CN103854706A - Preparation method of fusion reactor cladding neutrons and tritium breeding agent beryllium acid lithium pellets - Google Patents
Preparation method of fusion reactor cladding neutrons and tritium breeding agent beryllium acid lithium pellets Download PDFInfo
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Abstract
The invention discloses a preparation method of fusion reactor cladding neutrons and tritium breeding agent beryllium acid lithium pellets. The preparation method of the fusion reactor cladding neutrons and tritium breeding agent beryllium acid lithium pellets comprises the following steps: preparing a beryllium acid lithium material, representing, preparing beryllium acid lithium pellets with the diameter of 1mm, detecting performances, preparing lithium hydroxide and beryllium oxide raw materials at room temperature, putting into a container according to the proportion of 1 of Li/Bi molecule mole ratio, rotating and stirring for about 20 hours, mixing fully and uniformly, putting dried gel in a sintering furnace, warming to 1073K under an air environment, forging for 5 hours, and carrying out solid phase reaction fully; taking a beryllium acid lithium sample, grinding fully into particles, analyzing the formation of components by adopting XDR (external data representation; analyzing the Li/Bi mole ratio by adopting ICP-AES (inductively coupled plasma-atomic emission spectrometry). According to the invention, the problem that when lithium silicate or lithium titanate pellets are originally adopted as breeding agents, a plurality of layers of beryllium zone breeding neutrons are required to be arranged in a cladding is overcome, so that the utilization efficiency of breeding agents in a limited space of the cladding is improved extremely, and the fusion reactor tritium self-sustaining difficulty can be solved effectively.
Description
Technical field
The preparation method and the experimental system thereof that the present invention relates to fusion reactor blanket advanced person's neutron and tritium multiplication agent beryllium acid lithium bead, belong to advanced nuclear reactor fuel research field.
Background technology
Fusion energy is that the mankind forever solve one of potential effective way of energy problem, and construction and the operation of international thermonuclear fusion reaction experimental reactor (ITER) are laid a good foundation for building fusion power generating demonstration reactor in the future.The high-energy neutron (14.1Mev) that the thermonuclear fusion of fusion reactor high-temperature plasma deuterium tritium produces, enter flux of plasma parts propagation covering in heap, in covering, discharge huge energy with tritium-breeding material generation nuclear reaction, breed the needed fuel tritium of fusion reactor self simultaneously.At present, the fertile material that fusion reactor solid blanket develops mainly contains positive lithium metasilicate, lithium titanate, lithium zirconate, lithium aluminate and Lithia etc., and wherein main separation is positive lithium metasilicate and lithium titanate.For example European Union, China expection enter the cold solid blanket module of helium (TBM) that ITER carries out experiment and adopt positive lithium metasilicate as multiplication agent, and Japan's expection enters the water-cooled solid blanket module that ITER carries out experiment and selects lithium titanate as multiplication agent.
No matter select positive lithium metasilicate or lithium titanate as the fertile material in covering, owing to being subject to the restriction of lithium atom density, the tritium rate of increase is all difficult to meet the self-holding basic demand of fusion reactor tritium fuel, can maintain the consumption of himself from the tritium extracting in fusion reactor blanket.In order to improve the tritium rate of increase, multiple neutron multiplications district need to be set in covering, to breed neutron as much as possible.For example, according to neutronics design proposal, the metallic beryllium district of the lithium metasilicate district of covering internal breeding tritium and propagation neutron is arranged alternately, and the shared share in metallic beryllium district is greater than lithium metasilicate district conventionally.Therefore, it is larger that existing design proposal wants to obtain the tritium difficulty of controlling oneself, and in covering to be arranged alternately its proliferate efficiency of neutron multiplication district not good yet in limited breeding blanket.Based on above technical background, for the mission requirements of the special project of national magnetic confinement nuclear fusion energy developmental research (2013GB113004), special proposition patent of the present invention.
Summary of the invention
The technical matters that the present invention solves is: overcome the deficiencies in the prior art, the preparation method of a kind of fusion reactor blanket neutron and tritium multiplication agent beryllium acid lithium bead is provided, while having solved employing lithium metasilicate or lithium titanate bead as multiplication agent, must in covering, need to arrange the problem of multilayer beryllium district propagation neutron, covering finite space internal breeding agent utilization ratio is greatly improved, can effectively solves the self-holding difficult problem of fusion reactor tritium.
