess a relatively high gravimetric capacity of more than 200 mAh g−1, several drawbacks still exist, such as large irreversible capacity loss (20%−30%) at initial cycle and poor rate capability.20−23 Doping a small amount of Co into Li[Li0.2NixMn0.8‑x]O2 has been found to have the capacity to improve the rate capability of the materials and allow the removal of more Li from the lattice during the first charge.24,25 In addition, commercial

Environmental pollution, global warming, and energy exhaustion hinder the development of modern society. Thus, the investigation for clean and sustainable energy has gradually become an interesting topic in research. Lithium-ion batteries as efficient energy storage devices have been commercialized for many years.1−4 However, the energy density of current lithium-ion batteries does not satisfy the market requirements.5,6 Several alternative cathode materials, such as LiCoO2, LiFePO4, LiMn2O4, and LiNi0.33Co0.33Mn0.33O2, have been commercially used in lithium-ion batteries because cathode materials have important function on energy density.2,4 However, the reversible capacity of these materials has almost reached their limits (200 mAh g−1). Cathode materials delivering higher capacity are needed to meet the demand of ever growing energy density for transportation and grid.4,7−10 Li-rich Mn-based layered oxides, which have large reversible capacity and are a promising candidate for alternative energy sources, have attracted wide attention in recent years.11,12 © 2015 American Chemical Society

Received: September 8, 2015 Accepted: December 14, 2015 Published: December 14, 2015 208

DOI: 10.1021/acsami.5b08349 ACS Appl. Mater. Interfaces 2016, 8, 208−214

Research Article

ACS Applied Materials & Interfaces

reported.31 The mass loading of the Si anode was controlled to be around 1.0−1.1 mg cm−2. Before assembling to the full cell, the Si anode needed to be prelithiated. During the prelithiated process, the Si electrode was assembled to the half-cell with metal Li first and got charged to form SEI film. Then, this half-cell was disassembled. The Si electrode was picked out from it carefully and washed by electrolyte. LNCM electrode consists of 85 wt % active material, 10 wt % acetylene black, and 5 wt % polytetrafluoroethene (PTFE, 12 wt %) binder. The testing coin-type cells were assembled in an argon-filled glovebox. The electrolyte solutions were 1 M LiPF6-ethylene carbonate, dimethyl carbonate, and ethylmethyl carbonate (1:1:1 by volume). Galvanostatic charge−discharge tests were performed using LAND 2001A Battery Testing Systems (Wuhan LAND electronics Co., Ltd., P.R. China) controlled by a computer at 25 °C.

cathode materials of power batteries for electric vehicles do not only require the delivery of a high gravimetric capacity but also need to possess a high volumetric capacity. Larger spherical particles have been confirmed to have a higher tap density.26 Thus, the synthesis of Li-rich transition metal oxides containing Co, Mn, and Ni, with spherical morphology, large particle size, and satisfying electrochemical performance, is significant.27−30 High capacity cathode material should be matched with a high capacity anode material. In terms of anode materials, silicon (Si) appears to be an extremely attractive candidate owing to its high theoretical specific capacity (>3500 mAh g−1), low charge−discharge potential plateaus, abundance in nature, and environmental benignity.31 In this work, a new rechargeable lithium ion battery based on the spherical Li[Li0.2Ni0.16Co0.1Mn0.54]O2 cathode and Si anode was fabricated. Li[Li0.2Ni0.16Co0.1Mn0.54]O2 (LNCM) was synthesized by calcining spherical precursor (Ni0.200Co0.125Mn0.675) (OH)2 (denoted as MOH) with LiOH. The precursor was prepared through the coprecipitation method. The properties of as-prepared precursor have been confirmed to have a significant influence on the particle size, morphology, and tap density of LNCM powders.32,33 Therefore, the three factors (stirring speed, concentration of metal solution, and reaction time) in the coprecipitation process were discussed in detail. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were conducted to inspect the morphology and crystalline structure of both as-prepared precursor and cathode material. Full cells were assembled using Si as anode and LNCM as cathode. Furthermore, the electrochemical properties of fabricated cells were investigated.

