• Journal of the Korean Crystal Growth and Crystal Technology
• /
• v.31 no.1
• /
• pp.16-23
• /
• 2021

Lithium carbonate recovered from the waste solution generated during the lithium secondary battery manufacturing process contains heavy metals such as cobalt, nickel, and manganese. In this study, the recrystallization of lithium carbonate was performed to remove heavy metals contained in the powder and to increase the purity of lithium carbonate. First, the leaching efficiency of lithium carbonate according to pH in the aqueous hydrochloric acid solution was examined, and the effect on the recrystallization of lithium carbonate according to the equivalent and concentration of sodium carbonate was confirmed. As the equivalent and concentration of sodium carbonate increased, the recovery rate of lithium carbonate improved. And the SEM image showed that the crystal shape was changed depending on the reaction conditions with sodium carbonate. Finally, the high purity lithium carbonate of 99.9% or more was recovered by washing with water.

• Journal of the Korean Ceramic Society
• /
• v.37 no.10
• /
• pp.955-961
• /
• 2000

사티탄산칼륨을 리튬이온 전지의 양극재료로써 사용하고자 할 때 사티탄산칼륨의 합성 열처리 온도가 리튬이온 치환량에 미치는 영향에 대해 조사하였다. 사티탄산칼륨은 $K_2$O와 TiO$_2$의 몰 비를 1 : 3.91로 칭량하여 95$0^{\circ}C$, 100$0^{\circ}C$, 105$0^{\circ}C$에서 각각 합성하였다. 그 후, 사티탄산칼륨의 (Ti$_4$O$_{9}$ )$^{2-}$ 층간에 존재하는 $K^{+}$ 이온을 H$^{+}$ 이온으로 치환하고 이것을 다시 Li$^{+}$ 이온으로 치환하였다. 사티탄산칼륨의 합성 열처리 온도가 증가할수록 사티탄산칼륨의 (Ti$_4$O$_{9}$ )$^{2-}$ 층간의 거리가 감소했고 사티탄산칼륨의 길이가 증가했다. 95$0^{\circ}C$에서 열처리된 사티탄산칼륨의 리튬이온 치환량이 가장 많았다. 이는 상대적으로 낮은 합성 열처리 온도에서 사티탄산칼륨의 (Ti$_4$O$_{9}$ )$^{2-}$ 층간의 거리가 넓어져 리튬이온의 층간 이동이 쉬어졌고, 고온에서 열처리되어 길이가 긴 사티탄산칼륨에 비해 저온에서 열처리된 사티탄산칼륨은 길이가 짧아져 리튬이온이 (Ti$_4$O$_{9}$ )$^{2-}$ 층간으로 이동해 가는 거리가 짧아졌으며 아울러 짧은 사티탄산칼륨의 개수가 동일한 무게 당긴 사티탄산칼륨의 개수보다 많으므로 리튬이온의 치환량이 많아진다고 사료된다.

• Resources Recycling
• /
• v.29 no.6
• /
• pp.27-34
• /
• 2020

In order to remove sulfate(SO42-) and purify the Li2CO3, dissolution and recrystallization of crude Li2CO3 using distilled water and HCl solution was performed. When Li2CO3 was dissolved using distilled water, the amount of dissolved Li2CO3(wt.%) increased as the solution temperature decrease and showed about 1.50 wt.% at 2.5℃. In addition, when Na2CO3 was added and the Li2CO3 solution was recrystallized, the recrystallization(%) increased with increasing temperature, resulting in a 49.00 % at 95 ℃. On the other hand, when Li2CO3 was dissolved using HCl solution, there was no effect of reaction temperature. As the concentration of HCl solution increased, the amount of dissolved Li2CO3(wt.%) increased, indicating 7.10 wt.% in 2.0 M HCl solution. When the LiCl solution was recrystallized by adding Na2CO3, it exhibited a recrystallization(%) of 86.10 % at a reaction temperature of 70 ℃, and showed a sulfate ion removal(%) of 96.50 % or more. Finally, more than 99.10 % of Na and more than 99.90 % of sulfate were removed from the recrystallized Li2CO3 powder through water washing, and purified Li2CO3 with a purity of 99.10 % could be recovered.

