The hydrolysis of MgH_(2) delivers high hydrogen capacity(15.2 wt%),which is very attractive for real-time hydrogen supply.However,the formation of a surface passivation Mg(OH)_(2) layer and the large excess of H_(2)O...The hydrolysis of MgH_(2) delivers high hydrogen capacity(15.2 wt%),which is very attractive for real-time hydrogen supply.However,the formation of a surface passivation Mg(OH)_(2) layer and the large excess of H_(2)O required to ensure complete hydrolysis are two key challenges for the MgH_(2) hydrolysis systems.Now,a low-cost method is reported to synthesize MgH_(2)@Mg(BH_(4))_(2) composite via ball-milling MgH_(2) with cheap and widely available B_(2)O_(3)(or B(OH)_(3)).By adding small amounts of B_(2)O_(3),the in-situ formed Mg(BH_(4))_(2) could significantly promote the hydrolysis of MgH_(2).In particular,the MgH_(2)–10 wt%B_(2)O_(3) composite releases 1330.7 mL·g^(−1) H_(2)(close to 80%theoretical hydrogen generation H_(2))in H_(2)O and 1520.4 mL·g^(−1) H_(2)(about 95%)in 0.5 M MgCl_(2) in 60 min at 26℃ with hydrolysis rate of 736.9 mL·g^(−1)·min^(−1) and 960.9 mL·g^(−1)·min^(−1) H_(2) during the first minute of the hydrolysis,respectively.In addition,the MgCl_(2) solution allows repeated use by filtering and exhibits high cycle stability(20 cycles),therefore leading to much reduced capacity loss caused by the excess H_(2)O.We show that by introducing B_(2)O_(3) and recycling the 0.5 M MgCl_(2) solution,the system hydrogen capacity can approach 5.9 wt%,providing a promising hydrogen generation scheme to supply hydrogen to the fuel cells.展开更多
Mn-rich LiFe_(1-x)Mn_(x)PO_(4)(x>0.5),which combines the high operation voltage of LiMnPO_(4)with excellent rate performa nce of LiFePO4,is hindered by its sluggish kinetic properties.Herein,thermodynamic equilibri...Mn-rich LiFe_(1-x)Mn_(x)PO_(4)(x>0.5),which combines the high operation voltage of LiMnPO_(4)with excellent rate performa nce of LiFePO4,is hindered by its sluggish kinetic properties.Herein,thermodynamic equilibrium analysis of Mn^(2+)-Fe^(2+)-Mg^(2+)-C_(2)O_(4)^(2-)-H_(2)O system is used to guide the design and preparation of insitu Mg-doped(Fe_(0.4)Mn_(0.6))_(1-x)Mg_(x)C_(2)O_(4)intermediate,which is then employed as an innovative precursor to synthesize high-performance Mg-doped LiFe_(0.4)Mn_(0.6)PO_(4).It indicates that the metal ions with a high precipitation efficiency and the stoichiometric precursors with uniform element distribution can be achieved under the optimized thermodynamic conditions.Meanwhile,accelerated Li+diffusivity and reduced charge transfer resistance originating from Mg doping are verified by various kinetic characterizations.Benefiting from the contributions of inherited homogeneous element distribution,small particle size,uniform carbon layer coating,enhanced Li+migration ability and structural stability induced by Mg doping,the Li(Fe_(0.4)Mn_(0.6))_(0.97)Mg_(0.03)PO_(4)/C exhibits splendid electrochemical performance.展开更多
Both whisker and nanometer MgSO4·5Mg(OH)2·3H2O(MOS) were prepared by hydrothermal method at 140℃for different times, using NaOH and MgSO4·7H2O as raw materials. The MgSO4·5Mg(OH)2·3H2O part i...Both whisker and nanometer MgSO4·5Mg(OH)2·3H2O(MOS) were prepared by hydrothermal method at 140℃for different times, using NaOH and MgSO4·7H2O as raw materials. The MgSO4·5Mg(OH)2·3H2O part icles were characterized by powder X ray diffraction(XRD),thermal analysis(TGA DSC), infrared spectroscopy(FT IR),transmission electron microscopy(SEM) and scanning electron microscopy(TEM). The size distribution in whisker like and nanocrystalline materials arein the range of 10～50μm and 10～20nm respectively. The whisker MOS is metastable phase in MgSO4 NaOH H2O system at 140℃,whereas nanometer MOS is stable phase.展开更多
基金supported by the Basic and Applied Basic Research Foundation of Guangdong Province(No.2022A1515011832 and 2021A1515110676)supported by GDAS’Project of Science and Technology Development(2022GDASZH-2022010104,2022GDASZH-2022030604-04).
