CN114725534B - 金属离子掺杂Mn2V2O7的制备方法及其在水系锌离子电池的应用 - Google Patents
金属离子掺杂Mn2V2O7的制备方法及其在水系锌离子电池的应用 Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title description 3
- 239000011572 manganese Substances 0.000 claims abstract description 56
- 239000000243 solution Substances 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052751 metal Chemical class 0.000 claims abstract description 9
- 239000002184 metal Chemical class 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- 238000001291 vacuum drying Methods 0.000 claims abstract description 4
- 150000002696 manganese Chemical class 0.000 claims abstract description 3
- 239000007774 positive electrode material Substances 0.000 claims description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
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- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011268 mixed slurry Substances 0.000 claims description 2
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 150000003608 titanium Chemical class 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 7
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 7
- 229910016782 Mn2V2O7 Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 3
- -1 Transition Metal Vanadate Chemical class 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 101150017365 Per3 gene Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241000723873 Tobacco mosaic virus Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
Classifications
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- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
Abstract
本发明属于电化学储能领域,公开了一种金属离子掺杂Mn2V2O7正极材料的制备方法及其在水系锌离子电池的应用。本申请提供了一种金属离子掺杂Mn2V2O7纳米颗粒的制备方法,将溶解后的钒源溶液缓慢加入锰盐和金属盐的混合溶液中,调节混合液的pH值,室温条件下搅拌至沉淀析出,过滤沉淀物,分别用水和乙醇充分洗涤,并进行离心分离,于真空干燥箱干燥后,将得到的M‑V‑O纳米颗粒在空气气氛下,于马弗炉高温处理,得到Mn2V2O7/M纳米颗粒。本发明的制备方法简单易行,重复性好,环保无污染。金属离子的掺杂提高了MnV2O7导电率,使Mn2V2O7/M正极材料在锌离子电池中的稳定性显著提高,并将电压窗口扩展到0.1‑2.0V,具有优异的电化学性能。
Description
技术领域
本发明属于电化学储能领域,具体涉及一种金属离子掺杂Mn2V2O7的正极材料的制备方法及其在水系锌离子电池的应用。
背景技术
