A Novel Recovery Process of Metal Values from Spent Lithium-ion Secondary Batteries

Yu-Chuan Lin Prof. Rong-Chi Wang Prof. She-Huang Wu

Thesis for Master of Science Department of Chemical Engineering Tatung University July 2008

ACKNOWLEDGEMENTS

Firstly, I would sincerely appreciate my advisor, Dr. Rong-Chi Wang and Dr. She-huang Wu, for his conscientious guidance, education, discussion and encouragement throughout the course of this research during the study of master. Secondary, thanks are also due to the members of committee, Rong-Chi Wang, She-Huang Wu and Fu-Chang Huang, for their review and comments on this thesis. Finally, I would like to thank all my classmates and Zheng-Han Chen Wu for their assistance to finish this research and thankful to my parents for their support and concern.

Yu-Chuan Lin

ABSTRACT The simulated experiments with the separation and recovery of metal values such as cobalt, manganese, nickel and lithium from spent lithium-ion secondary batteries were studied. A leaching efficiency of more than 99% of cobalt, manganese, nickel and lithium could be achieved with 4 M HCl solution, 80 oC leaching temperature, 1 h leaching time and 1/50 g/ml solid-to-liquid ratio. The manganese in the leaching liquor was reacted selectively and nearly completely with KMnO4 reagent, then the manganese was recovered as MnO2 and manganese hydroxide. The nickel in the leaching liquor was adsorbed selectively and nearly completely with

dimethylglyoxime. An addition of 1M NaOH solution to reach pH=11 allowed the selective precipitation of cobalt hydroxides. The remaining lithium in the aqueous solution was readily recovered as lithium carbonate precipitate by the addition of a saturated sodium carbonate solution. The recovery of cobalt and manganese hydroxides would be used to synthesize LiCoO2 and LiMn2O4 as a cathode in a common lithium-ion battery configuration. The performance of the electrochemical properties was also tested.

Keywords: leaching, recovery, lithium-ion secondary batteries.

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LiCoO2LiMn2O4 LiCo1/3Ni1/3Mn1/3O2 4M 80oC 1 1/50 g/ml 99% KMnO4 dimethylglyoxime 1M pH 11 100oC LiCoO2 LiMn2O4

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TABLE OF CONTENTS PAGE ACKNOWLEDGEMENT ............................................................................... i ABSTRACT (ENGLISH)............................................................................... ii ABSTRACT (CHINESE) .............................................................................. iii TABLE OF CONTENTS............................................................................... iv LIST OF TABLES ....................................................................................... viii LIST OF FIGURES ....................................................................................... ix NOMENCLATURE..................................................................................... xiii CHARPTER 1 INTRODUCTION............................................................................. 1 2 LITERATURE REVIEW .................................................................. 6 2.1 Introduction of Lithium Ion Secondary Battery .......................... 6 2.1.1 Concept of the Secondary Lithium Ion Battery ................ 6 2.1.2 Cathode Materials ............................................................. 8 2.1.2.1 LiCoO2 Cathode Material....................................... 8 2.1.2.2 LiMn2O4 Cathode Material..................................... 9 2.1.2.3 LiMnO2 Cathode Material.................................... 10 2.1.2.4 LiNiO2 Cathode Material ......................................11 2.2 Lithium Ion Secondary Battery of Recycling Processes ........... 11 2.2.1 Physical Processes........................................................... 14 2.2.1.1 Mechanical Separation Processes......................... 14
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2.2.1.2 Thermal Treatment ............................................... 17 2.2.1.3 Mechanochemical Process ................................... 18 2.2.1.4 Dissolution Process .............................................. 20 2.2.2 Chemical Processes ......................................................... 21 2.2.2.1 Acid Leaching....................................................... 21 2.2.2.2 Bioleaching........................................................... 24 2.2.2.3 Solvent Extraction ................................................ 24 2.2.2.4 Chemical Precipitation ......................................... 27 2.2.2.5 Electrochemical Process....................................... 30 2.3 Effect of Reaction Operating Conditions................................... 32 2.3.1 Effect of Leaching Process.............................................. 32 2.3.1.1 Effect of Acid Concentration ............................... 34 2.3.1.2 Effect of Reaction Temperature ........................... 38 2.3.1.3 Effect of Reaction Time ....................................... 42 2.3.1.4 Effect of Solid-to-Liquid Ratio (S/L)................... 42 2.3.2 Effect of Recovery Materials Process............................. 47 2.3.2.1 Effect of Precipitate of Manganese ...................... 47 2.3.2.2 Effect of Precipitate of Nickel.............................. 48 2.3.2.3 Effect of Precipitate of Cobalt.............................. 51 2.3.2.4 Effect of Precipitate of Lithium ........................... 53 2.3.3 Effect of Preparation of the Cathode Electrode .............. 53 3 EXPERIMENTAL .......................................................................... 57 3.1 Materials..................................................................................... 57 3.2 Experimental Procedure............................................................. 62 3.2.1 Leaching Process............................................................. 62 3.2.1.1 Simulated Experiment of Leaching Process ........ 62
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3.2.2 Recovery Materials Process ............................................ 63 3.2.2.1 Leaching Process for the Mixture ........................ 65 3.2.2.2 Sedimentation Reaction........................................ 65 3.2.2.3 Precipitate of Manganese ..................................... 67 3.2.2.4 Precipitate of Nickel............................................. 67 3.2.2.5 Precipitate of Cobalt............................................. 68 3.2.2.6 Precipitate of Lithium........................................... 69 3.2.3 Purity Analyses of Recovery Materials .......................... 69 3.2.4 Electrochemical Analyses ............................................... 69 3.2.4.1 Powder Prepared by Solid-State Reaction ........... 69 3.2.4.1.1 Preparation of LiCoO2 Powder .................... 69 3.2.4.1.2 Preparation of LiMn2O4 Powder .................. 70 3.2.4.2 Preparation of the Cathode Electrode................... 70 3.2.4.3 Assembly of the Coin-Type Cell .......................... 71 3.3 Experimental Apparatus............................................................. 72 3.3.1 Leaching Process Apparatus ........................................... 72 3.3.2 Recovery Materials Process Apparatus........................... 72 3.3.3 pH Value Analyses Apparatus ........................................ 72 3.3.4 Filtration Experiments Apparatus ................................... 75 3.4 Characteristic Analysis of Cathode Active Material.................. 75 3.4.1 X-Ray Diffraction Analysis............................................. 75 3.4.2 Composition Determination ............................................ 75 3.4.2.1 Atomic Adsorption Spectroscopy Analysis ......... 75 3.4.2.2 Inductively Coupled Plasma Optical Emission Spectrometer Analysis ......................................... 77 3.4.3 Capacity Retention Studies ............................................. 78
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RESULTS AND DISCUSSION...................................................... 79 4.1 Leaching Process ....................................................................... 79 4.1.1 Simulated Experiment of Leaching Process ................... 79 4.1.1.1 Hydrochloric Acid Concentrations....................... 80 4.1.1.2 Leaching Temperature.......................................... 80 4.1.1.3 Leaching Time...................................................... 87 4.1.1.4 Solid-to-Liquid Ratio (S/L) .................................. 91 4.1.2 Leaching Process for the Mixture ................................... 95 4.2 Recovery Materials Process....................................................... 95 4.2.1 Sedimentation Reaction .................................................. 95 4.2.2 Precipitate of Manganese ................................................ 98 4.2.2.1 pH Value............................................................... 98 4.2.2.2 Molar Ratio of Mn++ to KMnO4 (MRMP), and Temperature ....................................................... 100 4.2.3 Precipitate of Nickel (Castillo et al., 2002)................... 103 4.2.3.1 pH Value............................................................. 103 4.2.3.2 Molar Ratio of [Ni(NH3)6]2+ to Dimethylglyoxime (MRDN) ............................................................. 105 4.2.3.3 Precipitate of Nickel........................................... 105 4.2.4 Precipitate of Cobalt (Contestabile et al., 2001) ........... 107 4.2.5 Precipitate of Lithium (Zhang et al., 1998)................... 107 4.3 Purity of Recovery Materials Tests ......................................... 108 4.4 Electrochemical Properties .......................................................113

CONCLUSIONS .......................................................................... 119

REFERENCES ........................................................................................... 122 APPENDIX A ............................................................................................. 133

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LIST OF TABLES TABLE 2.1 PAGE

Effect of solid-to-liquid ratio (S:L) on leaching of cobalt and lithium with various leachants (Zhang et al.,1998) ......................................... 23

2.2

Experimental conditions with standardized solutions (Castillo et al., 2002).................................................................................................... 31

2.3

Recovery processes for lithium-ion secondary batteries by different investigators......................................................................................... 33

2.4

Effect of pH on the Adsorption of Ni by DMG-Treated Foam (Lee and Halmann, 1976)................................................................................... 50

2.5 Determination of Mole Ratio of Ni and dimethylglyoxime(DMG) in the Treated Foam (Lee and Halmann, 1976) ............................................ 52 3.1 4.1 Experimental sources of chemical reagents......................................... 58 Leached percent of different metals in the mixtiue (LiCoO 2 : LiMn2O4:LiCo1/3Ni1/3Mn1/3O2 =1:1:1 in weight ratio) with CHCl=4M, T=80 oC, S/L=1/50 g/ml and t=1h....................................................... 96 4.2 Solubility products of chemical compounds (James and Speight, 2005) ............................................................................................................. 97 4.3 Purity analysis of recovery material of lithium ................................. 109 4.4 Purity analysis of recovery material of manganese ........................... 110 4.5 Purity analysis of recovery material of cobalt ................................... 111 4.6 Purity analysis of recovery material of nickel ................................... 112

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LIST OF FIGURES FIGURE 2.1 PAGE

The illustration of the intercalation reaction: (a) no reaction, (b) intercalation, (c) extraction reaction (Whittingham, 1982). ................. 7

2.2 Flow sheet of the hydrometallurgical recycling process of lithium ion secondary rechargeable batteries (Xu et al., 2008). ............................ 12 2.3 Flow sheet of the metal recovery process (Shin et al., 2005).............. 16 2.4 Scheme of the hydrometallurgical route evaluated in this paper to treat NiCd, NiMH and lithium-ion secondary rechargeable batteries (Mantuano et al., 2006). ...................................................................... 26 2.5 pH dependence of extraction of cobalt and lithium with 0.29 M D2EHPA and 0.30 M PC-88A in kerosene (feed solution: [Co] = 17.25, [Li] = 1.73 (g /L ); pH = 0.6) (Zhang et al., 1998).............................. 28 2.6 Flow-sheet of the recycling process for spent lithium-ion batteries (Contestabile et al., 2001). .................................................................. 29 2.7 Effect of HNO3 concentration on LiCoO2 leaching (20 g /L, 75 oC, 400 rpm, 30 min, 0.8 vol.% H2O2) ( Lee and Rhee, 2002). ....................... 35 2.8 Lithium recovery (%) vs. dissolution time in nitric acid at various concentrations (Castillo et al., 2002). ................................................. 36 2.9 Manganese recovery (%) vs. dissolution time in nitric acid at various concentrations (Castillo et al., 2002). ................................................. 37 2.10 Effect of temperature on leaching of cobalt and lithium with 6% sulfurous acid solution (t = 30 min, S:L = 1:100) (Zhang et al., 1998). ............................................................................................................. 39 2.11 Effect of H2SO4 concentration and reaction time on the dissolution of
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LiCoO2 at 50 oC (Nan et al., 2005). .................................................... 40 2.12 Effect of H2SO4 concentration and reaction time on the dissolution of LiCoO2 at 90 oC (Nan et al., 2005). .................................................... 41 2.13 Effect of reaction time on the dissolution of Co, Ni, and Cu using 3 mol L1 H2SO4 and 3 wt.% H2O2 at 70 C and S/L=1:15 (Nan et al., 2006).................................................................................................... 43 2.14 Effect of reaction time on leaching of cobalt and lithium with 1 M hydroxylamine hydrochloride solution (T = 80 oC, S:L = 1 : 100) (Zhang et al., 1998). ............................................................................ 44 2.15 Effect of pulp density on cobalt (a) and lithium (b) leaching (Shin et al., 2005).................................................................................................... 46 2.16 XRD patterns for LiCoO2 powder prepared by amorphous citrate precursor process (Lee and Rhee, 2002). ............................................ 55 3.1 XRD patterns of LiCoO2...................................................................... 59 3.2 XRD patterns of LiMn2O4 ................................................................... 60 3.3 XRD patterns of LiCo1/3Ni1/3Mn1/3O2 .................................................. 61 3.4 Simulated experiment of leaching process. (Cathode active material is LiCoO2 (A), LiMn2O4 (B) and LiCo1/3Ni1/3Mn1/3O2 (C).) ................... 64 3.5 Experimental procedure of the leached and recovery process for the mixture. (Cathode active material is LiCoO2 (A), LiMn2O4 (B) and LiCo1/3Ni1/3Mn1/3O2 (C).) .................................................................... 66 3.6 The coin-type cell fabrication. ............................................................. 73

