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Article
Stepwise Recovery of Valuable Metals from Spent LIBs by
Controllable Reduction and Selective Leaching and Precipitation
Yingchao Zhang, Wenqiang Wang, Jiehui Hu, Tao Zhang, and Shengming Xu
ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/
acssuschemeng.0c04106 • Publication Date (Web): 17 Sep 2020
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4 Stepwise recovery of valuable metals from spent LIBs by controllable
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7 reduction and selective leaching and precipitation
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9 Yingchao Zhanga, Wenqiang Wanga, Jiehui Hua, Tao Zhanga,b, Shengming Xua,c,d*
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11 a Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China.
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13 b Research Institute of Tsinghua University in Shenzhen, Shen Zhen 518057, China
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15 c Key Laboratory of Advanced Reactor Engineering and Safety of Ministry of Education,
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17 Tsinghua University，Beijing 100084, China.
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19 d Beijing Key Lab of Fine Ceramics, Tsinghua University, Beijing 100084, China.
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21 * Corresponding author.
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E-mail: [email protected] (Shengming Xu)
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ABSTRACT: The remarkably increasing consumption of lithium ion batteries (LIBs)
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has been an issue worldwide for the contained valuable metals and intrinsic toxicity in
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spent LIBs. Here, a novel process including selective leaching and precipitation has
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been developed for recovery of spent LIBs. The carbothermic reduction of spent
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32 LiNixCoyMn1-x-yO2 was applied to control the reduction degree of target metallic
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34 elements. Afterward, H3PO4 solution was utilized to selectively leach 99.1% of Li and
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36 96.3% of Mn, excellent leaching selectivity was achieved for that merely 4.5% of Co
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38 and 1.2% of Ni were dissolved. After increasing the concentrations of Li and Mn to
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40 23.14 and 53.03 g/L by two-stage cross-current leaching, Li and Mn were precipitated
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42 and recovered in sequence by simply adjusting pH of the leaching lixivium, and
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44 compounds of Mn3(PO4)2·3H2O and MnHPO4·3H2O, as well as Li3PO4 were obtained.
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46 The Ni-Co alloy contained in the filtration residue could be separated by wet magnetic
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48 separation and further recovered. It was the first time to synchronously leach Li and
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50 Mn while Co and Ni were separated simultaneously in a single leaching operation, this
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52 could greatly benefit the subsequent separation and recovery. The selective leaching
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54 and precipitation are efficient and facile, and enjoy superiority over conventional
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56 processes of recycling spent LIBs.
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58 KEYWORDS: spent lithium ion battery, carbothermic reduction, phosphoric acid,
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60 leaching selectivity, selective precipitation.
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4 INTRODUCTION
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6 With the ever-improving demands of energy storage and environmental quality,
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8 the development of lithium ion battery (LIB) is imperative for their merits such as
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10 excellent electrochemical performance, long cycle life, environmental friendliness and
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so on.1, 2 Lithium ion battery has overwhelming superiority for the application in
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portable electronic devices, and they are high-profile in promoting the global electric-
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vehicle revolution and the evolution of power supply systems.3 The global demands of
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LIB are estimated to reach 390 GWh by 2030,4 correspondingly, the fast-growing
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19 amounts of spent LIBs also attract extensive attention nowadays. The toxic organic
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21 chemicals as well as non-renewable metals (such as Li, Co, Ni, Mn) contained in LIBs
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23 could pose serious environmental risks and vital supply crisis if the spent LIBs are
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25 recycled inappropriately.5
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27 For spent LIBs, the majority of recoverable value accumulates in cathode,6, 7 and
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29 the cathode active materials are usually LiCoO2, LiNiO2, LiMn2O4, LiNixCoyMn1-x-yO2
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31 or LiFePO4.8-10 Direct regeneration of spent cathode active materials has been reported
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33 to be simple and eco-friendly because there is no further structure destruction for
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35 materials, 11, 12 however, it is hard to be applied in industry for the complexity of real
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37 spent cathode scraps like included impurities and damaged structures in various degree.
