CN116706027A - 一种碳包覆铜掺杂硫酸铁钠正极材料及其制备方法和应用 - Google Patents
一种碳包覆铜掺杂硫酸铁钠正极材料及其制备方法和应用 Download PDFInfo
- Publication number
- CN116706027A CN116706027A CN202310810305.8A CN202310810305A CN116706027A CN 116706027 A CN116706027 A CN 116706027A CN 202310810305 A CN202310810305 A CN 202310810305A CN 116706027 A CN116706027 A CN 116706027A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- sodium
- doped
- copper
- electrode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- YPPMLCHGJUMYPZ-UHFFFAOYSA-L sodium;iron(2+);sulfate Chemical compound [Na+].[Fe+2].[O-]S([O-])(=O)=O YPPMLCHGJUMYPZ-UHFFFAOYSA-L 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000011734 sodium Substances 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000010405 anode material Substances 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 10
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract 2
- 239000010949 copper Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 16
- 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 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 229920001940 conductive polymer Polymers 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 8
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical group O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 7
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 19
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M2004/028—Positive 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明涉及一种碳包覆铜掺杂硫酸铁钠正极材料,化学表达为Na2.4Fe1.8‑xCux(SO4)3@CNS,x=0.01至0.1,CNS是N和S掺杂的碳包覆层。本发明通过Cu体相掺杂显著提高了硫酸铁钠正极材料在低温下的电化学性能,通过表面碳包覆进一步提升了材料的界面电导率,作为钠离子电池的正极材料,在室温下具有良好的导电性、较高的克容量、循环稳定性以及倍率性能,同时在‑20℃的恶劣环境下也具有良好的循环稳定性。具有良好的应用前景。
Description
技术领域
本发明涉及钠离子电池技术领域,特别涉及一种碳包覆铜掺杂硫酸铁钠正极材料及其制备方法和应用。
背景技术
近年来,全球的环境问题日益严峻,对于新型可再生能源的开发已经迫在眉睫。钠离子电池由于钠资源极其丰富,而且制造成本低、性能优异,因此有望成为新能源行业发展后期的主要储能器件。正极材料作为整个电池体系的关键一环,其循环稳定性、输出电压、热稳定性、输出容量、功率密度等指标在整个电池体系中起到了决定性的作用,而钠离子电池的性能受限于正极材料。聚阴离子型正极材料具有高的工作电压、稳定的晶体结构、优异的储钠动力学特性等特点,硫酸铁钠作为聚阴离子型材料的一种,还兼具原材料成本低、制备工艺简单、绿色环保无污染、生产能耗低等优势,被认为是钠离子电池产业化最具可能性的正极材料。但是硫酸铁钠正极材料导电性差,导致较低的容量、较差的倍率性能和循环稳定性。并且该材料在热处理过程中,温度超过400℃会发生分解,而原位碳包覆通常是高温碳化,需要在较高的温度下发生碳化(500-800℃),因此通过高温碳化进行原位碳包覆提升导电性的策略难以适用于该材料