文摘The hydrolysis of MgH_(2) delivers high hydrogen capacity(15.2 wt%),which is very attractive for real-time hydrogen supply.However,the formation of a surface passivation Mg(OH)_(2) layer and the large excess of H_(2)O required to ensure complete hydrolysis are two key challenges for the MgH_(2) hydrolysis systems.Now,a low-cost method is reported to synthesize MgH_(2)@Mg(BH_(4))_(2) composite via ball-milling MgH_(2) with cheap and widely available B_(2)O_(3)(or B(OH)_(3)).By adding small amounts of B_(2)O_(3),the in-situ formed Mg(BH_(4))_(2) could significantly promote the hydrolysis of MgH_(2).In particular,the MgH_(2)–10 wt%B_(2)O_(3) composite releases 1330.7 mL·g^(−1) H_(2)(close to 80%theoretical hydrogen generation H_(2))in H_(2)O and 1520.4 mL·g^(−1) H_(2)(about 95%)in 0.5 M MgCl_(2) in 60 min at 26℃ with hydrolysis rate of 736.9 mL·g^(−1)·min^(−1) and 960.9 mL·g^(−1)·min^(−1) H_(2) during the first minute of the hydrolysis,respectively.In addition,the MgCl_(2) solution allows repeated use by filtering and exhibits high cycle stability(20 cycles),therefore leading to much reduced capacity loss caused by the excess H_(2)O.We show that by introducing B_(2)O_(3) and recycling the 0.5 M MgCl_(2) solution,the system hydrogen capacity can approach 5.9 wt%,providing a promising hydrogen generation scheme to supply hydrogen to the fuel cells.
基金financially supported by the National Natural Science Foundation of China(No.51904250)the China Postdoctoral Science Foundation(No.2021M692254)+2 种基金the Sichuan Science and Technology Program(No.2022YFG0098)the Fundamental Research Funds for the Central Universities(Nos.2021CDSN-02,2022SCU12002,2022CDZG-17,2022CDSN-08,2022CDZG-9)the Hohhot Science and Technology Program(No.2023-Jie Bang Gua Shuai-Gao-3)。
文摘Mn-rich LiFe_(1-x)Mn_(x)PO_(4)(x>0.5),which combines the high operation voltage of LiMnPO_(4)with excellent rate performa nce of LiFePO4,is hindered by its sluggish kinetic properties.Herein,thermodynamic equilibrium analysis of Mn^(2+)-Fe^(2+)-Mg^(2+)-C_(2)O_(4)^(2-)-H_(2)O system is used to guide the design and preparation of insitu Mg-doped(Fe_(0.4)Mn_(0.6))_(1-x)Mg_(x)C_(2)O_(4)intermediate,which is then employed as an innovative precursor to synthesize high-performance Mg-doped LiFe_(0.4)Mn_(0.6)PO_(4).It indicates that the metal ions with a high precipitation efficiency and the stoichiometric precursors with uniform element distribution can be achieved under the optimized thermodynamic conditions.Meanwhile,accelerated Li+diffusivity and reduced charge transfer resistance originating from Mg doping are verified by various kinetic characterizations.Benefiting from the contributions of inherited homogeneous element distribution,small particle size,uniform carbon layer coating,enhanced Li+migration ability and structural stability induced by Mg doping,the Li(Fe_(0.4)Mn_(0.6))_(0.97)Mg_(0.03)PO_(4)/C exhibits splendid electrochemical performance.
文摘Both whisker and nanometer MgSO4·5Mg(OH)2·3H2O(MOS) were prepared by hydrothermal method at 140℃for different times, using NaOH and MgSO4·7H2O as raw materials. The MgSO4·5Mg(OH)2·3H2O part icles were characterized by powder X ray diffraction(XRD),thermal analysis(TGA DSC), infrared spectroscopy(FT IR),transmission electron microscopy(SEM) and scanning electron microscopy(TEM). The size distribution in whisker like and nanocrystalline materials arein the range of 10～50μm and 10～20nm respectively. The whisker MOS is metastable phase in MgSO4 NaOH H2O system at 140℃,whereas nanometer MOS is stable phase.