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39 And two main recycling technologies are hydrometallurgical and pyrometallurgical
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41 process.13, 14
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43 Despite their complicated procedures and massive discharge of wastewater,
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45 Hydrometallurgical processes are widely adopted for their advantages of high recycling
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47 efficiency and selectivity, moderate operation condition and low energy consumption.15,
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49 Hydrometallurgical processes for recovering valuable metals from cathode of spent
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LIBs mainly consists of pretreatment, metal extraction, separation and purification. 17,
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For the metal extraction step, extensive studies have been reported to utilize various
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alkalis, mineral acids or organic acids in leaching procedure.19 Ammonia-based systems
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like NH3, NH4Cl, (NH4)2SO3, (NH4)2SO4, (NH4)2CO3 or other alkaline reagents could
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58 be employed to selectively dissolve specific elements such as Li, Co and Ni.20 For
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60 example, Li et al. proposed that NH4OH and (NH4)2C2O4 could be used to leach Ni and
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4 NH4OH and NH4HCO3 could be used to leach Co after using H2C2O4 to leach Li.21
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6 Different from the selective leaching by alkali agents, valuable metals could be
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8 dissolved together by most acid agents. Mineral acids like H2SO4, HCl and HNO3 are
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10 extensively applied for their merits of low price, satisfactory capability in leaching and
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suitability in the combination with subsequent treatment.22, 23 Organic acids including
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formic acid, oxalic acid, malic acid, citric acid and ascorbic acid are also widely
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investigated with advantages of being more environmental benign, whereas their high
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cost impedes their practical application.24, 25 Besides, the reducing agents need to be
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19 introduced in both mineral and organic acid leaching processes because transition
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21 metals present in spent cathode materials are usually at high valence and metals in low
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23 valence are much easier to be leached and more stable in solution. 26, 27 Many inorganics
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25 (like H2O2, NaHSO3, active metals, etc.) and organics (like glucose, lactic acid,
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27 cellulose, etc.) are exerted to be reducing agents, 28, 29 which increase the cost as well
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29 as complexities in latter waste disposal. The volatile H2O2 is the most common choice
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31 among reducing agents for its good performance and amity to environment despite its
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33 usual excess addition in leaching process.30
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35 Pyrometallurgical processes for spent LIBs are extensively utilized especially in
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37 industrial applications because they are simple, productive and highly adaptable to
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39 various raw materials.31, 32 Many recycling enterprises apply pyrometallurgical
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41 processes and carry out the thermal reduction under high temperatures which are
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usually more than 1000 °C. 8, 33 The target products are generally alloys containing
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45 valuable metallic elements like Co, Ni, Mn and Fe. However, high reduction
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47 temperature also results in high energy consumption and the loss of Li in slag.34 In
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49 recent years, many improved pyrometallurgical or combined processes have been
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reported such as carbothermic reduction.32 Carbonous materials such as spent graphite
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or lignite are utilized to reduce metallic elements before the leaching treatment.35 Hu et
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al.36, 37 added excess lignite to roast spent LIBs at 650 °C, and subsequently adopted
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carbonated water to leach generated Li2CO3 into more soluble LiHCO3 and enrich the
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58 concentration of Li to 4.37 g·L−1. Afterward, Ni, Co and Mn could be well leached by
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60 H2SO4. This process decreased the temperature of thermal treatment and successfully
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4 explored the selective recovery of Li though the concentration of Li was still not high
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6 enough for the industrial economical operation. CoO and NiO were proved to be
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8 leached by acid more easily than metallic Co and Ni, thus, lower roasting temperature
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10 and more facile leaching conditions could achieve in the recovery of LiCoO2 and
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LiNixCoyMn1-x-yO2.38, 39 Wang et al.40 use NaOH to catalyze the carbothermic reduction
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of spent LiCoO2 at 520 °C, and the controllable reduction products were Li2O and CoO.
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The Li concentration could be increased up to 14.99 g·L−1 by three-stage crosscurrent
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leaching, the further decreased roasting temperature and enriched concentration of Li
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19 could encourage researchers to apply this method to dispose spent LiNixCoyMn1-x-yO2.
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21 However, in all those processes, the valuable metals such as Co, Ni and Mn were
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23 leached by acid indistinguishably at the same time, which still put much pressure on
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25 the subsequent separation and recovery.
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27 In this work, carbothermic reduction was introduced to control the reduction
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29 degree of spent LiNixCoyMn1-x-yO2, and H3PO4 was applied for the selective leaching
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31 of lithium and manganese. The water-soluble Mn(H2PO4)2 and LiH2PO4 in leaching
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33 lixivium could be further precipitated and recovered in sequence by simply adjusting
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35 pH of the leaching lixivium, and the generated Ni-Co alloy could be recovered by wet
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37 magnetic separation. Considering that it’s the first time that Li and Mn are separated
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39 from Co and Ni in a leaching procedure for recovery of spent LIBs, the devised facile
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41 process was noticeably simplified and efficient, alleviating complicated separation and
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43 waste disposal in subsequent procedures. Thus, this proposed recovery process with
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45 novel selective leaching and precipitation procedure have great industrial potential for
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47 the sustainable recovery of spent LIBs.
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49 EXPERIMENTAL SECTION
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Materials and Reagents. The spent LiNixCoyMn1-x-yO2 cathode material powder
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and anode graphite powder were provided by Shenzhen Ruicycle Environmental
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Technology Corp., Ltd in China. The main contents of valuable metals in these two
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materials were measured using an ICP-OES (Optima 8000, PerkinElmer). The main
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58 metallic contents of cathode material is displayed in Table 1, and the content of Li, Co,
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60 Ni, Mn and Al accounts for 6.17%, 21.58%, 21.96%, 16.63% and 0.03%, respectively.
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4 As to the graphite material, no Li was detected by ICP-OES. Chemicals like H3PO4 and
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6 NaOH were supplied by Shanghai Macklin Biochemical Co., Ltd in China. In this work,
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8 all chemicals were employed as received without further depuration and reagents used
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10 were all in analytical grade. Deionized water was used to prepare specific solutions.
