Recycling Valuable Metals from Spent Lithium-Ion Batteries Using Carbothermal Shock Method

Pyrometallurgy technique is usually applied as a pretreatment to enhance the leaching efficiencies in the hydrometallurgy process for recovering valuable metals from spent lithium-ion batteries. However, traditional pyrometallurgy processes are energy and time consuming. Here, we report a carbothermal shock (CTS) method for reducing LiNi_0.3Co_0.2Mn_0.5O₂ (NCM325) cathode materials with uniform temperature distribution, high heating and cooling rates, high temperatures, and ultrafast reaction times. Li can be selectively leached through water leaching after CTS process with an efficiency of >90 %. Ni, Co, and Mn are recovered by dilute acid leaching with efficiencies >98 %. The CTS reduction strategy is feasible for various spent cathode materials, including NCM111, NCM523, NCM622, NCM811, LiCoO₂, and LiMn₂O₄. The CTS process, with its low energy consumption and potential scale application, provides an efficient and environmentally friendly way for recovering spent lithium-ion batteries.     

Adsorption of Li by a lithium ion-sieve using a buffer system and application for the recovery of Li from a spent lithium-ion battery

A lithium ion-sieve manganese oxide (MO) derived from Li-enriched MO was prepared by the glycolic acid complexation method. The Li adsorption performance in a LiCl–NH₃·H₂O–NH₄Cl buffer solution, simulated a spent lithium-ion battery (LIB) processing solution, and actual spent LIB processing solution were studied. An adsorption capacity of 27.4 mg/g was observed in the LiCl–NH₃·H₂O–NH₄Cl buffer solution (Li concentration of 0.2 mol/L, pH?=?9), and the adsorption behavior conformed to the Langmuir adsorption isotherm equation with a linear correlation coefficient (R²) of 0.9996. An adsorption capacity of 19 mg/g was observed in the simulated buffer spent battery solution (Li concentration of 0.15 mol/L, pH?=?7), and an adsorption capacity of 17.8 mg/g was observed in the actual spent battery solution (Li concentration of 0.15 mol/L, pH?=?7). X-ray diffraction, scanning electron microscope, and infrared spectrum results revealed that the structure and morphology of MO are stable before and after adsorption, and the adsorption of MO in all of the abovementioned buffer systems conforms to the Li⁺–H⁺ ion-exchange reaction mechanism. The lithium ion-sieve MO demonstrates promise for the recovery of lithium from spent LIBs.     

锰离子氧化沉淀法实现锂离子电池LiNi0.8Co0.05Mn0.15O2材料的回收和利用

以浓盐酸为浸出剂,以NaOH和NH₄HCO₃为沉淀剂,利用Mn²⁺在碱性条件下的氧化反应改变离子的沉淀次序进而分步回收的方案,探究了浓盐酸酸浸处理三元正极材料LiNi_0.8Co_0.05Mn_0.15O₂的最佳条件。在分步沉淀过程中,Mn²⁺被氧化为不溶于非还原性酸的MnO(OH)₂,并在酸性条件下回收。Ni、Co则在碱性条件下利用NaOH回收,而Li则利用NH₄HCO₃回收。该方法中Mn的回收率达到85.1%,产品纯度达到98.6%; Li的回收率达到95.0%,产品纯度达到99.3%。由回收材料重新合成的三元正极组装的软包电池的首圈放电比容量达到了175 mAh·g^-1,可以以超过99.5%的库仑效率稳定循环50圈。     

锰离子氧化沉淀法实现锂离子电池LiNi0.8Co0.05Mn0.15O2材料的回收和利用

以浓盐酸为浸出剂,以NaOH和NH₄HCO₃为沉淀剂,利用Mn²⁺在碱性条件下的氧化反应改变离子的沉淀次序进而分步回收的方案,探究了浓盐酸酸浸处理三元正极材料LiNi_0.8Co_0.05Mn_0.15O₂的最佳条件。在分步沉淀过程中,Mn²⁺被氧化为不溶于非还原性酸的MnO （OH）₂,并在酸性条件下回收。Ni、Co则在碱性条件下利用NaOH回收,而Li则利用NH₄HCO₃回收。该方法中Mn的回收率达到85.1%,产品纯度达到98.6%; Li的回收率达到95.0%,产品纯度达到99.3%。由回收材料重新合成的三元正极组装的软包电池的首圈放电比容量达到了175 mAh·g^-1,可以以超过99.5%的库仑效率稳定循环50圈。     

