CN117089857A - 一种一步制备锌离子电池用MnO2正极材料的方法 - Google Patents
一种一步制备锌离子电池用MnO2正极材料的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 45
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 13
- 238000000151 deposition Methods 0.000 claims abstract description 27
- 230000008021 deposition Effects 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 238000004070 electrodeposition Methods 0.000 claims abstract description 11
- 239000010405 anode material Substances 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
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- 238000001035 drying Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
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- 150000002500 ions Chemical class 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
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- 238000005520 cutting process Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 206010067484 Adverse reaction Diseases 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910007613 Zn—MnO2 Inorganic materials 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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Abstract
本发明公开了一种一步制备锌离子电池用MnO2正极材料的方法,分别采用了恒电位法和循环伏安法两种简单、高效的电化学沉积方法来制备MnO2正极材料。以碳纸为基底材料,碳纸有相对较大的比表面积而且表面更粗糙,可以较多的附着沉积物避免沉积物脱落;反应体系简单且环境污染小,反应物在电化学作用下使活性物质沉积在基底表面,流程短,成本低。通过计算机对电压、电流、电解液的浓度、沉积液的pH值、时间等参数进行调整,可以有效地掌握沉积物的形貌、沉积量和厚度变化等。本发明既能够有效提高锌离子电池正极材料MnO2的导电性能,又能大大提高锌离子电池正极材料MnO2的制备效率。
Description
技术领域
本发明涉及锌离子电池技术领域,特别涉及一种一步制备锌离子电池用MnO2正极材料的方法。
背景技术
水性可充电电池(ARB)使用廉价、安全但高离子导电性的水溶液作为电解液,因此几乎没有火灾风险。目前,市场上占主导地位的ARB是铅酸电池,在寻找铅酸电池的替代产品过程中,锌离子电池逐渐吸引了人们的视线。比起有机电解液电导率(10-3-10-2 S cm-1),锌离子电池中水系电解液的离子电导率(~1 S cm-1)要更高,电荷传输更顺畅,环境稳定性更好,安全性更高。不仅如此,水系电解液中锌的氧化还原电位较低(-0.76 V),因此电池的工作电压就较高,而且锌储量也比较大,在地壳中的金属元素中,其含量仅在铁、铝、铜之后,能满足市场需求,锌离子为二价离子,相比于一价锂离子和钠离子携带的电荷更多,存储的电荷量也大,对电池功率密度和能量密度的提高有很大帮助。锌离子电池的理论能量密度能够达到320 Wh/kg,这个数值要远高于铅酸电池的能量密度,受到了越来越多的重视。
