1 2 3 4 Supportng Informaton Novel Approach for In-stu Recovery of Lthum Carbonate from Spent Lthum Ion Batteres Usng Vacuum Metallurgy Jefeng Xao a, Ja L a,b*, Zhenmng Xu a 5 a School of Envronmental Scence and Engneerng, Shangha Jao Tong Unversty, 800 6 Dongchuan Road, Shangha 200240, People s Republc of Chna 7 b Nanjng Unversty & Yancheng Academy of Envronmental Protecton Technology and 8 Engneerng, Huanbao Road, Yancheng 224000, People s Republc of Chna 9 Correspondng authors: Ja L, Tel: +86 21 54747495, Fax: +86 21 54747495, E-mal: 10 11 12 weee@sjtu.edu.cn. Supportng Informaton Content 12 pages (ncludng the cover page) 13 Economc assessments 14 5 Fgures 15 3 Tables 16 Fgure S1 The pre-treatment process to obtan mxed electrode materals from spent batteres 17 Fgure S2 XRD pattern of whte crystals 18 Fgure S3 (a), (b) effect of temperature and holdng tme on graphte removal, and (c) XRD 19 patterns of burned powders at dfferent condton. Correspondng author: Ja L, Tel:+86 21 54747495; Fax:+86 21 54747495; E-mal: weee@sjtu.edu.cn S1
20 21 22 23 24 Fgure S4. XRD patterns of mxed electrode materals and calcned mxed electrode materals Fgure S5. XRD patterns of cathode materal and mxed materals calcned at 873 K for 45 mn Table S1. Man Composton of Mxed Electrode Powders Ganed by Mechancal Separaton Table S2. L-element Recovery Rate a from Dfferent Spent LIBs Table S3. Revenues of Products by Ths Recyclng Process 25 Economc Assessments 26 27 28 >0.8 mm 0.12-0.8 mm 29 Dschargng Crushng Screenng <0.12 mm 30 31 32 33 34 Fgure S1 The pre-treatment processes to obtan mxed electrode materals from spent batteres After dschargng, the batteres are fully crushed and screened to obtan mxed electrode materals whose ngredents are anode powders graphte and cathode powders LMn 2 O 4 (powders sze<0.12 mm) as shown n Fgure S1. 35 S2
36 37 Fgure S2 XRD pattern of whte crystals 38 39 40 41 42 43 Fgure S3 (a), (b) effect of temperature and holdng tme on graphte removal, and (c) XRD patterns of burned powders at dfferent condton. S3
44 45 46 47 48 49 50 51 52 53 54 55 56 After L recovery by water leachng process, effects of temperature and holdng tme on the purty of Mn resource n the flter resdues were nvestgated. In the process, the purty rato of Mn resource depended on the removal rato of graphte, so the weght loss rate was used to replace the purty rate. As shown n Fgure 3(a), a seres of experments were conducted at dfferent temperatures and the results showed that graphte can be completely removed at 1073 K for 30 mn. Besdes, Fgure 3(c) showed that MnO was oxdzed nto Mn 3 O 4 as the fnal product durng the graphte removal. Furthermore, effect of holdng tme was studed as Fgure 3(b). Wth the rse of holdng tme, the weght loss gradually ncreased and then reached a plateau. When holdng tme was 20 mn, the weght loss rate of resdues reached the maxmum and the purty rate of Mn 3 O 4 was 96.51%. In a word, the graphte n flter resdues was totally burned away at 1073 K for 20 mn and the fnal product as Mn 3 O 4 was obtaned as precursor of cathode materals. 57 58 59 Fgure S4. XRD patterns of mxed electrode materals and calcned mxed electrode materals 60 S4