在二次电池中,电解液以无水有机溶液为主,具有较宽的电位窗口,通常能够实现较高的能量密度。但是,有机电解液通常有毒且易燃,因此在使用过程中,电池存在很大的安全问题。电池必须在无水环境中,制作的苛刻条件使其生产成本增高,这些因素限制了其在大型储能领域的应用。在各种电化学存储系统中,水性可充电电池逐渐被视为更安全,更环保,更经济的重要储能装置之一。可充电水性锌离子电池(AZIB)凭借其低成本,丰富的原材料和环保性,良好的电解质相容性,具有广阔的发展前景。目前,对ZIB正极材料的探索包括:普鲁士蓝及其类似物、锰基材料、钒基材料及少数过渡金属二硫化合物等,然而,正极材料循环寿命不佳和有限的比能量使AZIB的发展受到限制。钒基材料,合成简单、成本低,是非常有潜力的锌离子电池正极材料,尤其是应用于大型储能设备。过渡金属钒酸盐 (TMVs)由于其丰富的价态、突出的离子储存机制、可调结构和丰富的资源等特点而成为电化学器件的研究热点,而钒酸锰因其良好的磁性和介电性能,备受关注。然而,钒酸锰在充放电过程中由于锰元素溶解和较差导电率,使钒酸锰表现出较差的循环稳定性和倍率性能,限制了钒酸锰正极材料的商业化,导致实施改性策略迫在眉睫,例如层间工程,缺陷工程,杂交或杂原子掺入等,用以提高电化学性能。
在此,我们在提供了一种金属离子掺杂Mn2V2O7的正极材料的制备方法,金属离子掺杂提高了Mn2V2O7导电率,提高了材料的稳定性,并将电压窗口扩展到0.1-2.0V,获得优异的电化学性能。
发明内容
本发明的目的是提供一种金属离子掺杂Mn2V2O7的正极材料(Mn2V2O7/M)的制备方法及其在水系锌离子电池的应用,Mn2V2O7/M正极材料合成简单、制备成本低,具有优异的电化学性能。
制备Mn2V2O7/M正极材料的具体制备步骤为:
(1)称取2-8mmol的水溶性锰源溶解于15mL蒸馏水,称取2-8mmol的金属盐溶解于10mL蒸馏水,4-16mmol的水溶性钒源溶解于85℃的25mL的蒸馏水;
(2)将步骤(1)的金属盐溶液和锰源溶液混合,再将水溶性钒源溶液缓慢加入水溶性锰盐溶液中,利用碱溶液调节该混合液,获得pH值为6-11混合溶液;
(3)将步骤(2)的pH值控制在6-11范围,混合溶液持续搅拌,室温条件下搅拌0.2-5h,有沉淀析出,用纯水洗涤沉淀物,离心弃掉上清液,反复操作3次,然后再用乙醇洗涤,离心弃掉上清液,反复操作2次,将离心后沉淀物置于表面皿上,转入真空干燥箱在 60-100℃条件下干燥12-36h,得到M-V-O纳米颗粒;
(4)将步骤(3)制备的M-V-O纳米颗粒样品于马弗炉250-650℃高温处理2-8h,得到Mn2V2O7/M纳米颗粒;
(5)取步骤(4)中的获得的正极材料、导电剂和粘结剂按照质量比7-8:1-2:1-2,滴入 N-甲基吡咯烷酮(如采用羧甲基纤维素做粘结剂,就不需要滴加N-甲基吡咯烷酮),用研钵研磨40-60min后,将混合浆料涂布在不锈钢箔上,真空条件下于60-110℃干燥10~24h,得到正极材料。
具体的,所述步骤(1)中可溶性钒源为偏钒酸铵、偏钒酸钠或五氧化二钒的其中的一种。
具体的,所述步骤(1)中可溶性锰源为硝酸锰、氯化锰或乙酸锰的其中的一种。
具体的,所述步骤(1)中金属盐为钾盐、铝盐、钛盐、钙盐、镁盐或铜盐的其中的一种。
具体的,所述步骤(2)中碱溶液为氢氧化钠溶液、氢氧化钾溶液或氨水的其中的一种。
具体的,所述步骤(5)中导电剂为乙炔黑、导电碳黑、石墨烯或碳纳米管中至少一种。
具体的,所述步骤(5)中粘结剂为聚偏氯乙烯、丙烯腈多元共聚物、丁苯橡胶或羧甲基纤维素中的一种。
本发明的制备方法具有工艺简单、重复性好等优点。
附图说明
图1是本发明实施例中Mn2V2O7/K正极材料的XRD分析图。
图2是本发明实施例中Mn2V2O7/Mg正极材料的XRD分析图。
图3是本发明实施例中Mn2V2O7/Al正极材料的XRD分析图。
图4是本发明实施例中Mn2V2O7/K正极材料应用于水系锌离子电池的循环性能图。
图5是本发明实施例中Mn2V2O7/Mg正极材料应用于水系锌离子电池的循环性能图。
图6是本发明实施例中Mn2V2O7/Al正极材料应用于水系锌离子电池的循环性能图。
具体实施方式
以下实施例是对本发明的进一步说明,而不是对本发明的限制。
实施例:
实施例中以偏钒酸铵、四水合乙酸锰和金属盐(氯化钾、硫酸镁、硫酸铝)为原料,称取2mmol的乙酸锰溶解于15ml蒸馏水,称取0.04mmol的氯化钾(0.04mmol的硫酸镁、0.24mmol的硫酸铝)溶解于10ml蒸馏水,4mmol的偏钒酸铵溶解于85℃的25ml的蒸馏水。将金属盐溶液和锰源溶液混合,上述的钒溶液缓慢倒入混合溶液中,并利用pH计调节混合液的酸碱度至8.3。将混合溶液在室温条件下持续搅拌1h后,将析出的沉淀用纯水洗涤,离心弃掉上清液,反复操作3次,然后再用乙醇清洗,离心弃掉上清液,反复操作2 次,离心后取沉淀物于表面皿中,在80℃真空干燥箱干燥12h,得到M-V-O纳米颗粒。将制备的M-V-O纳米颗粒样品于马弗炉250-650℃高温处理2-8h,分别得到Mn2V2O7/K、 Mn2V2O7/Mg、Mn2V2O7/Al纳米颗粒;