3.7 Schematic diagram of leaching and recovery cathode active material apparatus.............................................................................................. 74 3.8 Schematic diagram of filtration apparatus........................................... 76 4.1 Effect of hydrochloric acid concentration on leached percent of cathode
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active material, LiCoO2 (A) with t = 1h, S/L = 1/50 g/ml and T=80 oC. ............................................................................................................. 81 4.2 Effect of hydrochloric acid concentration on leached percent of cathode active material, LiMn2O4 (B) with t = 1h, S/L = 1/50 g/ml and T=80 oC. ............................................................................................................. 82 4.3 Effect of hydrochloric acid concentration on leached percent of cathode active material, LiCo1/3Ni1/3Mn1/3O2 (C) with t = 1h, S/L = 1/50 g/ml and T=80 oC. ....................................................................................... 83 4.4 Effect of leaching temperature on leached percent of cathode active material, LiCoO2 (A) with t = 1h, S/L = 1/50 g/ml and CHCl=4M...... 84 4.5 Effect of leaching temperature on leached percent of cathode active material, LiMn2O4 (B) with t = 1h, S/L = 1/50 g/ml and CHCl=4M. ... 85 4.6 Effect of leaching temperature on leached percent of cathode active material, LiCo1/3Ni1/3Mn1/3O2 (C) with t = 1h, S/L = 1/50 g/ml and CHCl=4M. ............................................................................................. 86 4.7 Effect of leaching time on leached percent of cathode active material, LiCoO2 (A) with CHCl=4M, T=80 oC and S/L = 1/50 g/ml................. 88 4.8 Effect of leaching time on leached percent of cathode active material, LiMn2O4 (B) with CHCl=4M, T=80 oC and S/L = 1/50 g/ml............... 89 4.9 Effect of leaching time on leached percent of cathode active material, LiCo1/3Ni1/3Mn1/3O2 (C) with CHCl=4M, T=80 oC and S/L = 1/50 g/ml. ............................................................................................................. 90 4.10 Effect of solid-to-liquid ratio (S/L) on leached percent of cathode active material, LiCoO2 (A) with CHCl=4M, T=80 oC and t=1h. ....... 92 4.11 Effect of solid-to-liquid ratio (S/L) on leached percent of cathode active material, LiMn2O4 (B) with CHCl=4M, T=80 oC and t=1h. ...... 93
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4.12 Effect of solid-to-liquid ratio (S/L) on leached percent of cathode active material, LiCo1/3Ni1/3Mn1/3O2 (C) with CHCl=4M, T=80 oC and t=1h. .................................................................................................... 94 4.13 Effect of pH value on recycle percent of leach liquor of cobalt, manganese, nickel and lithium. .......................................................... 99 4.14 Effect of pH value on recycle percent of cobalt, manganese, nickel and lithium (Mn++ : KMnO4= 2)........................................................ 101 4.15 Effect of molar ratio of Mn++ to KMnO4 and temperature on recycle percent of cobalt, manganese, nickel and lithium (pH=2). .............. 102 4.16 Effect of pH value on adsorb of cobalt, nickel and lithium (C4H8N2O2: [Ni(NH3)6]2+=2.5). ............................................................................ 104 4.17 Effect of molar ratio of C4H8N2O2 to [Ni(NH3)6]2+ on adsorb of cobalt, nickel and lithium (pH=9). ............................................................... 106 4.18 XRD pattern of the recovery synthesized LiCoO2 powder................114 4.19 XRD pattern of the recovery synthesized LiMn2O4 powder. ............115 4.20 Voltage vs. capacity profiles of 1st to 30th cycles at the C/10 rate for the recovery synthesized LiCoO2 phase. .................................................116 4.21 Capacity profiles vs. cycle number of 1st to 30th cycles at the C/10 rate for the recovery synthesized LiCoO2 phase.......................................117 5.1 Flowsheet of the hydrometallurgical process for the recovery of lithium, cobalt, nickel and manganese from spent lithium-ion secondary batteries (cathode active material: LiCoO2 (A), LiMn2O4 (B) and LiCo1/3Ni1/3Mn1/3O2 (C)). ........................................................... 121

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NOMENCLATURE CHCl LP hydrochloric acid concentration (M) leached percent

(= (solid concentrat ion before reaction - solid concentrat ion after reaction ) 100%, % )
solid concentrat ion before reaction

Ksp MRMP MRDN pH RP

solubility products of chemical compound molar ratio of Mn++ to KMnO4 molar ratio of C4H8N2O2 to [Ni(NH3)6]2+ pH value recycle percent
(= (liquid concentration before reaction - liquid concentration after reaction ) 100%, % )
liquid concentration before reaction

S Li2CO3
S/L T t

solubility of Li2CO3 in aqueous solution (g/100 g H2O) solid to liquid ratio (g/ml) leaching temperature (oC) leaching time (h)

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CHARPTER 1 INTRODUCTION Lithium primary batteries have been introduced to the market for about 25 years, while lithium-ion secondary batteries or storage batteries have less than 10 years of commercial development (Castillo et al., 2002). Extensive research is currently going on to improve the secondary lithium battery technology. Significant improvements consist in new design of electrolyte system (polymer electrolyte) and replacement of the lithium metal cathode electrode by lithium-storing materials, typically graphite carbon, while the positive electrode is a lithium-containing compound like LiCoO2, LiMn2O4, LiNiO2 or related oxides. These new storage batteries are usually referred to as lithium ion secondary batteries. A lithium ion secondary battery comprises a cathode, an anode, organic electrolyte, and a separator. The lamination of a cathode, an anode, and a separator by a pressing makes those electric contacts. The anode is a copper plate coated with a mixture of graphite carbon, conductor, binder, and additives. Similarly, the cathode is an aluminum plate coated with a mixture of active cathode material, electric conductor, binder, and additives. Here, LiCoO2, LiMn2O4, LiNiO2 or related oxides
1

are used as the cathode material for almost all commercialized lithium ion secondary batteries due to its suitable performances such as high energy density, ease of manufacture, etc. Nowadays, lithium-ion secondary batteries are widely used as electrochemical power sources in mobile telephones, personal computers, video-cameras and other modern-life appliances due to lithium ion secondary battery having many suitable performances such as (Yoshio et al., 1996): (a) High energy density (~ 120 Wh/kg). (b) High battery voltage (the average voltage of the lithium-ion batteries is 3.6 V, which is 3 times as large as that of the Ni-Cd battery or the nickel-metal hydride (Ni-MH) battery). (c) Long charging-discharging cycle (500-1000 cycles). (d) Large temperature range (- 20 to + 60C). The household battery industry in the USA is estimated to be a US$ 2.5 billion industry with annual sales of nearly 3 billion batteries. These batteries, also known as dry cells, are used in over 900 million battery operated devices (Lupi and Pilone, 2001). In Europe, 5 billion units of batteries were produced in year 2000 (Bernardes et al., 2004). Therefore,

the usage of lithium-ion secondary batteries has rapidly increased consumption and, consequently, increases the produced metal-containing hazardous waste. The worldwide production of lithium-ion secondary batteries is about 250 million tons every year. The annual production of spent lithium-ion secondary batteries which contain 515 wt%-Co and 27 wt%-Li is estimated to be 200500 metric tons (Fouad et al., 2007). The storage capacities of special waste dump sites are limited, and the disposal costs are very high. Moreover, the French law regarding collection and elimination or recycling of cells and storage batteries has been reinforced since January 2001 and it must be applied to all the types of batteries (Mortgat et al., 2000). So, recycling of the major components of spent cells appears to be a beneficial way to prevent environmental pollution and raw material consumption. Up to now, some typical hydrometallurgical and pyrometallurgical processes for the recycling of spent lithium-ion secondary batteries have been reported or patented. In these reported hydrometallurgical process, di-(2-ethylhexyl) phosphoric acid (D2EHPA), trioctylamine (TOA), diethylhexyl phosphoric acid (DEHPA) or 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC-88A) were usually used as extracts to

separate the metal values (Nan et al., 2006). In addition, using spent lithium-ion secondary batteries to prepare LiCoO2, LiMn2O4, LiNiO2 or related oxides electrode materials (Lee and Rhee, 2003; Contestabile et al., 2001; Nan et al., 2004; Castillo et al., 2002), metal hydride electrodes (Wang et al., 2002; Prickett et al., 2001) were also investigated. In October 2003, AEA Technology (AEAT) launched a 2 million pounds sterling research and development facility in Sutherland, North Scotland, for lithium-ion secondary batteries recycling. AEAT has developed a water based technique for the recycling of spent lithium-ion secondary batteries. The process consists of three steps: mechanical grinding, separation of electrolyte and electrode materials in aqueous solution, as well as reduction of LiCoO2 by electrolysis. One advantage of aqueous approaches is the low temperature ranges, which results in energy savings (Lain, 2001). In this study, the separation and recovery of metal values such as cobalt, manganese, nickel and lithium from spent lithium-ion secondary batteries were studied. Experiments have been carried out on dissolution in acid solution, neutralization, precipitation, oxidation reduction and filtering, various separation procedures using different oxidizing agents,

etc.

The

leaching

experimental

parameters

included

leaching

concentration, temperature, time and solid-to-liquid ratio on leaching of cobalt, manganese, nickel and lithium contained in the cathode material of the batteries. The experimental parameters of separation included oxidizing agent ratio and temperature, etc. The high effect and low cost are the objectives in separation and recovery spent lithium-ion secondary batteries.

CHAPTER 2 LITERATURE REVIEW 2.1 Introduction of Lithium Ion Secondary Battery 2.1.1 Concept of the Secondary Lithium Ion Battery Primary lithium ion batteries have been become commercial goods since 1970, however, they are not rechargeable. In 1978, the intercalating materials were introduced first by Murphy et al.. They found that Li-ions could migrate into/out from LiWO4 structure via intercalation /de-intercalation reactions. Intercalation and de-intercalation, the word in materials science, are considered as a guest material enters and leaves a host material without ruining the structure of host material as Li-ions diffusing into and out from the structure. For example, it is just similar to make water enter into and leave out a sponge by squeezing it, while the main structure of the sponge is not destroyed. As shown in Figure 2.1 (Whittingham, 1982), Armand et al. (1980) defined intercalation as LiyMnYm + AzBw Li(y-x)MnYm + LixAzBw. Though, the idea of rocking chair for rechargeable batteries was proposed in associated papers and patents published and agreed during 1980 ~ 1984(Padhi et al., 1997; Murphyetal et al., 1978; Belharouak et al.

Figure 2.1. The illustration of the intercalation reaction: (a) no reaction, (b) intercalation, (c) extraction reaction (Whittingham, 1982).