The technical solution used in the present invention is: the preparation method of fusion reactor blanket neutron and tritium multiplication agent beryllium acid lithium bead, comprises following steps:
S1: beryllium acid lithium (Li
2bi
2o
3) preparation of material
Get in advance i.e. not low 99.9% the lithium hydroxide (LiOH.H of quantitative high-purity ready
2o) and beryllia (BiO), the ratio that is 1～1.05 in Li/Bi molecule mol ratio is put into container, Stirring full and uniform mixing in 20～24 hours under 20 DEG C～30 DEG C conditions of room temperature; Dried gel is put into sintering furnace, under air ambient, heats to 1073K～1100K, and sintering 5～6 hours, fully carries out solid phase reaction, and its reaction equation is:
2LiOH.H
2O+2BiO→Li
2Bi
2O
3+3H
2O
After being down to room temperature, furnace temperature takes out sample analysis;
S2: the sample analysis of beryllium acid lithium material
Get the particle that appropriate beryllium acid lithium sample is fully milled into 2～3 μ m, adopt XDR to analyze beryllium acid lithium sample crystal grain composition, beryllium acid lithium sample is made up of single-phase beryllium acid lithium, adopt inductively coupled plasma atomic emissions spectrum (inductively coupled plasma atomic emission spectroscopy, ICP-AES) chemical composition of analysis beryllium acid lithium sample, the molecule mol ratio of Li/Bi is substantially constant;
S3: sol-gal process is prepared beryllium acid lithium bead
While adopting sol-gal process to prepare beryllium acid lithium bead, the beryllium acid lithium material of fully milling becomes even fine particle, add by the polyvinyl alcohol (PVA) (polyvinyl-alcohol of proportioning defined amount, and water PVA), wherein the ratio of beryllium acid lithium is 42wt%～44wt%, the ratio of polyvinyl alcohol (PVA) is 2.5wt%～3.5wt%, and the ratio of water is 52.5wt%～53.5wt%; Abundant mixed solution flows out into bead from drip nozzle and enters low temperature-30 DEG C～-35 DEG C of acetone solns, and under capillary effect, drop syneresis becomes bead; After aging through 1～2 hour under low temperature acetone soln environment, take out beryllium acid lithium bead in drying at room temperature 24～48 hours, under air ambient, be heated to 873K～923K calcination 6～8 hours, then put into sintering furnace and be warming up to 1073K～1123K sintering 4～6 hours;
S4: beryllium acid lithium bead Performance Detection
Get beryllium acid lithium bead sample, adopt scanning electron microscope (scanning electron microscopy, SEM) analytic sample surface and broken rear inner microstructure, adopt XDR analytic sample crystal grain composition, adopt mercury immersion method to survey sample rate, adopt the sphericity of digital image analysis bead, adopt the anti-extrusion magnitude of load of static pressure force method test bead.
In described step S1, along with the rising of sintering temperature, moisture content in sample constantly evaporates, example weight constantly reduces, the loss in weight approximately 40%～60%, the pyrolysis collection of illustrative plates of example weight variation with temperature and weight change process during adopting thermogravimetry technology (thermogravimetric/differential thermal analysis, TG – DTA) monitoring to heat, heating rate when sintering is 5 DEG C～6 DEG C/min.
In described step S2, beryllium acid lithium after sintering adds hydrochloric acid and sulfuric acid to form solution after milling in proportion, be heated to 713K beryllium acid lithium is fully dissolved, take out a certain amount of solution, adopt ICP-AES Model Optima2100DV (PerkinElmer company) to measure Li/Be ratio.
In described step S2, the one-tenth of beryllium acid lithium is grouped into and adopts X-ray diffractometer to scan, and the condition of scanning is the Ka radiation (λ) of Cu:
voltage: 40kV, electric current: 100mA, 2 θ scopes: 10～70 °, scan speed: 1.5 °/minute, gap width: 0.01 °.