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Table 1 Main metallic contents of spent cathode material
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14 Element Li Co Ni Mn Al
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Content (wt.%) 6.17 21.58 21.96 16.63 0.03
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19 Experimental Procedure. (1) Carbothermic reduction: The spent cathode
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21 material powder and anode graphite powder with a fixed ratio were first fully mixed in
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23 an agate mortar. The sufficient mixed sample was then moved to a tube furnace (SK-
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25 G08123K, Tianjin Zhonghuan Electric Furnace Corp., Ltd) to implement the
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27 carbothermic reduction experiments at expected temperature and roasting time with a
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29 heating rate of 8 °C/min under high-purity argon atmosphere. The pressure in the
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furnace was kept at 0.6 MPa in reduction roasting, afterwards, the roasted material was
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cooled to room temperature inside the furnace within the argon atmosphere. The
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exhausted HF and CO2 gas in this carbothermic reduction process were absorbed by
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36 NaOH solution.
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38 (2) Leaching of lithium and manganese: The roasted products were pulverized and
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40 several grams of which were leached by H3PO4 solutions with specific concentrations
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42 to selectively dissolve lithium and manganese. In each run, certain amount of H3PO4
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44 solution coupled with accurately weighted roasted products were added into a glass
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46 flask equipped with a vapor condenser. Then, the glass flask was placed in a water bath
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48 at constant temperature to implement leaching for a certain time under magnetic stirring
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50 at a speed of 450 rpm. Parameters of leaching operation were optimized, including
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52 handling temperature (25 - 85 °C), H3PO4 concentrations (2.25 - 3.00 mol/L), leaching
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54 time (5 – 120 min), and liquid to solid ratio (4 - 10 ml·g−1). Multiple-stage cross current
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56 leaching experiments were also carried out to investigate the optimal operations for
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58 industrial application. The three-stage cross-current leaching procedure was
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60 implemented by successively contacting the leaching solution with fresh roasted
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4 products for 10 min at 40 °C with a fixed L/S ratio of 6 ml·g−1. After each stage, the
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6 concentrations of Li+ and Mn2+ would increase while the concentration of H3PO4 would
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8 reduce, and the H3PO4 concentration of leaching solution was supplemented to maintain
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10 at 2.75 mol/L before next stage of leaching. After leaching, the lixivium was collected
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for concentration analysis and the subsequent precipitation of lithium and manganese.
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The leaching residue contained Ni-Co alloy and graphite could be detached from each
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other by wet magnetic separation.
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(3) Precipitation of lithium and manganese: The leaching lixivium including Li+
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19 and Mn2+ was continuously stirred at 25 °C with a speed of 450 rpm, and then an
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21 expected amount of NaOH solution (10.00 mol/L) was added to adjust pH of the
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23 solution system to stabilize at 5. After keeping stirring for another 30 min, 3.0 mL of
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25 solution was taken out by using 0.22 μm syringe filters to prepare for determination of
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27 Li+ concentration. Subsequently, the precipitation of manganese compounds was
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29 separated from the lithium-contained leach liquor by filtration through a vacuum pump.
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31 Thereafter, pH of the lithium-contained leach liquor was further adjusted to stabilize at
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33 13 by slowly adding NaOH solution (10.00 mol/L). After agitation for 3 h at 25 °C with
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35 a speed of 450 r/min, 3.0 mL of solution was taken out by a syringe and filtrated using
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37 0.22 μm syringe filters in order to examine the concentration of Li+. The final leaching
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39 solution was filtrated using a vacuum pump to obtain Li3PO4 residue. Both leaching
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41 residues of manganese compounds and Li3PO4 were completely washed and then dried
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43 in an oven at 60 °C overnight.
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45 Measurement and Characterization. The metallic contents of spent
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47 LiNixCoyMn1-x-yO2 cathode material, roasting products and leaching lixivium were
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49 analyzed by an inductively coupled plasma optical emission spectrometer (ICP-OES,
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Optima 8000, Perkin Elmer instruments, US). Thorough dissolution by aqua regia
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(volume ratio of HCl to HNO3 = 3:1) and appropriate dilution was necessary before
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ICP analysis. Simultaneous thermogravimetric and differential scanning calorimetry
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(TG/DSC, X70, NETZSCH, Germany) analysis was employed to investigate the
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58 process of carbothermic reduction, samples were heated in high-purity nitrogen
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60 atmosphere with a temperature range of 50 - 1000 °C and a heating rate of 10 °C/min.
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4 The phase compositions of samples were measured through X-ray powder diffraction
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6 (XRD, D8 ADVANCE, Bruker, Germany), utilizing Cu Kα1 radiation under operating
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8 conditions of 40 mA and 40 kV with a scan rate of 6 deg/min and a step size of 0.02
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10 deg. A field emission scanning electron microscopes (SEM-EDS, Zeiss Merlin,
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Germany) equipped with energy dispersive spectrometer (EDS, Oxford, X-MaxN, UK)
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was employed to study the morphology and elemental distribution of samples. All
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samples were sprayed with carbon to improve electrical conductivity before SEM-EDS
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characterization. In this work, leaching efficiency (ηM) of metal elements are calculated
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19 by Equation (1):
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21 CM × V
22 ηM = m0 × ωM × 100% (1)
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24 Where CM (g∙L-1) represents the concentration of element “M” (Li, Ni, Co, Mn),
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26 while V represents the corresponding volume of leaching solution; m0 represents the
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28 mass of the spent cathode material used, and ωM represents the mass fraction of element
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30 “M”.