因为电池的电化学特性主要依赖于电极材料(阳极和阴极)的性质和结构,因此对于锌离子电池大多数的研究仍聚焦于正极材料改性。在各种各样的正极材料中,MnO2被认为是一种高比容量、低成本、低毒性的合适的优质正极材料。然而,即使是这样的正极材料也有导电性差和循环中Mn2+不可逆溶解等不可忽视的问题。目前,锰氧化物主流制备手段有水热法、共沉淀法、固相烧结法等等。水热法需高温高压,共沉淀法步骤复杂,固相烧结法耗时长。
发明内容
本发明的目的在于克服背景技术中对电极材料存在的不足,解决MnO2正极材料导电性差及制备方法繁琐等问题,提供一种工艺简单、成本低的一步电化学沉积制备锌离子电池正极材料的方法。
为实现上述目的,本发明提供如下技术方案:
一种一步制备锌离子电池用MnO2正极材料的方法,采用碳纸为基底,利用电化学沉积法,在碳纸上沉积一层由纳米颗粒组成的MnO2。
进一步,包括以下步骤:首先是配制电解液,然后通过三电极体系,以碳纸为工作电极,使用恒电位法或循环伏安法将二氧化锰正极材料沉积在碳纸上;在电镀时,通过调整不同的沉积电位或扫速,可制备多种不同形貌正极材料。
进一步,所述电解液为MnSO4溶液和H2SO4溶液的混合液。
进一步,所述三电极体系是以铂片为对电极,以Ag/AgCl电极为参比电极,以碳纸为工作电极。
进一步,所述恒电位法沉积电位为1.0~1.8V,沉积时间为10~30min;所述循环伏安法扫速为10~50 v·s-1,沉积时间为10~20min。
有益效果
(1)本发明以碳纸为基底使用一步电化学沉积法解决了MnO2正极材料导电性差及制备方法繁琐的问题。碳纸具有极佳的传输电子能力,可以提高电导率,而且不可否认的是碳纸的热稳定性很好的同时化学稳定性也十分优异,碳纸中有空隙还能更多负载正极材料,增大接触面积,提高利用率。
(2)电化学沉积是一种通过释放电压或电流,促进金属阳离子在电极表面氧化从而沉积成金属氧化物的电化学方法。电沉积法中电子作为“反应试剂”反应体系简单且环境污染小,反应物在电化学作用下通过被氧化还原使活性物质沉积在基底表面,流程短,成本低。通过计算机对电压、电流、电解液的浓度、沉积液的pH值、时间等参数进行一定程度的调整,借此可以有效地掌握沉积物的形貌、沉积量和厚度变化等。
附图说明
图1是1.0V电压下得到的MnO2的扫描电镜照片
图2是恒电压法不同电压(a为1.2v,b为1.4v,c为1.6v,d为1.8v)得到的MnO2的扫描电镜照片。
图3是循环伏安法不同扫速(a为10 mv·s-1、b为20 mv·s-1、c为50 mv·s-1)得到的MnO2的扫描电镜图照片。
图4是M-1.0(a)、M-1.2(b)、M-1.4(c)、M-1.6(d)、M-1.8(e)所组装电池在0.1C电流密度下充放电曲线及循环性能测试(f)结果。
图5是M-10(a)、M-20(b)、M-50(c)所组装电池在0.1C电流密度下充放电曲线及循环性能测试(d)结果。
图6是对比例制得的α-MnO2/CTs和α-MnO2@δ-MnO2/CTs的扫描电镜照片。
具体实施方式
实施例1
将碳纸裁成3×3 cm大小置于烧杯中,倒入乙醇和水的混合液(1:1)然后将烧杯超声清洗10 min后放入烘箱中干燥备用;
称取1.69 g MnSO4·H2O溶于140 ml去离子水中并在其中滴入5滴1 M H2SO4溶液最终配置成沉积液;
组装三电极体系(工作电极:C纸、对电极:铂片、参比电极:Ag/AgCl电极);
将电解池连接电化学工作站,分别以1.0、1.2、1.4、1.6、1.8为沉积电压采用恒电位法沉积20 min,样品命名为M-1.0、M-1.2、M-1.4、M-1.6、M-1.8;
实施例2
将碳纸裁成3×3 cm大小置于烧杯中,倒入乙醇和水的混合液(1:1)然后将烧杯超声清洗10 min后放入烘箱中干燥备用;
