To investigate the porosity, permeability and rock mechanics of deep shale under temperature-pressure coupling, we selected the core samples of deep shale from the Lower Silurian Longmaxi Formation in the Weirong and ...To investigate the porosity, permeability and rock mechanics of deep shale under temperature-pressure coupling, we selected the core samples of deep shale from the Lower Silurian Longmaxi Formation in the Weirong and Yongchuan areas of the Sichuan Basin for porosity and permeability experiments and a triaxial compression and sound wave integration experiment at the maximum temperature and pressure of 120 ℃ and 70 MPa. The results show that the microscopic porosity and permeability change and the macroscopic rock deformation are mutually constrained, both showing the trend of steep and then gentle variation. At the maximum temperature and pressure, the porosity reduces by 34%–71%, and the permeability decreases by 85%–97%. With the rising temperature and pressure, deep shale undergoes plastic deformation in which organic pores and clay mineral pores are compressed and microfractures are closed, and elastic deformation in which brittle mineral pores and rock skeleton particles are compacted. Compared with previous experiments under high confining pressure and normal temperature,the experiment under high temperature and high pressure coupling reveals the effect of high temperature on stress sensitivity of porosity and permeability. High temperature can increase the plasticity of the rock, intensify the compression of pores due to high confining pressure, and induce thermal stress between the rock skeleton particles, allowing the reopening of shale bedding or the creation of new fractures along weak planes such as bedding, which inhibits the decrease of permeability with the increase of temperature and confining pressure. Compared with the triaxial mechanical experiment at normal temperature, the triaxial compression experiment at high temperature and high pressure demonstrates that the compressive strength and peak strain of deep shale increase significantly due to the coupling of temperature and pressure. The compressive strength is up to 435 MPa and the peak strain exceeds 2%, indicating that high temperature is not conducive to fracture initiation and expansion by increasing rock plasticity. Lithofacies and mineral composition have great impacts on the porosity, permeability and rock mechanics of deep shale. Shales with different lithologies are different in the difficulty and extent of brittle failure. The stress-strain characteristics of rocks under actual geological conditions are key support to the optimization of reservoir stimulation program.展开更多
Na2Ti3O7 has attracted much attention in the field of anode materials for Na-ion batteries thanks to its non-toxicity and very low working potential of 0.3 V vs Na0/Na+.Building a clearer picture of its formation from...Na2Ti3O7 has attracted much attention in the field of anode materials for Na-ion batteries thanks to its non-toxicity and very low working potential of 0.3 V vs Na0/Na+.Building a clearer picture of its formation from cheap Na_(2)CO_(3) and TiO_(2) starting materials is therefore of obvious interest.Here,we report new insights from an in-situ high temperature X-ray diffraction study conducted from room temperature to 800°C,complemented by ex-situ characterizations.We were thereby able to position the previously reported Na_(4)Ti_(5)O_(12) and Na_(2)Ti_(6)O_(13) intermediate phases in a reaction scheme involving three successive steps and temperature ranges.Shifts and/or broadening of a subset of the Na_(2)Ti_(6)O_(13) reflections suggested a combination of intra-layer disorder with the well-established ordering of successive layers.This in-situ study was carried out on reproducible mixtures of Na_(2)CO_(3) and TiO_(2) in 1:3 molar ratio prepared by spraydrying of mixed aqueous suspensions.Single-phase Na_(2)Ti_(3)O_(7) was obtained after only 8 h at 800°C in air,instead of a minimum of 20 h for a conventional solid-state route using the same precursors.Microstructure analysis revealed~15 mm diameter granules made up from rectangular rods of a fewmm length presenting electrochemical properties in line with expectations.In the absence of grinding or formation of intimate composites with conductive carbon,the specific capacity of 137 m Ah/g at C/5 decreased at higher rates.展开更多
First-row(3 d)transition metal oxyhydroxides have attracted increasing attention due to their various advantages.Although investigating the oxidation mechanism and processing such materials into hierarchical architect...First-row(3 d)transition metal oxyhydroxides have attracted increasing attention due to their various advantages.Although investigating the oxidation mechanism and processing such materials into hierarchical architectures are greatly desired for their further development,it remains unclear how the oxidation state change occurs,and efforts to produce hierarchical oxyhydroxides in compliance with high ecological and economic standards have progressed slowly.Here,we describe a facile one-step coprecipitation route for the preparation of hierarchical CoOOH,NiOOH and MnOOH,which involves the diffusion of NH_(3)originating from ammonium hydroxide solution into an aqueous solution containing metal ion salts and K_(2)S_(2)O_(8).Comprehensive characterizations by scanning electron microscope,transmission electron microscopy,X-ray diffraction analysis,X-ray photoelectron spectroscopy,ultraviolet-visible spectroscopy and in situ p H measurement demonstrated that K_(2)S_(2)O_(8)induces the oxidation state change of metal ion species after the start of hydrolysis.Meanwhile,it was found that,benefiting from the OH–concentration gradient created by the NH_(3)diffusion method and the suitable growth environment provided by the presence of K_(2)S_(2)O_(8)(high nucleation rate and secondary nucleation),the formation of hierarchical oxyhydroxide structures can be realized in aqueous solution at ambient temperature without the use of heat energy and additional structure-directing agents.The hierarchical CoOOH structures are performed as the electrocatalysts for the oxygen evolution reaction in alkaline media,which exhibit good activity with an overpotential of 320 m V at 10 m A cm^(-2)and a low Tafel slope of 59.6 m V dec^(–1),outperforming many congeneric electrocatalysts.Overall,our study not only provides important insights to understand the formation mechanism of hierarchical oxyhydroxides,but also opens up new opportunities for the preparation of hierarchical oxyhydroxides via a facile,green and low-cost method.展开更多
基金Supported by the National Natural Science Foundation of China(41872124,42130803)Sinopec Key Science and Technology Project(P20046).