61 62 63 Fgure S5. XRD patterns of cathode materal and mxed materals calcned at 873 K for 45 mn Table S1. Man Composton of Mxed Electrode Powders Ganed by Mechancal Separaton Elements L Mn Cu Al Fe Co N C Content 2.371 37.22 0.2307 0.2276 0.0627 0.0095 0.0062 30.83 (wt. %) 64 65 66 Table S2. L-element Recovery Rate a from Dfferent Spent LIBs LMn 2 O 4 LCoO 2 LCo x Mn y N z O 2 R (%) 81.90 82.70 66.25 67 a the pyrolyss powders were leached by water wth S:L of 25 g/l just the once. 68 69 70 71 72 73 Economc Assessments Assume that the treatment capacty s 10 ton (18650) spent LMn 2 O 4 per day n Chna. And the cost of collecton and transportaton of every battery s $0.15. And the total amount of batteres was about 27400. So the collecton and transportaton costs were calculated as the followng: S5
C C&T = $0.15 27400 = $4110 74 75 76 77 78 79 80 The workng day s 300 days per year (average 25 days per month) whle the work tme s about 8 hours every day. And the ndustral electrcty charge s $0.20 /kwh (maxmum), the ndustral water charge s $0.40/t (maxmum), the ndustral NaCl cost s $58/t. The average wage of per labor s $900 every month ($36 per day, 25 day per month). Consderng the resduals rate and nterest rate 1, deprecaton cost of equpment s calculated as Eq. (1) whle the cost of equpment mantenance cost s calculated as Eq. 81 (2): (1) 1 (1 + ) n C D deprecaton cost of equpment C o acquston cost of equpment r Resduals rate of equpment, 4% nterest rate, 10% 82 n sevce lfe, year M c mantenace cost of equpment C o acquston cost of equpment M c = C o 0.05 (2) 83 84 And the cost of electrc power, water and labor are calculated as Eq. (3), (4) and (5): C P = P t p e (3) C P cost of electrc power p e electrcty prce for ndustral uses, $0.20/kWh S6
t workng tme of equpment P Equpment power, Kw 85 C w = V p w (4) C w cost of water p w water prce for ndustral uses, $0.4/t V water consumpton, ton/day 86 C L = m p s (5) C L cost of labor 87 p s wage of per labr, $30/day m number of workers 88 89 90 91 92 93 94 95 Fnally, the cost of every process and revenue of products n ths study were calculated n detaled and then a day s proft was obtaned as follows. Process I: NaCl-dschargng: Requrement: dschargng n 5 w.t. % NaCl soluton for 12 h, batteres/soluton = 1:10 w/w (assume that the dschargng s done at the nght before); about 5 ton of NaCl and 30 ton of water were needed n the dschargng process; two sets of automatc conveyor belts (P w =7.5kW, per prce= $2000, 2.0 m/s, maxmum capacty= 1000 m 3 /h, servce lfe=5 years) work for 1 hour every day. 1 (1 + ) n = ($2000 2 1 300 ) (1 4%) 10% = $3.38 1 (1 + 10%) 5 M c = C o 0.05 = ($2000 2 1 ) 0.05 = $0.67 300 S7
96 C P = P t p e = 7.5 kw 1h $0.20/kWh 2 = $3.0 C NaCl + C w = 5 t $58/t + 100 t $0.4/t = $330 C L = 2per $36/per = $72 97 98 99 100 101 Total costs: $409.05 Besdes, the NaCl soluton can be used repeatedly to reduce the consumpton. Process II: Crushng and Screenng Requrements: One crusher (P w =11 kw, prce= $14400, maxmum capacty = 8 ton/hour, servce lfe = 5 years) works for 2 h every day. 1 (1 + ) n = ($14400 1 300 ) (1 4%) 10% = $12.16 1 (1 + 10%) 5 M c = C o 0.05 = ($14400 1 ) 0.05 = $2.4 300 102 C P = P t p e = 11 kw 2h $0.20/kWh = $4.4 C L = m p s = 2 per $36/per = $72 103 104 105 106 107 Total costs: $90.96 After ths process, 3.223 ton mxed electrode materals can be obtaned by mechancal separaton n ths study. Process III: Vacuum pyrolyss Requrements: four heatng equpment (P w = 55 kw, per prce = $216000, maxmum S8