Effects of oxidant and particle size on uranium leaching from coal ash

In this paper, uranium leaching efficiency from the coal ash was 45.82% on the condition of 0.3 M H₂SO₄, 1:20 g/L, 60 °C and 12 h. According to the result of Sequential chemical extraction, leaching trials and X-ray diffraction, oxidants promoted the uranium leaching with the generation of baratovite. There were differences between uranium content of leachable states and leaching trials. Although the uranium content bounding with exchangeable, carbonates and Fe–Mn oxides all peaked at particle size fraction 75–150 μm, the highest uranium content in leaching trials peaked at size fraction 48–75 μm.     

Interferences in the determination of aluminium by means of atomic absorption spectrophotometry

Summary The following substances have been investigated with regard to their interfering effect in the determination of aluminium by atomic absorption spectrophotometry: HCl, H₂SO₄, HNO₃, H₃PO₄, alkali and alkaline earth metals, Cu, Fe, Zn, Ni, Mn, Co, Mo, Ti, Cr, V, Si. Ternary systems with La have been examined also. Si exerts a strong depressive effect, whereas other elements in certain concentration ranges exhibit positive effects.

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Störungen bei der atomabsorptionsspektralphotometrischen Bestimmung von Aluminium

Zusammenfassung Folgende Substanzen wurden hinsichtlich einer möglichen Beeinflussung der Aluminiumbestimmung untersucht: HCl, H₂SO₄, HNO₃, H₃PO₄, Alkalimetalle, Erdalkalimetalle, Cu, Fe, Zn, Ni, Mn, Co, Mo, Ti, Cr, V, Si. Ternäre Systeme mit La wurden ebenfalls geprüft. Si übt eine stark depressive Wirkung aus, während andere Elemente in bestimmten Konzentrationsbereichen positiv wirken.

Lecture given on the 2nd Czechoslovak Conference on Flame Speotroscopy, Zvíkov, June 5–8, 1973.     

Synthesis and characterization of manganese-, nickel-, and cobalt-containing carbonate precursors for high capacity Li-ion battery cathodes

Mn-rich transition metal (Mn, Ni, Co) carbonate precursor was precipitated as the precursor for Li- and Mn-enriched composite material used as advanced cathode for lithium-ion battery. The pH zone that favors carbonate precipitation reactions for transition metals (Co, Ni, Mn) was predicted by taking into account the chemical equilibriums between metal elements Me (Co, Ni, Mn) and ammonia bicarbonate. The physical properties of the precursor and the final lithiated cathode material were characterized in detail, and the electrochemical properties of the prepared Li_1.2Ni_0.12Co_0.12Mn_0.56O₂ powder were evaluated. The study aids in understanding the precipitation and yields an optimal precipitation condition for the system.     

锂离子电池三元正极材料的研究进展

含有三种过渡金属元素的镍钴锰酸锂(Li(Ni,Co,Mn)O2,简称三元材料)作为最有商业化前途的锂离子电池正极材料,近年来受到了研究者和工业界广泛关注,有望成为动力电池的主要正极活性物质.本文对几种主要组成的三元材料(111,523,424,811)的合成工艺、材料掺杂和表面包覆改性、电解液匹配三方面的最新研究进展进行了综述,并对其商业化应用前景进行了展望和评价.     

NaM2OH(SO3)2 · 1 H2O mit M = Mg,Mn, Fe,Co, Ni und Zn Ein neuer Typ basischer Sulfite

NaM₂OH(SO₃)₂ · 1 H₂O with M = Mg, Mn, Fe, Co, Ni, and Zn. A New Class of Basic Sulfites Hitherto unknown hydroxide sulfites of the type NaM₂OH(SO₃)₂ · 1 H₂O with M = Mg, Mn, Fe, Co, Ni, and Zn have been obtained by crystallization from aqueous sulfite solutions containing Na⁺ and M²⁺ ions. Crystal structure, IR and Raman data, and the results of thermoanalytical studies are reported and discussed. The hydroxide sulfites show a strongly anisotropic thermal expansion due to the layer structure and exhibit an unusually high thermal stability compared to other solid hydrates. The magnesium compound, for example, decomposes at 355°C. The crystal data of the triclinic compounds see “Inhaltsübersicht”.     

