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Licoo2

Manufactured by Merck Group

LiCoO2 is a lithium cobalt oxide material used in the production of rechargeable lithium-ion batteries. It serves as the cathode active material in these batteries. The core function of LiCoO2 is to facilitate the reversible insertion and extraction of lithium ions during the charging and discharging processes of the battery.

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6 protocols using licoo2

1

Preparation and Characterization of Lithium-Ion Battery Components

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For electrolyte, LiN(SO2CF3)2 [lithium bis(trifluoromethanesulfonyl) imide,
LiTFSI, >99.7%, Kanto], HN(SO2CF3)2 [bis tri(fuloromethanesulfonly) imide, HTFSI, >99.0%, TCI], Li2SO4 (99.7% Alfa aesar), LiNO3 (reagent
plus, Sigma-Aldrich), LiClO4, (99.99%, Sigma-Aldrich),
and LiOH (>98%, Sigma-Aldrich) were used as received without any
purification.
For electrodes, LiCoO2 (99.8%), N-methylpyrrolidine
(NMP), and H2O2 (30% in H2O) were
purchased from Sigma-Aldrich, and NH4OH was purchased from
Fluka (5.0 M).
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2

Electrochemical Synthesis of Metal Oxides

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Co(NO3)2 ⋅6H2O (≥99.999 %), Co3O4 (99.99), CoO (99.99 %), LiCoO2 (>99.8 %), Mn(NO3)2 ⋅4H2O (≥99.99 %), Mn(SO4)2⋅xH2O (99.99), MnO2 (≥99 %), Mn3O4 (≥97 %), Mn2O3 (≥99.9 %), L‐(+)‐Tartaric acid (≥99.5 %) and (2 M and 0.1 M) NaOH solutions were ordered from Sigma‐Aldrich. Graphite foil (≥99.8) with a thickness of 0.254 mm ordered from VWR. All reactants were used as received, without any further treatment. Solutions were prepared with deionized water (>18 MΩ cm).
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3

Preparation of Li-excess Cathode Targets

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The Li excess Li1+xCoO2 targets were prepared by sintering a mixture of high purity LiCoO2 (Sigma-Aldrich) and 10% excess Li2O (Alfa Aesar) powders to compensate for Li loss during deposition. The mixed powders were ball milled for 72 h and dried at 80 °C for 2 h. The targets pressed into 1-inch diameter were sintered at 400 °C for 2 h and 1000 °C for 10 h.
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4

Spent LIB Cathode Material Recycling

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The powder of spent LIB
cathode materials was supplied by Matsuda Sangyo Co., Ltd (Tokyo,
Japan). LiCoO2, tetrabutylammonium thiocyanate ([N4444]SCN), and methanesulfonic acid (MSA) were purchased from
Sigma-Aldrich Co. Potassium thiocyanate (KSCN) and the polymer PPG400
were supplied by Kishida Chemical Co., Ltd. Acetic acid (AcOH), formic
acid (HCOOH), and amino acids, namely, Gly, proline (Pro), serine
(Ser), asparagine (Asn), histidine (His), cysteine (Cys), and glutamic
acid (Glu), were purchased from Kishida Chemical Co., Ltd. Ascor,
tartaric acid (TA), aceturic acid (Ac-Gly-OH), and glycine ethyl ester
hydrochloride (H-Gly-OEt·HCl) were purchased from Fujifilm Wako
Chemical Ltd. p-Toluenesulfonic acid (PTSA) was purchased
from Tokyo Chemical Industry Co., Ltd. Deionized water (Milli-Q, Merck
Millipore) was used in this work.
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5

Synthesis and Characterization of Oxygen- and Hydrogen-Annealed Li4Ti5O12

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The following active materials were employed in this work: Li4Ti5O12 (D50 1.9 μm) from MTI Corporation, LiCoO2 (7–10 μm) from Sigma–Aldrich, and anatase TiO2 (<10 nm) from Sachtleben Chemie. All components of the electrolyte, namely ethylene carbonate and dimethyl carbonate and LiPF6, and metallic lithium were purchased from Sigma–Aldrich (battery grade). Celgard 2500 and Ketjenblack EC-600 JD were courtesy of Azelis and AkzoNovel Polymer Chemicals.
The oxygen-annealed Li4Ti5O12 samples (O_LTO) were obtained by treatment commercially available Li4Ti5O12 (P_LTO) in flowing O2 (100 vol %) at 650 °C for 120 min. The O2-annealed sample (O_LTO) was then treated in flowing H2 (5 vol % in Ar) at 650 °C for 90 min to obtain hydrogen-annealed Li4Ti5O12 (H_LTO).
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6

Controlled Chemical Delithiation of LiCoO2 Cathode

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Commercially available LiCoO2 (Sigma Aldrich No: 442704-100G-A) here named as LCO0 was used. The chemically delithiated samples (namely LCO1, LCO2, LCO3, LCO4, LCO5, LCO6, LCO7 and LCO8) are prepared by stirring 5 g (LCO0) in 500 ml solution. The treating times, concentration of solutions, supernatant and chemical composition after delithiation are presented in Table 1. Acid solutions were prepared by diluting conc. HCl (37%) in milliQ deionised water. After this treatment, the filtered samples were washed several times with copious amounts of milliQ deionised water to remove all possibly formed LiCl and CoCl2 before drying at 100 °C.

Chemical composition after chemical delithiation of LiCoO2.

SampleSolutionTimeLi:Co in bulk% at. Co from bulk in supernatant% at. Li from bulk in supernatant
LCO00.9326
LCO1water1 week0.931710.51381.1305
LCO21 M HCl10 min0.85004.5236.040
LCO31 M HCl30 min0.83128.60616.76
LCO40.1 M HCl1 week2.1705.661
LCO50.75 M HCl1 week0.83725.797913.79
LCO60.5 M HCl1 week0.895710.8424.59
LCO72 M HCl17 h0.391837.1870.78
LCO81 M HCl22 h0.342537.4176.56
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