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(2) Master's Thesis. Optimization of Li1.17[Mn0.6Ni0.2Co0.2]0.83O2 Cathode Materials for Li-ion batteries. Sujin Park Department of Energy Engineering (Battery Science and Technology). Graduate School of UNIST 2017.
(3) Optimization of Li1.17[Mn0.6Ni0.2Co0.2]0.83O2 Cathode Materials for Li-ion batteries. Sujin Park. Department of Energy Engineering (Battery Science and Technology). Graduate School of UNIST.
(4) Optimization of Li1.17[Mn0.6Ni0.2Co0.2]0.83O2 Cathode Materials for Li-ion batteries. A thesis/dissertation submitted to the Graduate School of UNIST in partial fulfillment of the requirements for the degree of Master of Science. Sujin Park. 1. 11. 2017 Approved by _________________________ Advisor Jaephil Cho.
(5) Optimization of Li1.17[Mn0.6Ni0.2Co0.2]0.83O2 Cathode Materials for Li-ion batteries. Sujin Park. This certifies that the thesis/dissertation of Sujin Park is approved. 1. 11. 2017. signature ___________________________ Advisor: Jaephil Cho signature ___________________________ Youngsik Kim signature ___________________________ Nam-soon Choi.
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(7) Abstract In the face of growing green energy needs and pressure on the environment, lithium ion batteries have been paid lots of attention. Recently, with growing needs of energy have been significantly increased due to electric vehicles and energy storage system, bigger scale batteries are getting more important than before. Lithium rich materials with higher reversible capacity than 240 mAh/g is regarded the most encouraging cathode material to solve low energy density which is one of the biggest limits of commercialized LIBs cathode materials. However, there have been several problems needed to overcome for commercialization of lithium rich cathode materials. First of all, to achieve high tap density, preparation of powder is important. Co-precipitation method has been known as the best way to produce uniform distribution of powders with spherical shape which are key factors to have a high tap density, but this method is really hard to optimize because there are too many factors to optimize co-precipitation condition such as pH, the amount of chelating agent and stirring speed. Also, lithium rich cathode materials have several drawbacks on electrochemical properties. For example, this cathode material has low initial coulombic efficiency, which is the main problem of full-cell operation, compared to other cathode materials due to the activation process of Li2MnO3 component. Herein, to solve these problems of lithium rich cathode materials, we suggest the optimized co-precipitation condition under oxygen inert atmosphere for high tap density, and blending lithium rich with nickel rich cathode materials to overcome the drawbacks of electrochemical properties.. i.
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(9) Contents Abstract .......................................................................................................................................... i. List of figures ............................................................................................................................... iv. List of tables ............................................................................................................................... viii Ⅰ. Introduction ............................................................................................................................. 1 1.1. Lithium-ion batteries ................................................................................................... 1. 1.2. Li-rich Layered cathode materials: Li1+xM1-xO2 (x ≥ 0.1, M=Ni, Co and Mn)............ 2 1.2.1. The structure of lithium rich cathode materials................................................ 4. 1.2.2. Deterioration Mechanism of Lithium rich layered cathode materials .............. 6. 1.2.3. Structural Deterioration Mechanism: Cation Disordering ............................... 8. 1.2.4. Causes of capacity fading at the elevated temperature................................... 10. 1.2.5. Strategies to improve the electrochemical performance ................................ 12. 1.2.6. Strategies to improve the initial coulombic efficiency ................................... 19. 1.2.7 Synthesis of lithium rich cathode material by co-precipitation method .......... 24 Ⅱ. Experiment ............................................................................................................................ 26 2.1 Experimental method .................................................................................................... 26 2.1.1 Synthetic optimization of Ni0.2Co0.2Mn0.6(OH)2 by co-precipitation .................. 26 2.1.2. Benchmarking of lithium rich cathode materials .............................................. 26 2.1.3. Blending of lithium rich and nickel rich cathode materials .............................. 26 2.2 Electrochemical measurement ....................................................................................... 27 2.3 Instrumental analysis ..................................................................................................... 27 Ⅲ. Results and discussion........................................................................................................... 28 3. 1 Synthetic optimization of Ni0.2Co0.2Mn0.6(OH)2 by co-precipitation ............................ 28 3. 2 Preparation of Li1+x[Mn0.6Ni0.2Co0.2]1-xO2 ..................................................................... 33 3. 3 Benchmarking of lithium rich cathode materials ......................................................... 38 3. 4 Blending of NCM and lithium rich cathode materials ................................................. 45. IV. Conclusion ............................................................................................................................ 48. V. References .............................................................................................................................. 49 iii.
(10) List of figures Figure1. Comparison of the different battery technologies in terms of volumetric and gravimetric energy density 1. Figure 2. Energy density depends on various cathode materials 1. Figure 3. Layered structures of a)Li2MnO3, b)LiMO2 (M=Co, Ni, Mn) 16. Figure 4. X-Ray diffraction patterns of (a) xLi2MnO3 (1-x)LiMn0.5Ni0.5O2 for x = 0, 0.3, 0.4, 0.5; and (b) xLi2MnO3 (1-x) LiMn0.333Ni0.333Co0.333O2 for x = 0, 0.3, 0.5, 0.7 5. Figure 5. Deterioration mechanism of lithium rich cathode materials 16.. Figure 6. Structure transformation of atomic illustration. (a) R𝟑m structure; (b) The cation mixing phase with Fm𝟑m structure; (c) R𝟑m structure with lithium vacancies in highly charged state; (d) Partially cation mixed phase (transition metal ions are occupied in lithium slab. lithium atoms are shown in yellow while the transition metal ions are shown red color, coordinated by oxygen atoms in blue.) 20. Figure 7. Schematic drawing showing that the initial material is composed of three phases: R𝟑m, C2/m, and nanocompsite of intergrowth of R𝟑m and C2/m. The transition from the R𝟑m and C2/m layered structure to the spinel follows different routes, leading to different structural features of the spinel grains 23. Figure 8. Cycling performance of Li1.2Ni0.13Mn0.54Co0.13O2 with Al2O3 and TiO2 coatings 27. Figure 9. HR-TEM, HAADF (high angle annular dark field) photographs and EDS spectra HRTEM, HAADF photographs and EDS spectra of the uncoated (a, d and g), Al2O3 coated (b, e and h) and TiO2 coated (c, f and i)Li1.2Ni0.13Mn0.54Co0.13O 2 particles by ALD 27. Figure 10. DSC profiles of pristine and FePO4 coated Li1.2Ni0.13Co0.13Mn0.54O2 after the first cycle and charged to 4.8 V 28.. Figure. 11.. Capacity. retention. of. Li1.2Ni0.13Co0.13Mn0.54O2. and. CePO4. coated. Li1.2Ni0.13Co0.13Mn0.54O2 at 55℃, the insets show both electrodes stored in the electrolyte at 55℃ iv.
