CN105645421A - Mesoporous hollow lithium silicate microspheres as well as preparation and application of mesoporous hollow lithium silicate microspheres - Google Patents
Mesoporous hollow lithium silicate microspheres as well as preparation and application of mesoporous hollow lithium silicate microspheres Download PDFInfo
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- CN105645421A CN105645421A CN201511024570.5A CN201511024570A CN105645421A CN 105645421 A CN105645421 A CN 105645421A CN 201511024570 A CN201511024570 A CN 201511024570A CN 105645421 A CN105645421 A CN 105645421A
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- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/32—Alkali metal silicates
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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Abstract
The invention discloses mesoporous hollow lithium silicate microspheres as well as preparation and application of the mesoporous hollow lithium silicate microspheres. The mesoporous hollow lithium silicate microspheres are prepared by the method comprising the following steps: taking sodium-based montmorillonite powder as a raw material and taking 0.5mol/L to 10mol/L lithium hydroxide water solution as a solvent; sealing and reacting at 140 to 180 DEG C for 24 to 32 hours; after the reaction is finished, cooling to a room temperature and centrifuging; washing sediment with de-ionized liquid until a pH is 7 to 8; drying to obtain the mesoporous hollow lithium silicate microspheres. A lithium silicate phase prepared by the invention is mainly composed of Li2SiO3, has relatively high purity, takes the water as the solvent without adding a template agent, and is environmental friendly; technological parameters in a preparation process are controlled and the composition of a crystal phase and the distribution of grain diameters of crystals can be controlled in a certain range so as to control the form of the lithium silicate; prepared lithium silicate crystalline grains have uniform size and a relatively large specific surface area which reaches 40m<2>/g at maximum, and high dispersity; a preparation process is relatively simple and easy to operate; used raw materials are nontoxic and the reserved amount of the sodium-based montmorillonite is great, so that the mesoporous hollow lithium silicate microspheres are suitable for industrial production.
Description
(1) technical field
The present invention relates to the preparation method of a kind of tiny balloon, in particular to a kind of mesic hole hollow ball-shape lithium silicate method for preparing microsphere.
(2) background technology
The Economic development of the world today still relies on the Nonrenewable energy resources such as burning coal, oil and natural gas to obtain power and energy, the above-mentioned energy that burns certainly leads to a large amount of carbon dioxides, carbonic acid gas is the main greenhouse gas causing global warming, and being solidified and reclaiming is one of current research focus. Lithium silicate (Li2SiO3) all carbonic acid gas is had good absorptive character at ambient and elevated temperatures, can be used for the solidification of carbonic acid gas, recycle and reuse, and alleviation Global Greenhouse Effect is played an important role. In addition, because tritium has good solvability, lithium silicate also has good application prospect in nuclear industry. In addition, lithium silicate as inorganic paint, have good heat-resisting, do not fire, radiation hardness, wear-resisting, humidity, water tolerance, light permanency, anti-pollution and advantages of environment protection, can be applicable to offshore oil pipeline, boats and ships, bridge and New Building Materials etc. As surface treatment agent, can directly be used as metallic surface corrosion preventive pigment; Coated glass can form the coating that light transmission is excellent, reflectance is low; Coating galvanized iron micromicro prevents brine corrosion; Coating plastic film can improve obstruct humidity etc. Owing to lithium silicate is ion-conductive material, can be applicable to fast-ionic conductor ideal material.
The traditional method obtaining lithium silicate mainly contains solid phase method, the precipitator method, burning method and sol-gel method. Aforesaid method all faces certain problem, and such as the synthesis temperature height of solid phase method, the particle diameter of preparation is big, and it is serious to reunite. Therefore, domestic and international experts and scholars have carried out the research of other preparation method. Comparing novel method at present is hydrothermal method, and it is simple that it has technique, and synthesis temperature is lower, and particle diameter is relatively more even, and good dispersity, crystalline phase forms the advantages such as easy control.But it is raw material that forefathers adopt hydro-thermal to prepare lithium silicate mainly with other Chemicals, and the present invention then taking non-metallic minerals na-montmorillonite (Na-MMT) as raw material, has abundant raw material, the features such as cost is low, easy large-scale production.
Na-montmorillonite is a kind of natural layered silicate material pressing from both sides 1 layer of alumina octahedral by 2 layers of silicon-oxy tetrahedron, and its thickness in monolayer is about 1nm, and its good dispersion and ion-exchange performance receive much concern. The present invention is using na-montmorillonite as raw material, adopt hydrothermal method, spherical lithium silicate is prepared by adding different concns lithium hydroxide (LiOH), spheroid is hollow structure, and diameter is about 600nm, and ball wall is made up of tiny particle and hole, the diameter of small-particle is between 10-40nm, the aperture of hole is many at below 100nm, belongs to Jie hole category, and spherical particles has bigger specific surface area and good adsorption properties.