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32 RESULTS AND DISCUSSION
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34 Carbothermic Reduction of Spent Cathode Materials. To better understand the
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36 reductive processes of the spent cathode LiNixCoyMn1-x-yO2 in carbothermic reduction,
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the TG/DSC analysis was implemented, and the measured results of single spent
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cathode material and its mixture with graphite were similar to what we reported
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before.39 As presented in Figure 1, two exothermic peaks appearing at 673 and 714 °C
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can be ascribed to the carbothermic reaction between spent cathode material and
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45 graphite, indicating the reduction reaction occurred at around 600 - 750 °C. The TG
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47 changed very slightly below 750 °C, illustrating almost no release of gas and further
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49 revealing the formation of Li2CO3 by generated CO2 and Li2O. The rapid loss of weight
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51 occurred in the temperature range of 830 - 1000 °C, and two endothermic peaks
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53 appearing at 872 and 932 °C may attribute to the volatilization and decomposition of
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22 Figure 1. Simultaneous TG/DSC for carbothermic reduction of spent LiNixCoyMn1-x-yO2 cathode
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24 material.
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26 The changes of material morphology and elemental distribution before and after
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28 carbothermic reduction were determined by SEM and EDS characterization. As shown
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30 in Figure 2(a), the spent cathode LiNixCoyMn1-x-yO2 consists of spheroidal clusters in
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32 different sizes, and the surface morphology manifests they are accumulated of smaller
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34 particles. From the corresponding EDS results, it was indicated that the distribution of
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36 Co, Ni and Mn were approximately uniform in material. After carbothermic reduction,
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both the morphology and elemental distribution of roasted LiNixCoyMn1-x-yO2 changed
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significantly. As can be seen in Figure 2(b), the roasted product was composed of
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irregular geometrics with smooth surface as well as clusters of aggregated particles with
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bumpy surface. From the EDS results, the mass fractions of Co, Ni and Mn were
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45 generally consistent with results determined by ICP. Moreover, the distribution of
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47 elements was notably different from that before carbothermic reduction. Conspicuously,
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49 Co and Ni were highly concentrated at positions of irregular geometrics where the
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51 concentrations of manganese and oxygen were quite low. It illustrates those irregular
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53 geometrics with smooth surface should be the Ni-Co alloy. On the contrary, Mn was
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55 mainly agglomerated at clusters of aggregated particles with bumpy surface, which was
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57 similar with the distribution of oxygen. It indicated those clusters of aggregated
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59 particles were mainly composed of manganese oxide. The transformation of material
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4 morphology and elemental distributions after carbothermic reduction indicated that Co
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6 and Ni were mainly transformed into metallic states while Mn was reduced to new
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8 oxide. They were well consistent with the results analyzed by XRD.
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45 Figure 2. SEM images and EDS characterizations: (a) spent cathode material, (b) roasted product of
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47 spent cathode material after carbothermic reduction (750 °C, 14.3 wt.% graphite, 3 h).
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49 To investigate the influence of reduction temperature on phase conversion as well
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as leaching performance of roasted products, XRD characterization and leaching
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experiment were conducted. As presented in Figure 3(a), the spent LiNixCoyMn1-x-yO2
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could be reduced by graphite at 600 °C. The main phase was NiO (PDF 47-1049) and
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some very weak diffraction peaks of Li2CO3 (PDF 22-1141), metallic Co and Ni began
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58 to emerge. Although Co element accounts for around 20% in roasted product,
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60 diffraction peaks assigned to Co species were conspicuously too weak. According to
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4 our previous study,39 Co species should be exist in the form of amorphous CoO after
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6 carbothermic reduction with 14.3 wt.% graphite at 600 °C for 3 h, the absence of CoO
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8 phases were ascribed to the fact that diffraction peaks of CoO were weak. When the
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10 roasting temperature was increased to 650 °C, the diffraction peaks of NiO were
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disappeared while further reduced phases of metallic Ni (PDF 04-0850) and Co (PDF
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15-0806) became dominant. In addition, the diffraction peaks in accordance with MnO
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(PDF 07-0230) began to appear at 650 °C and the diffraction peaks of Li2CO3 became
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stronger. The diffraction peaks of reduced products after roasting at 650 and 700 °C
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19 were nearly the same apart from a little increase of peak intensities. With the roasting
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21 temperature further increased to 750 and 800 °C, the XRD patterns changed slightly
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23 except that crystallinity of MnO increased and new diffraction peaks at 70.78° and
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25 74.39° assigned to MnO could be observed. This phenomenon illustrated that more
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27 complete transformation of MnO took place with the roasting temperature increased to
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29 750 and 800 °C.
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31 The leaching efficiencies of metallic elements at different temperatures were
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33 presented in Figure 3(b). After carbothermic reduction at 650 °C for 3 h, the leaching
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35 efficiencies of Li, Mn, Co and Ni were 93.2%, 72.4%, 36.6%, 27.1% respectively.
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37 When the roasting temperature increased to 700 °C, both the leaching efficiencies of Li
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39 and Mn were higher than 90% while the leaching efficiencies of Co and Ni were further
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41 decreased to 15.5% and 7.7%. . With the temperature of carbothermic reduction further
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43 increased to 750 °C, the leaching efficiencies of Li and Mn could reach 99.1% and 96.3%
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45 while the leaching efficiencies of Co and Ni were only 4.5% and 1.2%. Considering
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47 that diffraction peaks assigned to MnO became sharper and some new peaks related to
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49 MnO emerged after roasting at 750 °C, the excellent H3PO4 leaching of manganese was
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mainly attributed to its deep reduction degree. When the roasting temperature further
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increased to 800 °C, the leaching selectivity improved extremely slightly, so the optimal
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roasting temperature for carbothermic reduction is 750 °C.
