CN103613085A - Carbon hollow sphere material with hierarchical porous structure and preparation method thereof - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 83
- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title description 5
- 239000011148 porous material Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- 239000007833 carbon precursor Substances 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- 239000005011 phenolic resin Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229910001410 inorganic ion Inorganic materials 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000002149 hierarchical pore Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
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Abstract
本发明公开一种具有多级孔结构的碳空心球材料，由碳壳和由碳壳围成的空心内腔组成，在碳壳上形成复数个大孔。本发明在碳壳上形成复数个大孔，使得电解液等其它物质可以进入碳空心球材料的内腔，从而充分利用碳空心球材料的内腔。
The invention discloses a carbon hollow sphere material with a multi-level pore structure, which is composed of a carbon shell and a hollow inner cavity surrounded by the carbon shell, and a plurality of large pores are formed on the carbon shell. The present invention forms a plurality of large holes on the carbon shell, so that electrolyte and other substances can enter the inner cavity of the carbon hollow sphere material, thereby making full use of the inner cavity of the carbon hollow sphere material.
Description
技术领域 technical field
本发明涉及一种碳空心球材料及其制备方法，尤其是指一种具有多级孔结构的碳空心球材料及其制备方法。 The invention relates to a carbon hollow sphere material and a preparation method thereof, in particular to a carbon hollow sphere material with a multi-level pore structure and a preparation method thereof.
背景技术 Background technique
多孔碳空心材料具有高孔隙率、高比表面积、良好的导电性和化学稳定性等特性，在催化、吸附分离、离子交换及电化学储能领域有重要的应用价值。而碳空心球材料具有优良的化学稳定性及热稳定性, 并且质量轻, 抗压性能好, 因此被广泛的应用于电极材料、储能储氢材料、吸附材料、润滑剂及催化剂载体等领域。 Porous carbon hollow materials have the characteristics of high porosity, high specific surface area, good electrical conductivity and chemical stability, and have important application value in the fields of catalysis, adsorption separation, ion exchange and electrochemical energy storage. The carbon hollow sphere material has excellent chemical and thermal stability, light weight, and good compression resistance, so it is widely used in the fields of electrode materials, energy storage and hydrogen storage materials, adsorption materials, lubricants, and catalyst carriers. .
现有技术公开的碳空心球材料，其在空心球的碳壳形成有微孔，所述微孔的数量很多，且孔的孔径为4nm以下。由于微孔的孔径非常小，使得电解液或其它物质很难进入碳空心球材料的内腔壁中，因此，碳空心球材料的内腔无法使用。如对于锂离子电池，电解液很难进入碳空心球材料的内腔，使得其放电倍率较低；作为催化剂载体，催化剂无法进入碳空心球材料的内腔，催化剂的活性较弱。 In the carbon hollow sphere material disclosed in the prior art, micropores are formed in the carbon shell of the hollow sphere, the number of the micropores is large, and the diameter of the pores is less than 4 nm. Since the pore size of the micropores is very small, it is difficult for electrolyte or other substances to enter the inner cavity wall of the carbon hollow sphere material, so the inner cavity of the carbon hollow sphere material cannot be used. For example, for lithium-ion batteries, it is difficult for the electrolyte to enter the inner cavity of the carbon hollow sphere material, resulting in a lower discharge rate; as a catalyst carrier, the catalyst cannot enter the inner cavity of the carbon hollow sphere material, and the activity of the catalyst is weak.
发明内容 Contents of the invention
本发明的目的在于提供一种内腔可以充分利用的具有多级孔结构的碳空心球材料及其制备方法。 The object of the present invention is to provide a carbon hollow sphere material with a multi-level pore structure whose inner cavity can be fully utilized and a preparation method thereof.
为达成上述目的，本发明的解决方案为： To achieve the above object, the solution of the present invention is:
一种具有多级孔结构的碳空心球材料，由碳壳和由碳壳围成的空心内腔组成，在碳壳上形成复数个大孔。 A carbon hollow sphere material with a multi-level pore structure is composed of a carbon shell and a hollow cavity surrounded by the carbon shell, and a plurality of large pores are formed on the carbon shell.
