CN106563479A - Two-dimensional carbide-supported rare earth fluoride nanometer powder, preparation method and applications thereof - Google Patents
Two-dimensional carbide-supported rare earth fluoride nanometer powder, preparation method and applications thereof Download PDFInfo
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- -1 rare earth fluoride Chemical class 0.000 title claims abstract description 51
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 50
- 239000000843 powder Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011858 nanopowder Substances 0.000 claims abstract description 47
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 229910052786 argon Inorganic materials 0.000 claims abstract description 3
- 239000000919 ceramic Substances 0.000 claims abstract description 3
- 239000001307 helium Substances 0.000 claims abstract description 3
- 229910052734 helium Inorganic materials 0.000 claims abstract description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 238000003860 storage Methods 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 6
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 6
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 2
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000002244 precipitate Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000003795 desorption Methods 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 5
- 238000002525 ultrasonication Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910017768 LaF 3 Inorganic materials 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 2
- 150000002221 fluorine Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910020187 CeF3 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910020828 NaAlH4 Inorganic materials 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
一种二维碳化物负载稀土氟化物纳米粉体的制备方法，步骤如下：（1）将MAX相陶瓷粉末浸没在溶解有氟化锂的盐酸溶液中，搅拌，离心分离，依次用去离子水和乙醇清洗，干燥后所得固体粉末即为二维碳化物；（2）将二维碳化物加入稀土硝酸盐水溶液中，搅匀后放置8‑24h，冷冻干燥得二维碳化物负载稀土硝酸盐复合前驱体；其中，稀土硝酸盐水溶液的浓度为0.1‑1g/mL，每1mL稀土硝酸盐水溶液中加入二维碳化物0.5~1g；（3）在氩气、氮气或者氦气保护下，400‑600℃焙烧0.5‑2h，洗涤、干燥即得二维碳化物负载稀土氟化物纳米粉体。
A preparation method of a two-dimensional carbide-loaded rare earth fluoride nanopowder, the steps are as follows: (1) immerse the MAX phase ceramic powder in a hydrochloric acid solution dissolved in lithium fluoride, stir, centrifuge, and successively wash with deionized water Wash with ethanol, and the solid powder obtained after drying is a two-dimensional carbide; (2) Add the two-dimensional carbide to the aqueous solution of rare earth nitrate, stir well, place it for 8-24 hours, and freeze-dry to obtain two-dimensional carbide-loaded rare earth nitrate Composite precursor; wherein, the concentration of the rare earth nitrate aqueous solution is 0.1‑1g/mL, and 0.5~1g of two-dimensional carbide is added to every 1mL of the rare earth nitrate aqueous solution; (3) Under the protection of argon, nitrogen or helium, 400 Calcined at ‑600°C for 0.5‑2h, washed and dried to obtain two-dimensional carbide-supported rare earth fluoride nanopowders.
Description
技术领域technical field
本发明属于纳米复合材料制备领域，具体涉及一种二维碳化物负载稀土氟化物纳米粉体、制备方法及其应用。The invention belongs to the field of preparation of nanocomposite materials, and in particular relates to a two-dimensional carbide-loaded rare earth fluoride nanopowder, a preparation method and an application thereof.
背景技术Background technique
Mxene是一种新型二维晶体过渡金属碳化物，具有和石墨烯相似的结构，通过采用氟盐和盐酸的混合溶液将前驱体MAX相中的A元素刻蚀制备得到，是MAX相三元层状化合物的总称，其中M是早期过渡金属元素，A是第三、四主族元素，X是碳或氮；到目前为止，已有70多种MAX相被报道，成功制备得到的MXene主要有以下几种：Ti3C2，Ti2C, Mo2C, (Ti0.5,Nb0.5)2C, Ti3CN, Sc2C，Ta4C3, Nb2C, V2C以及Nb4C3。通过液相制备的MXene具有相对较高的比表面积，以及排列均匀的片层结构，优异的热稳定性、电学及光学特性，使得MXene在催化领域，吸附材料领域等得到较好的应用。氢气作为一种清洁能源，其制备与储存是氢能源领域的研究热点，燃烧产物无污染，可以反复循环使用。锂离子电池作为能量存储装置，其优异的存储容量，循环稳定性，及较高的循环速率取决于锂电池的电极材料。因此有必要寻找新的途径和材料提高氢气产量和锂离子电池的性能。Mxene is a new type of two-dimensional crystalline transition metal carbide, which has a structure similar to graphene. It is prepared by etching the A element in the precursor MAX phase with a mixed solution of fluorine salt and hydrochloric acid. It is a ternary layer of MAX phase. The general term for MAX-like compounds, where M is an early transition metal element, A is the third and fourth main group elements, and X is carbon or nitrogen; so far, more than 70 MAX phases have been reported, and the successfully prepared MXene mainly includes The following types: Ti 3 C 2 , Ti 2 C, Mo 2 C, (Ti 0 . 5 ,Nb 0 . 5 ) 2 C, Ti 3 CN, Sc 2 C, Ta 4 C 3 , Nb 2 C, V 2 C and Nb 4 C 3 . MXene prepared in the liquid phase has a relatively high specific surface area, uniformly arranged lamellar structure, excellent thermal stability, electrical and optical properties, making MXene a better application in the field of catalysis and adsorption materials. As a clean energy, hydrogen is a research hotspot in the field of hydrogen energy for its preparation and storage. The combustion products are non-polluting and can be recycled repeatedly. Lithium-ion batteries are used as energy storage devices, and their excellent storage capacity, cycle stability, and high cycle rate depend on the electrode materials of lithium batteries. Therefore, it is necessary to find new ways and materials to improve hydrogen production and performance of lithium-ion batteries.