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17 Figure 3. Influence of roasting temperature on the carbothermic reduction of spent LiNixCoyMn1-x-
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19 yO2 (14.3 wt.% graphite, roasting time 3 h): (a)XRD patterns; (b) leaching efficiency of Li, Co, Ni
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21 and Mn: (2.75mol/L H3PO4, 40 °C, liquid to solid ratio = 6 ml·g−1, leaching time = 10 min).
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23 Figure 4 presented the XRD patterns and leaching efficiencies of metallic elements
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when the spent LiNixCoyMn1-x-yO2 were reduced by different dosages of graphite. As
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shown in Figure 4(a), when the dosages of graphite were 7.7 wt.% and 10 wt.%, the
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XRD patterns of roasted products were indistinguishable from each other. However,
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the corresponding leaching efficiencies of metallic elements displayed in Figure 4(b)
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32 differed a lot indicating that deeper reduction generated with the increase of graphite
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34 amount. With the dosage of graphite further added to 14.3 wt.% which means the mass
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36 ratio of spent LiNixCoyMn1-x-yO2 to graphite was 6:1, more diffraction peaks
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38 corresponding to MnO appeared. The associated leaching performance manifested
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40 superior selectivity among target metals: merely 4.5% of Co and 1.2% of Ni were
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42 dissolved whereas 99.1% of Li and 96.3% of Mn were leached. With the addition of
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44 another approximate 10 wt.% graphite to 25 wt.%, both the XRD patterns and leaching
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46 performance of roasted LiNixCoyMn1-x-yO2 changed very little. It revealed that desired
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48 selectivity of separation could be achieved by H3PO4 leaching when the graphite dosage
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50 was 14.3 wt.% in carbothermic reduction.
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18 Figure 4. Influence of graphite dosage on the carbothermic reduction of spent LiNixCoyMn1-x-yO2
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20 (roasting temperature 750 °C, roasting time 3 h): (a)XRD patterns; (b) leaching efficiency of Li, Co,
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22 Ni and Mn: (2.75mol/L H3PO4, 40 °C, liquid to solid ratio = 6 ml·g−1, leaching time = 10 min).
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24 The influence of roasting time was studied. As depicted in Figure 5(a), when the
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26 carbothermic reduction was conducted for 1 or 2 h, the XRD patterns of roasted
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28 LiNixCoyMn1-x-yO2 were nearly identical with each other. When the roasting time was
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30 increased to 3 or 4 h, diffraction peaks in accordance with MnO became sharper, and
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32 some new peaks located at 70.78° and 74.39° were also observed which can be assigned
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34 to MnO. After further increasing the roasting time to 6 h, there was few change except
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36 the emergence of more diffraction peaks. And those peaks located at 34.46°, 36.35° and
37
38
37.21° are assigned to Li2CO3. The influence of roasting time on the leaching efficiency
39
40
was displayed in Figure 5(b). Compared with Figure 3(b), the variation of leaching
41
efficiency was gentler, illustrating that roasting temperature was a more important
42
43
factor than roasting time. After roasting at 750 °C for 1 h, metallic elements could be
44
45 effectively separated by H3PO4 leaching. 98.8% of Li and 92.0% of Mn were leached
46
47 while only 13.0% of Co and 2.5% of Ni were extracted. With further increase of
48
49 roasting time to 3 h, the leaching efficiency of Mn continuously increased and leaching
50
51 efficiency of Co and Ni constantly decreased. It testified that deeper reduction of
52
53 manganese to MnO could benefit the leaching of Mn, while longer reduction roasting
54
55 would impede the leaching of Co and Ni. The leaching results improved little after
56
57 further increasing the roasting time to 6 h.
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17 Figure 5. Influence of roasting time on the carbothermic reduction of spent LiNixCoyMn1-x-yO2 (14.3
18
19 wt.% graphite, roasting temperature 750 °C): (a)XRD patterns; (b) leaching efficiency of Li, Co, Ni
20
21 and Mn: (2.75mol/L H3PO4, 40 °C, liquid to solid ratio = 6 ml·g−1, leaching time = 10 min).
22
23 Leaching of Li and Mn. The spent LiNixCoyMn1-x-yO2 was mainly transformed
24
25
into Ni-Co alloy, MnO, Li2O and Li2CO3 after carbothermic reduction. Subsequently,
26
27
H3PO4 was introduced to selectively leach Li and Mn. As shown in equation (2) - (4),
28
H3PO4 is a kind of inorganic triacid that the included H+ could be stepwise dissociated
29
30
in aqueous solution. Thus, both Li+ and Mn2+ may form water-soluble compounds of
31
32 LiH2PO4 and Mn(H2PO4)2 in high-concentration H3PO4 solution. This was quite similar
33
34 to the study reported by Chen, 41 in his research, Co2+ was precipitated by PO43- while
