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H3BO3
Chemical Science · 2024 ·Vol. 15 ·期 32 ·12964-12972 · IF 7.6

Improving the interfacial stability of ultrahigh-nickel cathodes with PEO-based electrolytes by targeted chemical reactions

Yuqing Dai,Zihan Hou,Gui Luo,Duo Deng,Wenjie Peng,Zhixing Wang,Huajun Guo,Xinhai Li,Guochun Yan,Hui Duan,Wenchao Zhang,Jiexi Wang

Benefiting from high energy density of ultrahigh-nickel cathode materials and good safety of PEO-based electrolytes, PEO-based ultrahigh-nickel solid-state lithium batteries (SLMBs) are considered to be new-generation energy storage devices. However, the incompatibility of ultrahigh-nickel cathode materials and PEO-based electrolytes is the main challenge due to serious interfacial side reactions. Therefore, the modification of the cathode/electrolyte interface is crucial. Herein, the residual lithium on the surface of LiNi0.9Co0.06Mn0.04O2 is utilized to construct an interfacial coating layer by reacting with H3BO3. The in situ formed xLi2O-B2O3 coating layer (LBO1-NCM) with high ionic conductivity can be regulated with different crystal structures during the sintering process. Besides, an all-solid-state three-electrode cell is fabricated, which verifies that the xLi2O-B2O3 coating can effectively stabilize the interface. Astonishingly, uneven Li anode deposition is observed in SLMBs, which is caused by the breakage of PEO molecular chains due to the strong oxidation of the cathode, while this crosstalk is also suppressed by the xLi2O-B2O3 coating layer. Consequently, Li|PEO|LBO1-NCM achieves a substantially improved electrochemical performance, exhibiting 90.5% of capacity retention after 100 cycles for the coin cell and 80.3% of capacity retention after 200 cycles for the pouch cell. Apparently, the targeted modification of interfaces should be paid as much attention as electrolyte optimization in SLMBs.

研究领域: 材料科学 · 电化学 · 能源存储
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JOURNAL OF CHEMICAL AND ENGINEERING DATA · 2023 · IF 2.6

Solid–Liquid Phase Equilibria of the Quaternary System NaCl–CaCl2–H3BO3–H2O at 323.15 K: Solubility Determination and Thermodynamic Model

Liwei Zhuang,Qinqin Hu,Shujing Wang,Ruyi Lin,Dan Li,Yong Ma,Lingzong Meng,Jiaoyu Peng

The solid–liquid phase equilibria of brine systems containing boric acid are the theoretical basis for the development of boric acid from brine resources. The phase equilibria of the systems NaCl–CaCl2–H3BO3–H2O and CaCl2–H3BO3–H2O at 323.15 K were investigated by the isothermal solution method. The phase diagram for the ternary system is composed of one co-saturation point, two univariant solubility curves, and two singe-salt crystallization fields of CaCl2·2H2O and H3BO3. The dry-salt phase diagram for the quaternary system consists of one invariant point, three univariant solubility curves, and three single-salt crystallization fields for NaCl, CaCl2·2H2O, and H3BO3. In the phase diagrams of the quaternary system at 298.15 and 323.15 K, the areas of sodium chloride and calcium chloride salt regions are enlarged, whereas the area of the H3BO3 region is diminished significantly with the increase of temperature. Using the Pitzer model, the lacking Pitzer parameters for H3BO3 were obtained by fitting the solubilities in the CaCl2–H3BO3–H2O system. The calculated solubilities with the Pitzer model were in accord with the experimental data.

研究领域: 化学热力学 · 无机化学
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JOURNAL OF CHEMICAL THERMODYNAMICS · 2022 · IF 3.269

Solubility isotherms determination of the H3BO3 + CsCl + H2O system at T = (273.15, 298.15, 323.15, 348.15 and 363.15) K and thermodynamic modeling

Ziyu Zhuang,Dongdong Li,Yanfei Fan,Dandan Gao,Dewen Zeng

The construction of a comprehensive thermodynamic model for boron-containing salt brine is important. However, the general lack of the solubility of H 3 BO 3  + salt + H 2 O ternary systems makes it difficult to determine model parameters involving boron species. Here, we systematically determined the solubility isotherms of the H 3 BO 3  +  CsCl  + H 2 O system at T = (273.15, 298.15, 323.15, 348.15 and 363.15) K. There are three solubility branches corresponding to H 3 BO 3(cr) , CsCl (cr) and a novel adduct in the system. The determined composition of the adduct is 2H 3 BO 3 ·3CsCl. Moreover, the single crystal structure of 2H 3 BO 3 ·3CsCl is solved, suggesting that H 3 BO 3 molecules keep it native plane-triangle structure, but the O atoms coordinate to the Cs ion. We modeled these ternary solubility isotherms using the Pitzer-Simonson-Clegg (PSC) model implemented in the ISLEC program. With the help of the model, a complete polythermal phase diagram of the system was constructed for the temperature range from 250 K to 373.15 K. The determined standard thermodynamic quantities of 2H 3 BO 3 ·3CsCl (cr) from the model are Δ f G m Θ  =  − 3182.26 kJ∙mol −1 , Δ f H m Θ  =  − 3496.19 kJ∙mol −1 , S m Θ  = 485.85 J∙K −1 ∙mol −1 , C p , m Θ  = 320 J∙K −1 ∙mol −1 , respectively.