分别取上述Mn2V2O7/K、Mn2V2O7/Mg、Mn2V2O7/Al纳米颗粒按照活性物质:乙炔黑:聚偏氟乙烯=7:1.5:1.5的比例混合并在玛瑙研钵中进行研磨,研磨的时间约为25min,使其充分混合后,滴加适量分散剂N-甲基吡咯烷酮(NMP),研磨约为15min,使其充分混合后,调整为适合稀稠度的浆料,将研磨好的浆料均匀地涂在不锈钢箔上,真空条件下于80℃干燥18h,得到正极材料。
然后将干燥后的极片裁成直径20mm的扣式电池极片,作为水系锌离子电池的正极材料,首先将称量好的极片放入事先清洗并烘干好的正极壳中,以打磨处理过的金属锌片为对电极,以玻璃纤维作为隔膜,配备好垫片、弹片、负极壳,用七水合硫酸锌和硫酸锰(摩尔比10:1)的混合溶液作为电解液,最后采用封装机进行电池的组装、封口,组装好的电池放置18h,使活性电极材料与电解液充分润湿后再进行电化学测试。
对实施例的正极材料产品的评价结果:
采用PA Nalytical X’Per3 power X射线衍射仪对所合成的Mn2V2O7/K纳米颗粒进行XRD 分析。在附图1中,Mn2V2O7/K的特征峰与Mn2V2O7(JCPDS NO.73-1806)标准图谱匹配,表明该样品是Mn2V2O7,K+离子含量太少,未见相关特征峰。
附图2是Mn2V2O7/Mg的XRD分析。从图中可以看出,Mn2V2O7/Mg的特征峰与 Mn2V2O7(JCPDS NO.73-1806)标准图谱匹配,表明该样品是Mn2V2O7,Mg2+离子含量太少,未见相关特征峰。
附图3是Mn2V2O7/Al的XRD分析。从图中可以看出,Mn2V2O7/Al的特征峰与 Mn2V2O7(JCPDS NO.73-1806)标准图谱匹配,表明该样品是Mn2V2O7,Al3+离子含量太少,未见相关特征峰。
采用CT-ZWJ-4`S-T-1U型充放电测试仪对所制备的锌离子电池进行充放电测试。附图4 是以Mn2V2O7/K作为正极材料的水系锌离子电池的循环性能图,从图中可以看出Mn2V2O7/K 具有较高的放电比容量,具有良好的循环性能。
图5是以Mn2V2O7/Mg作为正极材料的水系锌离子电池的循环性能图,从图中可以看出 Mn2V2O7/Mg具有较高的放电比容量,具有良好的循环性能。
图6是以Mn2V2O7/Al作为正极材料的水系锌离子电池的循环性能图,从图中可以看出 Mn2V2O7/Al具有较高的放电比容量。
Claims (1)
1.一种金属离子掺杂Mn2V2O7在水系锌离子电池的应用,其特征在于金属离子掺杂改性Mn2V2O7在水系锌离子电池中表现出较好的电化学性能和循环稳定性,所述金属离子掺杂Mn2V2O7的制备方法步骤为:
(1)称取2-8mmol的水溶性锰源溶解于15mL蒸馏水,称取2-8mmol的金属盐溶解于10mL蒸馏水,4-16mmol的水溶性钒源溶解于85℃的25mL的蒸馏水;
(2)将步骤(1)的金属盐溶液和锰源溶液混合,再将水溶性钒源溶液缓慢加入水溶性锰盐溶液中,利用碱溶液调节该混合液,获得pH值为6-11混合溶液;
(3)将步骤(2)的pH值控制在6-11范围,混合溶液持续搅拌,室温条件下搅拌0.2-5h,有沉淀析出,用纯水洗涤沉淀物,离心弃掉上清液,反复操作3次,然后再用乙醇洗涤,离心弃掉上清液,反复操作2次,将离心后沉淀物于表面皿上,在60-100℃真空干燥箱干燥12-36h,得到M-V-O纳米颗粒;
(4)将步骤(3)制备的M-V-O纳米颗粒样品于马弗炉250-650℃高温处理2-8h,得到Mn2V2O7/M纳米颗粒;
(5)取步骤(4)中的获得的正极材料、导电剂和粘结剂按照质量比7-8:1-2:1-2,滴入N-甲基吡咯烷酮(如采用羧甲基纤维素做粘结剂,就不需要滴加N-甲基吡咯烷酮),用研钵研磨40-60min后,将混合浆料涂布在不锈钢箔上,真空条件下于60-110℃干燥10~24h,得到正极材料;
(6)所述步骤(1)中可溶性钒源为偏钒酸铵、偏钒酸钠或五氧化二钒其中的一种,可溶性锰源为硝酸锰、氯化锰或乙酸锰其中的一种,金属盐为钾盐、铝盐、钛盐、钙盐、镁盐或铜盐的其中的一种;
(7)所述步骤(2)中碱溶液为氢氧化钠溶液、氢氧化钾溶液或氨水其中的一种;
(8)所述步骤(5)中导电剂为乙炔黑、导电碳黑、石墨烯或碳纳米管中至少一种,粘结剂为聚偏氯乙烯、丙烯腈多元共聚物、丁苯橡胶或羧甲基纤维素中的一种。
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