现有技术中研究的工作主要是MXene单组份及负载氧化物纳米复合材料及金属单质的吸附、锂电及超级电容器等方面性能，很少研究二维碳化物纳米材料与稀土氟化物纳米颗粒的负载。The research work in the prior art is mainly on the adsorption of MXene single-component and loaded oxide nanocomposites and metal simple substances, lithium batteries and supercapacitors, etc. There are few studies on the performance of two-dimensional carbide nanomaterials and rare earth fluoride nanoparticles. load.
发明内容Contents of the invention
本发明的目的是提供一种二维碳化物负载稀土氟化物纳米粉体、制备方法及其应用。The object of the present invention is to provide a two-dimensional carbide-supported rare earth fluoride nanopowder, a preparation method and an application thereof.
基于上述目的，本发明采取如下技术方案：Based on above-mentioned purpose, the present invention takes following technical scheme:
一种二维碳化物MXene负载稀土氟化物纳米粉体的制备方法，包括如下步骤：A preparation method of a two-dimensional carbide MXene loaded rare earth fluoride nanopowder, comprising the steps of:
（1）将MAX相陶瓷粉末浸没在溶解有氟盐的盐酸溶液中，搅拌，离心分离，依次用去离子水和乙醇清洗，干燥后所得固体粉末即为二维碳化物（即MXene）；(1) Immerse the MAX phase ceramic powder in the hydrochloric acid solution dissolved with fluorine salt, stir, centrifuge, wash with deionized water and ethanol in turn, and the solid powder obtained after drying is a two-dimensional carbide (i.e. MXene);
（2）将二维碳化物加入稀土硝酸盐水溶液中，搅匀后放置8-24h，冷冻干燥得二维碳化物负载稀土硝酸盐复合前驱体；其中，稀土硝酸盐水溶液的浓度为0.1-1g/mL，每1mL稀土硝酸盐水溶液中加入二维碳化物0.5~1g；(2) Add the two-dimensional carbide into the rare earth nitrate aqueous solution, stir well, place it for 8-24 hours, and freeze-dry to obtain the two-dimensional carbide-loaded rare earth nitrate composite precursor; wherein, the concentration of the rare earth nitrate aqueous solution is 0.1-1g /mL, add 0.5~1g of two-dimensional carbide per 1mL of rare earth nitrate aqueous solution;
（3）在氩气、氮气或者氦气保护下，400-600℃焙烧0.5-2h，洗涤、干燥即得二维碳化物负载稀土氟化物纳米粉体。(3) Under the protection of argon, nitrogen or helium, calcinate at 400-600°C for 0.5-2h, wash and dry to obtain two-dimensional carbide-loaded rare earth fluoride nanopowders.
进一步地，步骤（1）中所述二维碳化物MXene为Ti3C2、Ti2C或V2C。Further, the two-dimensional carbide MXene in step (1) is Ti 3 C 2 , Ti 2 C or V 2 C.
步骤（1）中稀土硝酸盐为硝酸镧、硝酸铈、硝酸钇、硝酸镝、硝酸铒、硝酸钕、硝酸钐、硝酸钆和硝酸铽中的至少一种。The rare earth nitrate in step (1) is at least one of lanthanum nitrate, cerium nitrate, yttrium nitrate, dysprosium nitrate, erbium nitrate, neodymium nitrate, samarium nitrate, gadolinium nitrate and terbium nitrate.
步骤（1）中冷冻干燥是指在真空度20Pa以上、温度-20℃以下干燥至少12h。Freeze-drying in step (1) refers to drying at a vacuum degree above 20 Pa and at a temperature below -20°C for at least 12 hours.