(11) for 60 hours 25.. Figure 12. HAADF-STEM images of the bare and surface coated 0.4Li2MnO3·0.6LiNi1/3Co1/3 Mn1/3O2 cathode material. a–c) STEM images of a primary particle of bare Li-rich oxide; d) atomic crystal model for layered LiMO2 with R𝟑m phase; e–g) STEM images of a primary particle of surface treated Li-rich oxide (image (g) is expanded view of (f)); and h) atomic crystal model for rock salt (Fm𝟑m) phase, in which TM occupy the original Li slab of R𝟑m phase 24.. Figure 13. The discharge capacity versus prolonged cycle of 0.4Li2MnO3·0.6LiNi1/3Co1/3Mn1/3 O2 and LiMgPO4 1.5 wt% 0.4Li2MnO3·0.6LiNi1/3Co1/3Mn1/3O2 at 60 °C with 1C/1C rate after 10 cycle’s formation 24. Figure 14. (a) SEM images of Li1+xNi1/6Co1/6Mn4/6O2.25+x/2 (0.1 ≤ x ≤ 0.7) initial charge/discharge curves of Li1+xNi1/6Co1/6Mn4/6O2.25+x/2 electrodes (b) the corresponding charge/discharge/irreversible capacities 1. Figure 15. (a) Initial charge-discharge curves between 2.0 and 4.6 V, for lithium cells with 0.5 Li2MnO3·0.5 LiNi0.44Co0.25Mn0.31O2 and HNO3-treated electrodes; (b) Cycling stability of with 0.5 Li2MnO3·0.5 LiNi0.44Co0.25Mn0.31O2 and HNO3-leached electrodes 31. Figure 16. Li insertion host blending/coating: (a) Initial charge/discharge curves of VO2 added Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cells and corresponding irreversible capacity and initial coulombic efficiency. (b) Initial charge/discharge curves of Li3PO4 coated Li1.18Co0.15Ni0.15Mn0.52O2 cells and corresponding irreversible capacity and initial coulombic efficiency; (c) first cycle CV curves of the pristine (black line), (b) 1.0 wt% (red line) and (c) 3.0 wt% (blue line) Li 3PO4 coated Li1.18Co0.15Ni0.15Mn0.52O2 cells Figure 17. SEM images of [Ni1/3Co1/3Mn1/3](OH)2 powders at various pH. (a) P1 11.0; (b) P2 11.5; and (c) P3 12.0.. Figure 18. SEM images of U1, U2 and U3. (Ni0.2Co0.2Mn0.6(OH)2 precursors prepared at different pH according to Table 1). Figure 19. SEM images of U4 and U5. (Ni0.2Co0.2Mn0.6(OH)2 precursors prepared at different the amount of NH4OH according to Table 1). v.
(12) Figure 20. SEM images of U3 and U6. (Ni0.2Co0.2Mn0.6(OH)2 precursors prepared at different stirring speed of agitator in the reactor according to Table 1) Figure 21. SEM images of Li1+x[Mn0.6Ni0.2Co0.2]1-xO2 samples from P5 to P9 calcined at 800oC for 10h and precursor of [Mn0.6Ni0.2Co0.2]OH2 Figure 22. Voltage profiles of P10, P11 and P13 cathodes in coin-type half cells between 2.0 and 4.6 V at 0.1C rate (= 20mAg-1) under 24oC.. Figure 23. Cycle performance during 100 cycles between 2.0 and 4.6 V at 1C rate of charge and discharge between 2.0 V and 4.6 V at 24oC.. Figure 24. Cycle performance during 50 cycles between 2.0 and 4.6 V at 1C rate of charge and discharge at 60oC.. Figure 25. SEM images of UNIST Bare, Benchmarking Sample A, B and C.. Figure 26. Voltage profiles of UNIST bare and CoPO4 coated Li1.17[Mn0.6Ni0.2Co0.2]0.83O2, Sample A, B and C between 2.0 V and 4.6 V at 0.1C rate of charge and discharge at 24oC.. Figure 27. Cycle performance of bare and CoPO4 coated UNIST during 100 cycles between 2.0 V and 4.6 V at 1C rate of charge and discharge at 24oC.. Figure 28. Cycle performance of benchmarking UNIST Bare, sample A, B and C during 100 cycles between 2.0 V and 4.6 V at 1C rate of charge and discharge at 24oC.. Figure 29. Cycle performance of bare and CoPO4 coated UNIST during 100 cycles between 2.0 V and 4.6 V at 1C rate of charge and discharge at 60oC.. Figure 30. Cycle performance of benchmarking sample A, B and C during 100 cycles between 2.0 V and 4.6 V at 1C rate of charge and discharge at 60oC. Figure 31. The comparison of by-product of UNIST, sample A, B and C after cycling at 24oC.. Figure 32. DSC of bare and CoPO4 coated UNIST samples at 4.6 V; electrodes after DSC measurement from 50 oC to 350 oC. vi.
(13) Figure 33. Voltage profiles of Li1.17[Mn0.6Ni0.2Co0.2]0.83O2, blended OLO: NCM= 5:5, blended OLO:NCM= 6:4, blended OLO:NCM= 7:3 and Li[Ni0.75Co0.1Mn0.15]O2 between 2.0 V and 4.6 V at 0.1C rate of charge and discharge at 24oC.. Figure 34. Cycle performance during 50 cycles of OLO, blended OLO:NCM = 5:5 and NCM between 2.0 V and 4.6 V at 1C rate of charge and discharge at 24oC.. Figure 35. Cycle performance during 50 cycles of OLO, blended OLO:NCM = 5:5 and NCM between 2.0 V and 4.6 V at 1C rate of charge and discharge at 60oC.. vii.
(14) List of tables Table 1. Synthetic conditions and physical property of U1 to U6 Ni0.2Co0.2Mn0.6(OH)2 powders.. Table 2. The comparsion electrochemical performance of Li1+x[Mn0.6Ni0.2Co0.2]1-xO2 depending on different calcination conditions.. Table 3. The comparsion electrochemical performance of Li1+x[Mn0.6Ni0.2Co0.2]1-xO2 depending on different calcination conditions.. Table 4. DSC of bare and CoPO4 coated UNIST samples at 4.6 V; electrodes after DSC measurement from 50oC to 350oC.. viii.
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(16) Ⅰ. Introduction 1.1 Lithium-ion batteries In the face of growing green energy needs and pressure on the environment, Lithium ion batteries (LIBs) have been widely used in energy storage. LIBs are more spotlighted than other power sources due to its high energy density, working voltage and lifetime which are suitable properties for energy conserve aspects as stationary energy storage, smart grid, electric transportation, etc. These properties of LIBs are strongly depending on materials, and many researchers have attempted to develop cathode materials. In the past, small sized LIBs had been mainly used. However, these days with growing world's energy need have been significantly increased due to electric vehicles and energy storage system, bigger scale batteries are getting more important than before as shown in figure 1. Especially, electric vehicles (EVs) have come to the fore, higher energy density and power with stable cyclabililty, safety and low cost are main directions to develop LIBs.. Figure 1. Comparison of the different battery technologies in terms of volumetric and gravimetric energy density 1. 1.
(17) 1.2 Li-rich Layered cathode materials: Li1+xM1-xO2 (x ≥ 0.1, M=Ni, Co and Mn). Lithium ion batteries (LIBs) have received worldwide attention as power sources for EVs and stationary energy storage. However, research to address the limited cycle life, rate capability, energy density, safety concern and cost issue of commercialized LiCoO2 (LCO), LiNixMnyCozO2 (NMC), LiNi0.80Co0.15Al0.05O2 (NCA) and LiFePO4 (LFP) is still ongoing for their large-scale application in EVs and the electricity grid. Lithium rich cathode materials hav e entered the spotlight due to its higher energy density compared to traditional other cathod e materials 2 . Lithium rich materials with higher reversible capacity than 240 mAh/g is considered the most encouraging cathode materials to solve low energy density which is one of the biggest limits of commercialized LIBs cathode materials 3. The energy density of LIBs is determined by the material’s capacity and operating voltage, and lithium rich have the high est operating voltage among cathode materials (~4.8 V vs. Li/Li+) Furthermore, lithium rich can demonstrate relatively good thermal stability with late onset of thermal decomposition t emperature about 250°C. Because of high manganese contents in lithium rich, this material has cheap price and low toxicity compared to others. Li-rich material can be expressed as Li1+xMO2 or xLi2MnO3 (1-x)LiMO2. Li2MnO3 phase is known as electrochemically inactive phase, and lithium ions can be extracted from this phase operating at high voltage range over 4.4 V 4. Lithium rich materials began to get lots of attention because of its highest energy density among cathode materials, highest discharge capacity, and cheap price and low toxicity of manganese, etc. Since then, many researches have concentrated on comprehending electrochemical properties of lithium rich materials and those studies showed that lithium rich materials have critical disadvantages of poor cycle life and rate performance though Li-rich can show the highest capacity 5. Formerly, modification of surface and doping used on LIB cathode were applied on lithium rich cathode materials to handle these drawbacks, and some modifications showed remarkable improvement. However, unsolved problems and limits have still existed to commercialize of the Li-rich materials.. 2.