, 2003). Until 1990, the first rechargeable lithium cell with components of LixC6 / LiClO4 in PC/EC / Li(1+x)CoO2 or Li(1+x)YO2 (Y = Ni or Mn) to adopt the principle was made. The secondary lithium cells, consisting of LiCoO2 as a cathode (positive electrode) and carbon as an anode (negative electrode), show good cycling performance and high energy density. They have been used as the major power sources for portable electric devices. 2.1.2 Cathode Materials During the recent years, tremendous researches have been done to find alternative cathode materials to replace LiCoO2 for its high cost and limit availability. A lot of efforts have also been done to improve the electrochemical characteristics of the cathode materials, such as LiCoO2 (Choi et al., 2004), LiMn2O4 (Venkatraman et al., 2004), LiNiO2 (Fan and Jiang, 2004), LiNi1-x-yMxMyO2 (Kang and Amine, 2003), LiFePO4 (Takahashi et al., 2005). 2.1.2.1 LiCoO2 Cathode Material Yoshio et al. (1996) indicated at present, LiCoO2 was the most commonly used cathode material for commercial rechargeable lithium ion batteries due to its advantage of easy preparation, high voltage (about

3.9V), good reversibility (upon 500th), and high theoretical capacity (about 280 mah/g). LiCoO2 is layered structure in witch the Li+ and Co3+ ions occupy alternating (1 1 1) layers of octahedral sites in a rock-salt structure. The typical reversible limit of delithiation for LixCoO2 in commercial batteries is x=0.5 at a voltage plateau of 3.8V (Choi and Manthiram, 2004), which corresponds to a discharge capacity of about 140 mahg-1. However, layered LiCoO2 often suffers from structure instability and safety programs. The charging reaction is (Zhang et al., 1998): LiCoO2 Li(1x)CoO2 + xLi+ +xe (2.1)

The delithiated phase of LiCoO2 contains Co(IV), a strong oxidant which can give a highly exothermic reaction upon contact with the electrolyte solvent. Caballero et al. (2004), Kobayashi et al. (2000) and Ceder et al. (1998) used various strategies to avoid this drawback, like replacing cobalt with another transition metal. 2.1.2.2 LiMn2O4 Cathode Material Wu et al. (2005) indicated that LiMn2O4 had the theoretical capacity about 147 mah/g, and the practical specific capacity is about 120 mah/g. It means that almost about 80% of Li-ion can be d-intercalated

from LiMn2O4. The LiMn2O4 material has many advantages including low material costs, low toxicity, high cell voltage and synthesis easily. However, it is suffered by two main issues, i.e., one is by the poor cycle life induced by the John-Teller distortion as it is reduced into LiMn2O4, and the other is the Mn2+ ion dissolution into the electrolyte after cycling. 2.1.2.3 LiMnO2 Cathode Material LiMnO2 may exist in the same layered structure as LiCoO2 exists in orthorhombic phase. The o-LiMnO2 has the high theoretical capacity of 285 mahg-1 based on the Mn3+/Mn4+ redox couple, and Mn is cheaper and lower toxicity than Ni and Co. It can be synthesized by a conventional solid state reaction methods, sol-gel, Pechini, ion-exchange, or hydrothermal methods (Armstrong and Bruce, 1996; Tabuchi et al., 1998). Vitins and West (1997) indicated that LiMnO2 was not

thermodynamically stable as a layered structure, but as an orthorhombic phase of o-LiMnO2. However, both the layered and orthorhombic LiMnO2 were observed to undergo a detrimental phase transformation into a spinel-like phase through minor atomic rearrangements during the first removal and subsequent cycling of Li, leading to eventual degradation of electrode performance.

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2.1.2.4 LiNiO2 Cathode Material Layered structure LiNiO2 cathode material was developed by Moli Energy Co. in 1990 in Canada after Sony introduced the LiCoO2 cathode material (Kubo et al., 1997). Song et al. (2004) indicated that LiNiO2 with moderate cost and specific capacity of 190 mah/g was thought to be a good candidate for the cathode material of lithium ion batteries, but synthesized a pure compound was complex and difficult. The ideal structure of LiNiO2 is layered, the same structure as LiCoO2, however, the Li-Ni-O system is characterized by existence of a Li1-xNi1+xO2 (0<x<1) solid solution. At low x values (0<x<0.2), the presence of Ni2+ cation in the Li layers is found in the structure (Capitaine et al., 1996). This result makes the preparation of LiNiO2 powders without cation mixing be difficult. 2.2 Lithium Ion Secondary Battery of Recycling Processes Xu et al. (2008) indicated that metallic scraps could be subject to different recycling processes, including the basic two classes of recycling processes: physical processes and chemical processes. The principal flowsheet shown in Figure 2.2 was mainly adopted in hydrometallurgical recycling processes of spent lithium-ion batteries. Firstly, the spent

11

12

lithium ion secondary battery should be experienced to some types of physical processes as pre-treatment processes such as skinning, removing of crust, crushing, sieving and separation of materials in order to separate the cathode materials from other materials. Secondly, the separated cathode materials will be used to recovered cobalt and other metals through a series of chemical processes. Safety precaution should be paid attention and be emphasized when lithium ion secondary battery are manually dismantled (Tong et al., 2005; Dorella and Mansur, 2007). First, the plastic cases of the batteries were removed using a small knife and a screwdriver. Second, in order to remove the metallic shell that covered the battery, it was immersed into liquid nitrogen for 4 min and fixed in a lathe. Such a cryogenic method was adopted for safety precautions. Third, the metallic shell was then cut using a saw; the ends of the metallic shell were removed firstly and a longitudinal cut was done aiming to access the internal material of the battery which was removed using pliers. Fourth, anode and cathode were uncurled manually, separated and dried for 24 h at 60 oC. All steps in the experimental procedure were carried out using glasses, gloves and gas masks for safe operation.

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2.2.1 Physical Processes Tenorio et al. (1999) reported among physical processes for recycling spent lithium ion secondary battery, mechanical separation techniques intend to separate materials according to different properties like density, conductivity, magnetic behavior, etc. Thermal processes are usually associated with the production of steel, ferromanganese alloys or other metallic alloys. Mechanochemical (MC) process is to use a grinding technique that makes the crystal structure of the LiCoO2, the positive electrode in the lithium ion secondary battery, into disordered system, enabling useful substances such as Co and Li easily extracted by acid leaching at room temperature from the lithium ion secondary battery scraps wastes. Dissolution process is to use special organic reagents to dissolve the adhesive substance (PVDF), which adheres the anode and cathode electrodes, and therefore this process can make LiCoO2 get separated from their support substrate easily and recovered effectively (Contestabile et al., 2001). 2.2.1.1 Mechanical Separation Processes Mechanical separation processes are usually applied as a pretreatment to treat the outer cases and shells and to concentrate the

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metallic fraction, which will be conducted to a hydrometallurgical or a pyrometallurgical recycling process in recycling of spent lithium ion secondary battery. Shin et al. (2005) presented a process for the recovery of metal from spent lithium ion secondary battery for possible application to a commercial scale plant, including mechanical separation of lithium cobalt oxide particles and a hydrometallurgical procedure for lithium and cobalt recovery. The experimental procedure is illustrated in Figure 2.3. A series of mechanical processes involving crushing, sieving, magnetic separation, fine crushing and classification were carried out to yield enriched particles of lithium cobalt oxide in sequence. Two stages of crushing and sieving resulted in satisfactory separation of the metal bearing particles from the waste. A magnetic separator was used to remove pieces of steel casing. In order to eliminate small pieces of aluminum foil attaching to the particles of lithium cobalt oxide, a fine crushing was followed. The reason why mechanical separation is emphasized before the metal leaching process here is that it improves the recovery efficiency of target metals and eliminates the need for a purification process of the leachate. Because PVDF binder does not dissolve in acid solution, it remains in the

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Al

Figure 2.3. Flow sheet of the metal recovery process (Shin et al., 2005).

16

cake after filtration. Also, carbon does not dissolve in acid solution, and instead it floats on the solution; from filtration it is separated in the cake. The electrolyte lithium exafluorophosphate (LiPF6) decomposes into lithium fluoride and phosphor pentafluoride in the crushing process, and the lithium dissolves in the acid solution during leaching. The organic solvents, propylene carbonate (PC) and diethyl carbonate (DEC) were evaporated in the crushing process. 2.2.1.2 Thermal Treatment Lee and Rhee (2002) applied a recycling process involving mechanical, thermal, hydrometallurgical and solgel steps to recover cobalt and lithium from spent lithium ion secondary battery and to synthesize LiCoO2 from leach liquor as cathode active materials. Electrode materials containing lithium and cobalt can be concentrated with a two-step thermal treatment. First, lithium ion secondary battery samples were thermally treated in a muffle furnace at 100-150 oC for 1 h. The samples were disassembled with a high-speed shredder. Second, a two step thermal treatment was performed in a furnace, and electrode materials were liberated from the current-collectors by a vibrating screening. Next, the cathode active material, LiCoO2, was obtained by
17

burning off carbon and binder in the temperature range 500-900 oC for 0.5-2 h. Third, after LiCoO2 in a nitric acid solution was leached in a reactor, the gel was placed inside a stainless steel crucible and calcined into powder in air for 2 h in the temperature range 5001000 oC. Castillo et al. (2002) reported that the solid residue coming from the operational step of the dilute HNO3 acid leaching of spent lithium ion secondary battery and consisting of iron, cobalt and nickel hydroxides mixture and some traces of Mn(OH)3, were introduced into a muffle furnace at 500 oC during 2 h to eliminate carbon and organic compounds. The alloy can then directly undergo beneficiation in metallurgical applications. 2.2.1.3 Mechanochemical Process Zhang et al. (2000) reported that room temperature extraction of valuable substances from LiCo0.2Ni0.8O2 scrap containing the PVDF has been carried out using 1N HNO3 solution after mechanochemical treatment by a planetary mill with and without Al2O3 powder. Crystalline LiCo0.2Ni0.8O2 in the scrap was pulverized and became amorphous by mechanochemical treatment for 60 and 240 min, respectively, with and without Al2O3 power. This shows that the addition of Al2O3 is very
18

effective for mechanochemical treatment. Accordingly, Co as well as Ni and Li were extracted at a high yield of more than 90% from the amorphous scrap sample. About 1% of fluorine in PVDF was dissolved in the filtrate when the Al2O3 powder was added to the scrap during the mechanochemical treatment, while no fluorine was detected in the filtrate obtained from the ground scrap sample without Al2O3 powder. Saeki et al. (2004) developed an effective process for recovering Co and Li from lithium ion secondary battery wastes by using mechanochemical method. The process consists of co-grinding LiCoO2 with polyvinyl chloride (PVC) in planetary ball mill in air to form Li and Co chlorides, and subsequent leaching with water of the ground product, to extract Co and Li. In the grinding stage, mechanochemical reaction between LiCoO2 and PVC takes place to form chlorides which are soluble in water. Therefore, grinding stage is important to improve the yield. PVC plays an important role as a chloride source for the mechanochemical reaction. The grinding facilitates mechanochemical reaction, and the extraction yields of both Co and Li are improved as the grinding progresses. The 30 min grinding makes the recoveries of Co and Li to reach over 90% and nearly 100%, respectively. Accordingly, about

19

90% of chlorine in the PVC sample has been transformed into the inorganic chlorides by the time. The concept of this process is to recycle useful materials from the both wastes of battery and PVC. 2.2.1.4 Dissolution Process Contestabile et al. (2001) presented a laboratory-scale spent lithium ion secondary battery recycling process without the separation of anode and cathode electrodes. The battery
o

rolls

were

treated

with

N-methylpyrrolidone (NMP) at 100

C for 1 h and LiCoO2 was

effectively separated from their support substrate and recovered. The recovery of both copper and aluminum in their metallic form was also achieved. Although this process was very convenient, the recovery effects of LiCoO2 were demonstrated to be influenced by the used adhesive agent and rolling method of electrodes. Xu et al. (2008) reported that this process has the advantage of making LiCoO2 get separated from their support substrate and recovered easily, and therefore this process greatly simplifies the separation procedures of cobalt and aluminum. It still has the disadvantage that the solvent for dissolving PVDF, N-methylpyrrolidone (NMP), is too expensive and consequently is not very suitable for scale up operation.

20

The further work to do in this respect is to develop much cheaper solvent and make it recycled and reused in order that this treatment cost could be decreased. 2.2.2 Chemical Processes Chemical processes are connected to leaching steps in acid or alkaline medium and purification processes in order to dissolve the metallic fraction and to recover metal solutions that could be used by the chemical industry. Recycling through chemical processes basically consists of acid leaching or base leaching, chemical precipitation, filtration, extraction or other processes. 2.2.2.1 Acid Leaching The dust, which has been separated from plastic, iron scraps and paper residues in the sorting and dismantling preliminary treatment step, is leached by an acidic solution in order to transfer the metals of interest from it to the aqueous liquor. The leaching of LiCoO2 from spent lithium ion secondary battery is usually carried out by using inorganic acids such as H2SO4 (Mantuano et al., 2006), HCl (Contestabile et al., 2001) and HNO3 (Castillo et al.,2002; Lee and Rhee, 2002) as leaching agents.