• Journal of the Korean Crystal Growth and Crystal Technology
• /
• v.29 no.5
• /
• pp.222-228
• /
• 2019

In this study, we carried out the experiment to prepare lithium carbonate powder through gas-liquid reactions with a lithium-containing solution and $CO_2$ gas using lithium hydroxide, lithium chloride, and lithium sulfate. Thermodynamically, the carbonation reaction of a lithium-containing solution showed that aqueous reaction of lithium hydroxide occurs spontaneously, but aqueous reactions of lithium chloride and lithium sulfate does not occur spontaneously. In the case of lithium hydroxide solution, the recovery rate of lithium carbonate was 69.8 % at room temperature ($25^{\circ}C$), and increased to 89.4 % at $60^{\circ}C$. In the case of lithium chloride and lithium sulfate solution, lithium carbonate could be prepared using sodium hydroxide as an additive, but the recovery rates were 19.2 % and 16.7 %, respectively.

• Resources Recycling
• /
• v.32 no.1
• /
• pp.21-32
• /
• 2023

Because the application of lithium has gradually increased for the production of lithium ion batteries (LIBs), more research studies about recycling using solvent extraction (SX) should focus on Li⁺ recovery from the waste solution obtained after the removal of the valuable metals nickel, cobalt and manganese (NCM). The raffinate obtained after the removal of NCM metal contains lithium ions and other impurities such as Na ions. In this study, we optimized a selective SX system using di-(2-ethylhexyl) phosphoric acid (D2EHPA) as the extractant and tri-n-butyl phosphate (TBP) as a modifier in kerosene for the recovery of lithium from a waste solution containing lithium and a high concentration of sodium (Li⁺ = 0.5 ~ 1 wt%, Na⁺ = 3 ~6.5 wt%). The extraction of lithium was tested in different solvent compositions and the most effective extraction occurred in the solution composed of 20% D2EHPA + 20% TBP + and 60% kerosene. In this SX system with added NaOH for saponification, more than 95% lithium was selectively extracted in four extraction steps using an organic to aqueous ratio of 5:1 and an equilibrium pH of 4 ~ 4.5. Additionally, most of the Na⁺ (92% by weight) remained in the raffinate. The extracted lithium is stripped using 8 wt% HCl to yield pure lithium chloride with negligible Na content. The lithium chloride is subsequently treated with high purity ammonium bicarbonate to afford lithium carbonate powder. Finally the lithium carbonate is washed with an adequate amount of water to remove trace amounts of sodium resulting in highly pure lithium carbonate powder (purity > 99.2%).

• Journal of the Korean Crystal Growth and Crystal Technology
• /
• v.31 no.2
• /
• pp.89-95
• /
• 2021

Research on the production of lithium hydroxide (LiOH) has been actively conducted in response to the increasing demand for high nickel-based positive electrode materials for lithium-ion batteries. Herein we studied the conversion of lithium oxide (Li2O) through thermal decomposition of lithium carbonate for the production of lithium hydroxide from lithium carbonate (Li2CO3). The reaction mechanism of lithium carbonate with alumina, quartz and graphite crucible during heat treatment was confirmed. When graphite crucible was used, complete lithium oxide powder was obtained. Based on the TG analysis results, reagent-grade lithium carbonate was heat-treated at 700℃, 900℃ and 1100℃ for various time and atmosphere conditions. XRD analysis showed the produced lithium oxide showed high crystallinity at 1100℃ for 1 hour in a nitrogen atmosphere. In addition, several reagent-grade lithium oxides were reacted at 100℃ to convert to lithium hydroxide. XRD analysis confirmed that lithium hydroxide (LiOH) and lithium hydroxide monohydrate (LiOH·H2O) were produced.

• Journal of the Korean Crystal Growth and Crystal Technology
• /
• v.30 no.2
• /
• pp.55-60
• /
• 2020

In the previous study, we reported the result to prepare lithium carbonate powder from various lithium-contained solution. Therefore, using the lithium hydroxide solution, it is conformed that the reaction could occur thermodynamically, and the recovery rate of lithium was 89.4 %. In this study, we carried out the experiment to prepare lithium carbonate powder through gas-liquid reactions with lithium hydroxide solution and CO₂ gas using ultrasound energy. In case ultrasonic energy is applied to the reaction of lithium carbonate, the recovery rate of lithium at room temperature was approximately 83.8 %, and the recovery rate of lithium was greatly increased to approximately 99.9 % at 60℃ reaction temperature. And when ultrasonic energy is not applied, the particle size of lithium carbonate powder was 7.7 ㎛ in D50. But the particle size of lithium carbonate powder was significantly reduced to 8.4 ㎛ in D50 under the influence of ultrasonic.

• Resources Recycling
• /
• v.31 no.4
• /
• pp.26-33
• /
• 2022

Owing to the demand for lithium-ion batteries, the recovery of valuable metals from waste lithium-ion batteries is required in future. A pyrometallurgical treatment is appropriate for recycling a large number of waste lithium-ion batteries, but Li loss to slag and dust present a significant challenge. This research investigated carbonation roasting and water leaching behaviors in Li-ion batteries by graphite addition to recover Li from the NCM-based cathode materials of waste Li-ion batteries. When 10 wt% of graphite was added, CO and CO₂ gases were emitted with a rapid weight reduction at apporoximately 850 K, when heated in Ar and CO₂ atmosphere. After the rapid weight reduction, NCM was decomposed and reduced to metal oxides and pure metals. In the carbonation roasting of black powder (NCM+graphite), O₂ is generated via the decomposition of NCM, and an oxides, such as Li₂O and NiO were were also generated. Subsequently, Li₂O reacts with CO₂ to generate Li₂CO₃, and a part of NiO was reduced by graphite to produce metal Ni. In addition, up to 94.5 % Li₂CO₃ with ~99.95 % purity was recovered via water leaching after carbonation roasting.

• Resources Recycling
• /
• v.22 no.4
• /
• pp.62-69
• /
• 2013

A study on the recovery of lithium and leaching behavior of NCM powder by carbon reduction for NCM-system Li-ion battery scraps was conducted. First of all, the oxide powders of NCM-system with layer structure were decomposed by carbon, lithium was converted to lithium carbonate by carbon reaction at above $600^{\circ}C$. The lithium carbonate powders with 99% purity were manufactured by washing method with water and concentration process for NCM powder after carbon reduction. The reaction yield was approximately 88% at $800^{\circ}C$ by carbon reduction. At this time, leaching efficiency at 2M sulfuric acid concentration was over 99% for cobalt, nickel and manganese.

• Resources Recycling
• /
• v.23 no.5
• /
• pp.21-27
• /
• 2014

A study on the solvent extraction for the recovery of Li from lithium-containing waste solution was investigated using $D_2EHPA$ as an extractant. The experimental parameters, such as the pH of the aqueous solution, concentration of extractant and phase ratio were observed. Experimental results showed that the extraction percentage of Li was increased with increasing the equilibrium pH. More than 50% of Li was extracted in eq. pH 6.0 by 20% $D_2EHPA$. From the analysis of McCabe-Thiele diagram, 95% of Li was extracted by four extraction stage at phase ratio(O/A) of 3.0. Stripping of Li from the loaded organic phases can be accomplished by sulfuric acid as a stripping reagent and 90 ~ 120 g/L of $H_2SO_4$ was effective for the stripping of Li. Finially, Li was concentrated about 11.85 g/L by continuous stripping process, and then lithium carbonate was prepared by precipitation method.