(18) Figure 2. Energy density depends on various cathode materials 1.. 3.
(19) 1.2.1 The structure of lithium rich cathode materials Lithium rich cathode material can be expressed as Li1+xMO2 or xLi2MnO3 (1-x)LiMO2 which is solid solution or nanocomposite of two phases. These layered structures are shown in Fig 2 6. The average oxidation state of the M cations is three in LiMO2 compounds. The structure of Li2MnO3 (1-x)LiMO2 is similar to LiMO2, but there is the only difference which the excessive lithium ions are substituted for transition metal ions and occupy the MO6 octahedral sites 7. There has been many debate whether Li2MnO3 (1-x)LiMO2 is a homogeneous solid solution or a composite. However, it is clear that this structure has homogeneous over long rage.. LiMO2 phase has rhombohedral structure and with a space group of R3m. In case of L2iMnO3, this structure is monoclinic with a space group of C2/m. Li2MnO3 structure resembling LiMO2 structure, and this is the reason of metal layer which has periodic sequence of one lithium and two manganese atoms in transition metal layer of LiMO2. Thus, both structures can be supposed to layered a-NaFeO2-type rock salt structures. Oxygen arrays with close-packed are occupied in all octahedral sites 8.. In Figure 3, all strong peaks can be indexed to the pseudo-trigonal unit cell with R3m because of the similar structural compatibility of layered Li2MnO3 and LiMO2 structures. These weak peaks between 21° ~ 25 °, which does not be matched with R3m symmetry, are consistent of LiMn6 cation ordering which occurs in transition metal layer of Li2MnO3 phase. The magnitude of these weak peaks are increased with the value of x, for both xLi 2MnO3 (1x)LiMO2, which means the consistent with the increase of Li2MnO3 phase.. Figure 3. Layered structures of a)Li2MnO3, b)LiMO2 (M=Co, Ni, Mn) 16.. 4.
(20) Figure 4. X-Ray diffraction patterns of (a) xLi2MnO3 (1-x)LiMn0.5Ni0.5O2 for x = 0, 0.3, 0.4, 0.5; and (b) xLi2MnO3 (1-x) LiMn0.333Ni0.333Co0.333O2 for x = 0, 0.3, 0.5, 0.7 5.. 5.
(21) 1.2.2 Deterioration Mechanism of Lithium rich layered cathode materials. To overcome intrinsic and practical limits for commercialize, it is necessary to understand deterioration mechanism of Li-rich material. The deterioration mechanism of Li-rich materials can be classified into two. First is phase distortion during cycles. It is widely known that the relationship between structural stability and reversible capacity is trade-off, which means if reversible capacity of cathode material is increased, structural stability of materials is dramatically decreased. When reversible capacity is increased, it means that there are lots of Li ion vacancies during delitiation process which leads serve phase transition after repeated cycles. In this regard, Li-rich materials have the highest reversible capacity among cathode materials, and we can easily infer that this material will show serious phase transition during cycling due to its high specific capacity 9. Many researches have mentioned ‘cation mixing’ which is TM migration from the TM layer to the lithium layer during charge and discharge process. Cation mixing is the main reason for structure deterioration mechanism 10. Formation of lithium ion vacancies are occurred from cathode materials during delitiation process due to lots of lithium ions extraction leading transition of phase from layered to spinel like structure, and then finally it becomes the rock-salt NiO phase. 11. . Also, main. problem of lithium rich materials is voltage decaying upon cycles with energy decrease. Many studies have showed that formation of spinel-like phase is the main reason which leads voltage decaying. Recently, spinel-like phase was found between surface MO cubic rock-salt phase and core layered phase with similar atomic arrangement by STEM analysis. This result demonstrates that spinel-like phase is the intermediate phase from layered to cubic rock-salt phase. Note that recently formation of spinel-like phase was also reported in Ni-based cathode materials. In conclusion, high energy layered cathode materials including nickel based materials (~190mAhg1. ) and lithium rich materials (>240mAhg-1) have the identical phase transition mechanism called. ‘cation mixing’ resulting in structure failure. This cation migration should be controlled to minimize for structure instability. The second deterioration mechanism of lithium rich materials is a side reaction caused by electrolyte on the surface. Lithium rich cathode has high operating voltage range above 4.6 V for activation of Li2MnO3 phase, and lots of side reactions occur between the surface of active materials and electrolyte upon cycles 12. These side reactions bring critical problems like thick solid-electrolyte interface layer and server transition metal ion dissolution during cycles. The conductivity of Li ion and electron can be decreased due to the formation of thick SEI layer, and phase distortion can be accelerated by this phenomenon which leads poor electrochemical properties such as cycle retention and rate properties. In addition, 6.
(22) cell short – circuit at elevated temperature can be occurred due to metal dissolution because dissolved TM ions can be reduced on the surface of anode and separator upon repeated cycles. There have been many studies of lithium rich which mainly concentrate to enhance its electrochemical properties. In general, there are three method to overcome intrinsic instability of lithium rich materials: they are doping, surface coating. 13. and chemical activation for Li2MnO3. phase. The purpose of doping method, which is similar to the case of most layered materials, is for substitution of unstable TM ions like Ni and Mg ions with other stable elements to make better structural stability. 14-15. . Cobalt is one of the most famous doping element 15, and usually. the amount of cobalt doping is decided with the composition of TM ions in normal layered phase. For example, in the case of synthesizing aLi2MnO3–[1-a] LiNixCoyMn1-x-yO2 (a>0), the Co concentration (y) is decided for stoichiometric compositions of LiNixCoyMn1-x-yO2 phase with the value of x:y:z as 1:1:1, 5:2:3 and 1:0:1, which are well known as the composition to stabilize Ni-based materials 16. The stability of lithium rich material is highly depended on the composition of general layered phase 17.. Figure 5. Deterioration mechanism of lithium rich cathode materials 16.. 7.
(23) 1.2.3 Structural Deterioration Mechanism of lithium rich Layered Cathode Materials: Cation Disordering Structural stability of Li-rich material has strong connection with cation mixing which is cation disordering between TM sites (octahedral 3a site) and Li sites (octahedral 3b site). 18. .. During the charge step, lots of lithium ion vacancies are formed inducing the migration of transition metal ions into the vacated lithium sites in the lithium slab. Most layered cathode materials have repeated O3 structure of oxygen-lithium-oxygen-TM-oxygen-lithium-oxygenTM-oxygen along the rhombohedral [001] direction, which is R3m structure 19, so TM sites (3a) and Li ion sites (3b) are totally separated in the perfect R3m structure. Ni ions have tended to exist as Ni2+ rather than Ni3+ in FCC octahedral site because Ni3+ is unstable due to the unpaired electron spin. 20. . It is known that the radius between Ni2+ (0.69 A) and Li+ (0.76 A) are very. similar. For this reason, Ni2+ ion can easily occupy the 3b Li ion sites in lithium slab, and this is called “cation mixing” or “cation disordering” 21.. 8.