35
36 Li+ was dissolved to be LiH2PO4 after leaching of spent LiCoO2 by dilute H3PO4 and
37
38 H2O2. Accordingly, probable reactions are listed in equation (2) - (6).
39
40
41 H3PO4 + H2O H2PO4- + H3O+ pKa1=2.12 (2)
42
43 H2PO4- + H2O HPO42- + H3O+ pKa2=7.20 (3)
44
45 (4)
46 HPO42- + H2O PO43- + H3O+ pKa3=12.37
47
48 2H3PO4(aq) + MnO(s) Mn2+(aq) + 2H2PO4-(aq) + H2O (5)
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50 2H3PO4(aq) + Li2CO3(s) 2Li+(aq) + 2H2PO4-(aq) + CO2(g) + H2O (6)
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52
53 Systematic experiments were conducted to investigate the H3PO4 leaching process.
54
55 From Figure 6(a), 98.9% of Li and 96.6% of Mn were leached while merely 4.1% of
56
57 Co and 0.7% of Ni were dissolved within 5 min, it illustrated that both Li+ and Mn2+
58
59 were selectively leached and dissolved in H3PO4 solution with appropriate
60
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2
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4 concentration. Simultaneously, it revealed that the leaching of Li+ and Mn2+ reacted
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6 very fast. With the extension of operational time, the leaching efficiency of Li changed
7
8 little, but the undesirable dissolution of Co and Ni were constantly increased.
9
10 Considering the operability, 10 min was chosen as the optimal leaching time while the
11
12
leaching efficiencies of Li, Mn, Co and Ni were 99.1%, 96.3%, 4.5% and 1.2%,
13
14
respectively.
15
To optimize the H3PO4 concentration for leaching procedure, a series of leaching
16
17
experiments were carried out at 40 °C for 10 min with a liquid to solid ratio of 6 ml·g−1
18
19 . As presented in Figure 6(b), when H3PO4 was 2.25 mol/L, only 91.4% of Li and 75.2%
20
21 of Mn were leached. With the increase of H3PO4 concentration from 2.25 to 2.75 mol/L,
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23 the leaching efficiency of Li and Mn increased obviously until respectively reaching up
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25 to 99.1% and 96.3%. When further increase the H3PO4 concentration from 2.75 to 3.00
26
27 mol/L, the leaching efficiencies of Li and Mn changed slightly. The very low leaching
28
29 efficiency of Co and Ni displayed a slight change within the H3PO4 concentration range
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31 of 2.25 to 3.00 mol/L, which further demonstrated H3PO4 has excellent leaching
32
33 selectivity for roasted valuable metals. Two groups of elements (Li and Mn vs. Co and
34
35 Ni) were efficiently divided by their different dissolvability in H3PO4 leaching.
36
37 The effect of temperature on leaching efficiency was investigated. Leaching
38
39 experiments were carried out using 2.75 mol/L H3PO4 at 25 - 80 °C for 10 min, and the
40
41 liquid to solid ratio was 6 ml·g−1. As exhibited in Figure 6(c), the leaching efficiencies
42
43 of Mn, Co and Ni were positively related with temperature, while little change was
44
45 observed for leaching efficiencies of Li. With the leaching temperature increased from
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47 25 to 40 °C, the leaching efficiency of Mn was increased from 90.8% to 96.3%, while
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49 the leaching efficiency of Co and Ni were respectively increased from 4.2% to 4.5%
50
51
and 0.9% to 1.2%. However, with the leaching temperature further increased from 40
52
53
to 85 °C, the undesirable leaching of Co and Ni increased fast, while only slight changes
54
were observed in the leaching of Li and Mn. To leach valuable elements with best
55
56
efficiency and selectivity, 40 °C was selected as the optimum leaching temperature in
57
58 this work.
59
60 To clarify the effect of liquid to solid ratio, leaching experiments was performed
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2
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4 utilizing 2.75 mol/L H3PO4 at 40 °C for 10 min. As displayed in Figure 6(d), the
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6 leaching of Li was always preferential and thorough within the liquid to solid ratio of 4
7
8 - 10 ml·g−1. When the liquid to solid ratio were 4 and 6 ml·g−1, 92.7% and 96.3% of
9
10 Mn were leached, respectively. And as the liquid to solid ratio was further risen to 10
11
12
ml·g−1, the leaching efficiency of Mn changed very slightly. The results of leaching
13
14
experiments also demonstrated that the enhancement of liquid to solid ratio would
15
promote the dissolution of Co and Ni. To control the dissolution of Co and Ni, and
16
17
leach out Mn and Li as much as possible, a liquid to solid ratio of 6 ml·g−1 was
18
19 optimized. More than 99.0% of Li and 96.0% of Mn could be leached while only 1.2%
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21 of Ni and 4.5% of Co were leached.
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Figure 6. Leaching efficiencies of metallic elements in H3PO4 solution under different conditions:
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52
(a) effect of leaching time(2.75 mol/L H3PO4, 40 °C, liquid to solid ratio = 6 ml·g−1); (b) effect of
53
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H3PO4 concentration (40 °C, 10 min, liquid to solid ratio = 6 ml·g−1); (c) effect of leaching
55
56 temperature (2.75mol/L H3PO4, 10 min, liquid to solid ratio = 6 ml·g−1); (d) effect of liquid-solid
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58 ratio(2.75mol/L H3PO4, 40 °C, 10 min).