21

Zhang et al. (1998) studied the leaching of LiCoO2 by the use of H2SO3, NH4OHHCl and HCl as leaching agents. The experimental results were show in Table 2.1. The experimental results indicated that the leaching efficiency of Co is highest in hydrochloric acid among these three leaching agents and higher the temperature, higher the leaching efficiency of Co. Mantuano et al. (2006) and Lee and Rhee (2002) studied the leaching of LiCoO2 by the use of H2SO4 and HNO3 to substitute HCl with the addition of hydrogen peroxide as a reducing agent respectively. Lee and Rhee (2002) indicated that in the process of reductive leaching with the addition of hydrogen peroxide as a reducing agent, the leaching efficiency increased by 45% for Co and 10% for Li compared with that in only nitric acid leaching. This behavior seems to be due to the reduction of Co3+ to Co2+, which is readily dissolved. The leaching efficiency of Co and Li increased with increasing HNO3 concentration, temperature, and hydrogen peroxide concentration and with decreasing S/L ratio. An effective condition for the leaching would be 1M HNO3, 10-20 g/L initial S/L ratio, 75oC, and 1.7 vol.% H2O2 addition.

22

Table 2.1. Effect of solid-to-liquid ratio (S:L) on leaching of cobalt and lithium with various leachants (Zhang et al.,1998)

23

2.2.2.2 Bioleaching It has been reported that bio-hydrometallurgical processes have been gradually replacing the hydrometallurgical one due to their higher efficiency, lower costs and few industrial requirements (Cerruti et al.,1998). Bio-hydrometallurgical processing of solid waste is similar to natural biogeochemical metal cycles and reduces the demand of resources, such as ores, energy and landfill space (Moore et al., 2002). The study of Mishra et al. (2008) was carried out on bioleaching method for the extraction of cobalt and lithium from spent lithium ion secondary batteries containing LiCoO2, using chemolithotrophic and acidophilic bacteria, acidithiobacillus ferrooxidans, which utilized elemental sulfur and ferrous ion as the energy source to produce metabolites like sulfuric acids and ferric ion in the leaching medium. The current technologies of bio-hydrometallurgical processes have not gotten mature in their applications for recycling lithium-ion secondary batteries and are still in the research stage until now (Xu et al., 2008). 2.2.2.3 Solvent Extraction Such extractants as di-(2-ethylhexyl) phosphoric acid (D2EHPA),

24

trioctylamine (TOA), diethylhexyl phosphoric acid (DEHPA) or 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC-88A) were usually used as extractants to separate the metals in some

hydrometallurgical process, in which Co, Li and Cu are usually recovered from spent lithium ion secondary batteries (Zhang et al., 1998; Lin et al., 2003; Tanii et al., 2003). Mantuano et al. (2006) indicated a hydrometallurgical plant involving metal purification/separation by liquidliquid extraction with Cyanex 272 (bis-2,4,4-trimethylpentyl phosphinic acid) as extractant, was found to be technically viable to separate base metals from NiCd, NiMH and lithium ion secondary battery of spent mobile phone. The route comprises the main steps schematically shown in Figure 2.4: preliminary treatment of batteries, followed by leaching with sulphuric acid and metal purification/separation by liquidliquid extraction with Cyanex 272 (bis-2,4,4-trimethylpentyl phosphinic acid) as extractant. Metal

separation by liquidliquid extraction with Cyanex 272 must be carried out in two sequential steps: firstly to extract aluminium at pH 2.5-3.0 and secondly to remove cobalt at pH 4.5, thus leaving lithium in solution. Zhang et al. (1998) indicated that separation of cobalt from lithium

25

Figure 2.4. Scheme of the hydrometallurgical route evaluated in this paper to treat NiCd, NiMH and lithium-ion secondary rechargeable batteries (Mantuano et al., 2006).

26

from the hydrochloric acid leach liquor was performed employing solvent extraction. Figure 2.5 gives the pH dependence of the extraction of cobalt and lithium from the leach solution containing 17.25 g/L Co and 1.73 g/L Li with 0.29 M di-(2-ethylhexyl) phosphoric acid (D2EHPA) and 0.30 M 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC-88A) in kerosene. It is found that the extraction of cobalt increases rapidly with the increase of pH in the region of pH < 5 and essentially complete extraction occurs when the pH is higher than 6.5. On the other hand, lithium is not extracted at all at pH < 5.5 in all cases. Above pH 5.5, lithium begins to extract slightly into the organic phase. It appears that the extraction ability of D2EHPA for lithium is greater than that of PC-88A. 2.2.2.4 Chemical Precipitation Contestabile et al. (2001) studied a laboratory process aiming to the treatment and recycling of spent lithium ion secondary batteries and being composed of sorting, crushing and riddling, selective separation of the active materials, lithium cobalt dissolution and cobalt hydroxide precipitation. The flow sheet of the recycling process is shown in Figure 2.6. The cobalt dissolved in the hydrochloric solution was recovered as

27

Figure 2.5. pH dependence of extraction of cobalt and lithium with 0.29 M D2EHPA and 0.30 M PC-88A in kerosene (feed solution: [Co] = 17.25, [Li] = 1.73 (g /L ); pH = 0.6) (Zhang et al., 1998).

28

Figure 2.6. Flow-sheet of the recycling process for spent lithium-ion batteries (Contestabile et al., 2001).

29

cobalt hydroxide Co(OH)2 by addition of one equivalent volume of a 4M NaOH solution. The precipitation of cobalt hydroxide begins at a pH value of 6 and can be considered to be completed at pH 8. Castillo et al. (2002) studied lithium and manganese are then separated adding sodium hydroxide solution. The operating conditions and separation results are reported in Table 2.2. The selective precipitation separation process was applied on spent Li ion batteries, after preliminary dissolution in acidic medium. The choice of the acid is reported hereafter. 2.2.2.5 Electrochemical Process Myoung et al. (2002) reported that cobalt ions, extracted from waste LiCoO 2 by using a nitric acid leaching solution, are potentiostatically transformed into cobalt hydroxide on a titanium electrode and cobalt oxide is then obtained via a dehydration procedure. In linear sweep voltammetry, distinct cathodic current peak is observed and indicates that hydroxide ions are formed near the electrode via the electroreduction of dissolved oxygen and nitrate ions give rise to an increase in the local surface pH of the titanium. Under appropriate pH conditions, island-shaped cobalt hydroxide is precipitated on the titanium

30

31

substrate and heat treatment of the cobalt hydroxide results in the formation of cobalt oxide. The detailed reaction mechanisms are considered to be: 2H2O + O2 + 4e = 4OH NO3 + H2O + 2e = NO2 + 2OH Co3+ + e = Co2+ Co2+ + 2OH / Ti = Co(OH)2 / Ti (2.2) (2.3) (2.4) (2.5)

The reduction of dissolved O2 and nitrate ion, i.e., reactions (2.2) and (2.3), could increase the local pH of the electrode. Thus, the precipitation of hydroxide films of Co(OH)2 (see Eq. (2.5)) under appropriate pH condition could be possible. Therefore, this process provides a good way for recovering cobalt oxide from LiCoO2. Finally, the differences of the lithium-ion secondary batteries of recycling processes depicted from different precursors have been studied as shown in Table 2.3. 2.3 Effect of Reaction Operating Conditions 2.3.1 Effect of Leaching Process Some reaction conditions such as acid concentration of leaching agent, leaching reaction temperature (T), leaching reaction time (t) and

32

Table 2.3. Recovery processes for lithium-ion secondary batteries by different investigators.

33

(this study)

solid-to-liquid ratio (S/L) can affect the leaching efficiency, the different operating conditions are described as follows. 2.3.1.1 Effect of Acid Concentration Lee and Rhee (2002) indicated the effects of HNO3 concentration in the presence of 0.8 vol.% H2O2 on the leaching of LiCoO2 at a S/L ratio of 20 g/Land 75 oC for 30 min are shown in Figure 2.7. The efficiencies of both Co and Li increase with increasing HNO3 concentration. Over 80% Co and 80% Li are readily extracted within 30 min at 1 M HNO3. Castillo et al. (2002) have carried out tests with nitric acid under the same conditions but concentration varying from 0.5 to 5 M. The spectrophotometric analyses results show that when the concentration is ranging between 1 and 2 M, we approximately recover 100% lithium as indicated in Figure 2.8. In the same time, samples have been analyzed at different times by ionic chromatography to quantify manganese. Results prove that manganese is even present for very dilute acid as shown in Figure 2.9. On the other hand, the filtrate does not contain other ions than Fe3+, Ni2+ and Co2+ if the nitric acid concentration does not reach 5 M. In this study, we have made the choice, during the first stage, to separate the

34

Figure 2.7. Effect of HNO3 concentration on LiCoO2 leaching (20 g /L, 75 oC, 400 rpm, 30 min, 0.8 vol.% H2O2) ( Lee and Rhee, 2002).

35

Figure 2.8. Lithium recovery (%) vs. dissolution time in nitric acid at various concentrations (Castillo et al., 2002).

36

Figure 2.9. Manganese recovery (%) vs. dissolution time in nitric acid at various concentrations (Castillo et al., 2002).

37

whole content of lithium and manganese from other metals with a nitric acid concentration of 2 M. We have then performed a separation method between lithium and manganese in the filtrate. 2.3.1.2 Effect of Reaction Temperature Zhang et al. (1998) indicated that Figure 2.10 illustrated the metal leaching to be significantly affected by temperature. The increase of temperature enhanced remarkably the leaching of the metals. However, in the case of sulfurous acid, when the temperature was raised from 60 oC to 80 oC, the percentages of cobalt and lithium leached decreased. This likely resulted from the evaporation of SO2 in the sulfurous acid at high temperature. Nan et al. (2005) indicated that the leaching efficiency of Co was relatively low at lower reaction temperature and acid concentration. With the increasing of H2SO4 concentration and temperature from 2 to 4 M and 5090 oC, respectively, the leaching efficiency increased. More than 95% Co was leached within 4 h when the temperature approached 90 oC. Figures 2.11 and 2.12 show the effect of H2SO4 concentration and reaction time on the leaching percentages of cobalt at 50 and 90 oC, respectively. At higher acid concentration and reaction temperature, the

38

Figure 2.10. Effect of temperature on leaching of cobalt and lithium with 6% sulfurous acid solution (t = 30 min, S:L = 1:100) (Zhang et al., 1998).

39

Figure 2.11. Effect of H2SO4 concentration and reaction time on the dissolution of LiCoO2 at 50 oC (Nan et al., 2005).

40

Figure 2.12. Effect of H2SO4 concentration and reaction time on the dissolution of LiCoO2 at 90 oC (Nan et al., 2005).

41

leaching efficiency of cobalt was favorable. 2.3.1.3 Effect of Reaction Time The effect of reaction time on the dissolution of Co, Ni, and Co is presented in Figure 2.13 (Nan et al., 2006). It is seen that the dissolution of powder residues is enhanced with the increase of dissolving time, and about 90% Co, Ni, and Co could be leached out after 5 h. In addition, it was also found that the dissolution of mixed RE was over 99.5% in 5 h under such dissolution conditions. The insoluble material could be put in the posterior batch. So, the dissolving time of 5 h was chosen in the given process. Figure 2.14 gives the time dependency of the leaching of cobalt and lithium with hydroxylamine hydrochloride solution (NH2OHHC1) (Zhang et al., 1998). It is apparent that increasing the reaction time is beneficial to metal leaching. About 92% of cobalt and lithium can be leached within 30 min in the case of hydroxylamine hydrochloride solution (NH2OHHC1). 2.3.1.4 Effect of Solid-to-Liquid Ratio (S/L) Shin et al. (2005) reported in these experiments with the concentration of sulfuric acid to be 2 M, and pulp density to be 50 g/L.

42

Figure 2.13. Effect of reaction time on the dissolution of Co, Ni, and Cu using 3 mol L1 H2SO4 and 3 wt.% H2O2 at 70 C and S/L=1:15 (Nan et al., 2006).

43

Figure 2.14. Effect of reaction time on leaching of cobalt and lithium with 1 M hydroxylamine hydrochloride solution (T = 80 oC, S:L = 1 : 100) (Zhang et al., 1998).