(3) summary of the invention
It is an object of the present invention to provide a kind of specific surface big, high dispersing, the synthetic method of the uniform lithium silicate of crystal grain.
The technical solution used in the present invention is:
The present invention provides the preparation method of a kind of meso-porous hollow lithium silicate microballoon, described method is: taking na-montmorillonite powder as raw material, taking 0.5��10mol/L lithium hydroxide aqueous solution as solvent, confined reaction 24��32h under 140��180 DEG C of conditions, reaction is cooled to room temperature after terminating, centrifugal, get precipitation and spend ion-cleaning to pH 7��8, dry, obtain meso-porous hollow lithium silicate microballoon.
Further, it is preferable that described lithium hydroxide aqueous solution concentration is 1.0��2.0mol/L, it is more preferable to 1.5��2.0mol/L.
Further, it is preferable that described lithium hydroxide aqueous solution volumetric usage counts 20��100ml/g with na-montmorillonite powder quality, it is preferable that 40��60ml/g.
Further, it is preferable that described reaction conditions is 140 DEG C of reaction 24h.
Further, it is preferable that described drying temperature is 85 DEG C.
Further, the preparation method of preferred described meso-porous hollow lithium silicate microballoon is: mix even by na-montmorillonite powder 1.5mol/L lithium hydroxide aqueous solution, confined reaction 24h under 140 DEG C of conditions, after reaction terminates, it is cooled to room temperature, centrifugal, get precipitation and spend ion-cleaning to pH 7��8,85 DEG C of dryings, obtain meso-porous hollow lithium silicate microballoon; Described lithium hydroxide aqueous solution volumetric usage counts 46.7ml/g with na-montmorillonite powder quality consumption.
The present invention also provides a kind of described meso-porous hollow lithium silicate microballoon as the application of gas entrapment medium, and meso-porous hollow lithium silicate microballoon of the present invention can as CO well known in the art2Deng the material of the process such as the absorption of gas, collection.
Na-montmorillonite of the present invention (Na-MMT) is that powder shape montmorillonite is formed, and buys in Zhejiang three ancient cooking vessel Science and Technology Ltd..
The technique effect of meso-porous hollow lithium silicate method for preparing microsphere of the present invention is mainly reflected in:
(1) the lithium silicate thing prepared forms mutually and is mainly Li2SiO3, purity is higher, taking water be solvent without the need to adding template, environmental protection.
(2) by the processing parameter in control preparation process, it is possible in the composition of certain scope inner control crystalline phase, the distribution of crystal particle diameter, thus control the shape looks of lithium silicate.
(3) the lithium silicate homogeneous grain size prepared, has bigger specific surface area and reaches as high as 40m2/ g, has the dispersion of height.
(4) preparation technology is comparatively simple, is easy to operation, and raw materials used nontoxic, na-montmorillonite reserves are huge, are suitable for suitability for industrialized production.
(4) accompanying drawing explanation
Fig. 1 is that embodiment 1 obtains Jie hole lithium silicate microballoon XRD figure.
Fig. 2 is that embodiment 2 obtains Jie hole lithium silicate microballoon XRD figure.
Fig. 3 is that embodiment 3 obtains Jie hole lithium silicate microballoon XRD figure.
In Fig. 4, embodiment 4 obtains Jie hole lithium silicate microballoon XRD figure.
Fig. 5 is that embodiment 5 obtains Jie hole lithium silicate microballoon XRD figure.
Fig. 6 is that embodiment 6 obtains Jie hole lithium silicate microballoon XRD figure.
Fig. 7 is that embodiment 7 obtains Jie hole lithium silicate microballoon XRD figure.
Fig. 8 is that embodiment 8 obtains Jie hole lithium silicate microballoon XRD figure.
Fig. 9 is that embodiment 9 obtains Jie hole lithium silicate microballoon XRD figure.
Figure 10 is that embodiment 10 obtains Jie hole lithium silicate microballoon XRD figure.
Figure 11 is that embodiment 11 obtains Jie hole lithium silicate microballoon XRD figure.
Figure 12 is that embodiment 12 obtains Jie hole lithium silicate microballoon XRD figure.
Figure 13 is that embodiment 13 obtains Jie hole lithium silicate microballoon XRD figure.
Figure 14 is that embodiment 14 obtains Jie hole lithium silicate microballoon XRD figure.