3. RESULT AND DISCUSSION 3.1. Morphology and Structural Characterizations of Precursor MOH. Five samples of precursor MOH have been synthesized in various conditions as listed in Table 1. Samples Table 1. Synthetic Conditions of MOH Powders no.

coprecipitation time t (h)

stirring rate (rpm)

concentration (metal solution/M)

concentration (NaOH/M)

P1 P2 P3 P4 P5

10 10 10 30 50

700 1000 1000 1000 1000

1.0 1.0 2.0 2.0 2.0

2.5 2.5 5.0 5.0 5.0

are labeled P1 to P5. Samples P1 and P2 are separately prepared under 700 and 1000 rpm stirring speed. The reaction times of P1 and P2 are 10 h. The concentration of metal solution is 1.0 M. The reaction times of samples P3, P4, and P5 are 10, 30, and 50 h, respectively. The stirring speed of P3, P4, and P5 is fixed at 1000 rpm. The concentration of metal solution is 2.0 M. In the coprecipitation process, distilled water and nitrogen protection are utilized to protect Mn2+ from oxidation. Ammonia has been used as a chelating agent to make the Ni2+, Co2+, and Mn2+ mixed metal ion precipitate together to possess a homogeneous and chemically composed hydroxide precipitation. Figure S1 shows the SEM images of as-prepared precursor powders corresponding to the samples P1 and P2. When the stirring speed is 700 rpm, the particle-size distribution of secondary particles is in the range of 1−7 μm, and the shape is irregular (Figure S1a). When the stirring speed increases to 1000 rpm, for example, P2, the secondary particles are uniformly agglomerated and well-distributed (Figure S1b). The precursor growth mechanism in these coprecipitated processes can be described as Formulas 1 and 2. When the metal ions are added into base solution, first, the ions coordinate with the ammonia to form a metal ion complex and then are slowly released to react with the OH− to yield large amounts of primary particles. Subsequently, these primary particles collide with each other, rotate along the inner wall of the reactor, and gradually agglomerate together to form the secondary particles.26,29,34 Thus, high stirring speed is a requirement to obtain spherical and homogeneous particles.

2. EXPERIMENTAL SECTION 2.1. Synthesis of MOH and LNCM. Precursor, MOH, was prepared through the coprecipitation method by using a 2 L continuous stirred tank reactor. Reagents used in this procedure were nickel sulfate hexahydrate (AREnox), manganese sulfate monohydrate (AR, Xilong Chemical Industry Co., Ltd.), cobalt sulfate heptahydrate (AR, Xilong Chemical Industry Co., Ltd.), sodium hydroxide (AR, Nanjing Chemical Reagent Co., Ltd.), and ammonium hydroxide (AR, Nanjing Chemical Reagent Co., Ltd.). In the coprecipitation process, 500 mL of 1 M NH3 (aq) was added into the reactor in advance as base solution and heated to 60 °C. Then, an aqueous solution of metal sulfates (Ni/Co/Mn = 8:5:27) deoxidized by N2 was slowly dropped into it. A NaOH (aq) solution was used to maintain the pH at 9.8, and a 10 M NH3 (aq) solution compensated the loss of ammonium. Overflowing pipe was fixed to keep the solution volume constant in the reactor. Finally, the as-prepared precursor was filtered and washed with deionized water and then dried in a drying oven at 80 °C for 10 h. As-prepared precursor MOH was thoroughly mixed with 3 wt % excess LiOH·H2O (AR, Sinopharm Chemical Reagent Co., Ltd.) powders; then, the mixture was transformed into the furnace and calcined at 750 °C for 12 h in air to obtain LNCM. 2.2. Structure and Morphology Characterizations. Phase composition of the as-prepared MOH and LNCM were identified by powder XRD (Ultima III, Rigaku Corporation) by using Cu Kα (λ = 1.5406 Å) radiation in the diffraction angle (2θ) from 10° to 90° at a scan rate of 2° per min. The structural analysis was further executed using the Rietveld refinement program (Bruker 2009, Total Pattern Analysis Solution Software V4.2). The morphologies of the samples were characterized by SEM (JSM-7000F). 2.3. Cell Assembling and Electrochemical Measurements. Electrochemical performances of both Li/LNCM half and Si/LNCM full cells were obtained using a 2032 coin-type cell at 25 °C. Si electrode consists of 60 wt % silicon submicroparticles, 20 wt % Naalginate binder, and 20 wt % super P carbon black, as previously