文摘To investigate the porosity, permeability and rock mechanics of deep shale under temperature-pressure coupling, we selected the core samples of deep shale from the Lower Silurian Longmaxi Formation in the Weirong and Yongchuan areas of the Sichuan Basin for porosity and permeability experiments and a triaxial compression and sound wave integration experiment at the maximum temperature and pressure of 120 ℃ and 70 MPa. The results show that the microscopic porosity and permeability change and the macroscopic rock deformation are mutually constrained, both showing the trend of steep and then gentle variation. At the maximum temperature and pressure, the porosity reduces by 34%–71%, and the permeability decreases by 85%–97%. With the rising temperature and pressure, deep shale undergoes plastic deformation in which organic pores and clay mineral pores are compressed and microfractures are closed, and elastic deformation in which brittle mineral pores and rock skeleton particles are compacted. Compared with previous experiments under high confining pressure and normal temperature,the experiment under high temperature and high pressure coupling reveals the effect of high temperature on stress sensitivity of porosity and permeability. High temperature can increase the plasticity of the rock, intensify the compression of pores due to high confining pressure, and induce thermal stress between the rock skeleton particles, allowing the reopening of shale bedding or the creation of new fractures along weak planes such as bedding, which inhibits the decrease of permeability with the increase of temperature and confining pressure. Compared with the triaxial mechanical experiment at normal temperature, the triaxial compression experiment at high temperature and high pressure demonstrates that the compressive strength and peak strain of deep shale increase significantly due to the coupling of temperature and pressure. The compressive strength is up to 435 MPa and the peak strain exceeds 2%, indicating that high temperature is not conducive to fracture initiation and expansion by increasing rock plasticity. Lithofacies and mineral composition have great impacts on the porosity, permeability and rock mechanics of deep shale. Shales with different lithologies are different in the difficulty and extent of brittle failure. The stress-strain characteristics of rocks under actual geological conditions are key support to the optimization of reservoir stimulation program.
基金supported by the Walloon Region under the “PE PlanMarshall2.vert”program(BATWAL–1318146)。
文摘Na2Ti3O7 has attracted much attention in the field of anode materials for Na-ion batteries thanks to its non-toxicity and very low working potential of 0.3 V vs Na0/Na+.Building a clearer picture of its formation from cheap Na_(2)CO_(3) and TiO_(2) starting materials is therefore of obvious interest.Here,we report new insights from an in-situ high temperature X-ray diffraction study conducted from room temperature to 800°C,complemented by ex-situ characterizations.We were thereby able to position the previously reported Na_(4)Ti_(5)O_(12) and Na_(2)Ti_(6)O_(13) intermediate phases in a reaction scheme involving three successive steps and temperature ranges.Shifts and/or broadening of a subset of the Na_(2)Ti_(6)O_(13) reflections suggested a combination of intra-layer disorder with the well-established ordering of successive layers.This in-situ study was carried out on reproducible mixtures of Na_(2)CO_(3) and TiO_(2) in 1:3 molar ratio prepared by spraydrying of mixed aqueous suspensions.Single-phase Na_(2)Ti_(3)O_(7) was obtained after only 8 h at 800°C in air,instead of a minimum of 20 h for a conventional solid-state route using the same precursors.Microstructure analysis revealed~15 mm diameter granules made up from rectangular rods of a fewmm length presenting electrochemical properties in line with expectations.In the absence of grinding or formation of intimate composites with conductive carbon,the specific capacity of 137 m Ah/g at C/5 decreased at higher rates.
基金funded by the Deutsche Forschungsgemeinschaft DFG and the Sino-German Center for Research Promotion(Grants GZ 1351 and CO 194/19-1)funded by a Chinese Scholarship Council stipend。
文摘First-row(3 d)transition metal oxyhydroxides have attracted increasing attention due to their various advantages.Although investigating the oxidation mechanism and processing such materials into hierarchical architectures are greatly desired for their further development,it remains unclear how the oxidation state change occurs,and efforts to produce hierarchical oxyhydroxides in compliance with high ecological and economic standards have progressed slowly.Here,we describe a facile one-step coprecipitation route for the preparation of hierarchical CoOOH,NiOOH and MnOOH,which involves the diffusion of NH_(3)originating from ammonium hydroxide solution into an aqueous solution containing metal ion salts and K_(2)S_(2)O_(8).Comprehensive characterizations by scanning electron microscope,transmission electron microscopy,X-ray diffraction analysis,X-ray photoelectron spectroscopy,ultraviolet-visible spectroscopy and in situ p H measurement demonstrated that K_(2)S_(2)O_(8)induces the oxidation state change of metal ion species after the start of hydrolysis.Meanwhile,it was found that,benefiting from the OH–concentration gradient created by the NH_(3)diffusion method and the suitable growth environment provided by the presence of K_(2)S_(2)O_(8)(high nucleation rate and secondary nucleation),the formation of hierarchical oxyhydroxide structures can be realized in aqueous solution at ambient temperature without the use of heat energy and additional structure-directing agents.The hierarchical CoOOH structures are performed as the electrocatalysts for the oxygen evolution reaction in alkaline media,which exhibit good activity with an overpotential of 320 m V at 10 m A cm^(-2)and a low Tafel slope of 59.6 m V dec^(–1),outperforming many congeneric electrocatalysts.Overall,our study not only provides important insights to understand the formation mechanism of hierarchical oxyhydroxides,but also opens up new opportunities for the preparation of hierarchical oxyhydroxides via a facile,green and low-cost method.