采用上述制备方法所制得的二维碳化物负载稀土氟化物纳米粉体。The two-dimensional carbide-loaded rare earth fluoride nanopowder prepared by the above preparation method.
上述二维碳化物负载稀土氟化物纳米粉体在催化储氢方面的应用。The application of the two-dimensional carbide-loaded rare earth fluoride nanopowder in catalytic hydrogen storage.
上述二维碳化物负载稀土氟化物纳米粉体在锂电池方面的应用。The application of the two-dimensional carbide-loaded rare earth fluoride nanopowder in lithium batteries.
本发明二维碳化物负载稀土氟化物纳米粉体的制备方法不需要添加任何催化剂，且稀土氟化物负载量可调，反应可在不同温度下进行，反应条件温和，MXene均匀排列有序的片层结构，为稀土氟化物纳米颗粒提供了较好的载体。本发明工艺方法简单、成本低廉、无需特殊工艺设备、方便高效、实现了稀土氟化物纳米颗粒在二维碳化物MXene表面及层间的均匀负载，该方法可以负载多种稀土氟化物纳米颗粒到MXene上，所制备的二维碳化物MXene负载稀土氟化物纳米粉体在储氢、锂电等领域具有良好的应用前景。The preparation method of the two-dimensional carbide-loaded rare earth fluoride nanopowder of the present invention does not need to add any catalyst, and the loading amount of rare earth fluoride is adjustable, the reaction can be carried out at different temperatures, the reaction conditions are mild, and the MXene sheets are uniformly arranged and orderly The layer structure provides a better carrier for rare earth fluoride nanoparticles. The process method of the present invention is simple, low in cost, does not need special process equipment, is convenient and efficient, and realizes the uniform loading of rare earth fluoride nanoparticles on the surface and between layers of two-dimensional carbide MXene. The method can load a variety of rare earth fluoride nanoparticles to On MXene, the prepared two-dimensional carbide MXene-loaded rare earth fluoride nanopowders have good application prospects in hydrogen storage, lithium batteries and other fields.
附图说明Description of drawings
图1为本发明实施例1制备的二维碳化物负载CeF3纳米粉体的X射线衍射图谱；Fig. 1 is the X-ray diffraction spectrum of the two-dimensional carbide supported CeF nanopowder prepared in Example 1 of the present invention;
图2为本发明实施例1制备的二维碳化物负载CeF3纳米粉体的场发射扫描电镜照片；Fig. 2 is the field emission scanning electron micrograph of the two-dimensional carbide loaded CeF nanopowder prepared in Example 1 of the present invention;
图3为本发明实施例2制备的二维碳化物负载YF3纳米粉体的X射线衍射图谱；Fig. 3 is the X-ray diffraction spectrum of the two-dimensional carbide loaded YF nanopowder prepared in Example 2 of the present invention;
图4为本发明实施例2制备的二维碳化物负载YF3纳米粉体的场发射扫描电镜照片；Fig. 4 is the field emission scanning electron micrograph of the two-dimensional carbide loaded YF nanopowder prepared in Example 2 of the present invention;
图5为本发明实施例1制备的二维碳化物负载CeF3纳米粉体的储氢性能测试结果；Fig. 5 is the hydrogen storage performance test result of the two-dimensional carbide supported CeF nanopowder prepared in Example 1 of the present invention;
图6为本发明实施例1制备的二维碳化物负载CeF3纳米粉体的锂电性能测试结果。Fig. 6 is the lithium battery performance test result of the two-dimensional carbide supported CeF 3 nanopowder prepared in Example 1 of the present invention.
具体实施方式detailed description
以下结合具体实施例对本发明的技术方案做进一步详细说明，但本发明的保护范围并不局限于此。The technical solution of the present invention will be described in further detail below in conjunction with specific examples, but the protection scope of the present invention is not limited thereto.