M2 + (aq) + x NH4OH(aq) → [M(NH3)n ]2 + (aq) + nH 2O + (x − n)NH4OH(aq) 209

(1) DOI: 10.1021/acsami.5b08349 ACS Appl. Mater. Interfaces 2016, 8, 208−214

Research Article


of samples is 0.196:0.132:0.672, which is in close agreement with the expected (Ni/Co/Mn = 0.200:0.125:0.675). Obtained precursor powders were characterized by the XRD. Figure 2 shows the XRD patterns and Rietveld refinement of

[M(NH3)n ]2 + (aq) + 2OH− + z H 2O → M(OH)2 (s) + z NH4OH + (n − z)NH3

(2)

To investigate the influence of metal solution to the coprecipitation reaction, two kinds of concentration of metal solution were selected as 1 and 2 M, corresponding to sample P2 and P3 in Table 1. Figure S2 shows the morphology of the precursor powders obtained using various concentrations of metal solutions, i.e., (a) 1 M and (b) 2 M. Sample P2 mainly presents a spherical secondary particle with primary nanoparticles, as seen in Figure S2a. A large amount of grains with a diameter of less than 3 μm can be observed. The morphology of sample P3 is shown in Figure S2b. The diameter distribution of sample P3 (ca. 5−8 μm) is narrower than that of sample P2, and the average particle size of sample P3 is also higher than sample P2. Noticeably, the concentration of metal solution affects the particle size and distribution. Increasing the concentration of metal solution to 2 M can promote chelating M2+ with ammonia to form [M(NH3)]2+. Accordingly, the increasing concentration of [M(NH3)]2+ facilitates its reaction with OH− (Formula 2), which eventually promotes the coprecipitation process. Therefore, the selected 2 M metal solution is an optimum condition for a coprecipitation reaction to prepare large spherical particles with narrow size distribution. Various reaction times ranging from 10 to 50 h were selected to synthesize the hydroxide precursors. Figure 1 exhibits the

Figure 2. Rietveld refinement plots of the XRD pattern for the asprepared precursor.

sample P5. Three main diffraction peaks can be separately observed at 18.8°, 35.6°, and 62.3°. In addition, the peaks are almost consistent with the typical fingerprint of M(OH)2 (M = Mn, Co, Ni). The crystal parameters are fitted according to P3 m1 space group. The hexagonal lattice constants a and c are 3.44 and 4.72 Å, respectively. 3.2. Morphology and Structural Characterization of LNCM. The final cathode material LNCM was obtained by calcining precursor powders (P5) with LiOH. The morphology of LNCM powders is shown in Figure 3. Noticeably, most

Figure 3. SEM images of Li[Li0.20Ni0.16Co0.10Mn0.54]O2 synthesized by P5 precursor calcined with LiOH.

secondary particle sizes are between 7 and 10 μm. After calcining at 750 °C for 12 h, the secondary particles retain the spherical shape. The primary particles are more densely agglomerated compared with the starting materials. The tap density of the final product is 2.25 g cm−3, which is higher than that of the sample prepared by the combustion method (1.49 g cm−3)35 and is also a considerably higher value among literature results.36−38 Powder XRD patterns of the obtained compound LNCM are shown in Figure 4. The data are in accordance with the fingerprint of layered structures, and it can be well fitted with the LiCoO2 (R3̅m) structure model.39 The small Bragg peaks between 21° and 23° are attributed to the ordering of Li+ and Mn2+ cations in Li-rich layered metal oxides and can be indexed as monoclinic (space group C2/m) reflections.19 The crystal parameters can be determined by refining XRD patterns based on the R3̅m space group. The hexagonal-lattice constants a and

Figure 1. SEM images of (Ni0.200Co0.125Mn0.675) (OH)2 powders for various reaction times. (a) P3 10 h; (b) P4 30 h; (c) P5 50 h; (d) magnified image of P5.

morphology of as-prepared precursor powders of P3, P4, and P5, i.e., (a) 10 h, (b) 30 h, and (c) 50 h. When M2+ concentration of 2 M and stirring speed of 1000 rpm is fixed, determined in the previous paragraph, prolonging the reaction time can obtain larger and denser particles. Sample P4 has the size of 7−11 μm. Compared with P3, P4 has a larger average diameter (ca. 9 μm). Size distribution of P5 is in the range of 7−11 μm which is closed to that of P4, whereas the average size of particles is higher than P4. Apparently, before reaching a stable value, the average particle size increases with the increase of reaction time. The elemental compositions of MOH have been determined by energy dispersive spectroscopy. The Ni/Co/Mn molar ratio 210


Research Article


Figure 4. Rietveld refinement profile of the XRD pattern for the final product Li[Li0.20Ni0.16Co0.10Mn0.54]O2.