Figure 15 is that embodiment 15 obtains Jie hole lithium silicate microballoon XRD figure.
Figure 16 is that embodiment 16 obtains Jie hole lithium silicate microballoon XRD figure.
Figure 17 is that embodiment 17 obtains Jie hole lithium silicate microballoon XRD figure.
Figure 18 is that embodiment 18 obtains Jie hole lithium silicate microballoon XRD figure.
Figure 19 is that embodiment 1 obtains Jie hole lithium silicate microballoon SEM and schemes, and A is sample dispersion photo, and B is sample collection photo.
Figure 20 is that embodiment 2 obtains Jie hole lithium silicate microballoon SEM and schemes, and A is sample dispersion photo, and B is sample collection photo.
Figure 21 is that embodiment 3 obtains Jie hole lithium silicate microballoon SEM and schemes, and A is sample dispersion photo, and B is sample collection photo.
Figure 22 is that embodiment 4 obtains Jie hole lithium silicate microballoon SEM and schemes, and A is sample dispersion photo, and B is sample collection photo.
Figure 23 is that embodiment 5 obtains Jie hole lithium silicate microballoon SEM and schemes, and A is sample dispersion photo, and B is sample collection photo.
Figure 24 is that embodiment 6 obtains Jie hole lithium silicate microballoon SEM and schemes, and A is sample dispersion photo, and B is sample collection photo.
Figure 25 is that embodiment 4 obtains Jie hole lithium silicate microballoon BET collection of illustrative plates, and A is sample adsorption thermoisopleth, and B is sample pore size distribution.
Figure 26 is that embodiment 5 obtains Jie hole lithium silicate microballoon BET collection of illustrative plates, and A is sample adsorption thermoisopleth, and B is sample pore size distribution.
Figure 27 is that embodiment 6 obtains Jie hole lithium silicate microballoon BET collection of illustrative plates, and A is sample adsorption thermoisopleth, and B is sample pore size distribution.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment of the present invention na-montmorillonite used is bought in Zhejiang three ancient cooking vessel Science and Technology Ltd..
Embodiment 1
(1) accurately taking 1.50g na-montmorillonite (Na-MMT) powder (after dry), configuration 70ml concentration is lithium hydroxide (LiOH) aqueous solution of 0.75mol/L;
(2) above-mentioned powder is joined in above-mentioned solution, fully stir and montmorillonite powder is dispersed in solution, then transfer in the reactor of sealing, then reactor is positioned in baking oven, is warmed up to 140 DEG C, reaction 24h;
(3) question response terminates, reactor cool to room temperature, for some time is left standstill after rinsing with 2000ml deionized water after being taken out by throw out, by lower sediment thing deionized water wash after its layering and precipitating, centrifugation, whizzer revolution is 8500r/min, and centrifugation time is 10 minutes, repeats aforesaid operations 5��6 times to pH 7��8. After washing, separation, solid sample obtains meso-porous hollow lithium silicate microballoon after drying at 85 DEG C. Adopting X ' the PertPRO type X-ray diffractometer of PANalytical company of Holland to be characterized by the crystalline phase composition of each stage sample, as shown in Figure 1, as we know from the figure, primary product is Li to its result2SiO3, containing a small amount of SiO2;The surface topography analysis of sample uses HitachiS-4700 II type field emission scanning electron microscope to observe, and its result is as shown in figure 19. As we know from the figure, na-montmorillonite unreacted is complete, also has lumphy structure.
Embodiment 2
(1) accurately taking na-montmorillonite (Na-MMT) powder (after dry) of 1.50g, configuration 70ml concentration is lithium hydroxide (LiOH) aqueous solution of 1.00mol/L;
(2) above-mentioned powder is mixed with solution, fully stir and montmorillonite is disperseed in the solution, then transfer in the reactor of sealing, then reactor is positioned in baking oven, is warmed up to 140 DEG C, reaction 24h;
(3) question response terminates, and reactor is as cold as room temperature, is taken out by throw out and uses 2000ml deionized water wash, centrifugation, and whizzer revolution is 8500r/min, and centrifugation time is 10 minutes, repeats aforesaid operations 5��6 times to pH 7��8. After washing, separation, solid sample obtains mesic hole hollow ball-shape lithium silicate microballoon after drying at 85 DEG C. Adopting X ' the PertPRO type X-ray diffractometer of PANalytical company of Holland to be characterized by the crystalline phase composition of each stage sample, result as shown in Figure 2, generates Li as we know from the figure2SiO3Product; The surface topography analysis of sample uses HitachiS-4700 II type field emission scanning electron microscope to observe, and as shown in figure 20, as we know from the figure, montmorillonite laminate structure reduces result gradually.
