CN115196674B - A battery electrode composite material and its preparation method and application - Google Patents
A battery electrode composite material and its preparation method and application Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229940073609 bismuth oxychloride Drugs 0.000 claims abstract description 31
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000010949 copper Substances 0.000 claims abstract description 24
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 18
- -1 transition metal oxychloride Chemical class 0.000 claims abstract description 18
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021381 transition metal chloride Inorganic materials 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000001035 drying Methods 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 150000001879 copper Chemical class 0.000 abstract description 4
- 150000003624 transition metals Chemical class 0.000 abstract description 4
- 239000000460 chlorine Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明涉及复合材料技术领域，公开了一种电池电极复合材料及其制备方法和应用，其制备步骤包括步骤S1：将二价铜盐超声溶于有机溶剂中，加入已超声溶解在有机溶剂中的均苯三甲酸的混合溶液，静置，加入有机溶剂，离心，干燥得到CuBTC；S2：将CuBTC在惰性气氛下退火得到Cu@C前驱体；S3：将Cu@C前驱体与过渡金属氯盐溶于有机溶剂中，搅拌，进行水热反应后，离心制得片状氯氧化铋。本发明提供的电池电极复合材料及制备方法，其片状氯氧化铋有较大的表面积、更大的容量、高钠离子迁移率，同时通过与过渡金属氯氧化物的协同作用，提高电池的稳定性。
The invention relates to the technical field of composite materials, and discloses a battery electrode composite material and its preparation method and application. The preparation steps include step S1: ultrasonically dissolve divalent copper salt in an organic solvent, and add the ultrasonically dissolved copper salt in the organic solvent. Mixed solution of trimesic acid, let stand, add organic solvent, centrifuge, and dry to obtain CuBTC; S2: anneal CuBTC in an inert atmosphere to obtain Cu@C precursor; S3: combine Cu@C precursor with transition metal chlorine The salt is dissolved in an organic solvent, stirred, and subjected to hydrothermal reaction, followed by centrifugation to obtain flaky bismuth oxychloride. In the battery electrode composite material and preparation method provided by the invention, the flaky bismuth oxychloride has a larger surface area, a larger capacity, and a high sodium ion mobility. At the same time, through the synergistic effect with the transition metal oxychloride, the battery performance is improved. stability.
Description
技术领域Technical field
本发明属于复合材料技术领域，特别涉及一种电池电极复合材料及其制备方法和应用。The invention belongs to the technical field of composite materials, and in particular relates to a battery electrode composite material and its preparation method and application.
背景技术Background technique
目前的电池负极材料容量较低，并不能满足现今电池的要求，其中金属硫化物材料在充放电过程中由于体积膨胀和穿梭效应导致容量下降，循环稳定性不好。过渡金属氯氧化物则结合了过渡金属和氧元素氯元素，从而具有较高的容量，而且对于形貌的可控制备，能够有效抑制材料在充放电过程中的体积膨胀，一定程度上缓解穿梭效应，获得更佳的循环稳定性。Current battery anode materials have low capacity and cannot meet the requirements of today's batteries. Among them, metal sulfide materials have reduced capacity due to volume expansion and shuttle effect during charge and discharge, and have poor cycle stability. Transition metal oxychloride combines transition metals and the oxygen element chlorine, so it has a higher capacity, and the controllable preparation of the morphology can effectively suppress the volume expansion of the material during the charge and discharge process, and alleviate the shuttle to a certain extent. effect, achieving better cycle stability.
过渡金属硫化物由于充放电过程中的电子转移反应可以提供高容量，但是，由于金属钠与电解液产生副反应，它的稳定性和倍率性能较差，导致低效的储钠过程，进而限制了其在钠离子电池中的应用。Transition metal sulfides can provide high capacity due to the electron transfer reaction during charge and discharge. However, due to side reactions between metallic sodium and the electrolyte, its stability and rate performance are poor, resulting in an inefficient sodium storage process, which further limits its application in sodium-ion batteries.