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60 As discussed above, the optimal conditions for H3PO4 leaching were to utilize 2.75
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4 mol/L H3PO4 at 40 °C for 10 min, and with a liquid to solid ratio of 6 ml·g−1 . To further
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6 complementally illustrate the leaching performance, characterizations including XRD,
7
8 SEM and EDS analysis of leaching residue under the optimum experimental conditions
9
10 were implemented. As shown in Figure 7, metallic Co and Ni were the main phase
11
12
contained in the leaching residue according to XRD characterization. And despite the
13
14
technical limitations of EDS analysis in measuring Li, the results of EDS analysis also
15
disclosed that the leaching residue was mainly composed of Co, Ni, C and a probable
16
17
small amount of Mn (at around 5.9 keV). The results of XRD and EDS characterizations
18
19 were quite consistent with that of ICP measurement in which the H3PO4 leaching
20
21 efficiencies of Li, Mn, Ni and Co were 99.1%, 96.3%, 1.2% and 4.5%. And these two
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23 characterizations complementally proved the excellent selectivity of separation in
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25 H3PO4 leaching.
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60 Figure 7. characterizations of leaching residue after leaching at 40 °C for 10 min, with 2.75mol/L

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4 H3PO4, and a liquid‒solid ratio of 6 ml·g−1 : (a) XRD patterns; (b) SEM image and corresponding
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6 EDS analysis.
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8 After H3PO4 leaching with single stage, 99.1% of Li and 96.3% of Mn were
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10 selectively leached and the concentration of them were 14.35 and 32.27 g/L,
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12
respectively. Considering that lixivium would be further treated to obtain products
13
14
through separation processes like extraction, precipitation or evaporation, higher
15
concentrations could remarkably benefit the recovery efficiency, energy saving and
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17
pollutant discharge reduction in industrial production. Accordingly, cross-current
18
19 leaching procedure was employed to raise the concentration of Li and Mn in lixivium
20
21 and the scheme was displayed in Figure 8(a). In each stage, the concentration of H3PO4
22
23 leaching agent was adjusted to maintain at 2.75 mol/L and the concentrations of Li and
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25 Mn were displayed in Figure 8(b). In the second leaching stage, the concentrations of
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27 Li and Mn reached up to 23.14 and 53.03 g/L, respectively. After the third stage was
28
29 conducted, the concentration of Li was enhanced to 29.51 g/L, while the concentration
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31 of Mn was enhanced very slightly because 54.28 g/L was very close to the saturated
32
33 solubility of Mn(H2PO4)2. Consequently, two-stage cross-current leaching procedure
34
35 was appropriate for the following treatment.
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18 Figure 8. (a) Scheme of the cross-current leaching procedure; (b) concentrations of Li and Mn in
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20 lixivium in different stages (40 °C, leaching time 10 min, liquid to solid ratio = 6 ml·g−1).
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22 Precipitation of Li and Mn. After H3PO4 leaching of the roasted LiNixCoyMn1-x-
23
24 yO2, Li+ and Mn2+ were successfully leached and separated from Ni-Co alloy. The
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26 extracted Li+ and Mn2+ existed in the form of water-soluble LiH2PO4 and Mn(H2PO4)2
27
28 in H3PO4 aqueous solution with relative high concentration, attributing to the
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30 predominant first-stage dissociation in equation (2). As illustrated in Figure 6(b), the
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32 leaching efficiency of Li+ and Mn2+ were found to be significantly influenced by the
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34 concentration of H3PO4. It indicated that insoluble compounds such as Li3PO4,
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36 Mn3(PO4)2 and MnHPO4 maybe precipitated with the decrease of solution acidity,
37
38
arising from the prevailing second-stage or third-stage dissociation in equation (3) - (4).
39
40
Similar precipitation of Co2+ was reported by Chen et al., 41 in their research, Co2+ was
41
precipitated to be Co3(PO4)2 while Li+ was dissolved to be LiH2PO4 in dilute H3PO4
42
43
and H2O2. Pinna42 reported that CoC2O4 and Li3PO4 were recovered by respectively
44
45 using H2C2O4 and NaOH as precipitating agents after H2O2-assistant H3PO4 leaching
46
47 of spent LiCoO2. Consequently, the further separation and recovery of Li and Mn could
48
49 be accomplished by adjusting pH of the leaching lixivium to change the dissociation
50
51 state of H3PO4. Possible reactions were proposed and listed in equation (7) - (9).