研究领域: 化学 · 物理化学
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JOURNAL OF CHEMICAL AND ENGINEERING DATA · 2026 · IF 2.4

Solid–Liquid Phase Equilibrium in the Quaternary System H3BO3 + CsCl + RbCl + H2O at 298.15 K and Identification of a Solid Solution Phase 2H3BO3·3(Cs,Rb)Cl

Ziyu Zhuang,Manman Zhang,Dandan Gao,Wolfgang Voigt,Dongdong Li,Haitao Feng

Previously, the formation of a stable adduct 2H3BO3·3CsCl (BC) was observed in CsCl(aq) but not in RbCl(aq). The phase equilibria of the H3BO3 + RbCl + CsCl + H2O system were studied to assess the potential for selective separation of Cs from Rb. Solubility isotherms were determined experimentally. Appropriate liquid composition ranges were preselected using modeling with ISLEC’s equilibrium software. Schreinemakers’ wet solid method, XRD, Raman and IR spectra, Roozeboom’s plots, and SEM-EDS were applied to identify the four phase regions H3BO3, 2H3BO3·3(Cs,Rb)Cl (Bss), (Rb,Cs)Cl, and (Cs,Rb)Cl. Notably, in the presence of RbCl, the BC phase incorporates Rb+, forming a substitutional solid solution, Bss, which inhibits selective separation of CsCl. Roozeboom’s plot analysis revealed that RbCl exhibits higher solubility in the Bss phase compared to the (Cs,Rb)Cl solid solution. The separation factor βCs/Rb between the solid Bss phase and the corresponding solution was 2.0, significantly lower than that of (Cs,Rb)Cl (βCs/Rb = 9.5) in the ternary system without H3BO3. This indicates a stronger coordination between CsCl and H3BO3 relative to that of RbCl in the ternary system without H3BO3. The above understanding provides new strategies designing novel B–OH compounds to enhance Cs/Rb separation efficiency in aqueous systems.

CAS / MDL: 7647-17-8 7791-11-9
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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

A highly efficient and suitable spectral profile Cr3+-doped garnet near-infrared emitting phosphor for regulating photomorphogenesis of plants

Xikun Zou,Xiaojun Wang,Haoran Zhang,Yunyan Kang,Xian Yang,Xuejie Zhang,Maxim S. Molokeev,Bingfu Lei

Far-red/phytochrome (P FR ) plays a key role in photomorphogenesis of plants. However, how to obtain a near-infrared (NIR) emitting phosphor with high external quantum efficiency (EQE), suitable spectral profile, and low thermal quenching remains a huge challenge. Herein, a NIR phosphor, Gd 2.4 Lu 0.6 Ga 4 AlO 12 :Cr 3+ ,H 3 BO 3 (GLGA:Cr 3+ ) was developed via regulating the crystal field environment and adding fluxes, which exhibits a peak maximum at 728 nm with a relatively narrow full-width at half maximum (FWHM) of 107 nm, matching well with the absorption band of P FR . Upon 450 nm excitation, the internal quantum efficiency (IQE) and EQE of the optimal phosphor are 90.3% and 32.0%, respectively. At 423 K, the integrated emission intensity of the investigated phosphor is about 75% of that at room temperature. Benefiting from the excellent optical performance, a NIR phosphor-converted light-emitting diode (pc-LED) was fabricated, which shows a NIR output power of 505.99 mW and photoelectric conversion efficiency of 11.24% at 300 mA. Moreover, plant growth experiments demonstrate that the biomass of pea seedlings is increased by 67.72% under supplementary NIR light irradiation. The findings of this research will motivate further research on new Cr 3+ -doped NIR phosphors for regulating photomorphogenesis of plants.

研究领域: 材料科学 · 光学 · 植物生物学 · 农业科学
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Journal of Energy Storage · 2024 · IF 8.9

B/N co-doped porous carbon nanosheets with high B/N doping contents and excellent supercapacitor performance

Jing Huang,Jiang Peng,Junqing Zeng,Liping Zheng,Huajie Chen

Despite the important advances on B/N co-doped porous carbons (BNCs), integrating high B/N-doping content and hierarchical porosity into carbon nanosheets remains a challenging task for supercapacitor application. Herein, we report a novel BNC nanosheet with both expected properties through one-step H 3 BO 3 -mediated carbonization/activation of a newly-developed N/O-rich polymer (DPP). In such a mixture system, an in-suit crossing-linked DPP@H 3 BO 3 composite is formed due to the formation of multiple intermolecular hydrogen bonds between the H 3 BO 3 and the ester groups of DPP. The improved thermal stability for such a composite enables the fixation of more B-/N-bearing species in the carbon skeleton during carbonization. Particularly the nanosheet-like BNC-850 shows a rather high B/N content (6.63/7.27 at.%), a large S BET value (766.5 m 2  g −1 ), and a hierarchical porosity, all of which are in favor of electrochemical performance in both aqueous supercapacitors and zinc-ion capacitors (ZICs). In 6 M KOH electrolyte, the BNC-850 electrodes deliver an impressive capacitance of 341.5 F g −1 at 0.5 A g −1 , a high capacitance retention of 79.2 % at 20 A g −1 , and a good cycling stability (95 % capacitance retention over 10,000 cycles at 5 A g −1 ). The energy density of BNC-850-based ZICs is as high as 126.0 Wh kg −1 at 459.0 W kg −1 , exhibiting an outstanding superiority compared to the reported carbon-based ZICs. This work offers a facile strategy for accessing BNCs with high B/N-doping contents, and highlights the importance of such materials in high-energy-density ZICs.

研究领域: 材料科学 · 电化学 · 能源存储
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