While adopting sol-gal process to prepare beryllium acid lithium bead in described step S3, the system of employing comprises: mixed solution tank, pressure controller, Vib., drip nozzle, crystal oscillator, amplifier, polyethylene pipe, temperature controller, refrigeratory, acetone container, control computing machine; Control computing machine and provide control signal, by the pressure in pressure controller control mixed solution tank, drive mixed solution to flow to Vib. along polyethylene pipe; Computing machine provides control signal, provides vibration frequency signal by crystal oscillator, through amplifier amplifying signal, drives Vib. vibration, controls drop in drip nozzle mass velocity in accordance with regulations and flows out, and drop falls into low temperature-30 DEG C～-35 DEG C of acetone solns of acetone container; Computer installation temperature controlling value, is worked by temperature controller control refrigeratory, guarantees in acetone container that low temperature acetone soln is in the temperature range of regulation.
In described step S3, while adopting sol-gal process to prepare the experiment of beryllium acid lithium bead, beryllium acid lithium bead size becomes diameter proportion with drop, and the mass flowrate of liquid-drop diameter d (cm), solution
the vibration frequency f(Hz of drip nozzle) be following relation:
According to experiment experience, when the vibration frequency f of drip nozzle is during in 80～250Hz scope, the sphericity of bead is better; In addition, liquid-drop diameter also to viscosity, drip nozzle diameter, mixed solution and the drip nozzle material of solution between wellability relevant; According to optimum experimental solution ratio, drip nozzle diameter and vibration frequency parameter, making the little mean diameter of a ball of beryllium acid lithium of preparing is 0.8mm～1.2mm, and sphericity is 0.95～1.05, anti-extrusion load 20～30N.
The present invention's advantage is compared with prior art: existing fusion reactor solid blanket selects positive lithium metasilicate or lithium titanate as multiplication agent, in order to improve the tritium rate of increase of covering, need to be arranged alternately tritium breeding blanket, lithium metasilicate district and metallic beryllium neutron multiplication district, the shared share in metallic beryllium district is greater than lithium metasilicate district conventionally.Therefore, it is larger that existing design proposal wants to obtain the self-holding difficulty of tritium, and in covering to be arranged alternately its proliferate efficiency of neutron multiplication district not good yet in limited breeding blanket.While adopting lithium metasilicate or lithium titanate bead as multiplication agent in order to overcome, must in covering, need to arrange the problem of multilayer beryllium district propagation neutron.The present invention adopts and makes beryllium acid lithium bead as multiplication agent, wherein beryllium is used for breeding neutron, lithium is used for breeding tritium, there is the function that same multiplication agent had not only been bred tritium but also bred neutron, without neutron multiplication district is set again, covering finite space internal breeding agent utilization ratio is greatly improved, can effectively solves the self-holding difficult problem of fusion reactor tritium, improve the competitiveness of the commercial heap of fusion.
Brief description of the drawings
Fig. 1 adopts sol-gal process to prepare beryllium acid lithium bead systematic schematic diagram in the present invention.
Embodiment
S1: beryllium acid lithium (Li
2bi
2o
3) preparation of material.Get in advance i.e. not low 99.9% the lithium hydroxide (LiOH.H of quantitative high-purity ready
2o) and beryllia (BiO), the ratio that is 1～1.05 in Li/Bi molecule mol ratio is put into container, Stirring full and uniform mixing in 20～24 hours under room temperature (20 DEG C～30 DEG C) condition; Dried gel is put into sintering furnace, under air ambient, heats to 1073～1100K, and sintering 5～6 hours, fully carries out solid phase reaction, and its reaction equation is:
2LiOH.H
2O+2BiO→Li
2Bi
2O
3+3H
2O
After being down to room temperature, furnace temperature takes out sample analysis;
S2: the sample analysis of beryllium acid lithium material.Get the particle that appropriate beryllium acid lithium sample is fully milled into 2～3 μ m, adopt XDR analytic sample crystal grain composition, sample is made up of single-phase beryllium acid lithium.The chemical composition that adopts inductively coupled plasma atomic emissions spectrum (inductively coupled plasma atomic emission spectroscopy, ICP-AES) analytic sample, the molecule mol ratio of Li/Bi is substantially constant;
S3: sol-gal process is prepared beryllium acid lithium bead.Providing the present invention below in conjunction with accompanying drawing adopts sol-gal process to prepare embodiment and the technical scheme of beryllium acid lithium bead.
As shown in Figure 1, the sol-gal process adopting in the present invention is prepared beryllium acid lithium bead system, comprises mixed solution tank 1, pressure controller 2, Vib. 3, drip nozzle 4, crystal oscillator 5, amplifier 6, pvc pipe road 7, temperature controller 8, refrigeratory 9, acetone container 10, controls computing machine 11.Wherein mixed solution tank 1, pressure controller 2, Vib. 3, pvc pipe road 7, drip nozzle 4 form drop forming system, crystal oscillator 5, amplifier 6, pressure controller 2, temperature controller 8, control computing machine 11 form drop control system, and refrigeratory 9, acetone container 10 form beryllium acid lithium bead formation system.
The course of work of system is: the beryllium acid lithium material of fully milling becomes even fine particle, add by the polyvinyl alcohol (PVA) (polyvinyl-alcohol of proportioning defined amount, PVA) and water put into the abundant mixing of mixed solution tank 1, wherein the ratio of beryllium acid lithium is 42wt%～44wt%, the ratio of polyvinyl alcohol (PVA) is 2.5wt%～3.5wt%, and the ratio of water is 52.5wt%～53.5wt%; Provide control signal by controlling computing machine 11, control the pressure in mixed solution tank 1 by pressure controller 2, drive mixed solution to flow to Vib. 3 along pvc pipe road 7; Computing machine 11 provides control signal, provides vibration frequency signal by crystal oscillator 5, through amplifier 6 amplifying signals, drives Vib. 3 to vibrate, and the mass velocity in accordance with regulations of the drop in control drip nozzle 4 flows out, and drop falls into low temperature acetone container 10; Computing machine 11 set temperature controlling values, control refrigeratory 9 by temperature controller 8 and work, guarantee that low temperature acetone container 10 interior solution are in the temperature range of regulation (30 DEG C～-35 DEG C), under capillary effect, drop syneresis becomes bead, makes the little ball forming of beryllium acid lithium; After aging through 1～2 hour under low temperature acetone soln environment, take out beryllium acid lithium bead in drying at room temperature 24～48 hours, under air ambient, be heated to 873K～923K calcination 6～8 hours, then put into sintering furnace and be warming up to 1073K～1123K sintering 4～6 hours;
S4: beryllium acid lithium bead Performance Detection.Get beryllium acid lithium bead sample, adopt scanning electron microscope (scanning electron microscopy, SEM) analytic sample surface and broken rear inner microstructure, adopt XDR analytic sample crystal grain composition, adopt mercury immersion method to survey sample rate, adopt the sphericity of digital image analysis bead, adopt the anti-extrusion magnitude of load of static pressure force method test bead.。
In above-mentioned steps S2, the beryllium acid lithium after sintering adds hydrochloric acid and sulfuric acid to form solution after milling in proportion, is heated to 713K beryllium acid lithium is fully dissolved.Take out a certain amount of solution, adopt ICP-AES Model Optima2100DV (PerkinElmer company) to measure Li/Be ratio.
In above-mentioned steps S2, the one-tenth of beryllium acid lithium is grouped into and adopts X-ray diffractometer to scan, and the condition of scanning is the Ka radiation (λ) of Cu:
voltage: 40kV, electric current: 100mA, 2 θ scopes: 10～70 °, scan speed: 1.5 °/minute, gap width: 0.01 °.
In above-mentioned steps S3, beryllium acid lithium bead size becomes diameter proportion with drop, and the mass flowrate of liquid-drop diameter d (cm), solution
the vibration frequency f(Hz of drip nozzle) be following relation:
According to experiment experience, when the vibration frequency f of drip nozzle is during in 80～250Hz scope, the sphericity of bead is better.In addition, liquid-drop diameter also to viscosity, drip nozzle diameter, solution and the drip nozzle material of solution between wellability relevant.According to parameters such as optimum experimental solution ratio, drip nozzle diameter and vibration frequencies, making the little mean diameter of a ball of beryllium acid lithium of preparing is 0.8mm～1.2mm, and sphericity is 0.95～1.05, anti-extrusion load 20～30N.
Although described above specific embodiment of the invention method; but those skilled in the art is to be understood that; these only illustrate; do not deviating under the prerequisite of the principle of the invention and realization; can make various changes or modifications to these embodiments; therefore, protection scope of the present invention is limited by appended claims.
Claims (6)
1. the preparation method of fusion reactor blanket neutron and tritium multiplication agent beryllium acid lithium bead, is characterized in that comprising following steps:
S1: beryllium acid lithium (Li
2bi
2o
3) preparation of material
Get in advance i.e. not low 99.9% the lithium hydroxide (LiOH.H of quantitative high-purity ready
2o) and beryllia (BiO), the ratio that is 1～1.05 in Li/Bi molecule mol ratio is put into container, Stirring full and uniform mixing in 20～24 hours under 20 DEG C～30 DEG C conditions of room temperature; Dried gel is put into sintering furnace, under air ambient, heats to 1073K～1100K, and sintering 5～6 hours, fully carries out solid phase reaction, and its reaction equation is:
2LiOH.H
2O+2BiO→Li
2Bi
2O
3+3H
2O
After being down to room temperature, furnace temperature takes out sample analysis;
S2: the sample analysis of beryllium acid lithium material
Get the particle that appropriate beryllium acid lithium sample is fully milled into 2～3 μ m, adopt XDR to analyze beryllium acid lithium sample crystal grain composition, beryllium acid lithium sample is made up of single-phase beryllium acid lithium, adopt inductively coupled plasma atomic emissions spectrum (inductively coupled plasma atomic emission spectroscopy, ICP-AES) chemical composition of analysis beryllium acid lithium sample, the molecule mol ratio of Li/Bi is substantially constant;
S3: sol-gal process is prepared beryllium acid lithium bead
While adopting sol-gal process to prepare beryllium acid lithium bead, the beryllium acid lithium material of fully milling becomes even fine particle, add by the polyvinyl alcohol (PVA) (polyvinyl-alcohol of proportioning defined amount, and water PVA), wherein the ratio of beryllium acid lithium is 42wt%～44wt%, the ratio of polyvinyl alcohol (PVA) is 3.5wt%～4.5wt%, and the ratio of water is 52.5wt%～53.5wt%; Abundant mixed solution flows out into bead from drip nozzle and enters low temperature-30 DEG C～-35 DEG C of acetone solns, and under capillary effect, drop syneresis becomes bead; After aging through 1～2 hour under low temperature acetone soln environment, take out beryllium acid lithium bead in drying at room temperature 24～48 hours, under air ambient, be heated to 873K～923K calcination 6～8 hours, then put into sintering furnace and be warming up to 1073K～1123K sintering 4～6 hours;
S4: beryllium acid lithium bead Performance Detection
Get beryllium acid lithium bead sample, adopt scanning electron microscope (scanning electron microscopy, SEM) analytic sample surface and broken rear inner microstructure, adopt XDR analytic sample crystal grain composition, adopt mercury immersion method to survey sample rate, adopt the sphericity of digital image analysis bead, adopt the anti-extrusion magnitude of load of static pressure force method test bead.
2. the preparation method of fusion reactor blanket neutron according to claim 1 and tritium multiplication agent beryllium acid lithium bead, it is characterized in that: in described step S1, along with the rising of sintering temperature, moisture content in sample constantly evaporates, example weight constantly reduces, the loss in weight 40%～60%, adopt thermogravimetry technology (thermogravimetric/differential thermal analysis, TG – DTA) monitoring heat during the pyrolysis collection of illustrative plates of example weight variation with temperature and weight change process, heating rate when sintering is 5 DEG C～6 DEG C/min.
3. the preparation method of fusion reactor blanket neutron according to claim 1 and tritium multiplication agent beryllium acid lithium bead, it is characterized in that: in described step S2, beryllium acid lithium after sintering adds hydrochloric acid and sulfuric acid to form solution after milling in proportion, being heated to 713K fully dissolves beryllium acid lithium, take out a certain amount of solution, adopt ICP-AES Model Optima2100DV (PerkinElmer company) to measure Li/Be ratio.
4. the preparation method of fusion reactor blanket neutron according to claim 1 and tritium multiplication agent beryllium acid lithium bead, it is characterized in that: in described step S2, the one-tenth of beryllium acid lithium is grouped into and adopts X-ray diffractometer to scan, and the condition of scanning is the Ka radiation (λ) of Cu:
voltage: 40kV, electric current: 100mA, 2 θ scopes: 10～70 °, scan speed: 1.5 °/minute, gap width: 0.01 °.