(24) Figure 6. Structure transformation of atomic illustration. (a) R𝟑m structure; (b) The cation mixing phase with Fm𝟑m structure; (c) R𝟑m structure with lithium vacancies in highly charged state; (d) Partially cation mixed phase (transition metal ions are occupied in lithium slab. lithium atoms are shown in yellow while the transition metal ions are shown red color, coordinated by oxygen atoms in blue.) 20. The activation barrier can be affected by cation mixing leading change the equilibrium of lithium slab distance. When cation disordering is occurred, Li slab distance is decreased. If Li slab distance is smaller, the activation energy barrier is higher, and this leads poor diffusivity of lithium ions. Therefore, rate capability of active materials is reduced with increasing cation disordering by repeated many cycles 22. Many studies have tried to develop the measurement the degree of disordering, and XRD analysis is the most well know method 23. TM ions are located in the Li site with generation of cation mixing like figure 6d.. 9.
(25) 1.2.4 Causes of capacity fading at the elevated temperature. It is necessary to solve capacity fading at high temperature because heat accumulation can be occurred in LIB system due to the closed space causing elevated temperature. This is needed to overcome for large scale applications. However, the stability of LIBs at high temperature is poor at delithiated state. Structure changed from layered to spinel, and then rock salt 24. Finally, the oxygen released from the cathodes leading thermal runway by reacting with electrolyte causing and explosion. It is well known that oxygen can be extracted from li-rich layer structure even at room temperature. Moreover, this oxygen extraction process and the migration of transition metal ions might have been caused at high temperature 25. Lithium rich cathode materials are composed of LiMO2 with a space group of R3m and Li2MnO3 with a space group of C2/m phases. The structural transition from layered phase to spinel phase is accomplished through the migration of transition metal ions to the lithium site without breaking down the lattice, but for Li2MnO3 C2/m case, this transition involves removal of Li+ and O2-, producing the large lattice strain and leading to breakdown of the parent lattice. Lithium rich cathode materials usually show voltage decaying and transition metal ions dissolution during cycling, which leads seriously reduce the energy density of the cell at elevated temperature 24. Moreover, side reactions on electrode surface with electrolyte can form thick solid electrolyte interface layer at high temperature. To achieve high capacity of lithium rich cathode material, they are needed to charge above 4.5 V, and this such a high cut-off voltage can lead severe electrolyte decomposition especially at high temperature. 26. . For this reason, reactivity with. electrolytes plays an important role for cycle retention, but all standard electrolyte mixtures have tendency to oxidize at voltage above 4.4 V, and form oxidation products on the surface 27.. 10.
(26) Figure 7. Schematic drawing showing that the initial material is composed of three phases: R𝟑m, C2/m, and nanocompsite of intergrowth of R𝟑m and C2/m. The transition from the R𝟑m and C2/m layered structure to the spinel follows different routes, leading to different structural features of the spinel grains 23.. 11.
(27) 1.2.5 Strategies to improve the electrochemical performance at elevated temperature To improve the electrochemical performance at elevated temperature is one of the main issues to commercialize of the lithium rich. Cycling performance of lithium rich cathodes at elevated temperature can be improved by surface coating, mild acidic treatment and fluorinated solution. Surface coating of inert materials can be very successful to minimize the capacity loss at high temperature due to the compatibility with electrolyte, high chemical and thermal stability. Fig 8 shows the comparison of cycling performance at room temperature and 55℃ after Al2O3 and TiO2 coating on lithium rich cathode materials 28. Al2O3 coating provided much improved cycling stability compared to bare and TiO3 coated samples at both and 55℃ temperature because the surface of Al2O3 sample displays vast uniformity and conformity. However, the coated TiO2 film showed as nanoparticles on the surface by HR-TEM as figure 9. This uniform coating layer acted as the protecting role of the surface films against the reaction between electrodes and electrolyte at the high operating voltage. Fig. 10 shows the thermal stability of FePO4 coated li-rich cathode material. FePO4 coated sample have much improved thermal stability. 29. . Thermal stability was enhanced because the amorphous FePO4 coating layer. protecting highly oxidized cathode from the electrolyte, and also have the role of reduce the exothermic reaction. There is another reason to improve thermal stability after coating which is FePO4 coating layer makes strong P=O bonding at the surface which can protect the active material surface and suppress the oxygen generation. Figure 11 reveals the cycle property of the pristine lithium rich cathode and CePO4 coated sample at 55℃. 26. . After CePO4 coating, it keeps. better cycle retentions than pristine because CePO4 can effectively prevent Mn and Co ions dissolution in electrolyte at elevated temperature. When both samples were stored in 6g electrolyte at 55℃ for 60 hours, the electrolyte with pristine turned to light brown color, while with CePO4 coated electrode kept the colorless which means less dissolution of transition metal ions.. 12.
(28) Figure 8. Cycling performance of Li1.2Ni0.13Mn0.54Co0.13O2 with Al2O3 and TiO2 coatings 27.. 13.
(29) Figure 9. HR-TEM, HAADF (high angle annular dark field) photographs and EDS spectra HRTEM, HAADF photographs and EDS spectra of the uncoated (a, d and g), Al2O3 coated (b, e and h) and TiO2 coated (c, f and i)Li1.2Ni0.13Mn0.54Co0.13O 2 particles by ALD 27.. 14.
(30) Figure 10. DSC profiles of pristine and FePO4 coated Li1.2Ni0.13Co0.13Mn0.54O2 after the first cycle and charged to 4.8 V 28.. 15.
(31) Figure. 11.. Capacity. retention. of. Li1.2Ni0.13Co0.13Mn0.54O2. and. CePO4. coated. Li1.2Ni0.13Co0.13Mn0.54O2 at 55℃, the insets show both electrodes stored in the electrolyte at 55℃ for 60 hours 25.. 16.
(32) Figure 12. HAADF-STEM images of the bare and surface coated 0.4Li2MnO3·0.6LiNi1/3Co1/3 Mn1/3O2 cathode material. a–c) STEM images of a primary particle of bare Li-rich oxide; d) atomic crystal model for layered LiMO2 with R𝟑m phase; e–g) STEM images of a primary particle of surface treated Li-rich oxide (image (g) is expanded view of (f)); and h) atomic crystal model for rock salt (Fm𝟑m) phase, in which TM occupy the original Li slab of R𝟑m phase 24.. 17.
(33) As another solution to enhance the cycle performance at elevated temperature is MgPO4 coating 25. Figure 12a-c indicates that the bare lithium rich with highly ordered layered structure which the transition metal layer has the highest contrast in the high angle annular dark field (HAADF) Z-contrast image. Figure 12e-g shows structural change at the surface after LiMg-PO4 coating, and cation mixing can be observed from figure 4g where part of lithium ion is replaced by transition metal ions. This results in NiO cation mixing phase in the inner surface region of Li-Mg-PO4. After coating, the cycle performance at high temperature was much improved because of this stable inactive inner surface layer which can control the side reaction with electrolyte reducing the formation of thick SEI layer. Furthermore, the presence of Mg2+ in lithium layer can control the cation mixing upon cycling.. Figure 13. The discharge capacity versus prolonged cycle of 0.4Li2MnO3·0.6LiNi1/3Co1/3Mn1/3 O2 and LiMgPO4 1.5 wt% 0.4Li2MnO3·0.6LiNi1/3Co1/3Mn1/3O2 at 60 °C with 1C/1C rate after 10 cycle’s formation 24.. 18.