108 109 110 111 112 113 capacty = 250 kg/per, servce lfe = 5 years) are needed to respectvely work for 4 h every day. In ths process, the obtaned mxed electrode materals were heated n batches of 16 by four devces, whch means every devce needs to work 4 tmes every day. About 200 kg was heated n every devce every tme. Electrc power charge: the workng tme ncludng temperature rse and hold s 1 hour every tme and the coolng tme s 0.5-1 hour. 1 (1 + ) n = ($216000 4 1 300 ) (1 4%) 10% = $730 1 (1 + 10%) 5 M c = C o 0.05 = ($216000 4 1 ) 0.05 = $144 300 114 C P = P t p e = 55 kw 1h $0.20/kWh 16 = $176 C L = m p s = 2 per $36/per = $72 115 116 117 118 119 120 121 122 Total costs: $1122 After ths process, the calcned powders are about 2.836 ton. Process IV: leachng and evaporaton Requrements: the calcned powders are leached by water twce wth S: L of 25 g/l for 20-30 mn. The supernatant lquor was fltered by 4 self-dschargng flterng machnes (P w = 20 kw, per prce = $5800, maxmum capacty = 4 ton/hour, servce year = 3 years) whle the slurry was bag-type fltered; about 123.6 ton of water s consumed S9
123 124 125 126 127 128 129 130 131 At the frst leachng, 73.22% of L 2 CO 3 was soluble n water and about 300 kg L 2 CO 3 crystals can be obtaned by evaporaton. Then, the flter resdues are washed agan and total 85 % L 2 CO 3 was leached by water. The water consumptons are both 56.8 ton. Every flterng machne needed to work about 4 hours every day. Specally, the frst leachng lqud s mechancally evaporated, whch s acheved by two multple-stage evaporators (P w = 48 kw, per prce = $72000, maxmum capacty = 7ton/hour, servce lfe = 5 years), whle the second one s naturally evaporated. Flterng: 1 (1 + ) n = ($5800 4 1 300 ) (1 4%) 10% = $30 1 (1 + 10%) 3 M c = C o 0.05 132 133 = ($5800 4 1 ) 0.05 = $3.87 300 C P = P t p e = 20 kw 4h $0.20/kWh 4 = $64 134 Evaporatng: 1 (1 + ) n = ($72000 2 1 300 ) (1 4%) 10% 1 (1 + 10%) 5 = $122 M c = C o 0.05 135 136 = ($72000 2 1 ) 0.05 = $24 300 C P = P t p e S10
= 48 kw 5h $0.20/kWh 2 = $96 C L = m p s = 4 per $36 per = $144 C w = V p w = 56.8 t 2 $0.4/t = $45.44 137 138 139 140 141 142 143 144 145 146 Total costs: $529.31 After ths process, about 297.83 kg of L 2 CO 3 (s) can be obtaned by mechancal evaporaton and about 47.93 kg of L 2 CO 3 (s) can be obtaned by natural evaporaton. Fnally, the flter resdues are about 2.490 ton. Process V: purfyng Requrements: the flter resdues are heated by 4 furnaces (P w = 20 kw, per prce=$20000, maxmum capacty=200 kg/per, servce lfe=5 years). In ths process, the flter resdues are heated n batches of 16 by four devces. About 170 kg was heated n every devce every tme. Electrc power charge: the workng tme ncludng temperature rse and hold s 1 hour every tme and the coolng tme s 0.5-1 hour. 1 (1 + ) n = ($20000 4 1 300 ) (1 4%) 10% = $68 1 (1 + 10%) 5 M c = C o 0.05 147 148 = ($20000 4 1 ) 0.05 = $13.33 300 C P = P t p e = 20 kw 1h $0.20/kWh 16 = $64 C L = m p s S11
= 2 per $36/per = $72 149 150 151 Total costs: $217.33. After ths process, about 1.76 ton Mn 3 O 4 powders can be obtaned and the purty rate of Mn 3 O 4 s 93 %. 152 153 154 155 156 Therefore, the total costs of whole processes (C T ) n ths study can be calculated: C T= $409.05 + &90.96 +$1122+$529.31+$217.33=$2368.65. Further, revenues of products ncludng L 2 CO 3 and Mn 3 O 4 are calculated as shown n Table SI. Table S3. Revenues of Products by Ths Recyclng Process Product Daly producton (kg) Purty rate (%) Prces(/t) Revenue a 297.83 $5228.11 L 2 CO 3 99.7 $17554 47.93 $841.36 Mn 3 O 4 1.76 93 $1430 $2517 Total revenues $8587 157 a L 2 CO 3 (s) was obtaned by two ways: mechancal evaporaton and natural 158 159 160 161 162 163 164 165 evaporaton. Thus, the day s proft (P) can be obtaned: P=R C C&T C T =$8587-$4110-$2368.65=$2108.35 In summary, the day s proft of ths recyclng process n ths study s $2108.35. Reference 1. Turton R., Bale R. C., B. W. W., A. S. J. Analyss, synthess and desgn of chemcal processes [M]. PTR Upper Saddle Rver, New Jersey, USA: Prentce Hall, 1998. S12