发明内容Contents of the invention
针对现有技术中金属硫化物材料及过渡金属硫化物作为电极材料存在的穿梭效应，循环稳定性不佳，倍率性能较差等技术问题，本发明提供电池电极复合材料、制备方法及其应用，具体制备一种氯氧化铋(BiOCl)，由含有合金型金属Bi的[Cl-Bi-O-Bi-Cl]切片组成的经典层状结构材料，通过相邻Cl之间的范德华相互作用组装而成，可以实现离子层之间的快速扩散路径，从而促进可逆氧化还原反应，增加循环过程的稳定性，以解决上述问题。In view of the technical problems such as shuttle effect, poor cycle stability, and poor rate performance of metal sulfide materials and transition metal sulfides as electrode materials in the prior art, the present invention provides battery electrode composite materials, preparation methods, and applications. Specifically, a kind of bismuth oxychloride (BiOCl) is prepared, which is a classic layered structure material composed of [Cl-Bi-O-Bi-Cl] slices containing alloy metal Bi, assembled through van der Waals interactions between adjacent Cl It can achieve a rapid diffusion path between ion layers, thereby promoting reversible redox reactions and increasing the stability of the cycle process to solve the above problems.
本发明提供如下的技术方案：The present invention provides the following technical solutions:
一种电池电极复合材料的制备方法，包括如下步骤：A method for preparing battery electrode composite materials, including the following steps:
S1：CuBTC的制备：将二价铜盐超声溶于有机溶剂中，加入已超声溶解在有机溶剂中的均苯三甲酸的混合溶液，静置，加入有机溶剂，离心，干燥得到所述CuBTC；S1: Preparation of CuBTC: Ultrasonically dissolve divalent copper salt in an organic solvent, add a mixed solution of trimesic acid that has been ultrasonically dissolved in the organic solvent, let it stand, add the organic solvent, centrifuge, and dry to obtain the CuBTC;
S2：Cu@C前驱体的制备：将所述CuBTC在惰性气氛下退火得到所述Cu@C前驱体；S2: Preparation of Cu@C precursor: anneal the CuBTC in an inert atmosphere to obtain the Cu@C precursor;
S3：片状过渡金属氯氧化物的制备：将所述Cu@C前驱体与过渡金属氯盐溶于有机溶剂中，搅拌，进行水热反应后，离心制得所述片状过渡金属氯氧化物。S3: Preparation of flaky transition metal oxychloride: Dissolve the Cu@C precursor and transition metal chloride salt in an organic solvent, stir, perform a hydrothermal reaction, and centrifuge to prepare the flaky transition metal oxychloride. things.
优选地，步骤S1所述二价铜盐为硝酸铜、氯化铜中的一种；Preferably, the divalent copper salt in step S1 is one of copper nitrate and copper chloride;
优选地，步骤S1所述硝酸铜与所述均苯三甲酸的质量比为1～3:1；Preferably, the mass ratio of the copper nitrate and the trimesic acid described in step S1 is 1 to 3:1;
优选地，步骤S1需静置2-6小时制备所述CuBTC；Preferably, step S1 needs to be left for 2-6 hours to prepare the CuBTC;
优选地，步骤S1所述有机溶剂为甲醇、乙二醇中的至少一种；Preferably, the organic solvent in step S1 is at least one of methanol and ethylene glycol;
优选地，步骤S2所述CuBTC退火时的升温速率为2-5℃/min，退火温度为500-700℃；Preferably, the temperature rise rate during annealing of CuBTC in step S2 is 2-5°C/min, and the annealing temperature is 500-700°C;
优选地，步骤S2所述惰性气氛为氮气氛围、氩气氛围、氦气氛围中的一种；Preferably, the inert atmosphere in step S2 is one of nitrogen atmosphere, argon atmosphere, and helium atmosphere;
优选地，步骤S3所述过渡金属氯盐为三价氯化铋；Preferably, the transition metal chloride in step S3 is trivalent bismuth chloride;
优选地，步骤S3所述片状过渡金属氯氧化物为片状氯氧化铋；Preferably, the flaky transition metal oxychloride in step S3 is flaky bismuth oxychloride;
优选地，步骤S3所述Cu@C前驱体与所述三价氯化铋的质量比为1:3-5；Preferably, the mass ratio of the Cu@C precursor and the trivalent bismuth chloride in step S3 is 1:3-5;
优选地，步骤S3所述水热反应的反应温度为100-150℃，反应时间为18-24h。Preferably, the reaction temperature of the hydrothermal reaction in step S3 is 100-150°C, and the reaction time is 18-24h.