(34) 1.2.6 Strategies to improve the initial coulombic efficiency The fundamental mechanism behind the unusual electrochemical behavior of Li-rich cathodes during the first charge/discharge process has been extensively investigated. A large first-cycle irreversible capacity loss and a low initial coulombic efficiency (≤80%) compared to other cathode materials is one of the main problems of lithium rich cathode materials for fullcell operation. The reason of this high irreversible capacity loss is originated in the activation process of the Li2MnO3 component, which is associated with the removal of lithium ions concomitant with an irreversible loss of oxygen 30. According to previous reports, it is possible to maintain the high reversible capacity and minimize the irreversible capacity. This drawback can be improved by synthesis conditions, chemical activation, substitution and coating. In case of synthesis condition, controlling of primary particle size is the key factors to achieve good electrochemical performance of lithium rich cathodes. It is generally accepted that a cathode material with large primary particle has low ionic conductivity due to its longer lithium ion diffusion pathway in the particles.. Figure 14. (a) SEM images of Li1+xNi1/6Co1/6Mn4/6O2.25+x/2 (0.1 ≤ x ≤ 0.7) initial charge/discharge curves of Li1+xNi1/6Co1/6Mn4/6O2.25+x/2 electrodes (b) the corresponding charge/discharge/irreversible capacities 1. 19.
(35) Figure 14. Shows SEM images of the Li1+xNi1/6Co1/6Mn4/6O2.25+x/2 cathodes prepared via lithiation of the precursors with different amounts of lithium source 1. The primary particles became larger after the lithiation process. Samples with x = 0.1–0.3 show small primary particle size from around 80 to 100 nm, but further increasing the amount of lithium source, samples show several micrometer-sized primary particles. For electrochemical performance, the discharge capacity is increased for samples with x = 0.1–0.3, and then decrease for samples with x = 0.3–0.7. The sample with lowest irreversible capacity loss is x = 0.3. This is contributed to its lower degree of cation mixing compared to the samples with x = 0.1 and 0.2, and its smaller primary particle size compared to the other samples. It is clear that the secondary particles composed with small primary particles have short Li-ion diffusion pathways and facile intercalation of Li+ ions into cathode materials which can provide high discharge capacity and high initial coulombic efficiency. Samples with x = 0.1–0.3 show small primary particle size from around 80 to 100 nm. The morphological change occurs at the sample with x = 0.4, which contains both nanometer-sized and micrometer-sized primary particles. By further increasing the amount of lithium source, samples of x = 0.5–0.7 show several micrometer-sized primary particles. Charge/discharge performance of these materials demonstrates that the charge capacity and irreversible capacity values rise with the increase of lithium content. However, the discharge capacity values increase for samples with x = 0.1–0.3, and then decrease for samples with x = 0.3–0.7. The highest discharge capacity of 288 mAh g-1 and the lowest initial coulombic efficiency was obtained for the sample with x = 0.3; this is attributed to its lower degree of cation mixing compared to the samples with x = 0.1 and 0.2, and its smaller primary particle size compared to the samples with x = 0.4 – 0.7. According to the trend between particle size and initial coulombic efficiency, the secondary particles that are composed of small primary particles give rise to short Li-ion diffusion pathways and facile intercalation of Li+ ions into cathode materials, so they can provide high discharge capacity and high initial coulombic efficiency. In this regard, proper lithium content and calcination temperature are two critical factors that have to be taken into account when optimizing synthesis of lithium rich cathode cathodes. Also, there are many factors which can seriously effect on primary particle size such as annealing temperature, co-precipitation process condition, lithium source, and so on 30. In case of chemical activation, there is acid and base treatment. During charge process, Li2MnO3 phase is electrochemically inactive under 4.4V and this is major cause for the instability of the surface structure and electrochemical performance. However, Li2O component in Li2MnO3 phase can be removed chemically by acid or base treatment. The main mechanism of this chemical activation can be classified with the ion-exchange reaction between Li+ / H+ and Li2O dissolution.. 20.
(36) Figure 15. (a) Initial charge-discharge curves between 2.0 and 4.6 V, for lithium cells with 0.5 Li2MnO3·0.5 LiNi0.44Co0.25Mn0.31O2 and HNO3-treated electrodes; (b) Cycling stability of with 0.5 Li2MnO3·0.5 LiNi0.44Co0.25Mn0.31O2 and HNO3-leached electrodes 31.. 21.
(37) As shown in figure 15, the first-cycle charge capacity is reduced with (NH4)2SO4 treatment. 31. . The reduction of charge capacity is proportional to treated (NH4)2SO4 content,. which is consistent with the amount of extracted lithium ions from the active material during the treatment. 32. . However, the acid-leached samples exhibited worsened capacity retention. compared to the untreated samples. These negative effects are more obvious with electrodes were preconditioned for longer times because this process can cause damage on the surface structure. In addition, the initial coulombic efficiency can be improved by surface coating or blending with proper materials. Figure 16 shows the improvement of initial coulombic efficiency by blending lithium rich cathode materials with other lithium-free/deficient materials including VO2, which can act as a lithium-free host coating material, and Li3PO4. Lithium-free host VO2 absorbs lithium ions extracted from the pristine material. This lithium-accepting ability results in decreased irreversible capacity and enhanced initial coulombic efficiency. In case of Li3PO4-coated sample, kinetic barrier for lithium ion intercalation into MnO2 component is reduced.. 22.
(38) Figure 16. Li insertion host blending/coating: (a) Initial charge/discharge curves of VO2 added Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cells and corresponding irreversible capacity and initial coulombic efficiency. (b) Initial charge/discharge curves of Li3PO4 coated Li1.18Co0.15Ni0.15Mn0.52O2 cells and corresponding irreversible capacity and initial coulombic efficiency; (c) first cycle CV curves of the pristine (black line), 1.0 wt% (red line) and 3.0 wt% (blue line) Li3PO4 coated Li1.18Co0.15Ni0.15Mn0.52O2 cells. 32. 23.
(39) 1.2.7 Synthesis of lithium rich cathode material by co-precipitation method It is important to have a high tap density for lithium ion battery because higher tap density leads high electrode density related with higher volumetric capacity in practical batteries. To achieve high tap density, preparation of powders is a key factor. It has been already reported that spherical particle can have higher tap density with less agglomeration which leads easy packing for electrode. 33. . Also, some of research groups have reported uniform distribution of. powders is necessary for high tap-density because irregular particles can lead serious agglomeration with lots of vacancies between particles results in bad fluidity. Co-precipitation is well-known for preparation method to have these key factors for high tap-density. Moreover, coprecipitation method is the best choice to prepare metal hydroxide because by this method, phase-pure oxide products can be essentially obtained. In case of solid-state reaction method, it has impure phase leading degradation of cell performance, and this method is not proper method to prepare lithium rich cathode materials despite of standpoint of economics 34. There are other methods such as sol-gel combustion method, but co-precipitation method has shown the most uniform distribution of transition metal which is very necessary for electrochemical properties due to enhanced structural stability 35. However, there is a serious drawback of co-precipitation method which is the hardest synthesis method to optimize the condition to control the morphology. Such as particle size, distribution and morphology are significantly depend on the synthetic condition of coprecipitation like pH, chelating agent, stirring speed, temperature and inert atmosphere 36. For example, optimize pH is a crucial part to prepare homogeneous powder especially for making formation of manganese oxide. Manganese oxide is favored to be generated when the inert temperature is higher than 60oC, and the pH range in which manganese hydroxide cannot be precipitated. 37. . Also, it has been investigated that pH during the co-precipitation decides the. particle size and morphology. Figure 17 shows the SEM images indicating the effect of controlling pH. With increasing pH, distribution of particle became not uniform and has smaller secondary particle size. The amount of chelating agent is also very important to optimize synthetic condition. NH3+ ion is known for promotion of formation dense sphere-like hydroxide 38. . It is hard to optimize co-precipitation condition for high tap density lithium rich cathode. materials, but morphologies of particles can be controlled by these factors, and it is possible to get dense and uniform metal hydroxide precipitates.. 24.