实施例1Example 1
一种二维碳化物Ti3C2负载稀土氟化物CeF3纳米粉体的其制备方法，包括如下步骤：A two-dimensional carbide Ti 3 C 2 supported rare earth fluoride CeF 3 nanometer powder, comprising the following steps:
（1）将5g MAX相Ti3AlC2粉末浸没在溶解有5g氟化锂的100mL 6M的盐酸溶液中，60℃温度下磁力搅拌48h，离心分离沉淀，经去离子水清洗至接近中性再采用无水乙醇清洗三遍，将沉淀在80℃温度下真空干燥12h，所得固体粉末即为二维碳化物Ti3C2；(1) Submerge 5g of MAX phase Ti 3 AlC 2 powder in 100mL 6M hydrochloric acid solution dissolved with 5g of lithium fluoride, stir magnetically at 60°C for 48h, centrifuge to separate the precipitate, wash with deionized water until nearly neutral and then Wash three times with absolute ethanol, and vacuum-dry the precipitate at 80°C for 12 hours, and the obtained solid powder is the two-dimensional carbide Ti 3 C 2 ;
（2）称取0.31g硝酸铈溶解在1mL去离子水中，室温搅匀，得硝酸铈水溶液；将1g二维碳化物Ti3C2固体粉末超声0.5h分散至上述硝酸铈水溶液中，搅拌均匀后放置12小时；之后在真空度为20Pa下，-20℃干燥12h得到Ti3C2负载硝酸铈复合前驱体；(2) Weigh 0.31g of cerium nitrate and dissolve it in 1mL of deionized water, stir well at room temperature to obtain a cerium nitrate aqueous solution; disperse 1g of two-dimensional carbide Ti 3 C 2 solid powder into the above cerium nitrate aqueous solution by ultrasonication for 0.5h, and stir evenly After leaving it for 12 hours; then dry it at -20°C for 12 hours under a vacuum of 20 Pa to obtain a Ti 3 C 2 loaded cerium nitrate composite precursor;
（3）在Ar气氛中，450℃焙烧1小时，反应结束后，将所得产物依次用去离子水洗涤三次、无水乙醇洗涤三次，真空80℃干燥12h，即得二维碳化物Ti3C2负载CeF3纳米粉体，产物标记为A-1，图1为其X射线衍射图谱，明显地出现了CeF3的衍射峰；图2为其场发射扫描电镜照片，可以看出，Ti3C2表面负载CeF3纳米颗粒粒径为20-400nm。(3) Calcined at 450°C for 1 hour in an Ar atmosphere. After the reaction, the obtained product was washed three times with deionized water and three times with absolute ethanol, and dried at 80°C for 12 hours in a vacuum to obtain a two-dimensional carbide Ti 3 C 2 Load CeF 3 nanopowder, the product is marked as A-1, Figure 1 is its X-ray diffraction pattern, and the diffraction peak of CeF 3 clearly appears; Figure 2 is its field emission scanning electron microscope photo, it can be seen that Ti 3 The particle size of CeF 3 nanoparticles loaded on the surface of C 2 is 20-400nm.
实施例2Example 2
一种二维碳化物V2C负载稀土氟化物YF3纳米粉体的其制备方法，包括如下步骤：A preparation method of a two-dimensional carbide V 2 C loaded rare earth fluoride YF 3 nanometer powder, comprising the following steps:
（1）将5g MAX相V2AlC粉末浸没在溶解有5g氟化钠的100mL 6M的盐酸溶液中，90℃温度下磁力搅拌72h，离心分离沉淀，经去离子水清洗至接近中性再采用无水乙醇清洗三遍，将沉淀在80℃温度下真空干燥12h，所得固体粉末即为二维碳化物V2C；(1) Submerge 5g MAX phase V 2 AlC powder in 100mL 6M hydrochloric acid solution dissolved with 5g sodium fluoride, stir magnetically at 90°C for 72h, centrifuge to separate the precipitate, wash with deionized water until it is nearly neutral, and then use Wash with absolute ethanol three times, dry the precipitate in vacuum at 80°C for 12 hours, and the obtained solid powder is the two-dimensional carbide V 2 C;
（2）称取0.15g硝酸钇溶解在1mL去离子水中，室温搅匀，得硝酸钇水溶液；将1g二维碳化物V2C固体粉末超声0.5h分散至上述硝酸钇水溶液中，搅拌均匀后放置12小时；之后在真空度为25Pa下，-25℃干燥12h得到V2C负载硝酸钇复合前驱体；(2) Weigh 0.15g of yttrium nitrate and dissolve it in 1mL of deionized water, stir well at room temperature to obtain an aqueous solution of yttrium nitrate; disperse 1g of two-dimensional carbide V 2 C solid powder into the above aqueous solution of yttrium nitrate by ultrasonication for 0.5h, stir well Stand for 12 hours; then dry at -25°C for 12 hours under a vacuum of 25 Pa to obtain a V 2 C loaded yttrium nitrate composite precursor;
（3）在Ar气氛中，450℃焙烧1小时，反应结束后，将所得产物依次用去离子水洗涤三次，无水乙醇洗涤三次，真空80℃干燥12h，即得二维碳化物V2C负载YF3纳米粉体，产物标记为A-2，图3为其X射线衍射图谱，明显地出现了YF3的衍射峰；图4为其场发射扫描电镜照片，可以看出，V2C表面负载YF3纳米颗粒粒径为20-400nm。(3) Calcined at 450°C for 1 hour in an Ar atmosphere. After the reaction, the obtained product was washed three times with deionized water and anhydrous ethanol three times, and dried in vacuum at 80°C for 12 hours to obtain a two-dimensional carbide V 2 C Loading YF 3 nano powder, the product is marked as A-2, Figure 3 is its X-ray diffraction pattern, and the diffraction peak of YF 3 clearly appears; Figure 4 is its field emission scanning electron microscope photo, it can be seen that V 2 C The particle size of the YF 3 nanoparticles loaded on the surface is 20-400nm.