5. the preparation method of fusion reactor blanket neutron according to claim 1 and tritium multiplication agent beryllium acid lithium bead, it is characterized in that: while adopting sol-gal process to prepare beryllium acid lithium bead in described step S3, the system of employing comprises: mixed solution tank (1), pressure controller (2), Vib. (3), drip nozzle (4), crystal oscillator (5), amplifier (6), polyethylene pipe (7), temperature controller (8), refrigeratory (9), acetone container (10), control computing machine (11); Control computing machine (11) and provide control signal, control the pressure in mixed solution tank (1) by pressure controller (2), drive mixed solution to flow to Vib. (3) along polyethylene pipe (7); Computing machine (11) provides control signal, provide vibration frequency signal by crystal oscillator (5), through amplifier (6) amplifying signal, drive Vib. (3) vibration, control drop in drip nozzle (4) mass velocity in accordance with regulations and flow out, drop falls into low temperature-30 DEG C～-35 DEG C of acetone solns of acetone container (10); Computing machine (11) set temperature controlling value, controls refrigeratory (9) work by temperature controller (8), guarantees that the interior low temperature acetone soln of acetone container (10) is in the temperature range of regulation.
6. the preparation method of fusion reactor blanket neutron according to claim 1 and tritium multiplication agent beryllium acid lithium bead, it is characterized in that: in described step S3, while adopting sol-gal process to prepare the experiment of beryllium acid lithium bead, beryllium acid lithium bead size becomes diameter proportion with drop, and the mass flowrate of liquid-drop diameter d (cm), solution
the vibration frequency f(Hz of drip nozzle) be following relation:
According to experiment experience, when the vibration frequency f of drip nozzle is during in 80～250Hz scope, the sphericity of bead is better; In addition, liquid-drop diameter also to viscosity, drip nozzle diameter, mixed solution and the drip nozzle material of solution between wellability relevant; According to optimum experimental solution ratio, drip nozzle diameter and vibration frequency parameter, making the little mean diameter of a ball of beryllium acid lithium of preparing is 0.8mm～1.2mm, and sphericity is 0.95～1.05, anti-extrusion load 20～30N.
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| CN108751975A (en) * | 2018-06-08 | 2018-11-06 | 安徽大学 | Preparation method of tritium-proliferated ceramic pellets in fusion reactor solid blanket |
| CN108858681A (en) * | 2018-05-24 | 2018-11-23 | 四川大学 | Mass prepares the equipment of bead biscuit and the preparation method of tritium multiplication agent nanostructure metatitanic acid lithium ceramic bead |
| CN110148478A (en) * | 2019-06-10 | 2019-08-20 | 中国科学院合肥物质科学研究院 | A kind of fusion reactor solid-state water cooling covering production tritium multiplication agent-neutron multiplication agent |
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| CN104200850A (en) * | 2014-08-22 | 2014-12-10 | 中国工程物理研究院核物理与化学研究所 | Lithium oxide centrifugal bead-making method and device |
| CN104200850B (en) * | 2014-08-22 | 2016-05-11 | 中国工程物理研究院核物理与化学研究所 | A kind of centrifugal ball making method and device of oxidate for lithium |
| CN107256724A (en) * | 2017-06-09 | 2017-10-17 | 山东东佳集团股份有限公司 | Tritium breeds the preparation method of ceramic material metatitanic acid lithium |
| CN107256724B (en) * | 2017-06-09 | 2018-12-11 | 山东东佳集团股份有限公司 | The preparation method of tritium proliferation ceramic material metatitanic acid lithium |
| CN108858681A (en) * | 2018-05-24 | 2018-11-23 | 四川大学 | Mass prepares the equipment of bead biscuit and the preparation method of tritium multiplication agent nanostructure metatitanic acid lithium ceramic bead |
| CN108751975A (en) * | 2018-06-08 | 2018-11-06 | 安徽大学 | Preparation method of tritium-proliferated ceramic pellets in fusion reactor solid blanket |
| CN110148478A (en) * | 2019-06-10 | 2019-08-20 | 中国科学院合肥物质科学研究院 | A kind of fusion reactor solid-state water cooling covering production tritium multiplication agent-neutron multiplication agent |
| CN110148478B (en) * | 2019-06-10 | 2021-01-01 | 中国科学院合肥物质科学研究院 | Fusion reactor solid-state water-cooled cladding tritium production breeder-neutron multiplier |
| CN115414922A (en) * | 2022-08-16 | 2022-12-02 | 华中农业大学 | Spherical Li 4 SiO 4 Radical CO 2 Method for preparing adsorbent |
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