称取1.69 g MnSO4·H2O溶于140 ml去离子水中并在其中滴入5滴1 M H2SO4溶液最终配置成沉积液;
组装三电极体系(工作电极:C纸、对电极:铂片、参比电极:Ag/AgCl电极);
将电解池连接电化学工作站,采用CV法设定不同扫速10 mv·s-1、20 mv·s-1、50mv·s-1沉积相同时间,样品命名为M-10、M-20、M-50;
对比例
一种可充电的高性能准固态柔性Zn-MnO2电池的制备方法,步骤如下:
(1) 柔性碳纤维布(CTs)的预处理
将碳纤维布(CTs)衬底在室温下浸泡在浓硝酸(70%)中24h以提高其亲水性,再将得到的CTs用蒸馏水冲洗至PH≈7.0,最后在烘箱中70℃风干燥5h;
(2) 自支撑α-MnO2@δ-MnO2/CTs正电极的制备
首先通过水热法将α-MnO2纳米线阵列直接生长在处理过的CTs上,具体步骤如下:
将预处理的碳纤维布浸入40mL的0.03M高锰酸钾(KMnO4)水溶液中,然后密封反应釜并放入烘箱中160 ℃保持4h,取出样品用去离子水冲洗后在70 ℃下干燥6h,即可得到α-MnO2纳米线阵列生长在CTs表面上(α-MnO2/CTs),如图6(a、b、c)所示;然后,采用电沉积方法在α-MnO2纳米线阵列表面包覆相互连接的δ-MnO2纳米片如图6(d、e、f)所示,具体步骤如下:将步骤(1)得到的α-MnO2/CTs作为工作电极,并用石墨棒和饱和甘汞电极(SCE)分别作为对电极和参比电极,将三电极浸入MnSO4和CH3COONa的混合水溶液(浓度为50mM)中,并在电流密度为5.0mA cm-2下电沉积时间30s、60s、90s和120s,随后将电沉积
得到的样品在70 ℃下干燥12h;
由附图可以观察到,对比例所制得α-MnO2 呈网状线型交织排布,材料表面更加粗糙,且制备采用两种工艺更为复杂,而本实施例则只通过电流、电压作用在碳纤维表面沉积了一层由纳米颗粒组成的MnO2,形貌呈花状,颗粒之间存在有大量空隙;通过阶梯式增大电压材料一次结构无变化,二次结构变致密,表面空隙消失,沉积层变厚并伴随有裂纹出现,这是由于随着沉积厚度在增加导致沉积层质脆且易断裂,只有在此临近电压之下进行沉积方可使得到的金属氧化物形貌完整且厚度可控的;由图3可知,通常沉积手段也会影响材料形貌,相比于恒电位法,循环伏安法沉积产物的二次结构直径更大,且沉积层没有恒电位法那么厚,CV法得到的膜层更不平整,材料附着力大大增加;此外沉积液调整为适宜弱酸环境,即可以抑制金属离子沉淀又避免过度酸化引起腐蚀或不良反应。
电化学测试的结果表明,两种电沉积法制得样品电化学性能表现均较为优异,但传统使用的恒电位法沉积量过少,而CV法不仅沉积量大,且电化学性能更为突出。
以上所述的实施例只是本发明的一种较佳的方案,并非对本发明作任何形式上的限制,在不超出权利要求所记载的技术方案的前提下还有其它的变体及改型。
Claims (5)
1.一种一步制备锌离子电池用MnO2正极材料的方法,其特征在于,采用碳纸为基底,利用电化学沉积法,在碳纸上沉积一层由纳米颗粒组成的MnO2。
2.如权利要求1所述一种一步制备锌离子电池用MnO2正极材料的方法,其特征在于,包括以下步骤:首先是配制电解液,然后通过三电极体系,以碳纸为工作电极,使用恒电位法或循环伏安法将二氧化锰正极材料沉积在碳纸上;在电镀时,通过调整不同的沉积电位或扫速,可制备多种不同形貌正极材料。
3.如权利要求2所述一种一步制备锌离子电池用MnO2正极材料的方法,其特征在于,所述电解液为MnSO4溶液和H2SO4溶液的混合液。
4.如权利要求2所述一种一步制备锌离子电池用MnO2正极材料的方法,其特征在于,所述三电极体系是以铂片为对电极,以Ag/AgCl电极为参比电极,以碳纸为工作电极。
5.如权利要求2所述一种一步制备锌离子电池用MnO2正极材料的方法,其特征在于,所述恒电位法沉积电位为1.0~1.8V,沉积时间为10~30min;所述循环伏安法扫速为10~50v·s-1,沉积时间为10~20min。
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