Embodiment 3
(1) accurately taking na-montmorillonite (Na-MMT) powder (after dry) of 1.50g, configuration 70ml concentration is lithium hydroxide (LiOH) aqueous solution of 1.25mol/L;
(2) above-mentioned powder is mixed with solution, fully stir and montmorillonite is disperseed in the solution, then transfer in the reactor of sealing, then reactor is positioned in baking oven, is warmed up to 140 DEG C, reaction 24h;
(3) question response terminates, and reactor is as cold as room temperature, is taken out by throw out and uses 2000ml deionized water wash, centrifugation, and whizzer revolution is 8500r/min, and centrifugation time is 10 minutes, repeats aforesaid operations 5��6 times to pH 7��8. After washing, separation, solid sample obtains mesic hole hollow ball-shape lithium silicate microballoon after drying at 85 DEG C. Adopt X ' the PertPRO type X-ray diffractometer of PANalytical company of Holland to be characterized by the crystalline phase of each stage sample composition, result as shown in Figure 3, lithium silicate product as we know from the figure; The surface topography analysis of sample uses HitachiS-4700 II type field emission scanning electron microscope to observe, and result as shown in figure 21, generates ellipsoidal configuration as we know from the figure.
Embodiment 4
(1) accurately taking na-montmorillonite (Na-MMT) powder (after dry) of 1.50g, configuration 70ml concentration is lithium hydroxide (LiOH) aqueous solution of 1.50mol/L;
(2) above-mentioned powder is mixed with solution, fully stir and montmorillonite is disperseed in the solution, then transfer in the reactor of sealing, then reactor is positioned in baking oven, is warmed up to 140 DEG C, reaction 24h;
(3) question response terminates, and reactor is as cold as room temperature, is taken out by throw out and uses 2000ml deionized water wash, centrifugation, and whizzer revolution is 8500r/min, and centrifugation time is 10 minutes, repeats aforesaid operations 5��6 times to pH 7��8. After washing, separation, solid sample obtains mesic hole hollow ball-shape lithium silicate microballoon after drying at 85 DEG C. Adopting X ' the PertPRO type X-ray diffractometer of PANalytical company of Holland to be characterized by the crystalline phase composition of each stage sample, result is as shown in Figure 4;Fig. 4 can find out that the structure of montmorillonite is destroyed, and the characteristic peak that montmorillonite is 5��6 �� completely dissolve, occurs obvious Li then2SiO3(PDF:00-015-0519) characteristic peak. This illustrates that the dominant of Fig. 4 is Li mutually2SiO3, also want a small amount of Li4SiO4(PDF:00-037-1472) phase.
The surface topography analysis of sample uses HitachiS-4700 II type field emission scanning electron microscope to observe, and result is as shown in figure 22. As can be seen from Figure 10, the shape looks of sample particle are spherical, and size is even, and diameter is between 300-600nm, and sphere structure is more intact, and can be observed spheroid from ball wall is construct by many tiny particles, the pores'growth between fine particle; In Figure 22, B is damaged microballoon. The spheroidal particle of this interpret sample is hollow structure. The BET performance test of sample uses Merck & Co., Inc of U.S. ASAP2010, and result as shown in figure 25, shows that product aperture be 31nm is mesoporous material.
Embodiment 5
(1) accurately taking na-montmorillonite (Na-MMT) powder (after dry) of 1.50g, configuration 70ml concentration is lithium hydroxide (LiOH) aqueous solution of 1.75mol/L;
(2) by above-mentioned sample mix, fully stirring and montmorillonite is disperseed in the solution, sealed reactor is placed in the baking oven of 140 DEG C, reaction 24h;
(3) question response terminates, and reactor is as cold as room temperature, is taken out by throw out and uses 2000ml deionized water wash, centrifugation, and whizzer revolution is 8500r/min, and centrifugation time is 10 minutes, repeats aforesaid operations 5��6 times to pH 7��8. After washing, separation, solid sample obtains mesic hole hollow ball-shape lithium silicate microballoon after drying at 85 DEG C. Adopting X ' the PertPRO type X-ray diffractometer of PANalytical company of Holland to be characterized by the crystalline phase composition of each stage sample, as shown in Figure 5, dominant is Li to result mutually2SiO3, also want a small amount of Li4SiO4; The surface topography analysis of sample uses HitachiS-4700 II type field emission scanning electron microscope to observe, and result as shown in figure 23 as we know from the figure, generates lithium silicate microballoon but has part ball wall damaged. The BET performance test of sample uses Merck & Co., Inc of U.S. ASAP2010, and result as shown in figure 26, shows that product aperture be 29.4nm is mesoporous material.