一种由上述制备方法制得的一种电池电极复合材料。A battery electrode composite material prepared by the above preparation method.
优选地，所述电池电极复合材料为上述制备方法制得的过渡金属氯氧化物。Preferably, the battery electrode composite material is transition metal oxychloride prepared by the above preparation method.
更优选地，所述电池电极复合材料为片状氯氧化铋。More preferably, the battery electrode composite material is flaky bismuth oxychloride.
采用上述方法制得的电池电极复合材料在钠离子电池材料领域的应用。Application of battery electrode composite materials prepared by the above method in the field of sodium ion battery materials.
优选地，所述电池电极复合材料为片状氯氧化铋；Preferably, the battery electrode composite material is flaky bismuth oxychloride;
更优选地，将所述片状氯氧化铋、乙炔黑(导电剂)、聚偏氟乙烯(粘结剂)按照质量比7:2:1混合均匀，再加入N-甲基吡咯烷酮制成浆料，再将所述浆料均匀涂抹在铜箔上制成负极，以钠片作为正极、浓度1mol/L的六氟磷酸钠溶液作为电解液、玻璃纤维作为隔膜，组装成半电池。More preferably, the flaky bismuth oxychloride, acetylene black (conductive agent), and polyvinylidene fluoride (binder) are mixed evenly according to a mass ratio of 7:2:1, and then N-methylpyrrolidone is added to form a slurry. material, and then apply the slurry evenly on the copper foil to form a negative electrode. Use sodium flakes as the positive electrode, sodium hexafluorophosphate solution with a concentration of 1 mol/L as the electrolyte, and glass fiber as the separator to assemble a half-cell.
与现有技术相比，本发明提供的电池电极复合材料、制备方法及其应用，具有以下优点及有益效果：Compared with the existing technology, the battery electrode composite material, preparation method and application provided by the present invention have the following advantages and beneficial effects:
1)引入铜离子和有机配体，有效引导构建了金属有机框架，后续通过高温煅烧，将有机配体移除，形成了碳包覆的铜单质前驱体。水热反应使得金属铜与铋离子发生交换，三氯化铋以金属铜为位点原位生长了片状氯氧化铋；1) Introduce copper ions and organic ligands to effectively guide the construction of a metal-organic framework. Subsequently, the organic ligands are removed through high-temperature calcination to form a carbon-coated copper elemental precursor. The hydrothermal reaction causes the exchange of metallic copper and bismuth ions. Bismuth trichloride uses metallic copper as the site to grow flaky bismuth oxychloride in situ;
2)片状氯氧化铋作为电极材料在拥有较大的表面积的同时，使得更多的活性位点暴露出来，能够让更多的钠离子能够在充放电过程当中脱嵌，从而获得了更大的容量；2) As an electrode material, flaky bismuth oxychloride has a larger surface area and exposes more active sites, allowing more sodium ions to be deintercalated during the charge and discharge process, thereby obtaining greater efficiency. capacity;
3)通过扩大了电极材料与电解液之间的接触面积，构建了离子层之间的快速扩散路径，提高钠离子的迁移率；3) By expanding the contact area between the electrode material and the electrolyte, a rapid diffusion path between ion layers is constructed to increase the mobility of sodium ions;
4)过渡金属氯氧化物的协同作用有利于电池的稳定性。4) The synergistic effect of transition metal oxychloride is beneficial to the stability of the battery.
附图说明Description of the drawings
利用附图对本发明作进一步说明，但附图中的实施例不构成对本发明的任何限制，对于本领域的普通技术人员，在不付出创造性劳动的前提下，还可以根据以下附图获得其它的附图。The present invention is further described using the accompanying drawings, but the embodiments in the accompanying drawings do not constitute any limitation to the present invention. For those of ordinary skill in the art, without exerting creative efforts, other embodiments can be obtained based on the following drawings. Picture attached.