(40) Figure 17. SEM images of [Ni1/3Co1/3Mn1/3](OH)2 powders at various pH. (a) P1 11.0; (b) P2 11.5; and (c) P3 12.0. 25.
(41) Ⅱ. Experiment 2.1 Experimental method 2.1.1 Synthetic optimization of Ni0.2Co0.2Mn0.6(OH)2 by co-precipitation To prepare Ni0.2Co0.2Mn0.2(OH)2, NiSO4･6H20, MnSO4･5H20, and CoSO4･7H2O were mixed with a molar ratio of Ni:Co:Mn = 2: 2: 6 and with a concentration of 2.0 mol/L in distilled water. The mixed transition metal solution was put into a CSTR (continuous stirred tank reactor) under O2 atmosphere. Simultaneously, 4.0 mol/L solution of NaOH and the desired amount of NH4OH solution as a chelating agent were separately fed into the CSTR at 50 oC. The pH, temperature, stirring speed and concentration of the mixture were monitored and controlled during the reaction process. Co-precipitation powders were filtered and washed. The washed powders were dried at 140 oC for overnight. The prepared Ni0.2Co0.2Mn0.2(OH)2 powder was mixed with LiOH･H2O, preheated at 450 oC and calcined.. 2.1.2. Benchmarking of lithium rich cathode materials To prepare the CoPO4 coated sample, the bare powder was immersed into the acidic solution of Co(NO3)2∙6H2O and H3PO4 (85 wt% in H2O) for the chemical activation. The mixture was stirred vigorously at 150℃ until water removal, and then the result powder was heated at 600℃ for 3 hours.. 2.1.3. Blending of lithium rich and nickel rich cathode materials Li1.17[Mn0.6Ni0.2Co0.2]0.83O2 and Li[Ni0.75Co0.1Mn0.15]O2 were selected as the cathode materials for blending. These two cathode materials were physically blended to enhance the balanced performance compared to individual compound.. 26.
(42) 2.2 Electrochemical measurement The cathode electrodes were consisted of 80 wt% prepared powders, 10 wt% super P carbon black, and 10 wt% polyvinylidene fluoride (PVDF) binder. The mixed slurry was coated on Al foil and dried in oven at 120℃ for 2 hours. After pressing of electrode, the electrochemical tests were carried out. CR2032 coin-type cell was used for assembling cell, which contains a cathode electrode and a lithium metal anode separated by the porous polypropylene. These were assembled in a glove box under Ar atmosphere. The electrolyte was 1.3M LiPF6 in ethylene carbonate (EC) and diethylene carbonate (DEC) in 3:7 volume ration (PANAX ETEC Co. LTd., KOREA). The galvanostatic charge-discharge tests were conducted in a voltage range of 4.6 to 2.0 V. Li/Li+. The active material loading density was 5.5 mg/cm2. Before electrochemical tests, the cells were galvanostatically charged to 4.6V at 0.1C rate, and maintained at 4.6 V until the current decrease to 0.02C rate, then discharged to 2.0V vs Li/Li+.. 2.3 Instrumental analysis Structural analysis: The crystalline phase of samples was analyzed by powder X-ray diffractometer (XRD, D/MAX-2200V, Rigaku) using Cu Ka radiation. XPS was measured using an Escalab instrument (Escalab 250 xi, Thermo Scientific, England). The morphology of samples were examined by scanning electron microscopy (SEM, S-4800, HITACHI).. 27.
(43) Ⅲ. Results and discussion 3. 1 Synthetic optimization of Ni0.2Co0.2Mn0.6(OH)2 by co-precipitation at oxygen atmosphere The precursor of Ni0.2Co0.2Mn0.6(OH)2 was successfully synthesized by co-precipitation method under oxygen inert atmosphere. In order to synthesize homogeneous and powder with spherical particle shape, it is important to control and optimize pH condition. If pH is too high, particle cannot be spherical shape leading lower tap density, and if it is too low, manganese oxide cannot be formed because manganese oxide is favored to form by increasing pH in the range of which manganese hydroxide is not precipitated. 39. . Therefore, to optimize synthetic. condition by co-precipitation at oxygen atmosphere, controlling of pH was carried out. Figure 19 shows the SEM images of Ni0.2Co0.2Mn0.6(OH)2 powders synthesized at different pH. The pH range was selected from 9.2 to 9.5 according to the previous experiments which were not mentioned here. When the pH was 9.2, it showed the particle size around 14 um which is the biggest particle size among the pH range. Therefore, the condition of pH was set as 9.2. It is well known that the amount of chelating agent which is NH4OH is important to optimize the co-precipitation condition. It has been reported that narrow distribution and spherical particles can be formed with increasing of NH3+. Also, NH3+ has the roles which prevent the formation of phase separation during co-precipitation, and promote homogeneous metal hydroxide. If NH4OH as the chelating agent is not added, Ni(OH)2, Co(OH)2 or Mn(OH)2 can be produced as impurity phase 39. Therefore, it is important to add the suitable amount of chelating agent. As shown in figure 19, with increasing of NH3+, spherical and uniform particle can be formed which leads higher tap-density. Finally, stirring speed was considered to optimize the co-precipitation condition. It is known that higher stirring speed can promote narrow particle size distribution under nitrogen atmosphere. However, under the oxygen atmosphere, the effect of controlling stirring speed has not been reported and it showed the opposite results compared to the previous researches under nitrogen atmosphere. Lower stirring speed showed the better morphology which has narrow particle size distribution, and spherical shaped powder. Figure 20 shows the effect of stirring speed under oxygen atmosphere. The final precursor product showed tap density of 1.41g/cc.. 28.
(44) (a). 5μm. (b). 5μm. (c). 20μm. Figure 18. SEM images of U1, U2 and U3. (Ni0.2Co0.2Mn0.6(OH)2 precursors prepared at different pH according to Table 1). 29.
(45) Figure 19. SEM images of U4 and U5. (Ni0.2Co0.2Mn0.6(OH)2 precursors prepared at different the amount of NH4OH according to Table 1). 30.
(46) Figure 20. SEM images of U3 and U6. (Ni0.2Co0.2Mn0.6(OH)2 precursors prepared at different stirring speed of agitator in the reactor according to Table 1). 31.
(47) Sample Name. pH. rpm. NH3/MSO4 (ml). Particle size (μm). U1. 9.55. 1460. 0.19. 8. U2. 9.38. 1460. 0.19. 13. U3. 9.20. 1460. 0.19. 15. U4. 9.55. 1460. 0.19. 11. U5. 9.55. 1460. 0.27. 11. U6. 9.20. 1100. 0.19. 15. Table 1. Synthetic conditions and physical property of U1 to U6 Ni0.2Co0.2Mn0.6(OH)2 powders.. 32.
(48) 3. 2 Preparation of Li1+x[Mn0.6Ni0.2Co0.2]1-xO2 After preparation of Ni0.2Co0.2Mn0.6(OH)2 as the precursor, the ratio of Li/TM and calcination temperature were considered as synthetic optimization factors. It has been investigated that higher calcination temperature leads growth of primary particle. If the primary particle is too big, diffusion length of lithium ion gets too long especially at the end of charge and discharge process. 40. . It was obviously observed from the experiment of. controlling the calcination temperature as shown in table 2. Calcination temperature was fixed to 800oC for 10 hours because it showed the highest reversible capacity among the other calcination conditions. Figure 21 displays the SEM images of Li1+x[Mn0.6Ni0.2Co0.2]1-xO2 samples from P5 to P9 calcined at 800oC.. Figure 21. SEM images of Li1+x[Mn0.6Ni0.2Co0.2]1-xO2 samples from P5 to P9 calcined at 800oC for 10h and precursor of [Mn0.6Ni0.2Co0.2]OH2. 33.