52
53
54 Mn2+(aq) + H2PO4-(aq) + OH-(aq) MnHPO4(s) + H2O (7)
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56 3Mn2+(aq) + 2H2PO4-(aq) + 4OH-(aq) Mn3(PO4)2(s) + 4H2O (8)
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58 3Li+(aq) + H2PO4-(aq) + 2OH-(aq) Li3PO4(s) + 2H2O (9)
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4 NaOH solution was utilized to adjust pH of the leaching lixivium including water-
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6 soluble LiH2PO4 and Mn(H2PO4)2 . After stabilizing pH of solution system to 5 for 30
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8 min at room temperature, the generated precipitation was collected by filtration,
9
10 washing and drying. As shown in Figure 9(a), the obtained precipitation of manganese
11
12
compound was pale lilac powder and mainly composed of Mn3(PO4)2·3H2O (PDF 03-
13
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0426) and MnHPO4·3H2O (PDF 25-0541) according to the analysis of XRD
15
characterization, and the overall recovery rate of Mn was 93.6%. Subsequently, the
16
17
filtrated lixivium with high concentration of Li+ was analyzed by ICP and further
18
19 precipitated by NaOH solution. After adjusting pH of lixivium was adjusted to 13 for 3
20
21 h at room temperature, the generated precipitation was collected and characterized by
22
23 ICP and XRD. As displayed in Figure 9(b), the obtained precipitation of lithium was
24
25 white powder and mainly composed of Li3PO4 (PDF 25-1030), and the overall recovery
26
27 rate of Li was 96.9%. Consequently, the H3PO4 leaching lixivium including Li+ and
28
29 Mn2+ was successfully separated and precipitated by simply adjusting pH of solution
30
31 system.
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46 Figure 9. Picture and XRD characterization of prepared products: (a) recovery product of
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48 Mn3(PO4)2 and MnHPO4; (b) recovery product of Li3PO4.
49
50 Recovery of Co and Ni. After carbothermic reduction and H3PO4 leaching, the
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52 residue which mainly consisted of Ni-Co alloy and excess graphite could be washed
53
54 and separated by physical method. Considering that both the density and magnetism of
55
56 graphite and Ni-Co alloy differed greatly from each other, wet magnetic separation can
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58 be applied to recover Ni-Co alloy. The subsequent separation technology of Ni and Co
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60 has maturely developed in academic research and industrial production, thus the
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4 repeated experiments were not implemented in this work.
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6 Recovery process. The proposed novel process for recovering valuable metals
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8 from cathode material of spent LIBs was presented in Figure 10. First, the spent
9
10 LiNixCoyMn1-x-yO2 cathode material powder and anode graphite powder were mixed to
11
12
undergo carbothermic reduction at 750 °C for 3 h. Afterwards, the roasted product was
13
14
leached by 2.75 mol/L H3PO4 solution at 40 °C for 10 min to selectively leach Li+ and
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Mn2+, the leaching residue containing Ni-Co alloy and graphite was separated by wet
16
17
magnetic separation. The recovered redundant graphite could return to carbothermic
18
19 reduction for reuse and the recovered Ni-Co alloy could be used to manufacture
20
21 products of nickel and cobalt. The leaching lixivium containing Li+ and Mn2+ were
22
23 precipitated by NaOH solution in sequence. Mn3(PO4)2·3H2O and MnHPO4·3H2O were
24
25 precipitated after stabilizing pH of solution at 5 for 30 min, Li3PO4 was precipitated
26
27 after stabilizing pH of solution at 13 for 3 h. The precipitations were filtrated, washed
28
29 and dried to obtain final products. Li3PO4 is a very important industrial chemical,
30
31 Mn3(PO4)2·3H2O and MnHPO4·3H2O can be used to fabricate LiMnPO4 composite for
32
33 lithium ion battery or used as catalysts.43-454 Considering that Na3PO4 as a kind of
34
35 alkaline detergent would decompose into Na2HPO4 and NaOH in water, the side stream
36
37 after precipitation of Li could use as alkaline detergent and supply for companies with
38
39 corresponding demand.
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Figure 10. Flowsheet of the combined method for recovering valuable metals from spent LIBs.
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30
CONCLUSIONS
31
32 In this study, combined with controllable carbothermic reduction and selective
33
34 leaching and precipitation, a novel process has been proposed for recovery of spent
35
36 LIBs. The spent LiNixCoyMn1-x-yO2 was first roasted to obtain Ni-Co alloy, MnO, Li2O
37
38 and Li2CO3 at 750 °C for 3 h by graphite recycled from spent anode. Subsequently,
39
40 2.75 mol/L H3PO4 was applied to selectively leach 99.1% of Li and 96.3% of Mn at 40
41
42 °C for 10 min, while merely 4.5% of Co and 1.2% of Ni were dissolved. The
43
44 concentrations of Li and Mn were respectively enriched to 23.14 and 53.03 g/L by two-
45
46 stage cross-current leaching and the remarkably high concentrations of Li and Mn could
47
48 alleviate the pressure in the subsequent operations such as precipitation and evaporation.
49
50 And thereafter, Li3PO4 as well as compound of Mn3(PO4)2·3H2O and MnHPO4·3H2O
51
52 were obtained by simply adjusting pH of the leaching lixivium. This original recovery
53
54 process divide the most valuable Co, Ni, Li and Mn contained in spent LiNixCoyMn1-x-
55
56 yO2 into two categories in a single H3PO4 leaching procedure, namely soluble
57
58 Mn(H2PO4)2 and LiH2PO4, and solid Ni-Co alloy. The devised facile process was
59
60 noticeably simplified, cost-effective and environmentally sustainable and have great
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4 potential for the industrial applicable recovery of spent LIBs.
5
6 ACKNOWLEDGMENTS
7
8 The authors gratefully acknowledge financial support from the State Key Program
9
10 of National Natural Science Foundation of China (No. 51834008) and the National Key
11
12
Research and Development Program of China (No. 2018YFC1902205).
13
14
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