图1为本发明实施例一BiOCl制备流程示意图；Figure 1 is a schematic diagram of the BiOCl preparation process according to Embodiment 1 of the present invention;
图2为本发明实施例一BiOCl的扫描电镜图；Figure 2 is a scanning electron microscope image of BiOCl in Example 1 of the present invention;
图3为本发明实施例一BiOCl的XRD图；Figure 3 is an XRD pattern of BiOCl in Example 1 of the present invention;
图4为本发明实施例一BiOCl的倍率循环曲线图(Cu@C:BiCl3质量比是1：4)；Figure 4 is a rate cycle curve diagram of BiOCl in Example 1 of the present invention (the mass ratio of Cu@C:BiCl 3 is 1:4);
图5为本发明实施例一BiOCl在1.0A/g电流密度下的循环性能图；Figure 5 is a cycle performance diagram of BiOCl at a current density of 1.0A/g in Example 1 of the present invention;
图6为本发明实施例一BiOCl的倍率循环曲线图(Cu@C:BiCl3质量比是1：3)；Figure 6 is a rate cycle curve diagram of BiOCl in Example 1 of the present invention (Cu@C:BiCl 3 mass ratio is 1:3);
图7为本发明实施例一BiOCl在1.0A/g电流密度下的循环性能图(Cu@C:BiCl3质量比是1：3)。Figure 7 is a cycle performance diagram of BiOCl at a current density of 1.0A/g in Example 1 of the present invention (the mass ratio of Cu@C:BiCl 3 is 1:3).
具体实施方式Detailed ways
为了更清楚的说明本发明，对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。In order to explain the present invention more clearly and have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solutions of the present invention are described in detail below, but this should not be understood as limiting the implementable scope of the present invention.
以下实施例中所用的原料、试剂或装置如无特殊说明，均可从常规商业途径得到，或者可以通过现有已知方法得到。Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources, or can be obtained by existing known methods.
以下结合附图及实施例对本发明作进一步描述。The present invention will be further described below in conjunction with the accompanying drawings and examples.
实施例一：Example 1:
本发明提供的电池电极复合材料的制备方法，参见图1，具体包括如下步骤：The preparation method of the battery electrode composite material provided by the present invention, see Figure 1, specifically includes the following steps:
S1：制备CuBTCS1: Preparation of CuBTC
将1.75g硝酸铜(Cu(NO3)2)溶于50mL甲醇溶液并超声半小时，将0.875g均苯三甲酸(H3BTC)溶于50mL甲醇溶液并超声半小时，把以上两种溶液混合静置2h，甲醇离心干燥，得到CuBTC；Dissolve 1.75g copper nitrate (Cu(NO 3 ) 2 ) in 50mL methanol solution and sonicate for half an hour. Dissolve 0.875g trimesic acid (H3BTC) in 50mL methanol solution and sonicate for half an hour. Mix the above two solutions and let stand. Leave for 2 hours, centrifuge and dry with methanol to obtain CuBTC;
S2：制备Cu@C前驱体S2: Preparation of Cu@C precursor
将CuBTC在氮气气氛下600℃退火，升温速率5min/℃，得到Cu@C；Anneal CuBTC at 600°C in a nitrogen atmosphere with a heating rate of 5 min/°C to obtain Cu@C;
S3：制备BiOClS3: Preparation of BiOCl
将Cu@C:BiCl3＝1:4的质量比溶于100mL乙二醇溶液中，搅拌30min，移到聚四氟乙烯水热釜中120℃加热18h，离心得到BiOCl。Dissolve Cu@C:BiCl3=1:4 in 100 mL ethylene glycol solution, stir for 30 minutes, move to a polytetrafluoroethylene hydrothermal kettle, heat at 120°C for 18 hours, and centrifuge to obtain BiOCl.
如图2，由上述制得的BiOCl的扫描电镜图可知，制备的过渡金属氯氧化物BiOCl为纳米片结构，如图3，过渡金属氯氧化物BiOCl已成功生长。As shown in Figure 2, the scanning electron microscope image of the BiOCl prepared above shows that the prepared transition metal oxychloride BiOCl has a nanosheet structure. As shown in Figure 3, the transition metal oxychloride BiOCl has been successfully grown.
实施例二：Example 2:
对实施例一制得的BiOCl进行电学性能测试实验。Conduct electrical performance testing experiments on the BiOCl prepared in Example 1.