(49) Table 2. The comparsion electrochemical performance of Li1+x[Mn0.6Ni0.2Co0.2]1-xO2 depending on different calcination conditions.. 34.
(50) Figure 22. Voltage profiles of P10, P11 and P13 cathodes in coin-type half cells between 2.0 and 4.6 V at 0.1C rate (= 20mAg-1) under 24oC.. As shown in table 2, P10, P11 and P13 showed the best electrochemical performance at the first cycle. The voltage profiles of these three samples during the first charge and discharge cycle are shown in figure 22. The coin type cells (2032R) were charged at 0.1C rate Sample. Composition. Name. Charge. discharge. (mAhg-1). (mAhg-1). Initial coulombic efficiency(%). 450℃ 5hr. P10. Li1.15[Ni0.2Co0.2Mn0.6]0.85O2. 292. 250. 86. 800℃ 10hr. P11. Li1.17[Ni0.2Co0.2Mn0.6]0.83O2. 296. 249. 84. P13. Li1.15[Ni0.2Co0.2Mn0.6]0.85O2. 295. 253. 86. 450℃ 10hr 800℃ 10hr. Table 3. The comparsion electrochemical performance of Li1+x[Mn0.6Ni0.2Co0.2]1-xO2 depending on different calcination conditions. 35.
(51) (1C=200mAhg-1) to 4.6V and maintained at 4.6V until the current decreased to 0.02C rates, then discharged at 0.1C rate (1C=200mAg-1) to 2.0V at 24oC. The first discharge capacities of the P10, P11 and P13 were 292, 296 and 295 mAh/g, respectively, at 0.1C rate.. Figure 23 shows a plot of the discharge capacities of P10, P11 and P13 samples in lithium half cells between 2.0V and 4.6V at 0.5C rate under at 24oC. After 50 cycles, the capacity retentions were 87%, 92% and 92%, respectively. P11 and P13 showed the same capacity retention higher than P10. However, as shown in figure 24 at 60oC, P13 exhibited the best capacity retention. P10, P11 and P13 showed 85%, 88% and 86%, respectively.. 36.
(52) Figure 23. Cycle performance during 100 cycles between 2.0 and 4.6 V at 1C rate of charge and discharge between 2.0 V and 4.6 V at 24oC.. Figure 24. Cycle performance during 50 cycles between 2.0 and 4.6 V at 1C rate of charge and discharge at 60oC.. 37.
(53) 3. 3 Benchmarking of lithium rich cathode materials To compare the properties of Li1.17[Ni0.2Co0.2Mn0.6]0.83O2 with other lithium rich cathode materials made by TODA, BASF and Samsung, several tests were carried out. Figure 25 shows the SEM images of Li1.17[Ni0.2Co0.2Mn0.6]0.83O2 (denoted as UNIST), benchmarking of samples A, B and C. UNIST and sample A were synthesized by coprecipitation method under oxygen inert atmosphere, however, samples B and C were made by carbonate co-precipitation method. As shown in SEM images of UNIST and Sample A, these samples made under oxygen atmosphere shows larger primary particle size, and sample B and C which were made by carbonate co-precipitation method shows smaller primary particle size with more spherical secondary particle shape.. Figure 25. SEM images of UNIST Bare, Benchmarking Sample A, B and C.. 38.
(54) The voltage profiles of UNIST Li1.17[Ni0.2Co0.2Mn0.6]0.83O2 (denoted as UNIST) and other benchmarking samples during first charge and discharge cycles are shown in figure 26. The coin type cells (2032R) were charged at 0.1C rate (1C=200mAg-1) to 4.6V and maintained at 4.6V until the current decreased to 0.02C rates, then discharged at 0.1C rate (1C=200mAg-1) to 2.0V at 24℃. The discharge capacity of UNIST, CoPO4 0.5wt % and CoPO4 1wt % coated on UNIST Li1.17[Ni0.2Co0.2Mn0.6]0.83O2 samples were 250, 235 and 232 mAhg-1, and coulombic efficiency of these samples were 84.7%, 79.4% and 80.1% respectively. The discharge capacities of coated samples were lower than that of UNIST bare because of the weight percent of coated materials. During the coating process, there was lithium ion extraction from Li 2MnO3 phase, and this leads capacity loss due to reduce of active materials. Also, the capacity of coated samples from constant voltage mode at 4.6V was much lower than that of oxide bare because the capacity from constant voltage mode is correlated with the overpotential. It means the CoPO4 coated samples have lower overpotential than oxide bare electrode. The discharge capacities of sample A, B, and C were 255, 255 and 260mAhg-1, and the coulombic efficiency of these samples were 93, 92 and 96 % respectively. These coulombic efficiencies were higher compared to UNIST because as shown in figure 25, primary and secondary particle sizes were much smaller than UNIST. Figure 27 displays the cycling performances of bare and CoPO4 coated UNIST during 100 cycles between 2.0 and 4.6 V at 1C charge / discharge at 24oC after 2.0-4.6 V, 0.1C initial cycle, and Figure 28 shows cycle performance of sample A, B and C 100 cycles between 2.0 and 4.6 V at 1C charge / discharge at 24oC after 2.0-4.6 V, 0.1C initial cycle. UNIST samples show the much higher capacity retention compared to other samples even without coating effect. It is assumed that sample A, B and C have much smaller primary particle than UNIST as shown in figure 25. This smaller primary particle size might lead improved initial coulombic efficiency at the first cycle, but increased surface area can cause severe side effect between electrolyte and cathode materials. In case of UNIST samples, there wasn’t significant improvement after coating because the presence of Li-Co-PO4 coating layer acting a physical protection layer to minimize the direct contact between electrolyte and active materials, but as shown in figure 31, by-product of UNIST after cycling at 24 oC was not severe compared to others. This means UNIST sample does not need protection coating layer at room temperature, and due to this reason, there wasn’t clear difference of cycling performance after coating.. 39.
(55) Figure 26. Voltage profiles of UNIST bare and CoPO4 coated Li1.17[Mn0.6Ni0.2Co0.2]0.83O2, Sample A, B and C between 2.0 V and 4.6 V at 0.1C rate of charge and discharge at 24oC.. 40.
(56) -1. Discharge Capacity /mAhg. 300 250 200 150 100 UNIST bare Li1.17[Mn0.6Ni0.2Co0.2]0.83O2. 50. CoPO4 0.5 wt% coated UNIST CoPO4 1.0 wt% coated UNIST. 0 0. 10. 20. 30. Number of Cycle. 40. 50. Figure 27. Cycle performance of bare and CoPO4 coated UNIST during 100 cycles between 2.0 V and 4.6 V at 1C rate of charge and discharge at 24oC.. Figure 28. Cycle performance of benchmarking UNIST Bare, sample A, B and C during 100 cycles between 2.0 V and 4.6 V at 1C rate of charge and discharge at 24oC.. 41.