Embodiment 6
(1) accurately taking na-montmorillonite (Na-MMT) powder (after dry) of 1.50g, configuration 70ml concentration is lithium hydroxide (LiOH) aqueous solution of 2.00mol/L;
(2) by above-mentioned sample mix, fully stirring and montmorillonite is disperseed in the solution, sealed reactor is placed in the baking oven of 140 DEG C, reaction 24h;
(3) question response terminates, and reactor is as cold as room temperature, is taken out by throw out and uses 2000ml deionized water wash, centrifugation, and whizzer revolution is 8500r/min, and centrifugation time is 10 minutes, repeats aforesaid operations 5��6 times to pH 7��8. After washing, separation, solid sample obtains mesic hole hollow ball-shape lithium silicate microballoon after drying at 85 DEG C. Adopting X ' the PertPRO type X-ray diffractometer of PANalytical company of Holland to be characterized by the crystalline phase composition of each stage sample, as shown in Figure 6, dominant is Li to result mutually2SiO3, also want a small amount of Li4SiO4; The surface topography analysis of sample uses HitachiS-4700 II type field emission scanning electron microscope to observe, and result is as shown in figure 24. Conclusion is microballoon ball wall badly broken as we know from the figure. The BET performance test of sample uses Merck & Co., Inc of U.S. ASAP2010, and result as shown in figure 27, shows that product aperture be 29.4nm is mesoporous material.
Embodiment 7
(1) accurately taking na-montmorillonite (Na-MMT) powder (after dry) of 1.50g, configuration 70ml concentration is lithium hydroxide (LiOH) aqueous solution of 1.50mol/L;
(2) by above-mentioned sample mix, fully stirring and montmorillonite is disperseed in the solution, sealed reactor is placed in the baking oven of 120 DEG C, reaction 24h;
(3) question response terminates, and reactor is as cold as room temperature, is taken out by throw out and uses 2000ml deionized water wash, centrifugation, and whizzer revolution is 8500r/min, and centrifugation time is 10 minutes, repeats aforesaid operations 5��6 times to pH 7��8. After washing, separation, solid sample obtains meso-porous hollow lithium silicate microballoon after drying at 85 DEG C. X ' the PertPRO type X-ray diffractometer of PANalytical company of Holland is adopted to be characterized by the crystalline phase composition of each stage sample. Result as shown in Figure 7, as we know from the figure, not yet generates good crystalline phase, only a small amount of Li2SiO3Generate.
Embodiment 8
(1) accurately taking na-montmorillonite (Na-MMT) powder (after dry) of 1.50g, configuration 70ml concentration is lithium hydroxide (LiOH) aqueous solution of 1.75mol/L;
(2) by above-mentioned sample mix, fully stirring and montmorillonite is disperseed in the solution, sealed reactor is placed in the baking oven of 120 DEG C, reaction 24h;
(3) question response terminates, and reactor is as cold as room temperature, is taken out by throw out and uses 2000ml deionized water wash, centrifugation, and whizzer revolution is 8500r/min, and centrifugation time is 10 minutes, repeats aforesaid operations 5��6 times to pH 7��8. After washing, separation, solid sample obtains mesic hole hollow ball-shape lithium silicate microballoon after drying at 85 DEG C. Adopt X ' the PertPRO type X-ray diffractometer of PANalytical company of Holland that the crystalline phase composition of each stage sample is carried out characterization result as shown in Figure 8, as we know from the figure owing to temperature is too low, do not obtain the lithium silicate product that crystallinity is good.
Embodiment 9
(1) accurately taking na-montmorillonite (Na-MMT) powder (after dry) of 1.50g, configuration 70ml concentration is lithium hydroxide (LiOH) aqueous solution of 2.00mol/L;
(2) by above-mentioned sample mix, fully stirring and montmorillonite is disperseed in the solution, sealed reactor is placed in the baking oven of 120 DEG C, reaction 24h;
(3) question response terminates, and reactor is as cold as room temperature, is taken out by throw out and uses 2000ml deionized water wash, centrifugation, and whizzer revolution is 8500r/min, and centrifugation time is 10 minutes, repeats aforesaid operations 5��6 times to pH 7��8. After washing, separation, solid sample obtains mesic hole hollow ball-shape lithium silicate microballoon after drying at 85 DEG C. Adopting X ' the PertPRO type X-ray diffractometer of PANalytical company of Holland to be characterized by the crystalline phase composition of each stage sample, result as shown in Figure 9, as we know from the figure, owing to temperature is too low, does not obtain the lithium silicate product that crystallinity is good.