44

High pulp density is desirable to raise processing throughput. Yet a density higher than 50 g/L yields lower leaching efficiency, as illustrated in Figure 2.15(a) for cobalt leaching and Figure 2.15(b) for lithium. The leaching temperature was 75 oC with an agitation of 300 rpm. The leaching rate was fast in the initial stage regardless of the hydrogen peroxide concentration, whereas leaching efficiency depends upon the amount of hydrogen peroxide. A concentration of 15 vol.% was enough for the full leaching of both metal components. Because polyvinylidene fluoride (PVDF) binder does not dissolve in acid solution, it remains in the cake after filtration. Also, carbon does not dissolve in acid solution, and instead it floats on the solution; from filtration it is separated in the cake. The electrolyte lithium hexafluorophosphate (LiPF6) decomposes into lithium fluoride and phosphor pentafluoride in the crushing process, and the lithium dissolves in the acid solution during leaching. The organic solvents of propylene carbonate (PC) and diethyl carbonate (DEC) were evaporated in the crushing process. The concentrations of copper and aluminum in the leachate were 0.46 g/L and 0.79 g/L, respectively, and the amounts in the cake were less than 0.01 g.

45

Figure 2.15. Effect of pulp density on cobalt (a) and lithium (b) leaching (Shin et al., 2005).
46

2.3.2 Effect of Recovery Materials Process 2.3.2.1 Effect of Precipitate of Manganese Arena et al. (2007) maximized the dispersion of the active phase to enhance the redox activity for getting an improved CWO performance, and has necessitated the design of an alternative synthesis route of the MnCeOx system accomplishing a mix of the oxide components at an atomic level. This is to overcome the major drawback of the conventional co-precipitation technique leading, as a rule, to mixtures of mono-phase precipitate particles because of different precipitation kinetics of each cation. Therefore, a selective cogeneration of the precipitating phases to further control specific interactions among proper precursors was the main objective of the new synthesis design. Preliminary experiments allowed that the precipitation of Ce3+ and Ce4+ cations (10-3 M) as hydroxide/oxides occurs at pH values of 8.4 and 3.1, corresponding to Ksp values of 1.6 10-20 and 2.5 10-47 for Ce(OH)3 and Ce (OH)4, respectively, while a Ksp value of 1.5 10-13 has been found for the Mn(OH)2 species to be ascertained. Then, redox reactions of MnO-4 with Ce3+-Mn2+ ions in basic solution were devised to attain a simultaneous precipitation of the MnO2 and CeO2 species and a
47

molecular mixing of the oxide species. Namely, the KMnO4 precursor (~10 g/L) was titrated with a solution of Ce3+ and Mn2+ ions at constant pH (8.0 0.3), to derive the following reactions: MnO-4 + 3e- + 2H2O MnO2 () + 4HOMn2+ + 4HO- MnO2 () + 2e- + H2O Ce3+ + 4HO- CeO2 () + e- + 2H2O (2.6) (2.7) (2.8)

Considering the concentration of the MnO-4, Mn2+, Ce3+, Ce4+, and OH- species and above Ksp values for a catalyst with a nominal Mnat/Ceat ratio of 1, the redox potentials of the above reactions (+0.57 V (2.6); -0.39 V (2.7); and -0.255 V (2.8)) confirm that the oxidation of the Ce3+ and Mn2+ cations by MnO-4 precursor should proceed owing to a cell-concentration effect. This approach matches the core issue of design, as the formation of the precipitated species occurs only further to direct and selective molecular interactions between the oxidant and the reducing species.

2.3.2.2 Effect of Precipitate of Nickel Castillo et al. (2002) reported in the standardized solution (2) of nickel (see Table 2.2), the solution was firstly treated with

48

dimethylglyoxime to form a red solid complex with the nickel. The complexation reaction is very selective and quantitative. Lithium and manganese are then separated adding sodium hydroxide solution. The operating conditions and separation results are reported in Table 2.2. Lee and Halmann (1976) determined the optimum pH range, the amount of Ni absorbed on the treated foam by the batch method at various pH value in Table 2.4. Ni was found to be optimally adsorbed from aqueous solution in the pH range of 8-10. These measurements were carried out in solutions containing an excess of Ni, relative to the amount of dimethylglyoxime (DMG) on the treated foam, so as to observe the differences in the amount of Ni adsorbed. On the other hand, quantitative adsorptions were possible even in solutions having both slightly lower and higher than the above optimum pH values, if dimethylglyoxime (DMG)-treated foam containing an excess of dimethylglyoxime (DMG) were applied. However, in strongly alkaline solutions, above pH 11, the amount of adsorbed Ni decreased, which may be due to an unfavorable reaction condition for formation of the Ni- dimethylglyoxime complex, or to low immobilizability of dimethylglyoxime on the treated foam in strongly alkaline medium.

49

Table 2.4. Effect of pH on the Adsorption of Ni by DMG-Treated Foam (Lee and Halmann, 1976)

50

The

amount

of

Ni

adsorbed

by

given

amount

of

dimethylglyoxime(DMG)-treated foam was measured in a series of solutions varying in Ni concentration from 50 to 400 g in Table 2.5. The results show that the mole ratio of Ni:DMG in the foam is about 19.6, even though the theoretical ratio for the Ni((DMG)2 complex is 1:2. Thus, a part of the dimethylglyoxime on the foam became unavailable to the reaction with nickel. 2.3.2.3 Effect of Precipitate of Cobalt Contestabile et al. (2001) studied the cobalt dissolved in the hydrochloric solution to be recovered as cobalt hydroxide Co(OH)2 by addition of one equivalent volume of a 4M NaOH solution. The solubility product of cobalt hydroxide is about 10-16; consequently, its precipitation begins at a pH value of 6 and can be considered to be completed at pH to be 8. Ideally, one could obtain Co(OH)2 precipitation by using an ammonia solution, i.e., by a weak base which forms a buffer solution at pH to be 9. Unfortunately, ammonia forms stable complexes with cobalt causing the partial dissolution of the hydroxide and thus, preventing from a quantitative recovery. Therefore, NaOH, which is a strong base and which allows to work with small volumes of solution, remains the best

51

Table 2.5. Determination of Mole Ratio of Ni and dimethylglyoxime(DMG) in the Treated Foam

(Lee and Halmann, 1976)

52

choice. On an industrial scale, this step can be controlled by using an adequate pH sensor. The Co(OH)2 precipitate can be easily separated from the solution by filtration, then to be recycled. 2.3.2.4 Effect of Precipitate of Lithium Nan et al. (2005) referred to the recovery process given by Zhang et al. (1998), the raffinate was concentrated and treated with a saturated sodium carbonate solution to precipitate lithium carbonate at 100oC. The lithium carbonate was recovered after filtration and washing with hot water to remove the residual mother liquor. The results showed that about 80% lithium was recovered as a precipitate, which is similar to Zhangs recovery ratio. In addition, the analytical results showed that the contents of cobalt and copper in the precipitate were less than 0.96 and 0.001%, respectively. 2.3.3 Effect of Preparation of the Cathode Electrode Contestabile et al. (2001) studied the recycled lithium cobalt oxide by first thermally treating on the recovered product, i.e., cobalt hydroxide at 450
o

C for 3 h, to obtain the Co3O4 oxide. This was then

stoichiometrically mixed with Li2CO3, i.e., another material which can be recovered from a lithium battery recycling process. This mixture was first

53

heated in a muffle furnace at 400 oC for 5 h and then, after homogenizing in a mortar, annealed at 700 oC for about 20 h to produce the desired lithium cobalt oxide LiCoO2. This was added with carbon (conductive component) and PVC (binder) in tetrahydrofuran (THF), to form slurry which was sprayed onto an aluminum foil (current collector). The electrode film formed in this way had the following composition (in wt.%): LiCoO2/Super P/PVC, 90/5/5. Lee and Rhee (2002) reported that various processes have been considered to produce LiCoO2 from the leach liquor. Of the many possible processes, the amorphous citrate precursor process has been applied to synthesize powders with a large specific surfacearea and an exact stoichiometry. After the nitric acid leaching of used LiCoO2, the molar ratio of Li:Co in the leach liquor was adjusted to 1.1 by adding a fresh LiNO3 solution. Then, a 1 M citric acid solution at 100% stoichiometry was also added to prepare a gelatinous precursor. When the precursor was treated at 950 oC for 24 h, a purely crystalline LiCoO2 was successfully obtained (Figure 2.16). Nan et al. (2005) studied lithium carbonate and cobalt oxalates

54

Figure 2.16. XRD patterns for LiCoO2 powder prepared by amorphous citrate precursor process (Lee and Rhee, 2002).

55

recovered from spent lithium ion secondary battery as precursors to produce LiCoO2 electrode material of lithium-ion batteries. The cobalt oxalate was baked, and a molar ratio of cobalt : lithium = 1:1 was ground until they were mixed equally. The mixed samples were heated firstly at 600 oC for 6 h, and then they were ground again and pressed into tablets. LiCoO2 active material was synthesized after the tablets were heated at 800 oC for 10 h in the tube type stove. Then, LiCoO2 material, graphite, ethyne and PVDF were mixed in a proportion of 86:6:2:6. The mixture with N-methylpyrrolidone as solvent was pasted on aluminum foil to prepare the test electrode; pure lithium piece was used as auxiliary electrode.

56

CHAPTER 3 EXPERIMENTAL The experimental facilities and procedures employed in carrying out experiments were described in this section. 3.1 Materials Table 3.1 shows all experimental sources of chemical reagents. During recovery process, cathode active material was used as spent lithium ion secondary batteries. The cathode active materials of LiCoO2 (A), LiMn2O4 (B) and LiCo1/3Ni1/3Mn1/3O2 (C) are performed in simulated experiment of leaching process, respectively. Then, the mixed cathode active materials of LiCoO2, LiMn2 O4 and LiCo1/3Ni 1/3Mn1/3O2 are employed in recovery materials process. Cathode active materials of LiMn2O4 and LiCo1/3Ni1/3Mn1/3O2 were used in this work supplied by Tatung Fine Chemicals Co., and LiCoO2 by Aldrich Chemical Company, Inc. The cathode active material components of LiCoO2, LiMn2O4, LiCo1/3Ni1/3Mn1/3O2 were identified by X-ray diffractometer (XRD-6000, Shimadzu Corporation, Japan). As reported in Figures 3.1 to 3.3, the resulting XRD patterns were compared with the JCPDS standard patterns to identify the compounds and the crystalline structures of the cathode

57

Table 3.1. Experimental sources of chemical reagents

Name Potassium Permanganate Dimethylgloxime Hydrochloric Acid Sodium Carbonate

Structure KMnO4 C4H8N2O2 HCl Na2CO3

Pure

Source

99+% Aldrich Chemical Company, Inc. 98% Wako Pure Chemical Industries 28% Showa Chemical Co. 35~37% Wako Pure Chemical Industries 97% Wako Pure Chemical Industries 100% Wako Pure Chemical Industries

Ammonia Solution NH3 Sodium Hydroxide NaOH

58

10000 8000

LiCoO2 LiCoO2

Intensity

6000 4000 2000 0 10 20 30 40

50

60

70

80

Figure 3.1. XRD patterns of LiCoO2.

59

700 600 500 LiMn2O4 LiMn2O4

Intensity

400 300 200 100 0 10 20 30 40

50

60

70

80

Figure 3.2. XRD patterns of LiMn2O4.

60

3000 2500 2000 LiCo1/3Ni1/3Mn1/3O2 LiCo1/3Ni1/3Mn1/3O2

Intensity

1500 1000 500 0 10 20 30 40 50 60 70 80

2
Figure 3.3. XRD patterns of LiCo1/3Ni1/3Mn1/3O2.

61

active material, i.e., LiCoO2, LiMn2O4, and LiCo1/3Ni1/3Mn1/3O2. Phase analysis of this cathode active material confirms that it is composed of LiCoO2, LiMn2O4, and LiCo1/3Ni1/3Mn1/3O2, individually. 3.2 Experimental Procedure It consisted of leaching process for each cathode active material and recovery materials process for the mixtures. The recovery materials process included sedimentation reaction, precipitate of manganese, separation of nickel, precipitates of nickel, cobalt and lithium. 3.2.1 Leaching Process The LiCoO2, LiMn2O4 and LiCo1/3Ni1/3Mn1/3O2 cathode active materials were used in the simulated experiment, respectively. Simulated experiment was employed to find the optimum leached efficiency for each cathode active material. 3.2.1.1 Simulated Experiment of Leaching Process In order to dissolve lithium, cobalt, nickel and manganese from cathode active materials, simulated experiment of acid leaching process was used. The cathode active material is LiCoO2 (A), LiMn2O4 (B) and LiCo1/3Ni1/3Mn1/3O2 (C) in simulated experiment of leaching process. Various factors which might affect the leaching efficiency were

62

examined. The effect on the leaching process of lithium, cobalt, nickel and manganese was investigated for a given set of leaching variables: hydrochloric acid concentration of leaching agent, leaching temperature (T), leaching time (t) and solid-to-liquid ratio (S/L). The simulated experiment of leaching process in this study was indicated in Figure 3.4. Cathode active material in different hydrochloric acid

concentration (2 to 6 M) and addition of different solid-to-liquid ratio (1/10, 1/20, 1/50 g/ml) was leached in a three neck glass extractor. A three neck glass extractor of 500 ml capacity was put into a hot plate, changing leaching temperature (T): 60, 70, 80 oC and changing leaching time (t): 0.5, 1, 2, 3, 4 h. The leaching material was agitated at a speed of 300 rpm. Each cathode active material was filtered and separated into leach liquor and insoluble residue. The amounts of lithium, cobalt, nickel and manganese in the leach liquor were measured to compute leaching efficiency. Chemical analyses for leach liquor were performed with an Atomic Adsorption Spectroscopy. 3.2.2 Recovery Materials Process The recovery materials process included leaching process for the

63

Figures 3.4. Simulated experiment of leaching process. (Cathode active material is LiCoO2 (A), LiMn2O4 (B) and

LiCo1/3Ni1/3Mn1/3O2 (C).)