发明内容
针对目前硫酸铁钠正极材料技术上的问题,本发明提供一种低温碳包覆的铜掺杂复合正极材料,该复合正极材料的碳包覆层中含有氮和硫元素,大大提高了碳层的导电性,并且和体相掺杂结合,利用协同作用来提高该材料的体相导电性和界面导电性,进而克服了其整体导电性差的问题,提高了该材料的克容量,倍率性能以及循环稳定性。
本发明的目的是通过以下技术方案实现的。
一种碳包覆铜掺杂硫酸铁钠正极材料,化学表达为Na2.4Fe1.8-xCux(SO4)3@CNS,x=0.01至0.1,CNS是N和S掺杂的碳包覆层。
进一步地,x=0.02至0.04。
本发明还提供了上述硫酸铁钠复合正极材料的制备方法,包括以下步骤:
(S1)按照化学计量比将钠源,亚铁源,铜源溶于去离子水中,溶解后进行喷雾干燥,得到前驱体;
(S2)将前驱体置于管式炉中,在惰性气氛下,300-400℃下热处理,得到将铜掺杂的硫酸铁钠正极材料;
(S3)将铜掺杂的硫酸铁钠正极材料分散于无水乙醇中,加入含有N和/.或S元素的导电高分子单体,及引发剂,室温下搅拌6-24小时,之后过滤、烘干即可得到导电高分子包覆的铜掺杂硫酸铁钠正极材料;
(S4)将上述导电高分子包覆的前驱体置于管式炉中,在惰性气氛下,300-400℃下热处理,得到硫/氮掺杂碳包覆的铜掺杂硫酸铁钠正极材料。
进一步地,步骤(S1)中,钠源为硫酸钠,亚铁源为硫酸亚铁,铜源为硫酸铜;钠源、亚铁源、铜源的摩尔比满足Na2.4Fe1.8-xCux(SO4)3。
进一步地,步骤(S2)中热处理2-12小时,优选6-10小时。
进一步地,步骤(S3)中,导电高分子单体为3,4-乙撑二氧噻吩和吡咯按照质量比1-2:1-2的混合物;所述引发剂为Fe(III)的盐,优选为三氯化铁,优选为为3,4-乙撑二氧噻吩和吡咯按照质量比1-1.3:1-1.3的混合物。
氮掺杂可以增加材料中的缺陷和活性位点,提高碳层电导率,当引入硫元素后,和氮元素表现出协同作用,提高了正极材料在低温条件下的循环稳定性。
更进一步地,含有N和S元素的导电高分子单体加入量是正极材料的30-60wt%,引发剂加入量是导电高分子单体的80-120wt%。
进一步地,步骤(S4)中热处理10-20小时,优选12-15小时。
本发明的有益效果:
一、本发明通过Cu体相掺杂显著提高了硫酸铁钠正极材料在低温下的电化学性能,这一点是通过掺杂其他金属,比如镁、锌等所不能做到的。发明人推测,可能Cu2+在热处理过程中更容易在材料中产生微量Cu0,降低材料功函数和离子扩散能垒,从而显著提升了低温下的电导率。
二、本发明通过表面碳包覆进一步提升了材料的界面电导率,由于导电高分子中含有氮和硫元素,进行低温热处理后,形成了氮硫杂原子共掺杂的碳层,进一步改善了硫酸铁钠正极材料的电化学性能,特别是低温下的循环稳定性。
三、本发明中所述的复合正极材料,作为钠离子电池的正极材料,在室温下具有良好的导电性、较高的克容量、循环稳定性以及倍率性能,同时在-20℃的恶劣环境下也具有良好的循环稳定性。具有良好的应用前景。
附图说明
图1是上述实施例和对比例制得正极材料的XRD图谱。
图2是实施例1制得正极材料的SEM图。
具体实施方式
下面结合附图和具体实施方式对本发明作进一步阐述,其中,所述方法如无特别说明均为常规方法,所述原材料如无特别说明均能从公开商业途径获得。
以下实施例中,电池组装的具体步骤如下:将实施例或对比例所制备的正极与导电炭黑(Super P)以及聚偏氟乙烯(PVDF)按照质量比7:2:1的比例称取,并将其充分研磨混合均匀后溶于N-甲基吡咯烷酮(NMP)溶液中,磁力搅拌4h后形成均匀浆料,使用刮刀法将浆料均匀涂抹在铝箔上,在真空环境下80℃干燥12h后,裁成极片,作为正极;以钠片作为负极,电解液为1M的高氯酸钠(NaClO4)溶解在体积比为1:1的碳酸乙烯酯/碳酸丙烯酯(EC/PC)体系同时添加5wt%的氟代碳酸乙烯酯(FEC),隔膜为玻璃纤维,在充满氩气的手套箱中组装为2032型纽扣电池。
实施例1
(1)将12mmol硫酸钠、17.8mmol硫酸亚铁、0.2mmol硫酸铜溶于50mL去离子水溶液中,搅拌溶解,形成溶液。
(2)将上述溶液进行喷雾干燥处理,得到前驱体产物。
(3)将前驱体产物在管式炉中,惰性气体条件下、380℃热处理6小时得到铜掺杂硫酸铁钠材料。
(4)将50mg铜掺杂的硫酸铁钠正极材料分散于无水乙醇中,加入质量比13.4mg的3,4-乙撑二氧噻吩(EDOT),13.4mg的吡咯(Py)及25mg三氯化铁,室温下搅拌6-24小时。之后过滤、烘箱中烘干即可。
(5)将上述导电高分子包覆的前驱体置于管式炉中,在惰性气氛下,300-400℃下热处理12小时,得到硫/氮掺杂碳包覆的铜掺杂硫酸铁钠正极材料,产物记为Na2.4Fe1.78Cu0.02(SO4)3@CNS。