Figure 6. Cycling performance of cathode Li[Li0.20Ni0.16Co0.10Mn0.54]O2 in a voltage range of 2.0−4.7 V.

c are calculated to be 2.86 and 14.21 Å, respectively, which is consistent with the previous report.25 3.3. Electrochemical Measurements. Electrochemical performance of as-prepared cathode materials is presented in Figure 5. LNCM electrode was cycled between 2 and 4.7 V. The charge−discharge curves of LNCM at the initial two cycles are exhibited in Figure 5a. LNCM electrode delivered a reversible capacity of 278 mAh g−1 with 89% columbic efficiency.40,41 The operating voltage of the first charging curve of LNCM almost linearly increases to an inflection point at 4.45 V, and then, it follows a plateau at 4.45 V. First, a “normal” deintercalation region, corresponding to the oxidation of Ni2+ to Ni4+ and Co3+ to Co4+ as Li+ is extracted from the lattice, is observed. Second, an “oxygen release” plateau above 4.45 V corresponding to irreversible loss of O2 gas from the particle surface with simultaneous reversible oxidation of O2− in the bulk as excess Li+ is extracted.42−46 While discharge of this material appears to occur in two steps. The first step is attributed tentatively to the reduction of Ni4+ to Ni2+ and Co4+ to Co3+ between 4.5 and 3.5 V, and the second step to the reduction of Mn4+ to Mn3+ between 3.5 and 2.9 V.47 The rate performance of LNCM electrode was measured after activating at 0.03 C between 2.0 and 4.7 V. Discharge capacities of 257, 202, and 160 mAh g−1 are obtained at 0.05, 0.5, and 2 C, respectively. Cycle performance was investigated after the first cycle activation at 0.03 C. The relation between the discharge capacity and cycle number is shown in Figure 6. After 50 cycles at 0.1 C, LNCM electrode retained a reversible capacity of 215 mAh g−1, corresponding to a 95% retention capacity. At 2 C

after 50 cycles, LNCM electrode can display a discharge capacity of 149 mAh g−1 with 94% retention capacity. This result indicates that the electrodes can retain a steady state during cycling under various current densities. Silicon can offer an extremely high theoretical specific capacity; thus, full cells were assembled using prelithiated silicon anode and LNCM cathode. The weight of active electrode materials of anode and cathode are 0.306 and 3.120 mg, respectively. Figure 7a illustrates the charge−discharge curves of full cells cycled between 0.80 and 4.69 V. The cell has been activated at 0.03 C, which delivers discharge capacity of 262 mAh g−1 based on the weight of active electrode material of cathode. When cycling at 0.2 C, full cell can exhibit an average voltage of about 3 V and represents an extremely high specific energy of 590 Wh kg−1, which is calculated using the formula: t

E=

I∫ U (t )dt 0

Mcathode + Manode

(3)

where I is the applied current, U(t) is the cell voltage which changes with operating time, t is the total operating time, and Mcathode or Manode is the weight of cathode or anode (including active materials and binder). The specific energy of this full cell is much higher than present commercial lithium-ion batteries.1,48−51 However, the cycling stability of this cell is still unsatisfactory. When cycling to the 15th cycle, the retention capacity of full cell decreased to 94%, which is much lower than that of half cells of LNCM material. Considering that the utilized Si anode

Figure 5. (a) The charge−discharge profiles of cathode Li[Li0.20Ni0.16Co0.10Mn0.54]O2 at 0.03 C rate in a voltage range of 2.0−4.7 V and (b) rate performance. 211


Research Article


Figure 7. (a) The voltage profiles of the full cell of Si/LNCM between 0.8 and 4.69 V in which specific capacity is obtained based on the weight of active electrode materials of cathode; (b) initial two cycles of lithium half cells of both cathode and anode materials at 0.03 C.

Notes

has severe volume changes during cycling, the occurrence of solid−electrolyte interface fractures is unavoidable and causes decomposition of electrolyte components on the freshly exposed Si surface.31 This decomposition of electrolyte eventually leads to irreversible capacity. Therefore, the poor cycling stability of full cell is likely associated with the stability of the Si anode. We will work to improve the cycle performance of the full cell in our future work.

