Sustainable Preparation of LiNi_1/3Co_1/3Mn_1/3O₂–V₂O₅ Cathode Materials by Recycling Waste Materials of Spent Lithium-Ion Battery and Vanadium-Bearing Slag

Waste streams containing heavy metals are always of concern from both environmental and resource-depleting points of view. The challenges are in most cases related to the effectiveness for high-value-added materials recovery from such waste, with which the environmental impacts during recycling shall be low. In this research, two typical heavy-metal-containing waste streams, i.e., spent lithium-ion batteries and vanadium-bearing slag, were simultaneously treated, and this enables regeneration of the LiNi_1/3Co_1/3Mn_1/3O₂ cathode materials which was considered difficult because of the dislocation of nickel and lithium ions during electrochemical performance. By using the intermediate product during vanadium-bearing slag treatment, the vanadium-embedded cathode material can be prepared which delivers excellent electrochemical performances with a specific capacity of 156.3 mA h g^–1 after 100 cycles at 0.1C with the capacity retention of 90.6%; even the additive amount is only 5%. A thin layer of vanadium oxide is found to be effective to promote electrochemical performance of the cathode material. Using the principles of green chemistry, this process enables high-performance cathode material regeneration without introducing extraction chemicals and with much lower environmental impacts as compared to traditional metallurgical technologies

The overexpression of Cry1 mRNA and protein in colorectal cancer tissues.

<p>(<b>A</b>) A representative image of Cry1 staining in colorectal cancer tissues is shown. (<b>B</b>) A representative image of Cry1 staining in adjacent noncancerous tissues is shown. (<b>C</b>) Cry1 protein expression level was higher in tumor tissues compared to adjacent control tissue as detected by immunoblotting (mean±SEM; n = 109; * **, <i>P</i><0.001). (<b>D</b>) Average T/N ratios of Cry1 mRNA expression in paired colorectal cancer (T) and normalmucosa tissues (N) were quantified by qPCR and normalized to GAPDH. Error bars represent the standard deviation of the mean (SD) calculated from three parallel experiments. Magnification is ×200.</p

The expression of Cry1 protein in colorectal cancer sections.

<p>Representative immunohistochemical images of colorectal cancer tissue specimens indicating negative or weakly detectable Cry1 staining (<b>A</b> and <b>B</b>); moderate Cry1 staining (<b>C</b>); and strong Cry1 staining (<b>D</b>) are shown. Magnification is ×200 (<b>A, B, C</b> and <b>D</b>).</p

Cry1 promoted CRC growth <i>in vivo</i>.

<p>(<b>A</b>) The expression of Cry1 was markedly increased in the stable cell line Cry1-HCT116 compared with control stable cell line ctrl-HCT116. GAPDH was used as an internal control. (<b>B</b>) Representative images of tumors derived from Cry1-HCT116 or ctrl-HCT116,following subcutaneous xenograft transplants in nude mice (<b>C</b>) Overexpression of Cry1 promoted colorectal cancer growth. Tumor cells were injected subcutaneously into nude mice. Mice were sacrificed after 4 weeks, and the volume of each tumor was measured every 4 days. Bars, ±SEM; *<i>P</i><0.05, ** <i>p</i> = 0.01.</p

Effects of Cry1 on cell growth.

<p>(<b>A</b>) Cry1 protein levels were upregulated in HCT116 cells and downregulated in SW480 cells. (<b>B</b>) MTT assays on HCT116 cells 24, 48, and 72 h after transfection with Cry1 or GFP control (***, p<0.001). (<b>C–D</b>) Colony formation assay of HCT116 cells transfected with Cry1 or GFP control (*, <i>p</i> = 0.033). (<b>E–F</b>) Inhibition of SW480 cell colony formation capacity by Cry1 siRNA relative to control (**, <i>p</i> = 0.007). Experiments were repeated at least three times, and representative data are presented; <i>bars</i>, SD.*, <i>P</i><0.05; **, <i>P</i><0.01, ***, <i>p</i><0.001.</p

Overexpression of Cry1 mRNA and protein in colorectal cancer cell lines.

<p>Expression of Cry1 mRNA and protein in colorectal cancer cell lines (SW480, SW620, HT29, THC8307, and HCT116) and FHC were examined by qPCR (<b>A</b>) and Western blotting (<b>B</b>). Expression levels were normalized to GAPDH. Error bars represent the standard deviation of the mean (SD) calculated from three parallel experiments, *, <i>P</i><0.05.</p

Clinicopathological findings and correlation with Cry1 expression.

*<p>Statistically significant. Numbers in parentheses indicate the proportion of tumors with a specific clinical or pathological feature in a given Cry1 subtype.</p>†<p>Analysis for this parameter was available for 167 cases.</p>††<p>Analysis for this parameter was available for 149 cases.</p>†††<p>Analysis for this parameter was available for 147cases.</p

The level of Cry1 protein expression affects overall survival and disease-free survival.

<p>Kaplan–Meier curves with univariate analysis (log-rank) for colorectal cancer patients with high Cry1 expression (n = 101) versus low or no Cry1 expression for overall survival (n = 67) (<b>A</b>) and disease-free survival (n = 67) (<b>B</b>) are shown. Higher expression of Cry1 positively correlated with the poor patientoutcomes.</p