The nickel-rich cathode LiNi0.8Co0.1Mn0.1O2 (NCM811) is deemed as a prospective
material
for high-voltage lithium-ion batteries (LIBs) owing to its merits
of high discharge capacity and low cobalt content. However, the unsatisfactory
cyclic stability and thermostability that originate from the unstable
electrode/electrolyte interface restrict its commercial application.
Herein, a novel electrolyte composed of a polyethylene (PE) supported
poly(vinylidene fluoride-co-hexafluoropropylene)
(P(VdF-HFP)) based gel polymer electrolyte (GPE) strengthened by a
film-forming additive of 3-(trimethylsilyl)phenylboronic acid (TMSPB)
is proposed. The porous structure and good oxidative stability of
the P(VdF-HFP)/PE membrane help to expand the oxidative potential
of GPE to 5.5 V compared with 5.1 V for the liquid electrolyte. The
developed GPE also has better thermal stability, contributing to improving
the safety performance of LIBs. Furthermore, the TMSPB additive constructs
a low-impedance and stable cathode electrolyte interphase (CEI) on
the NCM811 cathode surface, compensating for GPE’s drawbacks
of sluggish kinetics. Consequently, the NCM811 cathode matched with
3% TMSPB-containing GPE exhibits remarkable cyclicity and rate capability,
maintaining 94% of its initial capacity after 100 cycles at a high
voltage range of 3.0–4.35 V and delivering a capacity of 133.5
mAh g–1 under 15 C high current rate compared with
68% and 75.8 mAh g–1 for the one with an additive-free
liquid electrolyte. By virtue of the enhanced stability of the NCM811cathode,
the cyclability of graphite||NCM811 full cell also increases from
48 to 81% after 100 cycles. The incorporation of P(VdF-HFP)-based
GPE and TMSPB electrolyte additive points out a viable and convenient
pathway to unlock the properties of high energy density and satisfactory
safety for next-generation LIBs.
The nickel-rich cathode LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) possesses the advantages of high reversible specific capacity and low cost, thus regarded as a promising cathode material for lithiumion batteries (LIBs). However, the capacity of the NCM811 decays rapidly at high voltage due to the extremely unstable electrode/electrolyte interphase. The discharge capability at low temperature is also impaired because of the increasing interfacial impedance. Herein, a low-cost film-forming electrolyte additive with multi-function, phenylboronic acid (PBA), was employed to modify the interphasial properties of the NCM811 cathode. Theoretical calculation and experimental results showed that PBA constructed a highly conductive and steady cathode electrolyte interphase (CEI) film through preferential oxidation decomposition, which greatly improved the interfacial properties of the NCM811 cathode at room (25 °C) and low temperature (À 10 °C). Specifically, the capacity retention of NCM811/Li cell was increased from 68 % to 87 % after 200 cycles with PBA additive. Moreover, the NCM811/Li cell with PBA additive delivered higher discharge capacity under À 10 °C at 0.5 C (173.7 mAh g À 1 vs. 111.1 mAh g À 1 ). Based on the improvement of NCM811 interphasial properties by additive PBA, the capacity retention of NCM811/graphite full-cell was enhanced from 49 % to 65 % after 200 cycles.
Although immune checkpoint inhibitors have improved the overall survival rate of skin cutaneous melanoma (SKCM) patients, there is a wide variation and low response rate to these treatments in clinical immunotherapy for melanoma patients. These problems can be addressed through the induction of immunogenic cell death (ICD).We constructed an ICD-based prognostic model to predict the prognosis of SKCM patients and the efficacy of immunotherapy. Information on melanoma and normal samples obtained by TCGA and GTEx was stratified by ICD-related genes. The samples were divided into two subtypes according to high and low expression of ICD using an unsupervised clustering method (K-means). Patients with ICD-high subtype showed longer overall survival. We found that the ICD-related differential genes were associated with several cell death and immune-related pathways through GO, KEGG and GSEA. Immunoscore and tumor purity of ICD-associated genes was calculated using ESTIMATE, and ICD-high subtypes had higher immunoscore and lower tumor purity than ICD-low subtypes. Seven ICD-associated genes were obtained by one-way Cox regression and Lasso regression of ICD genes. Risk models were constructed to classify melanoma patients into high- risk and low-risk groups. The expression of ICD-related pivotal genes was lower in the high-risk group than in the low-risk group, and the survival time was significantly higher in the low-risk group than in the high-risk group. We then found that ICD risk characteristics had predictive value for the clinical efficacy of immunotherapy, with higher ICD risk scores in the immunotherapy non-responsive group. Combined with clinicopathological factors, a nomogram was established. the ROC and calibration curves assessed the ability of the nomogram to predict prognosis. We developed a new classification system for SKCM based on the characteristics of ICDs. This stratification has important clinical implications for estimating the prognosis and immunotherapy of SKCM patients.
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