对比例1
按照实施例1的方法,区别是不进行步骤(4),产物记为Na2.4Fe1.78Cu0.02(SO4)3。
实施例2
按照实施例2的方法,区别是步骤(1)硫酸铜为0.4mmol,产物记为Na2.4Fe1.78Cu0.04(SO4)3@CNS。
对比例2
按照实施例1的方法,区别是步骤(4)中只加入53.6%的3,4-乙撑二氧噻吩(EDOT)及25mg三氯化铁,产物记为Na2.4Fe1.8(SO4)3@CS。
对比例3
按照实施例1的方法,区别是步骤(4)中只加入26.8mg吡咯(Py)及25mg三氯化铁,产物记为Na2.4Fe1.8(SO4)3@CN。
对比例4
按照实施例1的方法,区别是硫酸铜摩尔量为0,产物记为Na2.4Fe1.8(SO4)3@CNS。
电化学性能测试结果如下表1所示。
表1
由实验结果可知,实施例1中体相铜的掺杂在一定程度上提升了其本体的导电性,电化学性能也得到了提升。表面包覆中,由于含氮的单体吡咯和含硫的单体3,4-乙撑二氧噻吩同时包覆于材料表面,低温碳化后形成了氮硫共掺杂碳包覆层,大大提升了正极材料电化学性能,特别是低温下循环稳定性。使用单一的导电高分子包覆、碳化后只能得到单一杂原子(氮或硫)掺杂的碳包覆层,虽然对电化学性能也有提升,但低温的循环稳定性较差。
本发明提供的体相掺杂和界面包覆协同改性硫酸铁钠正极材料的策略显著提升了其导电性,进一步提升了该材料的容量、倍率性能及循环稳定性。
Claims (10)
1.一种碳包覆铜掺杂硫酸铁钠正极材料,其特征在于,化学表达为Na2.4Fe1.8-xCux(SO4)3@CNS,x=0.01至0.1,CNS是N和S掺杂的碳包覆层。
2.根据权利要求1所述的碳包覆铜掺杂硫酸铁钠正极材料,其特征在于,x=0.02至0.04。
3.权利要求1或2所述的碳包覆铜掺杂硫酸铁钠正极材料的制备方法,其特征在于,包括以下步骤:
(S1)按照化学计量比将钠源,亚铁源,铜源溶于去离子水中,溶解后进行喷雾干燥,得到前驱体;
(S2)将前驱体置于管式炉中,在惰性气氛下,300-400℃下热处理,得到将铜掺杂的硫酸铁钠正极材料;
(S3)将铜掺杂的硫酸铁钠正极材料分散于无水乙醇中,加入含有N和/.或S元素的导电高分子单体,及引发剂,室温下搅拌6-24小时,之后过滤、烘干即可得到导电高分子包覆的铜掺杂硫酸铁钠正极材料;
(S4)将上述导电高分子包覆的前驱体置于管式炉中,在惰性气氛下,300-400℃下热处理,得到硫/氮掺杂碳包覆的铜掺杂硫酸铁钠正极材料。
4.根据权利要求3所述的制备方法,其特征在于,步骤(S1)中,钠源为硫酸钠,亚铁源为硫酸亚铁,铜源为硫酸铜;钠源、亚铁源、铜源的摩尔比满足Na2.4Fe1.8-xCux(SO4)3。
5.根据权利要求3所述的制备方法,其特征在于,步骤(S2)中热处理2-12小时,优选6-10小时。
6.根据权利要求3所述的制备方法,其特征在于,步骤(S3)中,导电高分子单体为3,4-乙撑二氧噻吩和吡咯按照质量比1-2:1-2的混合物;所述引发剂为Fe(III)的盐。
7.根据权利要求6所述的制备方法,其特征在于,导电高分子单体为3,4-乙撑二氧噻吩和吡咯按照质量比1-1.3:1-1.3的混合物;所述引发剂为三氯化铁。
8.根据权利要求3所述的制备方法,其特征在于,含有N和S元素的导电高分子单体加入量是正极材料的30-60wt%,引发剂加入量是导电高分子单体的80-120wt%。
9.根据权利要求3所述的制备方法,其特征在于,步骤(S4)中热处理10-20小时,优选12-15小时。
10.一种钠离子电池,其特征在于,其正极材料为权利要求1或2所述的碳包覆铜掺杂硫酸铁钠正极材料,或者权利要求3-9任一项所述制备方法制备得到的碳包覆铜掺杂硫酸铁钠正极材料。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310810305.8A CN116706027A (zh) | 2023-07-04 | 2023-07-04 | 一种碳包覆铜掺杂硫酸铁钠正极材料及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310810305.8A CN116706027A (zh) | 2023-07-04 | 2023-07-04 | 一种碳包覆铜掺杂硫酸铁钠正极材料及其制备方法和应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN116706027A true CN116706027A (zh) | 2023-09-05 |
Family
ID=87833942