实施例3Example 3
一种二维碳化物Ti3C2负载稀土氟化物LaF3纳米粉体的其制备方法，包括如下步骤：A two-dimensional carbide Ti 3 C 2 loaded rare earth fluoride LaF 3 nano-powder and its preparation method, comprising the following steps:
（1）将5g MAX相Ti3AlC2粉末浸没在溶解有5g氟化锂的100mL 6M的盐酸溶液中，60℃温度下磁力搅拌48h，离心分离沉淀，经去离子水清洗至接近中性再采用无水乙醇清洗三遍，将沉淀在80℃温度下真空干燥24h，所得固体粉末即为二维碳化物Ti3C2；(1) Submerge 5g of MAX phase Ti 3 AlC 2 powder in 100mL 6M hydrochloric acid solution dissolved with 5g of lithium fluoride, stir magnetically at 60°C for 48h, centrifuge to separate the precipitate, wash with deionized water until nearly neutral and then Wash three times with absolute ethanol, and vacuum-dry the precipitate at 80°C for 24 hours, and the obtained solid powder is the two-dimensional carbide Ti 3 C 2 ;
（2）称取0.31g硝酸镧溶解在1mL去离子水中，室温搅匀，得硝酸镧水溶液；将0.5g二维碳化物Ti3C2固体粉末超声1h分散至上述硝酸镧水溶液中，搅拌均匀后放置24小时；之后在真空度为30Pa下，-20℃干燥24h得到Ti3C2负载硝酸镧复合前驱体；(2) Weigh 0.31g of lanthanum nitrate and dissolve it in 1mL of deionized water, stir well at room temperature to obtain an aqueous solution of lanthanum nitrate; disperse 0.5g of two-dimensional carbide Ti 3 C 2 solid powder into the above aqueous solution of lanthanum nitrate by ultrasonication for 1 hour, and stir well Leave it for 24 hours; then dry it at -20°C for 24 hours at a vacuum of 30 Pa to obtain a Ti 3 C 2 loaded lanthanum nitrate composite precursor;
（3）在Ar气氛中，600℃焙烧1小时，反应结束后，将所得产物依次用去离子水洗涤三次、无水乙醇洗涤三次，真空100℃干燥12h，即得二维碳化物Ti3C2负载LaF3纳米粉体。(3) Calcined at 600°C for 1 hour in an Ar atmosphere. After the reaction, the obtained product was washed three times with deionized water and three times with absolute ethanol, and dried at 100°C for 12 hours in vacuum to obtain a two-dimensional carbide Ti 3 C 2 loaded LaF 3 nanopowder.
实施例4Example 4
一种二维碳化物V2C负载稀土氟化物TbF3纳米粉体的其制备方法，包括如下步骤：A preparation method of a two-dimensional carbide V 2 C loaded rare earth fluoride TbF 3 nanometer powder, comprising the following steps:
（1）将5g MAX相V2AlC粉末浸没在溶解有5g氟化钠的100mL 6M的盐酸溶液中，90℃温度下磁力搅拌72h，离心分离沉淀，经去离子水清洗至接近中性再采用无水乙醇清洗三遍，将沉淀在100℃温度下真空干燥12h，所得固体粉末即为二维碳化物V2C；(1) Submerge 5g MAX phase V 2 AlC powder in 100mL 6M hydrochloric acid solution dissolved with 5g sodium fluoride, stir magnetically at 90°C for 72h, centrifuge to separate the precipitate, wash with deionized water until it is nearly neutral, and then use Wash with absolute ethanol three times, dry the precipitate in vacuum at 100°C for 12 hours, and the obtained solid powder is two-dimensional carbide V 2 C;
（2）称取0.31g硝酸铽溶解在1mL去离子水中，室温搅匀，得硝酸铽水溶液；将1g二维碳化物V2C固体粉末超声40min分散至上述硝酸铽水溶液中，搅拌均匀后放置8小时；之后在真空度为25Pa下，-40℃干燥12h得到V2C负载硝酸铽复合前驱体；(2) Weigh 0.31g of terbium nitrate and dissolve it in 1mL of deionized water, stir well at room temperature to obtain a terbium nitrate aqueous solution; disperse 1g of two-dimensional carbide V 2 C solid powder into the above-mentioned terbium nitrate aqueous solution by ultrasonication for 40min, stir evenly and place 8 hours; then drying at -40°C for 12 hours at a vacuum of 25 Pa to obtain a V 2 C-loaded terbium nitrate composite precursor;
（3）在Ar气氛中，500℃焙烧1小时，反应结束后，将所得产物依次用去离子水洗涤三次，无水乙醇洗涤三次，真空80℃干燥18h，即得二维碳化物V2C负载TbF3纳米粉体。(3) Calcined at 500°C for 1 hour in an Ar atmosphere. After the reaction, the obtained product was washed three times with deionized water and anhydrous ethanol three times, and dried at 80°C for 18 hours in vacuum to obtain a two-dimensional carbide V 2 C Loaded TbF 3 nanopowder.