将BiOCl、乙炔黑(导电剂)、聚偏氟乙烯(粘结剂)按照质量比7:2:1混合均匀，再加入适量N-甲基吡咯烷酮制成浆料，再将浆料均匀涂抹在铜箔上制成负极，以钠片作为正极、浓度1mol/L的六氟磷酸钠溶液(溶剂为二甲醚)作为电解液、玻璃纤维作为隔膜，组装成半电池，在不同电流密度进行充放电测试。Mix BiOCl, acetylene black (conductive agent), and polyvinylidene fluoride (binder) in a mass ratio of 7:2:1, then add an appropriate amount of N-methylpyrrolidone to make a slurry, and then apply the slurry evenly on The negative electrode is made on the copper foil, and a sodium sheet is used as the positive electrode, a sodium hexafluorophosphate solution with a concentration of 1 mol/L (the solvent is dimethyl ether) is used as the electrolyte, and glass fiber is used as the separator. A half-cell is assembled and charged at different current densities. Discharge test.
如图4和图6，在0.1A/g电流密度下放电容量为280mAh/g，在5A/g电流密度下放电容量为150mAh/g)；图4中，Cu@C:BiCl3质量比是1：4；图6中，Cu@C:BiCl3质量比是1：3。As shown in Figure 4 and Figure 6, the discharge capacity at the current density of 0.1A/g is 280mAh/g, and the discharge capacity at the current density of 5A/g is 150mAh/g); in Figure 4, the Cu@C:BiCl 3 mass ratio is 1:4; in Figure 6, the mass ratio of Cu@C:BiCl 3 is 1:3.
如图5和图7，在1A/g电流密度下，首圈库伦效率较高，随后的库伦效率基本维持在100％左右，且1000圈循环后仍然保持150mAh/g的比容量，说明了材料结构稳定，且材料的比容量较高。图5中，Cu@C:BiCl3质量比是1：4；图7中，Cu@C:BiCl3质量比是1：3。As shown in Figure 5 and Figure 7, at a current density of 1A/g, the Coulombic efficiency of the first cycle is relatively high, and the subsequent Coulombic efficiency is basically maintained at around 100%, and the specific capacity of 150mAh/g is still maintained after 1000 cycles, which illustrates that the material The structure is stable and the material has a high specific capacity. In Figure 5, the mass ratio of Cu@C:BiCl 3 is 1:4; in Figure 7, the mass ratio of Cu@C:BiCl 3 is 1:3.
本发明上述实施例提供的制备方法及由上述方法制得的电池电极复合材料，以及该电池电极复合材料在电池应用，其片状氯氧化铋有较大的表面积、更大的容量、高钠离子迁移率，同时通过与过渡金属氯氧化物的协同作用，提高电池的稳定性；具有以下特点：1)片状氯氧化铋作为电极材料在拥有较大的表面积的同时，使得更多的活性位点暴露出来，能够让更多的钠离子能够在充放电过程当中脱嵌，从而获得了更大的容量；2)通过扩大了电极材料与电解液之间的接触面积，构建了离子层之间的快速扩散路径，提高钠离子的迁移率；3)过渡金属氯氧化物的协同作用有利于电池的稳定性。According to the preparation method provided by the above embodiments of the present invention and the battery electrode composite material prepared by the above method, and the battery electrode composite material is used in batteries, its flaky bismuth oxychloride has a larger surface area, larger capacity, and higher sodium content. Ion mobility, while improving the stability of the battery through synergy with transition metal oxychloride; has the following characteristics: 1) Flake bismuth oxychloride as an electrode material has a larger surface area, making it more active The exposed sites allow more sodium ions to be deintercalated during the charge and discharge process, thereby obtaining a greater capacity; 2) By expanding the contact area between the electrode material and the electrolyte, an ion layer is constructed The rapid diffusion path between them improves the mobility of sodium ions; 3) The synergistic effect of transition metal oxychloride is beneficial to the stability of the battery.
最后应当说明的是，在本发明记载的范围内，具体选择其他的组分、配比及制备工艺参数，均可以实现本发明的技术效果，故不再将其一一列出。同时，以上实施例仅用以说明本发明的技术方案，而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细地说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。Finally, it should be noted that within the scope of the present invention, the technical effects of the present invention can be achieved by specifically selecting other components, proportions and preparation process parameters, so they will not be listed one by one. At the same time, the above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the present invention can be The technical solution may be modified or equivalently substituted without departing from the essence and scope of the technical solution of the present invention.
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