64

mixture, sedimentation reaction, precipitate of manganese, precipitates of nickel, cobalt and lithium as shown in Figure 3.5. 3.2.2.1 Leaching Process for the Mixture In this study, cathode active material (1g) in hydrochloric acid concentration 4 M, 50ml with solid-to-liquid ratio of 1/50 (g/ml) was also leached in a three neck glass extractor. A three neck glass extractor of 500 ml capacity was put into hot plate, leaching temperature (T), 80oC, leaching time, 1 h and being agitated at a speed of 300 rpm. Each cathode active material was filtered and separated into leach liquor and insoluble residue. The amounts of lithium, cobalt, nickel and manganese in the leach liquor were measured to compute leaching efficiency. Chemical analyses for leach liquor were also performed with an Atomic Adsorption Spectroscopy (AAS Model 3000, Varian). 3.2.2.2 Sedimentation Reaction Sodium hydroxide solution of 1M is added to the hydrochloric acid leach liquor until pH = 1 to 14. The results can obtain the precipitate efficiency of lithium, cobalt, manganese and nickel at different pH values.

65

66

Figures 3.5. Experimental procedure of the leached and recovery process for the mixture.

(The cathode active material is LiCoO2 (A), LiMn2O4 (B) and LiCo1/3Ni1/3Mn1/3O2 (C).)

3.2.2.3 Precipitate of Manganese Recovery of manganese in the mixture solution of lithium, cobalt, manganese and nickel after sedimentation was performed by employing potassium permanganate (KMnO4) reagent. The effect on the recovery of manganese was investigated for a given set of variables: pH value, molar ratio of Mn++ to KMnO4 and temperature (T). Hydrochloric acid with leach liquor from the leaching process is added 1M sodium hydroxide solution until pH=1, 2 and 3, changing leaching temperature (T): 40, 50 oC, and changing molar ratio of Mn++ to KMnO4: 2, 3, 6, in a three neck glass extractor. The mixture was agitated at a speed of 300 rpm. After reaction, it was filtered and separated into leach liquor and precipitate. The amounts of lithium, manganese, cobalt and nickel in the leach liquor were measured to compute recovery efficiency of manganese. 3.2.2.4 Precipitate of Nickel Separation of nickel after the recovery of manganese from leach liquor was performed by employing dimethylglyoxime (C4H8N2O2) reagent. The effect on the recovery of nickel was investigated for a given set of variables: pH value and molar ratio of C4H8N2O2 to [Ni(NH3)6]2+.
67

The leach liquor after the recovery of manganese in addition of 28 % NH3 solution until pH=3 to 13, changing molar ratio of C4H8N2O2 to [Ni(NH3)6]2+: 1, 1.5, 2, 2.5, 3, as well as reaction time to be 10 min, in a three neck glass extractor with agitation at a speed of 300 rpm were investigated. After reaction, it was filtered and separated into leach liquor and precipitate. The amounts of lithium, cobalt and nickel in the leach liquor were measured to compute recovery efficiency of nickel. Recovery of nickel from the precipitate (red solid complex) was performed by employing hydroxide precipitation. It was filtered and separated into dimethylglyoxime (C4H8N2O2) and nickel ion solution. Dimethylglyoxime (C4H8N2O2) was recovered by dissolving the red solid complex in the 50 ml, 4M hydrochloric acid solution. It will repeatedly be used after separation. Nickel was recovered by addition of 1M sodium hydroxide solution onto the nickel ion solution until pH=11, then filtered and separated into leach liquor and precipitate. 3.2.2.5 Precipitate of Cobalt Recovery of cobalt from the leach liquor ([Co(NH3)6]3+) after the separation of nickel was performed by employing hydroxide precipitation, i.e., addition of a hydrochloric acid solution until pH=0. Cobalt was

68

recovered by addition of 1M sodium hydroxide solution onto the leached liquor until pH=11. It was filtered and separated into leach liquor and precipitate. 3.2.2.6 Precipitate of Lithium After the recovery of cobalt, the leach liquor was concentrated and treated with a saturated sodium carbonate solution to precipitate lithium as lithium carbonate. The precipitation process was performed at 100C, approximately. The lithium carbonate was recovered after filtration and washing with hot water to remove the residual liquor. 3.2.3 Purity Analyses of Recovery Materials The purity analyses of the recovery materials were carried out by Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES Optima 2100 DV, Perkin Elmer instruments, U.S.A.), after dissolving weighted powders (about 1 g) in hydrochloric acid solution at 90oC for 30 minutes and diluting to appropriate concentration with distilled water, then cooling to room temperature. 3.2.4 Electrochemical Analyses 3.2.4.1 Powder Prepared by Solid-State Reaction 3.2.4.1.1 Preparation of LiCoO2 Powder
69

Recovery cobalt powders (0.05 moles) were mixed with recovery lithium powders to make Li/Co molar ratio to be 1. Putting the mixture and the YTZ ball of 3mm diameter together into a PE bottle, alcohol being added to 80% full, then the powder was mixed for 24 hours. The slurry was taken out and dried under the IR light for 3 hours, then put the dried slurry into vacuum oven at 70oC for 24 hrs. The dried powder was ground at room temperature, then calcined at 850oC for 10 h with the heating rate to be 5oC/min. 3.2.4.1.2 Preparation of LiMn2O4 Powder Recovery manganese powders (0.05mole) were mixed with recovery lithium powders to make Li/Mn molar ratio to be 0.5. Putting the mixture and the YTZ ball of 3mm diameter together into a PE bottle, alcohol being added to 80% full, then the powder was mixed for 24 hrs. The slurry was taken out and dried under the IR light for 3 hours, then put the dried slurry into vacuum oven at 70oC for 24 hrs. The dried powder was ground at room temperature, then calcined at 850oC for 8 h with the heating rate to be 5oC/min. 3.2.4.2 Preparation of the Cathode Electrode Polyvinylidene fluoride (PVDF, Kynar 740, ELF, Germany) was

70

dissolved in adequate amount of N-methylpyrollidone (NMP, ultra, ISP Technologies Inc., U.S.A.). The prepared powder and acetylene black were added to the above solution with weight ratio to PVDF of 80:10:10, stirred for 24 h to sufficiently mix. The slurry prepared in the previous step was smeared on the aluminum foil (thickness of 25 m) by tape casting. The green tape was dried in vacuum oven of 80 oC for 24 hrs to remove the residual solvent. The dried tape was punched into round plate with diameter of 10 mm as the cathode electrode. The electrode plate was pressed under pressure of 200 psi for 1 min to compact it. The electrode plate was placed in the vacuum oven and heated under temperature of 80oC for 8 hrs. Then the weight of the electrode plate was measured. 3.2.4.3 Assembly of the Coin-Type Cell The prepared electrode (diameter of 10 mm) and separator (diameter of 18 mm, Celgard, Hoechst, U.S.A.) were put into the argon-filled glove box (82-2 Spez, MacPlex, Switzerland). Lithium foil (thickness of 0.18 mm, 99%, FMC, U.S.A.) was punched into round plate (diameter of 12 mm) as the anode in the glove box. 2032 coin cells were assembled with the components of the cell and 1M LiPF6 in EC-DEC-PC (1:1:1 vol.) (Tomiyama, Japan) as electrolyte in the glove box. The parts

71

of the coin-type cell are shown in Figure 3.6. 3.3 Experimental Apparatus 3.3.1 Leaching Process Apparatus The leaching was conducted in the apparatus as shown in Figure 3.7. A three neck glass extractor of 500 ml capacity was put into oil-bath tank with the reaction temperature being controlled within 0.5oC, a stirrer/hot plate (BARHSTEAD INTERNATIONAL). A condenser was used to minimize evaporation loss of water and hydrochloric acid concentration. During the procedure of reaction, the weight of samples was measured by an electro balance (METTLER TOLEDO) after each leached process. 3.3.2 Recovery Materials Process Apparatus The recovery materials process was conducted in the apparatus as indicated in Figure 3.7, which is the same as leaching process apparatus in simulated experiment. 3.3.3 pH Value Analyses Apparatus pH meter (Jenco, Model 6200) was used during the procedure of pH value analyses.

72

Figure 3.6.The coin-type cell fabrication.

73

a. thermometer b b. condenser c. Teflon stirrer a d. three neck glass extractor e. stirrer / hot plate f. oil-bath tank d c e f

Figures 3.7. Schematic diagram of leaching and recovery cathode active material apparatus.

74

3.3.4 Filtration Experiments Apparatus The filtration experiments were conducted in the apparatus as shown in Figure 3.8. The filtration experiments used aspirator (TOKYO RLKAKLAL CO.), Micro-filtration (Techologies, INC) apparatus and 500 ml filter flask (RYREX). During the procedure of filtration, glass microfiber filter (0.2/47mm, ADVNTEC, Japan) was used as the filter paper for each filtration process. 3.4 Characteristic Analysis of Cathode Active Material 3.4.1 X-Ray Diffraction Analysis X-ray diffraction was used to obtain the structure and composition of crystalline materials. Wide-angle X-ray diffractograms measurements were performed at room temperature (ca. 25oC) on a Shimadzu XRD-6000 X-ray diffractometer (operation at 40 kV and 30 mA) with graphite-monochromatized Cu K radiation (=1.5418). The scanning rate was 1/min over a range of 2=10-80. Measurements were performed with film specimens of about 0.1 mm in thickness. 3.4.2 Composition Determination 3.4.2.1 Atomic Adsorption Spectroscopy Analysis Atomic Adsorption Spectroscopy (AAS Model 3000, Varian) was

75

a. Micro-filtration apparatus b. filter flask

c. aspirator

Figures 3.8. Schematic diagram of filtration apparatus.

76

used to determine the concentration of cobalt, manganese, nickel and lithium ions dissolved in the separation and recovery experiments. The procedures for cobalt, manganese, nickel and lithium ions concentration determination were described as follows: (1) A series of standard cobalt, manganese, nickel and lithium solutions were prepared by diluting cobalt, manganese, nickel and lithium Atomic Adsorption Spectroscopy standard solution (1000 2 ppm, Merk, Germany ) with de-ionized water. (2) Measure the Atomic Adsorption Spectroscopy absorbance of the standard solutions. Plot the absorbance versus concentration data and fit them by linear regression to prepare a calibration curve. (3) Dilute the samples to adequate concentration, the cobalt, manganese, nickel and lithium concentrations of a given sample were determined from the Atomic Adsorption Spectroscopy absorbance and the calibration curve mentioned above. 3.4.2.2 Inductively Coupled Plasma Optical Emission Spectrometer Analysis The composition of the prepared powders was determined with inductively coupled plasma optical emission spectrometer (ICP-OES

77

Optima 2100 DV, Perkin Elmer instruments, U.S.A.) by dissolving weighted powders (about 1 g) in concentrated HCl solution at 90oC for 30 minutes and diluting to appropriate concentration with distilled water after cooling to room temperature. Standard solutions were prepared for calibration and concentration determination. 3.4.3 Capacity Retention Studies The assembled 2032 coin-type cells were used for the capacity retention test at 30oC by using a home-made battery tester. The testing was performed galvanostatically with the cut-off charge-discharge potentials ranging between 3 and 4.3 V with C/10 rate. C rate =

cathode active material of weight theoretical capacity (3-1) 1000

LiMn2O4 and LiCoO2 have the theoretical capacities about 147 and 280 mAh/g, respectively.

78

CHAPTER 4 RESULTS AND DISCUSSION 4.1 Leaching Process 4.1.1 Simulated Experiment of Leaching Process Theoretically, only LiCoO2, LiMn2O4 and LiCo1/3Ni1/3Mn1/3O2 are soluble constituents in battery scraps for hydrochloric acid solution with lower concentration range. In order to reduce the volatilization pollution caused by reactants, hydrochloric acid with suitable concentration was chosen as a more suitable leaching reagent as compared to sulfuric acid and nitric acid. From the standpoint of price of the leaching agent and investment cost, hydrochloric acid would be a better leaching reagent than hydroxylamine hydrochloride (Zhang et al., 1998). The LiCoO2, LiMn2O4 and LiCo1/3Ni1/3Mn1/3O2 with HCl reaction, respectively are as follows: 4LiCoO2 + 12HCl 4LiCl + 4CoCl2 + 6H2O + O2 4LiMn2O4 + 20HCl 4LiCl + 8MnCl2 + 10H2O + 3O2 (4-1) (4-2)

12LiCo1/3Ni1/3Mn1/3O2 + 36HCl 12LiCl + 4MnCl2 + 4CoCl2 + 4NiCl2+ 18H2O + 3O2 (4-3)

To obtain the optimum conditions for the leaching of cathode active

79

materials of LiCoO2, LiMn2O4 and LiCo1/3Ni1/3Mn1/3O2, several sets of leaching experiments were carried out that included various hydrochloric acid concentrations (CHCl), leaching temperature (T), leaching time (t) and solid-to-liquid ratio (S/L). 4.1.1.1 Hydrochloric Acid Concentrations Figures 4.1 to 4.3 show the effect of hydrochloric acid concentration on leaching of cathode active materials: LiCoO2 (A), LiMn2O4 (B) and LiCo1/3Ni1/3Mn1/3O2 (C) with one hour leaching time, solid-to-liquid ratio of 1/50 g/ml and 80oC leaching temperature. It indicates that the leaching efficiencies of lithium, cobalt, nickel and manganese are relatively low at lower hydrochloric acid concentration. It is evident that the leaching of cathode active material is enhanced with the increase of hydrochloric acid concentration (Zhang et al., 1998). Over 99 percentages of lithium, cobalt, nickel and manganese can be leached when hydrochloric acid concentrations are over 4M. Thus, hydrochloric acid concentration of 4M is chosen as the optimum leaching concentration. 4.1.1.2 Leaching Temperature Figures 4.4 to 4.6 show the effect of leaching temperature on

80

100 80 60 40 20 0

LP, %

Co Li

CHCl, M
Figure 4.1. Effect of hydrochloric acid concentration on leached percent of cathode active material, LiCoO2 (A) with t = 1h, S/L = 1/50 g/ml and T=80 oC.

81

100 80

LP, %

60 40 20 0

Mn Li

CHCl, M
Figure 4.2. Effect of hydrochloric acid concentration on leached percent of cathode active material, LiMn2O4 (B) with t = 1h, S/L = 1/50 g/ml and T=80 oC.

82

100 80

LP, %

60 40 20 0
Co Ni Mn Li

CHCl, M
Figure 4.3. Effect of hydrochloric acid concentration on leached percent of cathode active material, LiCo1/3Ni1/3Mn1/3O2 (C) with t = 1h, S/L = 1/50 g/ml and T=80 oC.

83

100 80 60

LP, %

40 20 0 55
Co Li

60

65
o

70

75

80

T, C
Figure 4.4. Effect of leaching temperature on leached percent of cathode active material, LiCoO2 (A) with t = 1h, S/L = 1/50 g/ml and CHCl=4M.

84

100 80 60

LP, %

40 20 0 55

Mn Li

60

65
o

70

75

80

T, C
Figure 4.5. Effect of leaching temperature on leached percent of cathode active material, LiMn2O4 (B) with t = 1h, S/L = 1/50 g/ml and CHCl=4M.

85

100 80

LP, %

60 40 20 0 55
Co Ni Mn Li

60

65
o

70

75

80

T, C
Figure 4.6. Effect of leaching temperature on leached percent of cathode active material, LiCo1/3Ni1/3Mn1/3O2 (C) with t = 1h, S/L = 1/50 g/ml and CHCl=4M.

86

leaching of cathode active materials LiCoO2 (A), LiMn2O4 (B) and LiCo1/3Ni1/3Mn1/3O2 (C) with 1h leaching time, solid-to-liquid ratio of 1/50 g/ml and 4M hydrochloric acid concentration. It indicates that the leaching efficiency of lithium, cobalt, nickel and manganese is relatively low at lower leaching temperature. The leaching efficiency increases with the increase of leaching temperature. When temperature is higher than 80
o

C, over 99 percentages of lithium, cobalt, nickel and manganese are

leached. The increase of temperature enhances remarkably the leaching of the metals (Zhang et al., 1998). Thus, leaching temperature of 80 oC is chosen as the optimum temperature. Under this leaching temperature, almost all of the lithium, cobalt, nickel and manganese can be leached out. 4.1.1.3 Leaching Time The effect of leaching time on the leaching percent of cathode active materials LiCoO2 (A), LiMn2O4 (B) and LiCo1/3Ni1/3Mn1/3O2 (C)

with leaching temperature of 80oC, solid-to-liquid ratio of 1/50 g/ml and 4M hydrochloric acid concentration is presented in Figures 4.7 to 4.9. It is seen that the leached cathode active material is increased with the increase of leaching time (Nan et al., 2006), and about 99 percentages

87

100 80 60 40 20 0
Co Li

LP, %

t, h
Figure 4.7. Effect of leaching time on leached percent of cathode active material, LiCoO2 (A) with CHCl=4M, T=80 oC and S/L = 1/50 g/ml.

88

100 80 60 40 20 0
Mn Li

LP, %

t, h
Figure 4.8. Effect of leaching time on leached percent of cathode active material, LiMn2O4 (B) with CHCl=4M, T=80 oC and S/L = 1/50 g/ml.

89

100 80 60 40 20 0
Co Ni Mn Li

LP, %

t, h
Figure 4.9. Effect of leaching time on leached percent of cathode active material, LiCo1/3Ni1/3Mn1/3O2 (C) with CHCl=4M, T=80 oC and S/L = 1/50 g/ml.

90

lithium, cobalt, nickel and manganese can be leached out after 1 hour. So, the leaching time of 1 h is chosen in this simulated experiment. 4.1.1.4 Solid-to-Liquid Ratio (S/L) The leaching behavior with different solid-to-liquid ratio (S/L) is presented in Figures 4.10 to 4.12 at a fixed condition of hydrochloric acid concentration 4M, leaching temperature 80oC and leaching time 1h. The leaching efficiency of metals is decreased with increasing solid-to-liquid ratio (Lee et al., 2003). High solid-to-liquid ratio is desirable to raise processing throughput. Yet, a solid-to-liquid ratio higher than 1/50 (g/ml) yields lower leaching efficiency. Over 99 percentages of lithium, cobalt, nickel and manganese are readily leached out at a solid-to-liquid ratio of 1/50 g/ml. In summary, the final optimum operating conditions are determined as follows: 4M hydrochloric acid solution, 80C leaching temperature, 1 h leaching time, 1/50 g/ml solid-to-liquid ratio. Under these experimental conditions, almost all of metals from the cathode active materials of LiCoO2, LiMn2O4 and LiCo1/3Ni1/3Mn1/3O2 can be leached out. The experimental works using cathode active material of LiCoO2 from China was also shown in Appendix A as a contrast. The

91

100 80
Co Li

LP, %

60 40 20 0.02 0.04 0.06 0.08 0.10

S/L, g/ml
Figure 4.10. Effect of solid-to-liquid ratio (S/L) on leached percent of cathode active material, LiCoO2 (A) with CHCl=4M, T=80 oC and t=1h.

92

100 80
Mn Li

LP, %

60 40 20 0

0.02

0.04

0.06

0.08

0.10

S/L, g/ml
Figure 4.11. Effect of solid-to-liquid ratio (S/L) on leached percent of cathode active material, LiMn2O4 (B) with CHCl=4M, T=80 oC and t=1h.

93

100 80
Co Ni Mn Li

LP, %

60 40 20 0

0.02

0.04

0.06

0.08

0.10

S/L, g/ml
Figure 4.12. Effect of solid-to-liquid ratio (S/L) on leached percent of cathode active material, LiCo1/3Ni1/3Mn1/3O2 (C) with CHCl=4M, T=80 oC and t=1h.

94

experimental results show the same trend. 4.1.2 Leaching Process for the Mixture Leaching process using the mixture of cathode active materials of LiCoO2, LiMn2O4 and LiCo1/3Ni1/3Mn1/3O2 is 1:1:1 in weight ratio. Table 4.1 shows the result of leaching percent with different metals. The mixture of LiCoO2, LiMn2O4 and LiCo1/3Ni1/3Mn1/3O2 is leached with 4M hydrochloric acid solution, 80 oC leaching time, 1 h leaching time and 1/50 g/ml solid-to-liquid ratio. Under these experimental conditions, 99.5% cobalt, 99.9% lithium, 99.8% nickel and 99.8% manganese are readily leached out. 4.2 Recovery Materials Process The recovery materials process includes sedimentation reaction, precipitate of manganese, nickel, cobalt and lithium. 4.2.1 Sedimentation Reaction The recovery material, i.e., valuable metal is selectively precipitated in its stable hydroxide form as a function of the pH value, according to its values of solubility product as indicated in Table 4.2 (James and Speight, 2005). Sodium hydroxide solution (1M) is added onto the 4M hydrochloric acid leach liquor until pH reaches a certain
95

Table 4.1. Leached percent of different metals in the mixtiue (LiCoO2: LiMn2O4:LiCo1/3Ni1/3Mn1/3O2 =1:1:1 in weight ratio) with CHCl=4M, T=80 oC, S/L=1/50 g/ml and t=1h

Metal

Li 99.9

Co 99.5

Ni 99.8

Mn 99.8

Leached percent (%)

96

Table 4.2. Solubility products of chemical compounds (James and Speight, 2005) Compound Cobalt Carbonate Lithium Carbonate Manganese Carbonate Nickel Carbonate Cobalt Hydroxide (II) Cobalt Hydroxide (III) Manganese Hydroxide Nickel Hydroxide Formula CoCO3 Li2CO3 MnCO3 NiCO3 Co(OH)2 Co(OH)3 Mn(OH)2 Ni(OH)2 Ksp 1.410-13 2.510-2 2.3410-11 1.4210-7 5.9210-15 1.610-44 1.910-13 5.4810-16

97

value. Figure 4.13 shows the effect of pH value on recycle percent of leach liquor of lithium, cobalt, manganese and nickel. Consequently, precipitation of manganese begins at pH value of 1 and precipitates completely at pH value of 12. Precipitation of nickel begins at pH value of 2 and completely at pH value of 7. Precipitation of cobalt begins at pH value of 3 and completely at pH value of 10. Lithium does not precipitate with different pH values because lithium is not reacted with hydroxide ion (Atlas of Elechemical Equilibria in Aqueous Solution, 1974). 4.2.2 Precipitate of Manganese The manganese in the leach liquor is a redox reaction selectively and nearly completely with a potassium permanganate reagent. The redox reaction is described as follows: 3Mn2+ + 2MnO4- + 2H2O 5MnO2 + 4H+ (4.4)

The effect on the precipitate of manganese is investigated for a given set of variables as: pH value, molar ratio of Mn++ to KMnO4, and temperature. 4.2.2.1 pH Value Separation of manganese from lithium, cobalt and nickel from the hydrochloric acid leach liquor is performed by employing redox reaction.

98

100 80 60
Co Mn Ni Li

RP, %

40 20 0

10

12

14

pH
Figure 4.13. Effect of pH value on recycle percent of leach liquor of cobalt, manganese, nickel and lithium.