Synthesis and structural studies of 2-acetylthiophene-2-thenoylhydrazone complexes of oxovanadium(IV), manganese(II), cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II) and mercury(II)

Complexes with chemical compositions VO(Hatth)₂SO₄, VO(Hatth)₂SO₄·py, [M(Hatth)₂Cl·H₂O]Cl [M = Mn(II), Co(II) and Ni(II)], [Cu(Hatth)₂Cl]₂Cl₂, [Cu(Hatth)₂· Cl·py]Cl, [Cd(Hatth)₂Cl]Cl, M(Hatth)₂Cl₂ [M = Zn(II) and Hg(II)], VO(atth)₂, VO(atth)₂py, M(atth)₂(py)₂ [M = Mn(II) and Cu(II)], M(atth)₂(H₂O)₂ [M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)], Hatth = 2-acetylthiophene-2-thenoylhydrazone, and atth, its deprotonated form, have been prepared and characterized by analytical data, molar conductance, magnetic susceptibility, electronic and photoacoustic, ESR, IR and NMR spectral studies. X-ray diffraction study has been used to determine the shape and the dimensions of the unit lattice of copper(II) complexes.     

Spectral and Thermal Studies of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) Complexes with 3-methylglutaric Acid

Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) 3-methylglutarates were prepared as solids with general formula MC₆ H₈ O₄ ×n H₂ O, where n =0–8. Their solubilities in water at 293 K were determined (7.0×10⁻² −4.2×10⁻³ mol dm⁻³ ). The IR spectra were recorded and thermal decomposition in air was investigated. The IR spectra suggest that the carboxylate groups are mono- or bidentate. During heating the hydrated complexes lose some water molecules in one (Mn, Co, Ni, Cu) or two steps (Cd) and then mono- (Cu) or dihydrates (Mn, Co, Ni) decompose to oxides directly (Mn, Cu, Co) or with intermediate formation of free metals (Co, Ni). Anhydrous Zn(II) complex decomposes directly to the oxide ZnO. This revised version was published online in July 2006 with corrections to the Cover Date.     

Complexation study of Schiff base ligand: pyridin-2-ylimino methyl naphthanol with Co+2, Mn+2 and Ni+2 ions in solid and solution phase

Schiff base pyridin-2-ylimino methyl naphthanol (HL) was synthesized and characterized by spectroscopic (FTIR, ESIMS, and NMR) techniques. The ligand was reacted with perchlorate salts of Mn⁺², Co⁺², and Ni⁺². ESIMS mass spectra indicate the formation of mononuclear complex ML₂ for all three complexes. CoL₂ crystallizes in P₂1/n space group, adopting a distorted tetrahedral geometry where Co is in a N₂O₂ donor environment. Structure of the Co complex was optimized by DFT calculation. Solution-phase complexation between the ligand and the three metals ions: Mn⁺², Co⁺², and Ni⁺² (pH 7.2 in tris buffer), in CH₃CN–H₂O was performed spectrophotometrically by UV–vis spectral study. Job’s plot from each titration suggests a 1 : 2 metal to ligand combination. The association constants for the formation of ML₂ are as follows: Mn (19.80 × 10³ M^?1), Co (14.54 × 10³ M^?1) and Ni (19.04 × 10³ M^?1).     

Investigation of binuclear metal phthalocyanines as electrocatalysts for Li/SOCl<Subscript>2</Subscript> battery

Three novel series of the binuclear metal phthalocyanines M₂Pc₂, M₂Pc₂Hc, and M₂Nc₂ (M?=?Mn(II), Fe(II), Co(II), Ni(II), and Cu(II)) were synthesized and characterized. The electrocatalytic performance of the binuclear compounds to lithium–thionyl chloride battery was evaluated by operating these compounds in the electrolyte of the battery. The results indicated that the binuclear metal phthalocyanines improved the capacity of the battery by an increase of approximately 30–58 %. Of all, Cu₂Pc₂Hc and Fe₂Nc₂ displayed the highest increments of 56 and 57 %, respectively.     

New lithium salts in electrolytes for lithium-ion batteries (Review)

The properties of electrolyte systems based on standard nonaqueous solvent composed of a mixture of dialkyl and alkylene carbonates and new commercially available lithium salts potentially capable of being an alternative to thermally unstable and chemically active lithium hexafluorophosphate LiPF₆ in the mass production of lithium-ion rechargeable batteries are surveyed. The advantages and drawbacks of electrolytes containing lithium salts alternative to LiPF₆ are discussed. The real prospects of substitution for LiPF₆ in electrolyte solutions aimed at improving the functional characteristics of lithium-ion batteries are assessed. Special attention is drawn to the efficient use of new lithium salts in the cells with electrodes based on materials predominantly used in the current mass production of lithium-ion batteries: grafitic carbon (negative electrode), LiCoO₂, LiMn₂O₄, LiFePO₄, and also solid solutions isostructural to lithium cobaltate with the general composition LiMO₂ (M = Co, Mn, Ni, Al) (positive electrode).     

Variable temperature PXRD investigation of the phase changes during the dehydration of potassium Tutton salts

The thermal dehydration of the potassium Tutton salts K₂M(SO₄)₂·6H₂O (M = Mg, Co, Ni, Cu, Zn) was investigated using thermal gravimetric analysis (TG), differential scanning calorimetry (DSC), FTIR, and variable temperature powder X-ray diffraction. While each Tutton salts lost all six waters of hydration when heated to 500 K, the decomposition pathway depended on the divalent metal cation. K₂Ni(SO₄)₂·6H₂O lost all six waters in a single step, and K₂Cu(SO₄)₂·6H₂O consistently lost water in two steps in capped and uncapped cells. In contrast, multiple decomposition pathways were observed for the magnesium, cobalt, and zinc Tutton salts when capped and uncapped TG cells were used. K₂Zn(SO₄)₂·6H₂O lost the waters of hydration in a single step in an uncapped cell and in two steps in a capped cell. Both K₂Mg(SO₄)₂·6H₂O and K₂Co(SO₄)₂·6H₂O decomposed in a series of steps where the stability of the intermediates depended on the cell configuration. A greater number of phases were often observed in DSC and capped-cells TG experiments. A quasi-equilibrium model is presented that could explain this observation. These results highlight that experimental conditions play a critical role in the observed thermal decomposition pathway of Tutton salts.     

Linear-chain antiferromagnetism in the compounds MII(N2H5)2(SO4)2 with M = Mn,Fe, Co,Ni, and Cu

Powder-susceptibility measurements in the temperature region 2–80° K on the chain compounds M^II(N₂H₅)₂(SO₄)₂, with M = Mn, Fe, Co, Ni, and Cu, show that the magnetic properties of these compounds can be interpreted in terms of antiferromagnetic linear-chain systems. The experimental results provide information on the magnitude of the intrachain interactions. In addition, ESR linewidth experiments were used for a determination of the intrachain interaction in Mn(N₂H₅)₂ (SO₄)₂. For the interpretation of the data on Fe(N₂H₅)₂(SO₄)₂, the parallel susceptibility of Ising chains with S = 2 is calculated theoretically. An estimate for the ratio between the intra- and interchain coupling is given. Use is made of preliminary results of specific heat measurements on these compounds for the interpretation of the magnetic data.     

Mononuclear transition and non-transition complexes of amlodipine besylate as antihypertensive agent: synthesis,spectral, thermal,and antimicrobial studies