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS This work was partially supported financially by the National Basic Research Program of China (973 Program) (2014CB932302, 2014CB932303), National Natural Science Foundation of China (21373111, 21403107), Natural Science Foundation of Jiangsu Province of China (BK2012309, BK20140055), PAPD of Jiangsu Higher Education Institutions, and Open Fund of Jiangsu Key Laboratory of Materials and Technology for Energy Conversion (MTEC-2015M02).

4. CONCLUSION A new rechargeable lithium ion battery based on spherical Li[Li0.2Ni0.16Co0.1Mn0.54]O 2 cathode and Si anode was fabricated. Si/LNCM full cells can deliver an extremely specific energy of 590 Wh kg−1, which is much higher than current commercial lithium-ion batteries. Spherical Li[Li0.2Ni0.16Co0.1Mn0.54]O2 cathode material, i.e., LNCM powders, was synthesized by the coprecipitation method. By controlling pH and temperature in the coprecipitation reaction, a homogeneous distribution of metal cations is ensured. The shape and size distribution of the secondary particles of MOH can be controlled by the regulation of stirring speed, concentration of metal solution, and reaction time during the coprecipitation. Under optimal conditions (stirring speed of 1000 rpm, metal solution of 2 M, and reaction time of 50 h), spherical and uniform metal hydroxide precipitates can be obtained, with size of 7−11 μm. After calcination of the asprepared precursor with LiOH, LNCM powders can be prepared and exhibit a high tap density of 2.25 g cm−3. In the voltage range of 2.0−4.7 V, the specific gravimetric discharge capacity of the LNCM electrode is 278 mAh g−1 at 0.03 C. After 50 cycles at 0.1 C, the LNCM electrode retained a reversible capacity of 215 mAh g−1, corresponding to 95% retention capacity.

■

■

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.5b08349.

■

REFERENCES

(1) Tarascon, J.-M.; Armand, M. Issues and Challenges Facing Rechargeable Lithium Batteries. Nature 2001, 414, 359−367. (2) Whittingham, M. S. Lithium Batteries and Cathode Materials. Chem. Rev. 2004, 104, 4271−4302. (3) Armand, M.; Tarascon, J.-M. Building Better Batteries. Nature 2008, 451, 652−657. (4) Goodenough, J. B.; Kim, Y. Challenges for Rechargeable Li Batteries†. Chem. Mater. 2010, 22, 587−603. (5) He, P.; Yu, H.; Li, D.; Zhou, H. Layered Lithium Transition Metal Oxide Cathodes Towards High Energy Lithium-Ion Batteries. J. Mater. Chem. 2012, 22, 3680−3695. (6) Thackeray, M. M.; Wolverton, C.; Isaacs, E. D. Electrical Energy Storage for TransportationApproaching the Limits of, and Going Beyond, Lithium-Ion Batteries. Energy Environ. Sci. 2012, 5, 7854− 7863. (7) Nishimura, S.-i.; Nakamura, M.; Natsui, R.; Yamada, A. New Lithium Iron Pyrophosphate as 3.5 V Class Cathode Material for Lithium Ion Battery. J. Am. Chem. Soc. 2010, 132, 13596−13597. (8) Yamada, A.; Iwane, N.; Harada, Y.; Nishimura, S. i.; Koyama, Y.; Tanaka, I. Lithium Iron Borates as High-Capacity Battery Electrodes. Adv. Mater. 2010, 22, 3583−3587. (9) Barpanda, P.; Ati, M.; Melot, B. C.; Rousse, G.; Chotard, J.-N.; Doublet, M.-L.; Sougrati, M. T.; Corr, S.; Jumas, J.-C.; Tarascon, J.-M. A 3.90 V Iron-Based Fluorosulphate Material for Lithium-Ion Batteries Crystallizing in the Triplite Structure. Nat. Mater. 2011, 10, 772−779. (10) Yu, H.; Zhou, H. High-Energy Cathode Materials (Li2MnO3− LiMO2) for Lithium-Ion Batteries. J. Phys. Chem. Lett. 2013, 4, 1268− 1280. (11) Lu, Z.; Dahn, J. R. Understanding the Anomalous Capacity of Li/Li[ NixLi (1/3−2 x/3) Mn (2/3−x/3)]O2 Cells Using in Situ X-Ray Diffraction and Electrochemical Studies. J. Electrochem. Soc. 2002, 149, A815−A822. (12) Thackeray, M. M.; Kang, S.-H.; Johnson, C. S.; Vaughey, J. T.; Benedek, R.; Hackney, S. A. Li2 MnO3-Stabilized LiMO2 (M= Mn, Ni, Co) Electrodes for Lithium-Ion Batteries. J. Mater. Chem. 2007, 17, 3112−3125.