99

If potassium permanganate reagent is directly input to hydrochloric acid leach liquor, there is no precipitate, because hydrochloric acid leach liquor is excessively acidic. Therefore, the KMnO4 reagent is input drop by drop after changing the pH value. Figure 4.14 shows the effect of pH value on recycle percent of cobalt, manganese, nickel and lithium with Mn++: KMnO4=2. It is seen that the precipitate of manganese is enhanced with the increase of pH value. It is found that the precipitate of manganese increases rapidly and is completely precipitated when pH=2. Over 99 percentages of manganese are readily in precipitate at pH=2. Above pH=2, cobalt and nickel begin to precipitate because the cobalt and nickel are precipitated in its stable hydroxide form as a function of the pH. Thus, the final optimum pH value for the manganese redox reaction is determined as pH=2. 4.2.2.2 Molar Ratio of Mn++ to KMnO4 (MRMP), and Temperature In order to raise the operating capacity, the molar ratio of Mn++ to KMnO4 in the 4M hydrochloric acid leach liquor should be changed. Figure 4.15 shows the effect of molar ratio of Mn++ to KMnO4 and temperature on recycle percent of cobalt, manganese, nickel and lithium with pH=2. It is obvious that temperatures between 40oC and 50oC do not

100

100 80 60 40 20 0
Mn Co Ni Li

RP, %

pH
Figure 4.14. Effect of pH value on recycle percent of cobalt, manganese, nickel and lithium (Mn++ : KMnO4= 2).

101

100 80 60 40 20 0 0 2 4

50 C Mn Co Ni Li

40 C Mn Co Ni Li

RP, %

MRMP
Figure 4.15. Effect of molar ratio of Mn++ to KMnO4 and temperature on recycle percent of cobalt, manganese, nickel and lithium (pH=2).

102

have any significant effect on manganese precipitation. It is therefore advisable that this treatment should be applied at temperature 40oC as previously described. The manganese in the leach liquor is precipitated selectively and nearly completely with a potassium permanganate reagent at molar ratio of 2, pH=2, then the manganese is recovered as MnO2 and manganese hydroxide with high purity. 4.2.3 Precipitate of Nickel (Castillo et al., 2002) Separation of nickel from leach liquor after the recovery of manganese is performed by employing dimethylglyoxime reagent (C4H8N2O2). In addition of 28% NH3 into the solution to make nickel as [Ni(NH3)6]2+, the dimethylglyoxime forms a red solid complex. The complexation reaction is very selective and quantitative (Castillo et al. 2002). The effect on the recycle percent of nickel is investigated for a given set of pH value and molar ratio of dimethylglyoxime to [Ni(NH3)6]2+. 4.2.3.1 pH Value Figure 4.16 shows the effect of pH value on adsorption of cobalt, nickel and lithium with C4H8N2O2: [Ni(NH3)6]2+ = 2.5. Consequently, it can be seen that over 99 percentages adsorb of nickel can be obtained

103

100 80 60 40 20 0
Co Ni Li

RP, %

10 11 12 13

pH
Figure 4.16. Effect of pH value on adsorb of cobalt, nickel and lithium (C4H8N2O2: [Ni(NH3)6]2+=2.5).

104

among the pH values of 8-11 and cobalt and lithium can not be adsorbed. Nickel is found to be optimally adsorbed from aqueous solution in the pH range of 8-10 (Lee and Halmann, 1976). However, in strongly alkaline solutions, e.g., above pH=11, the amount of adsorbed nickel is decreased, which may be due to an unfavorable reaction condition for formation of the nickel-dimethylglyoxime complex (Lee and Halmann, 1976). It is therefore advisable that this treatment should be applied at pH value of 9. 4.2.3.2 Molar Ratio of [Ni(NH3)6]2+ to Dimethylglyoxime (MRDN) Figure 4.17 shows the effect of molar ratio of dimethylglyoxime to [Ni(NH3)6]2+on adsorb of cobalt, nickel and lithium with pH value of 9. The results present that the optimum molar ratio of nickel to dimethylglyoxime is about 2. Over 99 percentages adsorb of nickel can be separated from the liquor of lithium, cobalt and nickel, which can be conformed to the theoretical ratio for the dimethylglyoxime-nickel complex to be 2 (Lee and Halmann, 1976). This means that all of the dimethylglyoxime becomes available to react with nickel. 4.2.3.3 Precipitate of Nickel The red solid complex can be dissolved in the 50 ml, 4M hydrochloric acid solution and recovered as dimethylglyoxime

105

100 80
Ni Co Li

RP, %

60 40 20 0 0.0

0.5

1.0

1.5

2.0

2.5

3.0

MRDN
Figure 4.17. Effect of molar ratio of C4H8N2O2 to [Ni(NH3)6]2+ on adsorb of cobalt, nickel and lithium (pH=9).

106

(C4H8N2O2) reagent (white powder) and nickel ion solution. The nickel ion solution can be recovered as nickel hydroxide by addition of 1M sodium hydroxide solution until pH=11 as described in Figure 4.13. Then, it is filtered and separated into leach liquor and precipitate. Ideally, nickel can be completely recovered in this study. 4.2.4 Precipitate of Cobalt (Contestabile et al., 2001) Cobalt which is recovered after the separation of nickel as leach liquor ([Co(NH3)6]3+) is performed by employing hydroxide precipitation. First, a hydrochloric acid solution is added until pH=0, this solution then recovers cobalt by addition of 1M sodium hydroxide solution until pH=11, as indicated in Figure 4.13. It is filtered and separated into leach liquor and precipitate. Also, cobalt can be recovered completely. 4.2.5 Precipitate of Lithium (Zhang et al., 1998) After the recovery of cobalt, the leach liquor is treated with a saturated solution of sodium carbonate to precipitate lithium as lithium carbonate. Since the solubility of lithium carbonate in an aqueous solution is inversely proportional to temperature, e.g., S Li2CO3 =1.52 at 0C and S Li2CO3 =0.71 (g/100 g H2O) at 100C (Langes Handbook of Chemistry), the precipitation process is performed at a temperature close

107

to 100 C. The lithium carbonate is recovered after filtration and washed with hot water to remove the residual liquor. Lithium should be recovered completely, however, the analytical results show that 80 1% of the lithium is recovered as a precipitate. 4.3 Purity of Recovery Materials Tests The purity analyses of the recovery materials is carried out by inductively coupled plasma optical emission spectrometer (ICP-OES Optima 2100 DV, Perkin Elmer instruments, U.S.A.), after dissolving weighted powders (about 1 g) in concentrated hydrochloric acid solution at 90oC for 30 min. and diluting to appropriate concentration with distilled water at room temperature. The purity of recovery materials of lithium, manganese, cobalt and nickel in this experiment is indicated in Tables 4.3 to 4.6, respectively. From the results, it is obvious that the purity of recovery materials of lithium, manganese, cobalt and nickel are 96.97, 98.23, 96.94 and 97.43 wt%, respectively. Analysis shows that the major impurity is Na which may be attributed to the residual Na ion in the washing step although it does not exceed 2.5 wt% for each recovery material.

108

Table 4.3. Purity analysis of recovery material of lithium

109

Table 4.4. Purity analysis of recovery material of manganese

110

Table 4.5. Purity analysis of recovery material of cobalt

111

Table 4.6. Purity analysis of recovery material of nickel

112

4.4 Electrochemical Properties The XRD patterns of the synthesized LiCoO2 and LiMn2O4 from the recovery materials are shown in Figures 4.18 and 4.19, respectively. The X-ray diffractograms of the recovered and renovated powder are compared with those of the LiCoO2 and LiMn2O4 reference phases. It is apparent that no XRD peaks of possible impurities, such as Co(OH)2, Co3O4 and Mn3O4, etc. are detected. The recovery materials are assembled as the coin-type cells to perform charge/discharge behavior between 3.0 V and 4.3 V at C/10 rate. The charge-discharge curves for the recovery synthesized LiCoO2 are shown in Figures 4.20 and 4.21. They indicate that the charge capacity in the first cycle is 161 mAh/g and the discharge capacity is 15l mAh/g. The discharge efficiency is 93.8%. A capacity loss is observed with increasing the cycle number. After 30 cycles, the discharge capacity is only 25mAh/g. The capacity becomes so small, which may be due to an unfavorable reaction conditions for calcined temperature and calcined time. The calcined temperature should influence the physical and electrochemical characteristics of the electrode profoundly (Wang et al., 2005). Calcined time and temperature strongly affect not only the

113

Recovery synthesized LiCoO2 LiCoO2

Intensity (a.u.)
10

20

30

40

50

60

70

80

2
Figure 4.18. XRD pattern of the recovery synthesized LiCoO2 powder.

114

Recovery synthesized LiMn2O4 LiMn2O4

intensity(a.u.)
10

20

30

40

50

60

70

80

2
Figure 4.19. XRD pattern of the recovery synthesized LiMn2O4 powder.

115

4.5

30

4.0 Voltage, V

3.5

3.0

30 voltage range:3~4.3V c rate:C/10

2.5

20

40

60

80

100 120 140 160 180

Capacity, mAh/g
Figure 4.20. Voltage vs. capacity profiles of 1st to 30th cycles at the C/10 rate for the recovery synthesized LiCoO2 phase.

116

220 200 180

charge discharge

Capacity, mAh/g

160 140 120 100 80 60 40 20 0 0 5 10 15 20 25 30

Cycle number
Figure 4.21. Capacity profiles vs. cycle number of 1st to 30th cycles at the C/10 rate for the recovery synthesized LiCoO2 phase.

`
117

structure and morphology, but also the electrochemical characteristics (Wu et al., 2005). The experimental works also assemble the recovery synthesized LiMn2O4 as a coil-type cell and perform charge-discharge experiment. Unfortunately, it fails because of the incorrect calcined temperature and calcined time being operated. Further experiments should be examined to obtain the charge-discharge characteristics of the synthesized LiMn2O4 from the recovery materials.

118

CHAPTER 5 CONCLUSIONS The study of the recovery process of metal values from spent lithium ion secondary batteries has given rise to the following conclusions: 1. Based on the simulated experiments of leaching process, the optimum leaching conditions are chosen to be 4M hydrochloric acid solution, 80oC leaching temperature, 1 h leaching time and 1/50 solid-to-liquid ratio. Under these experimental conditions, almost all of the cathode active materials can be leached out. 2. Based on the recovery material process, (a) the optimum operating conditions of the precipitate of manganese are determined as Mn++ to KMnO4 molar ratio of 2, 40oC reaction temperature and 10 min reaction time. Under these experimental conditions, almost all of the manganese can be precipitated; (b) the optimum operating conditions in separation of nickel are determined as follows: pH=9 and molar ratio of dimethylglyoxime to [Ni(NH3)6]2+ = 2;
119

(c) an addition of 1M NaOH solution to reach pH=11 allows the selection precipitation of cobalt hydroxides; (d) the recovery of lithium is accomplished by a conventional precipitation method as lithium carbonate at a temperature close to 100C. 3. An overall process flowsheet, based on the experimental

investigations, is shown in Figure 5.1.

120

121

Figure 5.1. Flowsheet of the hydrometallurgical process for the recovery of lithium, cobalt, nickel and manganese from

spent lithium-ion secondary batteries (Cathode active material: LiCoO2 (A), LiMn2O4 (B) and LiCo1/3Ni1/3Mn1/3O2 (C)).

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APPENDIX A

100 80

LP, %

60 40 20 0
Co (Aldrich) Li (Aldrich) Co (China) Li (China)

CHCl, M
Figure A.1. Effect of hydrochloric acid concentration on leached percent of cathode active materials LiCoO2 (China) and LiCoO2 (Aldrich) with t = 1h, S/L = 1/50 g/ml and T=80 oC.

133

100 80 60 40 20 0 65
Co (Aldrich) Li (Aldrich) Co (China) Li (China)

LP, %

70

75

80

T, C

Figure A.2. Effect of leaching temperature on leached percent of cathode active materials LiCoO2 (China) and LiCoO2 (Aldrich) with t = 1h, S/L = 1/50 g/ml and CHCl=4M.

134

100 80 60 40 20 0
Co (Aldrich) Li (Aldrich) Co (China) Li (China)

LP, %

t, h
Figure A.3. Effect of leaching time on leached percent of cathode active materials LiCoO2 (China) and LiCoO2 (Aldrich) with CHCl=4M, T=80 oC, and S/L = 1/50 g/ml.

135

100 80 60

LP, %

40 20 0
Co (Aldrich) Li (Aldrich) Co (China) Li (China)

0.02

0.04

0.06

0.08

0.10

S/L, g/ml
Figure A.4. Effect of solid-to-liquid ratio (S/L) on leached percent of cathode active materials LiCoO2 (China) and LiCoO2 (Aldrich) with CHCl=4M, T=80 oC and t=1h.

136