Mononuclear Mn(II), Co(II), Ni(II), Zn(II), Cd(II), Mg(II), Sr(II), Ba(II), Ca(II), Pt(IV), Au(III), and Pd(II) complexes of the drug amlodipine besylate (HL) have been synthesized and characterized by elemental analysis, spectroscopic technique (IR, UV–Vis, solid reflectance, scanning electron microscopy, X-ray powder diffraction, and ¹H-NMR) and magnetic measurements. The elemental analyses of the complexes are confirmed by the stoichiometry of the types [M(HL)(X)₂(H₂O)]·nH₂O [M = Mn(II), Co(II), Zn(II), Ni(II), Mg(II), Sr(II), Ba(II), and Ca(II); X = Cl^? or NO₃ ^?], [Cd(HL)(H₂O)]Cl₂, [Pd(HL)₂]Cl₂, [Pt(L)₂]Cl₂, and [Au(L)₂]Cl, respectively. Infrared data revealed that the amlodipine besylate drug ligand chelated as monobasic tridentate through NH₂, oxygen (ether), and OH of besylate groups in Mn(II), Co(II), Ni(II), Zn(II), Cd(II), Mg(II), Sr(II), Ba(II), Ca(II), and Au(III) complexes, but in Pt(IV) and Pd(II) complexes, the amlodipine besylate coordinates via NH₂ and OH (besylate) groups. An octahedral geometry is proposed for all complexes except for the Cd(II), Pt(IV), and Pd(II) complexes. The amlodipine besylate free ligand and the transition and non-transition complexes showed antibacterial activity towards some Gram-positive and Gram-negative bacteria and the fungi (Aspergillus flavus and Candida albicans).     

Trimellitate complexes of divalent transition metals with hydrazinium cation

New dihydrazinium divalent transition metal trimellitate hydrates of empirical formula (N₂H₅)₂M(Html)₂·nH₂O, where n = 1 for M = Co or Ni, and n = 2 for M = Mn, Zn, or Cd (H₃tml = trimellitic acid), and monohydrazinium cadmium trimellitate, [(N₂H₅)Cd(Html)_1.5·2H₂O] have been prepared and characterized by physico-chemical methods. Electronic spectroscopic, and magnetic moment data suggest that Co and Ni complexes adopt an octahedral geometry. The IR spectra confirm the presence of monodentate carboxylate anion (Δν = ν_asy(COO^?) ? ν_sym(COO^?) > 190 cm^?1) and coordinated N₂H₅ ⁺ ion (ν_N–N 1015 ? 990 cm^?1) in all the complexes. All the complexes undergo endothermic decomposition eliminating CO₂ in the temperature region 200–250 °C, followed by exothermic decomposition (in the range of 500–570 °C) of organic moiety to give the respective metal carbonate as the end products except nickel and cobalt complexes, which leave respective metal oxides. X-ray powder diffraction patterns reveal that Ni and Co complexes are isomorphous as are those of, Zn(II) and Cd(II) of the type, (N₂H₅)₂M(Html)₂·2H₂O.     

Experimental study of the heat generations of Li/SOCl2 and Li/SO2 batteries using a phase-change measurement method

A paraffin phase-change measurement method for the heat generation of spirally wound cylindrical Li/SOCl₂ and Li/SO₂ batteries at different ambient temperatures and discharge currents is proposed. The electrical and thermal insulations of the measurement system have been greatly improved, and the accuracy of the measurement system is 4.6 % based on calibration experiments. Compared with accelerated rate calorimetry, isothermal microcalorimetry, and radiation calorimetry methods, the phase-change measurement method is simpler, but with a high accuracy. The experimental results reveal that the heat generation of the batteries during discharge is weakly dependent on the ambient temperature in the range of 38–50 °C, but strongly affected by the discharge current. As the discharge current increases, the heat generated by the Li/SOCl₂ and Li/SO₂ batteries increases as a quadratic polynomial function. The Li/SO₂ battery generates more heat than the Li/SOCl₂ battery at the same discharge current, which is demonstrated by the qualitative analysis of the internal resistance. Furthermore, the phase-change measurement method for heat generation has a strong universality, and can be applicable for heat generation measurement of various battery types.     

Complexation of 2,3-dihydroxyquinaline with some bivalent <Emphasis Type="Italic">d</Emphasis> metals. Crystal and molecular structures of 2,3-dihydroxyquinoline

The reactions of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Cd with 2,3-dihydroxyquinoline (H₂L) were used to synthesize and identify the complexes M(HL)₂ · 2H₂O (M = Mn, Ni, Cu), Fe(HL)OH · 2H₂O, Co(HL)OH · H₂O, Cd(H₂L)Cl₂, where H₂L participates in the coordination in the monoanionic or neutral forms with the formation of the chelate cycles. Single crystal was isolated and the crystal structure of H₂L was determined. The spectral characteristics of a neutral and anionic form of the ligand were measured, and its complexation with MCl₂ was studied in the ethanol solutions. The acidity constant of H₂L and the formation constants of the complexes in solutions were calculated.