Structural characterizations and supplementary figures. (PDF)

AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. 212


Research Article


0.02) Via Co-Precipitation Method. J. Power Sources 2007, 174, 565− 568. (33) Lee, K.-S.; Myung, S.-T.; Moon, J.-S.; Sun, Y.-K. Particle Size Effect of Li[Ni0.5Mn0.5]O2 Prepared by Co-Precipitation. Electrochim. Acta 2008, 53, 6033−6037. (34) van Bommel, A.; Dahn, J. Synthesis of Spherical and Dense Particles of the Pure Hydroxide Phase Ni1/ 3Mn1/ 3Co1/ 3(OH)2. J. Electrochem. Soc. 2009, 156, A362−A365. (35) Zheng, J. M.; Wu, X. B.; Yang, Y. A Comparison of Preparation Method on the Electrochemical Performance of Cathode Material Li[Li0.2Mn0.54Ni0.13Co0.13]O2 for Lithium Ion Battery. Electrochim. Acta 2011, 56, 3071−3078. (36) Zhang, C.; Hou, P.; Shi, X.; Song, D.; Song, J.; Zhang, L. Synthesis and Electrochemical Characteristics of Li1.2(Ni0.2Mn0.6)x(Co0.4Mn0.4)y(Ni0.4Mn0.4)1−x−yO2 (0≤ x+y ≤ 1) Cathode Materials for Lithium Ion Batteries. RSC Adv. 2015, 5, 36015−36021. (37) Kim, H. J.; Jung, H. G.; Scrosati, B.; Sun, Y. K. Synthesis of Li[Li1.19Ni0.16Co0.08Mn0.57]O2 Cathode Materials with a High Volumetric Capacity for Li-Ion Batteries. J. Power Sources 2012, 203, 115− 120. (38) Lee, M. H.; Kang, Y. J.; Myung, S. T.; Sun, Y. K. Synthetic Optimization of Li[Ni1/3Co1/3Mn1/3]O2 Via Co-Precipitation. Electrochim. Acta 2004, 50, 939−948. (39) Bréger, J.; Dupré, N.; Chupas, P. J.; Lee, P. L.; Proffen, T.; Parise, J. B.; Grey, C. P. Short-and Long-Range Order in the Positive Electrode Material, Li(NiMn)0.5O2: A Joint X-Ray and Neutron Diffraction, Pair Distribution Function Analysis and Nmr Study. J. Am. Chem. Soc. 2005, 127, 7529−7537. (40) He, W.; Yuan, D.; Qian, J.; Ai, X.; Yang, H.; Cao, Y. Enhanced High-Rate Capability and Cycling Stability of Na-Stabilized Layered Li1.2[Co0.13Ni0.13Mn0.54]O2 Cathode Material. J. Mater. Chem. A 2013, 1, 11397−11403. (41) Wang, Y.; Shang, K.; He, W.; Ai, X.; Cao, Y.; Yang, H. Magnesium-Doped Li1. 2[Co0. 13Ni0. 13Mn0. 54]O2 for Lithium-Ion Battery Cathode with Enhanced Cycling Stability and Rate Capability. ACS Appl. Mater. Interfaces 2015, 7, 13014−13021. (42) Armstrong, A. R.; Holzapfel, M.; Novák, P.; Johnson, C. S.; Kang, S.-H.; Thackeray, M. M.; Bruce, P. G. Demonstrating Oxygen Loss and Associated Structural Reorganization in the Lithium Battery Cathode Li[Ni0. 2Li0. 2Mn0. 6]O2. J. Am. Chem. Soc. 2006, 128, 8694− 8698. (43) Holzapfel, M.; Würsig, A.; Scheifele, W.; Vetter, J.; Novák, P. Oxygen, Hydrogen, Ethylene and Co2 Development in Lithium-Ion Batteries. J. Power Sources 2007, 174, 1156−1160. (44) Li, H. H.; Yabuuchi, N.; Meng, Y. S.; Kumar, S.; Breger, J.; Grey, C. P.; Shao-Horn, Y. Changes in the Cation Ordering of Layered O3 LixNi0.5Mn0.5O2 During Electrochemical Cycling to High Voltages: An Electron Diffraction Study. Chem. Mater. 2007, 19, 2551−2565. (45) Ohzuku, T.; Nagayama, M.; Tsuji, K.; Ariyoshi, K. HighCapacity Lithium Insertion Materials of Lithium Nickel Manganese Oxides for Advanced Lithium-Ion Batteries: Toward Rechargeable Capacity More Than 300 Ma H G−1. J. Mater. Chem. 2011, 21, 10179−10188. (46) Rowe, A. W.; Dahn, J. R. Positive Electrode Materials in the LiMn-Ni-O System Exhibiting Anomalous Capacity Growth During Extended Cycling. J. Electrochem. Soc. 2014, 161 (3), A308−A317. (47) Johnson, C. S.; Li, N.; Lefief, C.; Thackeray, M. M. Anomalous Capacity and Cycling Stability of xLi2MnO3·(1−x)LiMO2 Electrodes (M = Mn, Ni, Co) in Lithium Batteries at 50°C. Electrochem. Commun. 2007, 9, 787−795. (48) Iwamura, S.; Nishihara, H.; Ono, Y.; Morito, H.; Yamane, H.; Nara, H.; Osaka, T.; Kyotani, T. Li-Rich Li-Si Alloy as a LithiumContaining Negative Electrode Material Towards High Energy Lithium-Ion Batteries. Sci. Rep. 2015, 5, 8085. (49) Zhao, Q.; Lu, Y.; Zhu, Z.; Tao, Z.; Chen, J. Rechargeable Lithium-Iodine Batteries with Iodine/Nanoporous Carbon Cathode. Nano Lett. 2015, 15, 5982−5987.