Embodiment 10
(1) accurately taking na-montmorillonite (Na-MMT) powder (after dry) of 1.50g, configuration 70ml concentration is lithium hydroxide (LiOH) aqueous solution of 1.50mol/L;
(2) by above-mentioned sample mix, fully stirring and montmorillonite is disperseed in the solution, sealed reactor is placed in the baking oven of 160 DEG C, reaction 24h;
(3) question response terminates, and reactor is as cold as room temperature, is taken out by throw out and uses 2000ml deionized water wash, centrifugation, and whizzer revolution is 8500r/min, and centrifugation time is 10 minutes, repeats aforesaid operations 5��6 times to pH 7��8.After washing, separation, solid sample obtains mesic hole hollow ball-shape lithium silicate microballoon after drying at 85 DEG C. Adopting X ' the PertPRO type X-ray diffractometer of PANalytical company of Holland to be characterized by the crystalline phase composition of each stage sample, result as shown in Figure 10, obtains the good lithium silicate product of crystallinity as we know from the figure, but assorted peak is more.
Embodiment 11
(1) accurately taking na-montmorillonite (Na-MMT) powder (after dry) of 1.50g, configuration 70ml concentration is lithium hydroxide (LiOH) aqueous solution of 1.75mol/L;
(2) by above-mentioned sample mix, fully stirring and montmorillonite is disperseed in the solution, sealed reactor is placed in the baking oven of 160 DEG C, reaction 24h;
(3) question response terminates, and reactor is as cold as room temperature, is taken out by throw out and uses 2000ml deionized water wash, centrifugation, and whizzer revolution is 8500r/min, and centrifugation time is 10 minutes, repeats aforesaid operations 5��6 times to pH 7��8. After washing, separation, solid sample obtains mesic hole hollow ball-shape lithium silicate microballoon after drying at 85 DEG C. Adopt X ' the PertPRO type X-ray diffractometer of PANalytical company of Holland to be characterized by the crystalline phase composition of each stage sample, as shown in figure 11, can generate lithium silicate product under this condition from figure, but assorted peak is more.
Embodiment 12
(1) accurately taking na-montmorillonite (Na-MMT) powder (after dry) of 1.50g, configuration 70ml concentration is lithium hydroxide (LiOH) aqueous solution of 2.00mol/L;
(2) by above-mentioned sample mix, fully stirring and montmorillonite is disperseed in the solution, sealed reactor is placed in the baking oven of 160 DEG C, reaction 24h;
(3) question response terminates, and reactor is as cold as room temperature, is taken out by throw out and uses 2000ml deionized water wash, centrifugation, and whizzer revolution is 8500r/min, and centrifugation time is 10 minutes, repeats aforesaid operations 5��6 times to pH 7��8. After washing, separation, solid sample obtains mesic hole hollow ball-shape lithium silicate microballoon after drying at 85 DEG C. Adopting X ' the PertPRO type X-ray diffractometer of PANalytical company of Holland to be characterized by the crystalline phase composition of each stage sample, as shown in figure 12, product dominant is Li to result mutually as we know from the figure2SiO3, also want a small amount of Li4SiO4Phase, but peak intensity is lower, crystallinity is poor, assorted mutually more.
Embodiment 13
(1) accurately taking na-montmorillonite (Na-MMT) powder (after dry) of 1.50g, configuration 70ml concentration is lithium hydroxide (LiOH) aqueous solution of 1.50mol/L;
(2) by above-mentioned sample mix, fully stirring and montmorillonite is disperseed in the solution, sealed reactor is placed in the baking oven of 180 DEG C, reaction 24h;
(3) question response terminates, and reactor is as cold as room temperature, is taken out by throw out and uses 2000ml deionized water wash, centrifugation, and whizzer revolution is 8500r/min, and centrifugation time is 10 minutes, repeats aforesaid operations 5��6 times to pH 7��8. After washing, separation, solid sample obtains mesic hole hollow ball-shape lithium silicate microballoon after drying at 85 DEG C. Adopting X ' the PertPRO type X-ray diffractometer of PANalytical company of Holland that the crystalline phase composition of each stage sample is carried out characterization result as shown in figure 13, product dominant is Li mutually as we know from the figure2SiO3, also want a small amount of Li4SiO4Phase, but peak intensity is lower, crystallinity is poor, assorted mutually more.