(57) -1. Discharge Capacity /mAhg. 350 300 250 200 150 100 UNIST bare Li1.17[Mn0.6Ni0.2Co0.2]0.83O2. 50. CoPO4 0.5 wt% coated UNIST CoPO4 1.0 wt% coated UNIST. 0 0. 20. 40. 60. Number of Cycle. 80. 100. Figure 29. Cycle performance of bare and CoPO4 coated UNIST during 100 cycles between 2.0. Discharge Capacity /mAhg. -1. V and 4.6 V at 1C rate of charge and discharge at 60oC.. 350 300 250 200 150 100 Sample A Sample B Sample C. 50 0 0. 20. 40. 60. Number of Cycle. 80. 100. Figure 30. Cycle performance of benchmarking sample A, B and C during 100 cycles between 2.0 V and 4.6 V at 1C rate of charge and discharge at 60oC.. 42.
(58) The cycling performances of bare and CoPO4 coated UNIST, Sample A, B and C during 100 cycles between 2.0 and 4.6 V at 60oC were displayed in figure 29, 30. UNIST showed much enhanced the capacity retention compared to sample A, B and C. The capacity retention was much improved after coating, and 1.0 wt% coated sample showed slightly better retention than 0.5 wt % coated sample because spinel phase and LiCoPO4 layers formed at the surface of coated sample can prevent from directly exposure to electrolyte which leads side reaction.. Figure 31. The comparison of by-product of UNIST, sample A, B and C after cycling at 24oC.. The thermal stability was evaluated by differential scanning calorimetry (DSC) analysis were carried out. Figure 32 shows the DSC measurement results of the bare and CoPO4 0.5 wt % and CoPO4 1.0 wt % at 4.6V in the presence of the electrolyte. Lithium ion half-cell was carefully disassembled after first charge/discharge and second charge process, and DSC measurement was carried out from 50℃ to 350℃ in Ar blowing condition. The main peaks of coated samples were 206.4℃ and 207.5℃ which are higher than that of bare at 198.5℃. Moreover, after coated samples showed significantly lower heat of 598.7 Jg-1 and 432.1 Jg-1. The improved thermal property is ascribed to the double protection cation-doped spinel and LiCoPO4 layers with good thermal stability. This protective layer on the cathode surface can prevent from directly exposure to electrolyte which leads side reaction and exothermic reaction.. 43.
(59) Figure 32. DSC of bare and CoPO4 coated UNIST samples at 4.6 V; electrodes after DSC measurement from 50oC to 350oC.. Table 4. DSC of bare and CoPO4 coated UNIST samples at 4.6 V; electrodes after DSC measurement from 50oC to 350oC. 44.
(60) Potential /V vs. Li/Li. +. 3. 4 Blending of NCM and lithium rich cathode materials. 4.5 4.0 3.5 Li1.17[Mn0.6Ni0.2Co0.2]0.83O2. 3.0. blended OLO:NCM=5:5 blended OLO : NCM=6:4 blended OLO : NCM=7:3 Li[Ni0.75Co0.1Mn0.15]O2. 2.5 0. 50. 100. 150. 200. 250 -1. Specific Capacity / mAh g. Figure 33. Voltage profiles of Li1.17[Mn0.6Ni0.2Co0.2]0.83O2, blended OLO: NCM= 5:5, blended OLO:NCM= 6:4, blended OLO:NCM= 7:3 and Li[Ni0.75Co0.1Mn0.15]O2 between 2.0 V and 4.6 V at 0.1C rate of charge and discharge at 24oC.. Lithium rich cathode material has high manganese contents results in cheap cost, the highest capacity among the cathode materials, and good thermal stability. However, impedance at low SOC is higher, and this material has low initial coloumbic efficiency and low tap density. Due to the low tap density, lithium rich cathode material has low volumetric energy density, and substantial voltage decay over repeated cycling owing to a transformation to spinel-like phase. 41. On the other hand, Ni-based cathode material approaches a capacity of 220 mAhg-1 with. almost 80% reversible extraction of lithium in the host structure. 42. , and higher density than. lithium rich cathode materials. However, due to the similar radius of lithium ion and nickel ion, non-stoichiometric structure can be usually found as the result of cation mixing. This phenomenon causes serious problems such as capacity loss and structure deterioration and surface side reaction 43. The purpose of blending these two materials was to take the advantages of each material and optimize the performance in low cost. 44. . Figure 33 shows the first-cycle. charge and discharge curves for separate half cells of Li1.17[Mn0.6Ni0.2Co0.2]0.83O2 (denoted as OLO), blended OLO: NCM= 5:5, blended OLO:NCM= 6:4, blended OLO:NCM= 7:3 and Li[Ni0.75Co0.1Mn0.15]O2 (denoted as NCM) cathodes. 45.
(61) -1. Discharge Capacity /mAhg. 250 200 150 100 50. Li1.17[Mn0.6Ni0.2Co0.2]0.83O2 blended OLO:NCM=5:5 Li[Ni0.75Co0.1Mn0.15]O2. 0 0. 10. 20. 30. Number of Cycle. 40. 50. Figure 34. Cycle performance during 50 cycles of OLO, blended OLO:NCM = 5:5 and NCM. Discharge Capacity /mAhg. -1. between 2.0 V and 4.6 V at 1C rate of charge and discharge at 24oC.. 300 250 200 150 100 Li1.17[Mn0.6Ni0.2Co0.2]0.83O2. 50. blended OLO:NCM=5:5 Li[Ni0.75Co0.1Mn0.15]O2. 0 0. 10. 20. 30. Number of Cycle. 40. 50. Figure 35. Cycle performance during 50 cycles of OLO, blended OLO:NCM = 5:5 and NCM between 2.0 V and 4.6 V at 1C rate of charge and discharge at 60oC.. 46.
(62) Figure 34 and 35 plot the discharge capacity as a function of cycle number of OLO, blended OLO:NCM = 5:5 and NCM at 24oC and 60oC. At 24oC, blended cathode material showed the same cycle retention of 90 % as UNIST Li1.17[Ni0.2Co0.2Mn0.6]0.83O2. After blended, it exhibited much enhanced cycling performance compared to the NCM because although both Lirich and Ni-rich cathode materials have the similarity in their basic composition and structures, but they have significant difference in their electrochemical behavior and properties and crystal chemistries. As shown in figure 33, after blended these two cathode materials, initial coulombic efficiency was improved from 80% to 86% compared to lithium rich cathode material. Also with increasing the ratio of lithium rich to nickel rich cathode materials, it showed increased over-potential. However, at 60oC blended cathode materials with the ratio of 5:5 displayed lower discharge cycle retention than both of lithium rich and nickel rich cathode materials. This result might be due to the inadaptable cut-off voltage for this electrochemical test because the usual working voltage of this material is between 2.5V to 4.5V, but to activate the lithium rich cathode material, this electrochemical tests were carried out between 2.0V to 4.6V.. 47.
(63) IV. Conclusion In summary, to overcome the drawbacks of lithium rich cathode materials, we suggest the optimized co-precipitation synthetic conditions under inert oxygen atmosphere for high-tap density cathode materials, and showed the best electrochemical properties compared to other lithium rich cathode materials. Ni0.2Co0.2Mn0.6(OH)2 was successfully synthesized by coprecipitation method at oxygen atmosphere by controlling the pH, the amount of chelating agent and stirring speed. After preparation of precursor, lithiation process depending on the calcination temperature was investigated, and final optimized Li1.15[Mn0.6Ni0.2Co0.2]0.85O2 showed the best electrochemical properties. Also, to take advantage and achieve more balanced performance, blended lithium rich with nickel rich cathode materials were investigated. These various methods to overcome the drawbacks of lithium rich cathode materials could improve electrochemical properties and tap density.. 48.
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Table 2. 이후 쇼크와 다장기부전이 갑작스럽게 발생한다. 혈청 creatinine kinase 농도의 증가는 괴사근막염이나 근육염을 의심하게 하는 소견이다.. Hippocrates