(13) Johnson, C.; Kim, J.; Lefief, C.; Li, N.; Vaughey, J.; Thackeray, M. The Significance of the Li2 MnO3 Component in ‘Composite’xLi2MnO3·(1− x)LiMn0.5Ni0.5O2. Electrochem. Commun. 2004, 6, 1085−1091. (14) Thackeray, M. M.; Johnson, C. S.; Vaughey, J. T.; Li, N.; Hackney, S. A. Advances in Manganese-Oxide ‘Composite’electrodes for Lithium-Ion Batteries. J. Mater. Chem. 2005, 15, 2257−2267. (15) Croy, J.; Kang, S.-H.; Balasubramanian, M.; Thackeray, M. Li2MnO3-Based Composite Cathodes for Lithium Batteries: A Novel Synthesis Approach and New Structures. Electrochem. Commun. 2011, 13, 1063−1066. (16) Meng, Y.; Ceder, G.; Grey, C.; Yoon, W.-S.; Shao-Horn, Y. Understanding the Crystal Structure of Layered LiNi0.5Mn0.5O2 by Electron Diffraction and Powder Diffraction Simulation. Electrochem. Solid-State Lett. 2004, 7, A155−A158. (17) Lu, Z.; MacNeil, D.; Dahn, J. Layered Cathode Materials Li[NixLi (1/3−2 x/3) Mn (2/3−x/3)]O2 for Lithium-Ion Batteries. Electrochem. Solid-State Lett. 2001, 4, A191−A194. (18) Lu, Z.; MacNeil, D.; Dahn, J. Layered Li[NixCo1−2xMnx]O2 Cathode Materials for Lithium-Ion Batteries. Electrochem. Solid-State Lett. 2001, 4, A200−A203. (19) Lu, Z.; Beaulieu, L.; Donaberger, R.; Thomas, C.; Dahn, J. Synthesis, Structure, and Electrochemical Behavior of Li[NixLi (1/3−2 x/3) Mn (2/3−x/3)]O2. J. Electrochem. Soc. 2002, 149, A778−A791. (20) Lee, D.-J.; Lee, K.-S.; Myung, S.-T.; Yashiro, H.; Sun, Y.-K. Improvement of Electrochemical Properties of Li1.1Al0.05Mn1.85O4 Achieved by an AlF3 Coating. J. Power Sources 2011, 196, 1353−1357. (21) Yabuuchi, N.; Yoshii, K.; Myung, S.-T.; Nakai, I.; Komaba, S. Detailed Studies of a High-Capacity Electrode Material for Rechargeable Batteries, Li2MnO3−LiCo1/3Ni1/3Mn1/3O2. J. Am. Chem. Soc. 2011, 133, 4404−4419. (22) Kim, H.-J.; Jung, H.-G.; Scrosati, B.; Sun, Y.-K. Synthesis of Li[Li1.19Ni0.16Co0.08Mn0.57]O2 Cathode Materials with a High Volumetric Capacity for Li-Ion Batteries. J. Power Sources 2012, 203, 115− 120. (23) Martha, S. K.; Nanda, J.; Veith, G. M.; Dudney, N. J. Electrochemical and Rate Performance Study of High-Voltage Lithium-Rich Composition: Li1.2Mn0.525Ni0.175Co0.1O2. J. Power Sources 2012, 199, 220−226. (24) Lu, Z.; Dahn, J. The Effect of Co Substitution for Ni on the Structure and Electrochemical Behavior of T2 and O2 Structure Li2/3[CoxNi1/3−xMn2/3]O2. J. Electrochem. Soc. 2001, 148, A237−A240. (25) Kang, S.