Embodiment 14
(1) accurately taking na-montmorillonite (Na-MMT) powder (after dry) of 1.50g, configuration 70ml concentration is lithium hydroxide (LiOH) aqueous solution of 1.75mol/L;
(2) by above-mentioned sample mix, fully stirring and montmorillonite is disperseed in the solution, sealed reactor is placed in the baking oven of 180 DEG C, reaction 24h;
(3) question response terminates, and reactor is as cold as room temperature, is taken out by throw out and uses 2000ml deionized water wash, centrifugation, and whizzer revolution is 8500r/min, and centrifugation time is 10 minutes, repeats aforesaid operations 5��6 times to pH 7��8. After washing, separation, solid sample obtains mesic hole hollow ball-shape lithium silicate microballoon after drying at 85 DEG C. Adopting X ' the PertPRO type X-ray diffractometer of PANalytical company of Holland that the crystalline phase composition of each stage sample is carried out characterization result as shown in figure 14, product dominant is Li mutually as we know from the figure2SiO3, also want a small amount of Li4SiO4Phase, but peak intensity is lower, crystallinity is poor, assorted mutually more.
Embodiment 15
(1) accurately taking na-montmorillonite (Na-MMT) powder (after dry) of 1.50g, configuration 70ml concentration is lithium hydroxide (LiOH) aqueous solution of 2.00mol/L;
(2) by above-mentioned sample mix, fully stirring and montmorillonite is disperseed in the solution, sealed reactor is placed in the baking oven of 180 DEG C, reaction 24h;
(3) question response terminates, and reactor is as cold as room temperature, is taken out by throw out and uses 2000ml deionized water wash, centrifugation, and whizzer revolution is 8500r/min, and centrifugation time is 10 minutes, repeats aforesaid operations 5��6 times to pH 7��8. After washing, separation, solid sample obtains mesic hole hollow ball-shape lithium silicate microballoon after drying at 85 DEG C. Adopting X ' the PertPRO type X-ray diffractometer of PANalytical company of Holland that the crystalline phase composition of each stage sample is carried out characterization result as shown in figure 15, product dominant is Li mutually as we know from the figure2SiO3, also want a small amount of Li4SiO4Phase, but peak intensity is poor compared with low-crystalline, assorted mutually more.
Embodiment 16
(1) accurately taking na-montmorillonite (Na-MMT) powder (after dry) of 1.50g, configuration 70ml concentration is lithium hydroxide (LiOH) aqueous solution of 1.50mol/L;
(2) by above-mentioned sample mix, fully stirring and montmorillonite is disperseed in the solution, sealed reactor is placed in the baking oven of 140 DEG C, reaction 20h;
(3) question response terminates, and reactor is as cold as room temperature, is taken out by throw out and uses 2000ml deionized water wash, centrifugation, and whizzer revolution is 8500r/min, and centrifugation time is 10 minutes, repeats aforesaid operations 5��6 times to pH 7��8. After washing, separation, solid sample obtains mesic hole hollow ball-shape lithium silicate microballoon after drying at 85 DEG C. Adopting X ' the PertPRO type X-ray diffractometer of PANalytical company of Holland that the crystalline phase composition of each stage sample is carried out characterization result as shown in figure 16, product dominant is Li mutually as we know from the figure2SiO3, also want a small amount of Li4SiO4Phase, owing to the reaction times is shorter, causes non-formation phase, crystallinity poor, assorted mutually more.
Embodiment 17
(1) accurately taking na-montmorillonite (Na-MMT) powder (after dry) of 1.50g, configuration 70ml concentration is lithium hydroxide (LiOH) aqueous solution of 1.50mol/L;
(2) by above-mentioned sample mix, fully stirring and montmorillonite is disperseed in the solution, sealed reactor is placed in the baking oven of 140 DEG C, reaction 28h;
(3) question response terminates, and reactor is as cold as room temperature, is taken out by throw out and uses 2000ml deionized water wash, centrifugation, and whizzer revolution is 8500r/min, and centrifugation time is 10 minutes, repeats aforesaid operations 5��6 times to pH 7��8.After washing, separation, solid sample obtains mesic hole hollow ball-shape lithium silicate microballoon after drying at 85 DEG C. Adopting X ' the PertPRO type X-ray diffractometer of PANalytical company of Holland that the crystalline phase composition of each stage sample is carried out characterization result as shown in figure 17, product dominant is Li mutually as we know from the figure2SiO3, also want a small amount of Li4SiO4Phase.