实施例5Example 5
一种二维碳化物V2C负载稀土氟化物NdF3纳米粉体的其制备方法，包括如下步骤：A preparation method of a two-dimensional carbide V 2 C loaded rare earth fluoride NdF 3 nanometer powder, comprising the following steps:
（1）将5g MAX相V2AlC粉末浸没在溶解有5g氟化钠的100mL 6M的盐酸溶液中，90℃温度下磁力搅拌72h，离心分离沉淀，经去离子水清洗至接近中性再采用无水乙醇清洗三遍，将沉淀在80℃温度下真空干燥12h，所得固体粉末即为二维碳化物V2C；(1) Submerge 5g MAX phase V 2 AlC powder in 100mL 6M hydrochloric acid solution dissolved with 5g sodium fluoride, stir magnetically at 90°C for 72h, centrifuge to separate the precipitate, wash with deionized water until it is nearly neutral, and then use Wash with absolute ethanol three times, dry the precipitate in vacuum at 80°C for 12 hours, and the obtained solid powder is the two-dimensional carbide V 2 C;
（2）称取0.31g硝酸钕溶解在1mL去离子水中，室温搅匀，得硝酸钕水溶液；将0.5g二维碳化物V2C固体粉末超声0.5h分散至上述硝酸钕水溶液中，搅拌均匀后放置12小时；之后在真空度为35Pa下，-30℃干燥12h得到V2C负载硝酸钕复合前驱体；(2) Weigh 0.31g of neodymium nitrate and dissolve it in 1mL of deionized water, stir well at room temperature to obtain an aqueous solution of neodymium nitrate; disperse 0.5g of two-dimensional carbide V 2 C solid powder into the above aqueous solution of neodymium nitrate by ultrasonication for 0.5h, and stir well After that, it was placed for 12 hours; then, it was dried at -30°C for 12 hours at a vacuum degree of 35 Pa to obtain a V 2 C loaded neodymium nitrate composite precursor;
（3）在Ar气氛中，550℃焙烧1小时，反应结束后，将所得产物依次用去离子水洗涤三次，无水乙醇洗涤三次，真空90℃干燥16h，即得二维碳化物V2C负载NdF3纳米粉体。(3) Calcined at 550°C for 1 hour in an Ar atmosphere. After the reaction, the obtained product was washed three times with deionized water and anhydrous ethanol three times, and dried in vacuum at 90°C for 16 hours to obtain a two-dimensional carbide V 2 C Loaded with NdF 3 nanopowder.
二维碳化物负载稀土氟化物纳米粉体在催化储氢方面的应用Application of two-dimensional carbide-supported rare earth fluoride nanopowders in catalytic hydrogen storage
分别称取0.9g的NaAlH4和0.1g所制备的二维碳化物或0.1g实施例1制得的二维碳化物Ti3C2负载CeF3纳米粉体，并在行星式球磨机中研磨12h，得到的混合粉体分别在100℃下测试其恒温放氢性能。测试结果如图5所示，二维碳化物Ti3C2负载CeF3纳米粉体在100℃温度下催化NaAlH4放氢的速率明显提高，3h内即可释放3.10wt%的H2，6h可以释放3.33wt%的H2；相比之下，二维碳化物催化NaAlH4放氢明显较差，6h的放氢量仅有2.83wt%，且放氢速率较慢。通过对比发现，MXene负载稀土氟化物纳米粉体比纯MXene具有更加优异的催化性能，可显著提高NaAlH4的放氢速率，提高放氢量，从而改善NaAlH4的储氢性能。此外，对实施例2至5得到的纳米粉体在同样条件下也进行了催化储氢方面的测试，结果证明实施例2至5得到的纳米粉体催化NaAlH4的放氢速率和二维碳化物Ti3C2负载CeF3纳米粉体相当，因此，实施例2至5得到的纳米粉体在催化储氢方面也具有良好的应用前景。Weigh 0.9g of NaAlH 4 and 0.1g of prepared two-dimensional carbide or 0.1g of two-dimensional carbide Ti 3 C 2 supported CeF 3 nanopowder prepared in Example 1, and grind in a planetary ball mill for 12h , and the obtained mixed powders were tested for their constant-temperature hydrogen desorption performance at 100°C. The test results are shown in Figure 5. The two-dimensional carbide Ti 3 C 2 supported CeF3 nanopowder catalyzes the hydrogen desorption rate of NaAlH4 at a temperature of 100 °C. 3.33wt% H 2 ; in contrast, the dehydrogenation of NaAlH 4 catalyzed by two-dimensional carbides is significantly poorer, with only 2.83wt% hydrogen desorption in 6h, and the hydrogen desorption rate is slower. Through comparison, it is found that MXene-loaded rare earth fluoride nanopowders have better catalytic performance than pure MXene, which can significantly increase the hydrogen desorption rate of NaAlH 4 and increase the amount of hydrogen desorption, thereby improving the hydrogen storage performance of NaAlH 4 . In addition, the nanopowders obtained in Examples 2 to 5 were also tested for catalytic hydrogen storage under the same conditions, and the results proved that the nanopowders obtained in Examples 2 to 5 catalyzed the hydrogen desorption rate and two-dimensional carbonization of NaAlH The Ti 3 C 2 supported CeF 3 nanopowders are comparable, therefore, the nanopowders obtained in Examples 2 to 5 also have good application prospects in catalytic hydrogen storage.
二维碳化物负载稀土氟化物纳米粉体在锂电池方面的应用Application of two-dimensional carbide-supported rare earth fluoride nanopowders in lithium batteries
称取实施例1制得的二维碳化物Ti3C2负载CeF3纳米粉体、乙炔黑和聚四氟乙烯按0.3457g：0.0432g：0.0432g的质量比混合研磨均匀，加入大约35滴N-甲基吡咯烷酮，搅拌成均匀的浆体，涂覆在铜箔上，110℃真空干燥12h，将铜箔裁成直径为14mm圆片作为负极，金属锂作为正极，锂离子电池电解液（型号：电解液14712，购自东莞市杉杉电池材料有限公司）作为电解液，在手套箱中组装成纽扣电池，再进行恒流充放电测试。测试结果如图6所示，MXene负载CeF3纳米粉体作为电池电极的首次放电容量为305.75mAh/g，而MXene作为电池电极的首次放电容量为221.0mAh/g，即MXene负载稀土氟化物纳米粒后的锂电池能明显比纯MXene具有更高的放电容量。此外，对实施例2至5得到的纳米粉体在同样条件下也进行了恒流充放电测试，结果证明实施例2至5得到的纳米粉体的放电容量和二维碳化物Ti3C2负载CeF3纳米粉体相当，因此，实施例2至5得到的纳米粉体在锂电池方面也具有良好的应用前景。Weigh the two-dimensional carbide Ti 3 C 2 loaded CeF 3 nanopowder, acetylene black and polytetrafluoroethylene prepared in Example 1 and mix and grind evenly according to the mass ratio of 0.3457g: 0.0432g: 0.0432g, and add about 35 drops N-methylpyrrolidone, stirred into a uniform slurry, coated on the copper foil, vacuum-dried at 110 ° C for 12 hours, the copper foil was cut into a disc with a diameter of 14mm as the negative electrode, metal lithium as the positive electrode, lithium-ion battery electrolyte ( Model: Electrolyte 14712, purchased from Dongguan Shanshan Battery Material Co., Ltd.) as the electrolyte, assembled into a button battery in a glove box, and then subjected to a constant current charge and discharge test. The test results are shown in Figure 6. The initial discharge capacity of MXene-loaded CeF 3 nanopowder as a battery electrode is 305.75mAh/g, while the initial discharge capacity of MXene as a battery electrode is 221.0mAh/g, that is, MXene-loaded rare earth fluoride nano The granulated lithium batteries can obviously have a higher discharge capacity than pure MXene. In addition, the nano-powders obtained in Examples 2 to 5 were also subjected to constant current charge and discharge tests under the same conditions. The results proved that the discharge capacity of the nano-powders obtained in Examples 2 to 5 and the two -dimensional carbide Ti 3 C The supported CeF 3 nanopowders are comparable, therefore, the nanopowders obtained in Examples 2 to 5 also have good application prospects in lithium batteries.
最后要说明的是，以上所述仅为本发明的优选实例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进润饰等，均应包含在本发明的保护范围之内。Finally, it should be noted that the above descriptions are only preferred examples of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modifications, equivalent replacements, improvements and modifications made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.
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| CN109896524A (en) * | 2019-01-30 | 2019-06-18 | 合肥国轩高科动力能源有限公司 | Preparation method and application of two-dimensional crystal MXene nano material |
| CN110002448A (en) * | 2019-05-10 | 2019-07-12 | 东北大学 | A kind of two dimension rare-earth yttrium carbon compound material and preparation method thereof |
| CN110615440A (en) * | 2019-09-24 | 2019-12-27 | 黑龙江科技大学 | MXene nanosheet with large size and rich oxygen functional group and preparation method and application thereof |
| CN112175275A (en) * | 2020-09-29 | 2021-01-05 | 中北大学 | A kind of maikene/ethylene-vinyl acetate copolymer flexible sensing material and preparation method thereof |
| CN113533449A (en) * | 2021-07-05 | 2021-10-22 | 广西师范大学 | Preparation method of MXene graphene composite structure gas sensor |
| CN113941355A (en) * | 2021-10-18 | 2022-01-18 | 湖北方圆环保科技有限公司 | Preparation method and application of special catalyst for non-methane total hydrocarbon analysis based on MXene |
| CN113956846A (en) * | 2021-09-28 | 2022-01-21 | 哈尔滨工业大学 | Rare earth oxide nanoparticle doped Mxene material for space charged particle radiation protection, composite coating and preparation method |
| EP4095944A1 (en) * | 2021-05-28 | 2022-11-30 | FDK Corporation | Negative electrode for alkaline storage battery and alkaline storage battery including the negative electrode |
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| CN109650391B (en) * | 2019-01-29 | 2022-03-18 | 武汉科技大学 | Preparation method of two-dimensional vanadium carbide MXene |
| CN109650391A (en) * | 2019-01-29 | 2019-04-19 | 武汉科技大学 | The preparation method of two-dimentional vanadium carbide MXene |
| CN109896524A (en) * | 2019-01-30 | 2019-06-18 | 合肥国轩高科动力能源有限公司 | Preparation method and application of two-dimensional crystal MXene nano material |
| CN110002448A (en) * | 2019-05-10 | 2019-07-12 | 东北大学 | A kind of two dimension rare-earth yttrium carbon compound material and preparation method thereof |
| CN110615440A (en) * | 2019-09-24 | 2019-12-27 | 黑龙江科技大学 | MXene nanosheet with large size and rich oxygen functional group and preparation method and application thereof |
| CN110615440B (en) * | 2019-09-24 | 2022-02-11 | 哈尔滨师范大学 | MXene nanosheet with large size and rich oxygen functional group and preparation method and application thereof |
| CN112175275A (en) * | 2020-09-29 | 2021-01-05 | 中北大学 | A kind of maikene/ethylene-vinyl acetate copolymer flexible sensing material and preparation method thereof |
| EP4095944A1 (en) * | 2021-05-28 | 2022-11-30 | FDK Corporation | Negative electrode for alkaline storage battery and alkaline storage battery including the negative electrode |
| CN113533449A (en) * | 2021-07-05 | 2021-10-22 | 广西师范大学 | Preparation method of MXene graphene composite structure gas sensor |
| CN113533449B (en) * | 2021-07-05 | 2023-08-25 | 广西师范大学 | A kind of preparation method of MXene graphene composite structure gas sensor |
| CN113956846A (en) * | 2021-09-28 | 2022-01-21 | 哈尔滨工业大学 | Rare earth oxide nanoparticle doped Mxene material for space charged particle radiation protection, composite coating and preparation method |
| CN113956846B (en) * | 2021-09-28 | 2022-06-17 | 哈尔滨工业大学 | Rare earth oxide nanoparticle doped Mxene material and composite coating for space charged particle radiation protection and preparation method |
| CN113941355A (en) * | 2021-10-18 | 2022-01-18 | 湖北方圆环保科技有限公司 | Preparation method and application of special catalyst for non-methane total hydrocarbon analysis based on MXene |
| CN113941355B (en) * | 2021-10-18 | 2024-05-03 | 湖北方圆环保科技有限公司 | Preparation method and application of catalyst special for non-methane total hydrocarbon analysis based on MXene |
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