-H.; Johnson, C.; Vaughey, J.; Amine, K.; Thackeray, M. The Effects of Acid Treatment on the Electrochemical Properties of 0.5 Li2MnO3·0.5LiNi0. 44Co0. 25Mn0. 31O2 Electrodes in Lithium Cells. J. Electrochem. Soc. 2006, 153, A1186−A1192. (26) Lee, M.-H.; Kang, Y.-J.; Myung, S.-T.; Sun, Y.-K. Synthetic Optimization of Li[Ni1/3Co1/3Mn 1/3]O2 Via Co-Precipitation. Electrochim. Acta 2004, 50, 939−948. (27) Amine, K.; Tukamoto, H.; Yasuda, H.; Fujita, Y. A New ThreeVolt Spinel Li1+xMn1. 5Ni0. 5O4 for Secondary Lithium Batteries. J. Electrochem. Soc. 1996, 143, 1607−1613. (28) Jouanneau, S.; Eberman, K.; Krause, L.; Dahn, J. Synthesis, Characterization, and Electrochemical Behavior of Improved Li[NixCo1−2xMnx]O2 (0.1⩽ x⩽ 0.5). J. Electrochem. Soc. 2003, 150, A1637−A1642. (29) van Bommel, A.; Dahn, J. Analysis of the Growth Mechanism of Coprecipitated Spherical and Dense Nickel, Manganese, and CobaltContaining Hydroxides in the Presence of Aqueous Ammonia. Chem. Mater. 2009, 21, 1500−1503. (30) Zhou, F.; Zhao, X.; van Bommel, A.; Rowe, A. W.; Dahn, J. Coprecipitation Synthesis of Nix Mn1−x(OH)2 Mixed Hydroxides†. Chem. Mater. 2010, 22, 1015−1021. (31) Zhang, L.; Zhang, L.; Chai, L.; Xue, P.; Hao, W.; Zheng, H. A Coordinatively Cross-Linked Polymeric Network as a Functional Binder for High-Performance Silicon Submicro-Particle Anodes in Lithium-Ion Batteries. J. Mater. Chem. A 2014, 2, 19036−19045. (32) Bang, H.; Park, B.-C.; Prakash, J.; Sun, Y.-K. Synthesis and Electrochemical Properties of Li[Ni 0.45Co0.1Mn0.45−xZrx]O2 (x= 0, 213


Research Article

ACS Applied Materials & Interfaces (50) Liu, X.; Huang, T.; Yu, A. A New, High Energy Rechargeable Lithium Ion Battery with a Surface-Treated Li1.2Mn0.54Ni0.13Co0.13O2 Cathode and a Nano-Structured Li4Ti5O12 Anode. J. Alloys Compd. 2015, 648, 7−12. (51) Zhang, T.; Zhang, F.; Zhang, L.; Lu, Y.; Zhang, Y.; Yang, X.; Ma, Y.; Huang, Y. High Energy Density Li-Ion Capacitor Assembled with All Graphene-Based Electrodes. Carbon 2015, 92, 106−118.

214


Fabrication and Performance of High Energy Li-Ion ... - ACS Publications

Recommend Documents