Embodiment 18
(1) accurately taking na-montmorillonite (Na-MMT) powder (after dry) of 1.50g, configuration 70ml concentration is lithium hydroxide (LiOH) aqueous solution of 1.50mol/L;
(2) by above-mentioned sample mix, fully stirring and montmorillonite is disperseed in the solution, sealed reactor is placed in the baking oven of 140 DEG C, reaction 32h;
(3) question response terminates, and reactor is as cold as room temperature, is taken out by throw out and uses 2000ml deionized water wash, centrifugation, and whizzer revolution is 8500r/min, and centrifugation time is 10 minutes, repeats aforesaid operations 5��6 times to pH 7��8. After washing, separation, solid sample obtains mesic hole hollow ball-shape lithium silicate microballoon after drying at 85 DEG C. Adopting X ' the PertPRO type X-ray diffractometer of PANalytical company of Holland that the crystalline phase composition of each stage sample is carried out characterization result as shown in figure 17, product dominant is Li mutually as we know from the figure2SiO3, also want the Li of more amount4SiO4Phase, owing to the reaction times is longer, causes Li2SiO3To Li4SiO4Transform.
Claims (7)
1. a meso-porous hollow lithium silicate microballoon, it is characterized in that described meso-porous hollow lithium silicate microballoon is prepared as follows: taking na-montmorillonite powder as raw material, taking 0.5��10mol/L lithium hydroxide aqueous solution as solvent, confined reaction 24��32h under 140��180 DEG C of conditions, reaction is cooled to room temperature after terminating, centrifugal, get precipitation and spend ion-cleaning to pH 7��8, dry, obtain meso-porous hollow lithium silicate microballoon.
2. meso-porous hollow lithium silicate microballoon as claimed in claim 1, it is characterised in that described lithium hydroxide aqueous solution concentration is 0.75��2.0mol/L.
3. meso-porous hollow lithium silicate microballoon as claimed in claim 1, it is characterised in that described lithium hydroxide aqueous solution volumetric usage counts 20��100ml/g with na-montmorillonite powder quality.
4. meso-porous hollow lithium silicate microballoon as claimed in claim 1, it is characterised in that described reaction conditions is 140 DEG C of reaction 24h.
5. meso-porous hollow lithium silicate microballoon as claimed in claim 1, it is characterised in that described drying temperature is 85 DEG C.
6. meso-porous hollow lithium silicate microballoon as claimed in claim 1, it is characterized in that described method is: mix even by na-montmorillonite powder 1.5mol/L lithium hydroxide aqueous solution, confined reaction 24h under 140 DEG C of conditions, after reaction terminates, it is cooled to room temperature, centrifugal, get precipitation and spend ion-cleaning to pH 7��8,85 DEG C of dryings, obtain meso-porous hollow lithium silicate microballoon; Described lithium hydroxide aqueous solution volumetric usage counts 46.7ml/g with na-montmorillonite powder quality consumption.
7. meso-porous hollow lithium silicate microballoon described in a claim 1 is as the application of gas entrapment medium.
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| CN110127712A (en) * | 2019-05-15 | 2019-08-16 | 浙江工业大学 | The method that the preparation of ordinary-pressure hydrolysis method has the mesoporous lithium metasilicate hollow sphere of micro-nano structure |
| CN111916817A (en) * | 2020-07-01 | 2020-11-10 | 浙江工业大学 | Lithium ion battery with high capacity and cycle performance |
| CN113244881A (en) * | 2021-06-25 | 2021-08-13 | 桂林理工大学 | Method for preparing lithium orthosilicate material by taking KIT-6 as silicon source, modification and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110127712A (en) * | 2019-05-15 | 2019-08-16 | 浙江工业大学 | The method that the preparation of ordinary-pressure hydrolysis method has the mesoporous lithium metasilicate hollow sphere of micro-nano structure |
| CN111916817A (en) * | 2020-07-01 | 2020-11-10 | 浙江工业大学 | Lithium ion battery with high capacity and cycle performance |
| CN111916817B (en) * | 2020-07-01 | 2021-07-30 | 浙江工业大学 | Lithium ion battery with high capacity and cycle performance |
| CN113244881A (en) * | 2021-06-25 | 2021-08-13 | 桂林理工大学 | Method for preparing lithium orthosilicate material by taking KIT-6 as silicon source, modification and application thereof |
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Denomination of invention: Preparation and Application of Mesoporous Hollow Lithium Silicate Microspheres Effective date of registration: 20221111 Granted publication date: 20180504 Pledgee: Bank of China Limited by Share Ltd. Guangzhou Zengcheng branch Pledgor: Werner fluorine materials (Guangzhou) Co.,Ltd. Registration number: Y2022980021747 |