进一步，所述大孔的孔径大于等于20nm。 Further, the diameter of the macropores is greater than or equal to 20 nm.
进一步，所述内腔的体积占总体积的10-90%。 Further, the volume of the inner cavity accounts for 10-90% of the total volume.
进一步，所述碳壳的含碳量大于等于80%。 Further, the carbon content of the carbon shell is greater than or equal to 80%.
进一步，所述大孔为直孔。 Further, the large holes are straight holes.
进一步，所述大孔的几何总面积为碳空心球材料几何表面积的10-90%。 Further, the total geometric area of the macropores is 10-90% of the geometric surface area of the carbon hollow sphere material.
一种具有多级孔结构的碳空心球材料制备方法，包括以下步骤： A method for preparing a carbon hollow sphere material with a hierarchical porous structure, comprising the following steps:
一，使用溶胶凝胶法将碳前驱体包覆在模板表面，同时加入造孔剂，溶解分散于水中； 1. Use the sol-gel method to coat the carbon precursor on the surface of the template, add a pore-forming agent, dissolve and disperse in water;
二，将步骤一形成的混合液放入烘箱中凝胶得到前驱体； 2. Put the mixed solution formed in step 1 into an oven to gel to obtain a precursor;
三，将步骤二获得的前驱体进行高温烧结，得到具有多级孔结构的碳空心球材料。 Third, the precursor obtained in step two is sintered at a high temperature to obtain a carbon hollow sphere material with a hierarchical porous structure.
进一步，步骤一中所述模板为有机模板聚苯乙烯（PS）、聚甲基丙烯酸甲酯（PMMA），或者为无机模板SiO2、MnO。 Further, the template in step 1 is an organic template polystyrene (PS), polymethyl methacrylate (PMMA), or an inorganic template SiO2, MnO.
进一步，步骤一中所述碳前躯体为酚醛树脂、环氧树脂。 Further, the carbon precursor described in step 1 is phenolic resin or epoxy resin.
进一步，步骤一中所述造孔剂为聚合物造孔剂聚乙二醇（ＰＥＧ）、聚乙烯吡咯烷酮（ＰＶＰ）、聚乙烯醇缩丁醛（ＰＶＢ），或者为有机造孔剂间三甲苯，或者为无机离子造孔剂铁盐、钴盐、NH4HCO3、(NH4)2C2O4。 Further, the pore-forming agent described in step 1 is a polymer pore-forming agent polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl butyral (PVB), or an organic pore-forming agent m-trimethylbenzene , or inorganic ion pore formers iron salt, cobalt salt, NH 4 HCO 3 , (NH4) 2 C 2 O 4 .
进一步，步骤三中高温烧结温度为500-1500℃。 Further, the high-temperature sintering temperature in step three is 500-1500°C.
采用上述方案后，本发明在碳壳上形成复数个大孔（相对于现有技术孔径为4nm以下的微孔），使得电解液等其它物质可以进入碳空心球材料的内腔，从而充分利用碳空心球材料的内腔。如对于锂离子电池而言，由于电解液自由进入内腔，扩散半径下降一半，有利于材料的放电倍率；如作为催化剂载体，由于催化剂进入内腔，提高了催化剂的活性；由于物质进入内腔，该物质也可以作为一些物质的载体而充分利用内腔。 After adopting the above scheme, the present invention forms a plurality of macropores on the carbon shell (compared to the micropores with a pore diameter below 4nm in the prior art), so that other substances such as electrolyte can enter the inner cavity of the carbon hollow sphere material, thereby making full use of The inner cavity of the carbon hollow sphere material. For example, for lithium-ion batteries, since the electrolyte enters the inner cavity freely, the diffusion radius is reduced by half, which is beneficial to the discharge rate of the material; as a catalyst carrier, the activity of the catalyst is improved because the catalyst enters the inner cavity; because the substance enters the inner cavity , the substance can also be used as a carrier of some substances to make full use of the inner cavity.
附图说明 Description of drawings
图1是本发明结构示意图； Fig. 1 is a structural representation of the present invention;
图2是本发明制备流程图。 Fig. 2 is the preparation flow chart of the present invention.
标号说明 Label description
碳壳1 大孔11
Carbon shell 1
内腔2 碳前驱体3
模板4 造孔剂5 Template 4 Pore Builder 5
前驱体6。 Precursor 6.
具体实施方式 Detailed ways
以下结合附图及具体实施例对本发明作进一步说明。 The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.
参阅图1所示，本发明揭示的一种具有多级孔结构的碳空心球材料，由碳壳1和由碳壳1围成的空心内腔2组成，在碳壳1上形成复数个大孔11（相对于现有技术孔径为4nm以下的微孔而言）。大孔11为直孔，孔径大于等于10nm。所述大孔11的几何总面积为碳空心球材料几何表面积的10-90%。同时，所述内腔2的体积占总体积的10-90%。所述碳壳1的含碳量大于等于80%。
Referring to Fig. 1, a carbon hollow sphere material with a multi-level porous structure disclosed by the present invention is composed of a carbon shell 1 and a
参阅图2所示，所述具有多级孔结构的碳空心球材料制备方法，包括以下步骤： Referring to Figure 2, the method for preparing a carbon hollow sphere material with a hierarchical porous structure comprises the following steps:
一，使用溶胶凝胶法将碳前驱体3包覆在模板4表面，同时加入造孔剂5，溶解分散于水中；其中，碳前驱体3为酚醛树脂、环氧树脂；造孔剂5为聚合物造孔剂聚乙二醇（ＰＥＧ）、聚乙烯吡咯烷酮（ＰＶＰ）、聚乙烯醇缩丁醛（ＰＶＢ），或者为有机造孔剂间三甲苯，或者为无机离子造孔剂铁盐、钴盐、NH4HCO3、(NH4)2C2O4。 1. Use the sol-gel method to coat the carbon precursor 3 on the surface of the template 4, and add a pore-forming agent 5 at the same time, dissolve and disperse in water; wherein, the carbon precursor 3 is phenolic resin and epoxy resin; the pore-forming agent 5 is Polymer pore forming agent polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl butyral (PVB), or organic pore forming agent m-trimethylbenzene, or inorganic ion pore forming agent iron salt, Cobalt salts, NH 4 HCO 3 , (NH4) 2 C 2 O 4 .
二，将步骤一形成的混合液放入烘箱中凝胶得到前驱体6。 2. Put the mixed solution formed in step 1 into an oven to gel to obtain precursor 6.
三，将步骤二获得的前驱体6进行高温烧结，得到具有多级孔结构的碳空心球材料，高温烧结温度为500-1500℃。 Three, the precursor 6 obtained in step two is sintered at a high temperature to obtain a carbon hollow sphere material with a hierarchical pore structure, and the high temperature sintering temperature is 500-1500° C.
实施例一 Embodiment one
一种具有多级孔结构的碳空心球材料制备方法，包括以下步骤：一，2g的酚醛树脂（间苯二酚：甲醛mol比为1:2），1.2g的模板PMMA微球（配成PMMA乳液30ml）和0.5g的造孔剂PEG，溶解分散在10ml水中，搅拌10min；二，密封放入85℃烘箱凝胶3天，打开烘干得到前驱体；三，在800℃进行高温烧结，在烧结的过程中PMMA（聚甲基丙烯酸甲酯）和PEG（聚乙二醇）分解形成空腔和碳壳的大孔。 A method for preparing a carbon hollow sphere material with a hierarchical porous structure, comprising the following steps: 1. 2g of phenolic resin (resorcinol: formaldehyde mol ratio is 1:2), 1.2g of template PMMA microspheres (formulated PMMA emulsion (30ml) and 0.5g pore-forming agent PEG, dissolved and dispersed in 10ml water, stirred for 10min; 2. Sealed and placed in an oven at 85°C for 3 days, then opened and dried to obtain the precursor; 3. High temperature sintering at 800°C , PMMA (polymethyl methacrylate) and PEG (polyethylene glycol) decompose during sintering to form cavities and macropores in the carbon shell.
所述方法制备的具有多级孔结构的碳空心球材料，大孔的孔径为20nm，大孔的几何总面积为碳空心球材料几何表面积的10%，内腔的体积占总体积的27%，碳壳的含碳量98%。 The carbon hollow sphere material with hierarchical pore structure prepared by the method, the pore diameter of the macropore is 20nm, the geometric total area of the macropore is 10% of the geometric surface area of the carbon hollow sphere material, and the volume of the inner cavity accounts for 27% of the total volume , The carbon content of the carbon shell is 98%.
实施例二 Embodiment two
一种具有多级孔结构的碳空心球材料制备方法，包括以下步骤：一，2g的酚醛树脂（间苯二酚：甲醛mol比为1:2），2.1g的模板PMMA微球（配成PMMA乳液70ml）和0.5g的造孔剂PEG，溶解分散在10ml水中，搅拌10min；二，密封放入85℃烘箱凝胶3天，打开烘干得到前驱体；三，在800℃进行高温烧结，在烧结的过程中PMMA（聚甲基丙烯酸甲酯）和PEG（聚乙二醇）分解形成空腔和碳壳的大孔。 A method for preparing a carbon hollow sphere material with a hierarchical porous structure, comprising the following steps: 1. 2g of phenolic resin (resorcinol: formaldehyde mol ratio is 1:2), 2.1g of template PMMA microspheres (formulated PMMA emulsion (70ml) and 0.5g of pore-forming agent PEG, dissolved and dispersed in 10ml of water, stirred for 10min; 2, sealed and placed in an oven at 85°C for 3 days, opened and dried to obtain the precursor; 3, high-temperature sintering at 800°C , PMMA (polymethyl methacrylate) and PEG (polyethylene glycol) decompose during sintering to form cavities and macropores in the carbon shell.
所述方法制备的具有多级孔结构的碳空心球材料，大孔的孔径为50nm，大孔的几何总面积为碳空心球材料几何表面积的40%，内腔的体积占总体积的55%，碳壳的含碳量98%。 The carbon hollow sphere material with hierarchical pore structure prepared by the method, the pore diameter of the macropore is 50nm, the geometric total area of the macropore is 40% of the geometric surface area of the carbon hollow sphere material, and the volume of the inner cavity accounts for 55% of the total volume , The carbon content of the carbon shell is 98%.
实施例三 Embodiment Three
一种具有多级孔结构的碳空心球材料制备方法，包括以下步骤：一，1g的酚醛树脂（间苯二酚：甲醛mol比为1:2），1.2g的模板SiO2球和0.5g的造孔剂PVP，溶解分散在10ml水中，搅拌10min；二，密封放入85℃烘箱凝胶3天，打开烘干得到前驱体；三，在1500℃进行高温烧结，烧结后用HF酸洗掉模板SiO2。 A method for preparing a carbon hollow sphere material with a hierarchical porous structure, comprising the following steps: 1. 1g of phenolic resin (resorcinol: formaldehyde mol ratio is 1:2), 1.2g of template SiO spheres and 0.5g The pore-forming agent PVP was dissolved and dispersed in 10ml of water, and stirred for 10 minutes; second, sealed and placed in an oven at 85°C for 3 days, opened and dried to obtain the precursor; third, sintered at 1500°C at high temperature, and washed with HF acid after sintering Drop the template SiO 2 .
所述方法制备的具有多级孔结构的碳空心球材料，大孔的孔径为50nm，大孔的几何总面积为碳空心球材料几何表面积的40%，内腔的体积占总体积的85%，碳壳的含碳量95%。 The carbon hollow sphere material with hierarchical pore structure prepared by the method, the pore diameter of the macropore is 50nm, the geometric total area of the macropore is 40% of the geometric surface area of the carbon hollow sphere material, and the volume of the inner cavity accounts for 85% of the total volume , The carbon content of the carbon shell is 95%.
实施例四 Embodiment Four
包括以下步骤：一，1g的酚醛树脂（间苯二酚：甲醛mol比为1:2），0.6g的模板SiO2球和1.0g的造孔剂NH4HCO3，溶解分散在10ml水中，搅拌10min；二，密封放入85℃烘箱凝胶3天，打开烘干得到前驱体；三，在1500℃进行高温烧结，烧结后用HF酸洗掉模板SiO2。 The following steps are included: 1. 1g of phenolic resin (resorcinol: formaldehyde molar ratio is 1:2), 0.6g of template SiO 2 balls and 1.0g of pore-forming agent NH 4 HCO 3 are dissolved and dispersed in 10ml of water, Stir for 10 minutes; 2. seal and put in an oven at 85°C for 3 days, open and dry to obtain the precursor; 3. perform high-temperature sintering at 1500°C, and wash off the template SiO 2 with HF acid after sintering.
所述方法制备的具有多级孔结构的碳空心球材料，大孔的孔径为20nm，大孔的几何总面积为碳空心球材料几何表面积的20%，内腔的体积占总体积的25%，碳壳的含碳量95%。 The carbon hollow sphere material with hierarchical pore structure prepared by the method, the pore diameter of the macropore is 20nm, the geometric total area of the macropore is 20% of the geometric surface area of the carbon hollow sphere material, and the volume of the inner cavity accounts for 25% of the total volume , The carbon content of the carbon shell is 95%.
本发明碳壳的大孔的产生是因为在合成的过程中加入了造孔剂，而空腔的产生是因为在合成的过程中加入了模板。在高温煅烧后，腔内的模板和模板包覆层中的造孔剂热解为气体逸出，从而形成具有大孔的空心碳球。利用碳壳凿开的大孔，可以充分利用球的内腔，可以应用于多个领域。碳空心球材料自身可以用作锂离子电池和超级电容器的电极，还可以当做载体和模板应用于太阳能电池、燃料电池、催化、生物医药以及环境净化等多个领域。 The large pores of the carbon shell of the present invention are generated because a pore-forming agent is added during the synthesis process, and the cavity is generated because a template is added during the synthesis process. After high-temperature calcination, the template in the cavity and the pore-forming agent in the template cladding layer are pyrolyzed to gas and escape, thereby forming hollow carbon spheres with large pores. The large hole cut out by the carbon shell can make full use of the inner cavity of the ball and can be used in many fields. The carbon hollow sphere material itself can be used as an electrode of lithium-ion batteries and supercapacitors, and can also be used as a carrier and template in many fields such as solar cells, fuel cells, catalysis, biomedicine, and environmental purification.
以上所述仅为本发明的较佳实施例，并非对本案设计的限制，凡依本案的设计关键所做的等同变化，均落入本案的保护范围。 The above descriptions are only preferred embodiments of the present invention, and are not limitations on the design of this case. All equivalent changes made according to the design key of this case all fall within the scope of protection of this case.
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| CN107555415A (en) * | 2017-09-26 | 2018-01-09 | 四川大学 | A kind of method that hydro-thermal method prepares PVA-based carbosphere |
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| CN114373949A (en) * | 2020-10-15 | 2022-04-19 | 丰田自动车株式会社 | Porous carbon, catalyst carrier, and method for producing porous carbon |
| CN113081971A (en) * | 2021-05-14 | 2021-07-09 | 江西中医药大学 | Traditional Chinese medicine porous core-shell type composite particle powder and preparation method and application thereof |
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