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310810305.8A Pending CN116706027A (zh) | 2023-07-04 | 2023-07-04 | 一种碳包覆铜掺杂硫酸铁钠正极材料及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116706027A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117239138A (zh) * | 2023-11-15 | 2023-12-15 | 华北电力大学 | 钠离子电池正极材料、其制备方法及钠离子电池 |
-
2023
- 2023-07-04 CN CN202310810305.8A patent/CN116706027A/zh active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117239138A (zh) * | 2023-11-15 | 2023-12-15 | 华北电力大学 | 钠离子电池正极材料、其制备方法及钠离子电池 |
CN117239138B (zh) * | 2023-11-15 | 2024-01-23 | 华北电力大学 | 钠离子电池正极材料、其制备方法及钠离子电池 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108598390B (zh) | 一种锂硫电池用正极材料的制备方法及锂硫电池 | |
Gao et al. | Preparation and modification of MIL-101 (Cr) metal organic framework and its application in lithium-sulfur batteries | |
Feng et al. | Nitrogen and oxygen dual-doped porous carbon derived from natural ficus microcarpas as host for high performance lithium-sulfur batteries | |
Wang et al. | Multi-stage explosion of lignin: a new horizon for constructing defect-rich carbon towards advanced lithium ion storage | |
CN116706027A (zh) | 一种碳包覆铜掺杂硫酸铁钠正极材料及其制备方法和应用 | |
CN113659143A (zh) | 钠离子电池负极材料的制备方法及负极材料,钠离子电池 | |
CN113644269B (zh) | 氮掺杂硬碳材料的制备方法及其产品和应用 | |
CN113363488A (zh) | 基于2-丙烯腈的均聚物可低温碳包覆电极材料的方法 | |
CN113241431A (zh) | 一种ZnS纳米花@NC的锂离子电池负极材料的制法和应用 | |
CN116169295A (zh) | 一种双碳层修饰Na3.5Mn0.5V1.5(PO4)3正极材料的制备与应用 | |
CN115863566A (zh) | 一种硬炭/软炭/石墨三元复合碳材料及其制备方法与应用 | |
CN114751395A (zh) | 一种氮掺杂多孔碳球/s复合材料及其制备方法和在锂硫电池中的应用 | |
CN108110232A (zh) | 一种锂电池硬碳负极的表面处理方法 | |
CN114057180A (zh) | 一种碳量子点改性ptcda基炭材料的制备方法及其应用 | |
CN112103502A (zh) | 一种锂硫二次电池及其制备方法与应用 | |
CN113173570B (zh) | 一种类石墨烯片状氮掺杂多孔碳材料的制备方法及应用 | |
CN111261857B (zh) | 一种钠离子电池用FePS3/NC复合负极材料及其制备方法、钠离子电池 | |
CN117832462B (zh) | 氟掺杂碳负载红磷负极材料的制备方法及材料、钠电池及制备方法 | |
CN117623307B (zh) | 一种无烟煤钠电软碳负极材料新型制备方法 | |
CN103456959A (zh) | 一种石墨烯复合材料及其制备方法 | |
CN117317146A (zh) | 基于纤维表面浸润制备多孔超薄锂金属负极的方法和应用 | |
CN116947016A (zh) | 一种储能用功率型钠离子负极材料、电池及制备方法和应用 | |
CN115579582A (zh) | 一种复合隔膜及其制备方法、锂硫电池 | |
CN116454241A (zh) | 氮、硫配位的碳基铁单原子-硫正极材料及其制备方法 | |
CN117059913A (zh) | 一种水系混合离子电解液及其应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |