CN105839129B - 一种硫掺杂纳米碳及其电化学制备方法与用途 - Google Patents
一种硫掺杂纳米碳及其电化学制备方法与用途 Download PDFInfo
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 80
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 68
- 239000011593 sulfur Substances 0.000 title claims abstract description 68
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 65
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 18
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 239000005864 Sulphur Substances 0.000 claims abstract description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000003487 electrochemical reaction Methods 0.000 claims abstract description 7
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 7
- 231100000719 pollutant Toxicity 0.000 claims abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 6
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 12
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 230000001413 cellular effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VRVAZSINCAZFLH-UHFFFAOYSA-N oxygen(2-) tin(4+) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Sn+4] VRVAZSINCAZFLH-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
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Abstract
本发明涉及一种硫掺杂纳米碳及其电化学制备方法与用途，其使用碱金属碳酸盐作为熔盐电解质体系；采用惰性材料为阳极，以金属或非金属材料为阴极；采用电化学反应装置；将含有CO2和SO2的火电厂、水泥厂、化工厂除尘脱硫后的工业烟气通入熔盐电解质中，在350‑900℃的温度范围内，进行电解，制得硫掺杂纳米碳。本发明的有益效果是：方法工艺简单，制备的硫掺杂纳米碳硫含量可控、碳材料的形貌可控。该硫掺杂的纳米碳相对于单纯的纳米碳粉，表现出更广泛及优异的应用性能，可作为超级电容器用储能材料、锂离子电池正极材料、电催化材料以及吸附水体中及空气中的污染物。
Description
技术领域
本发明涉及一种硫掺杂纳米碳及其电化学制备方法与用途，属于炭材料领域，也属于电化学领域。
背景技术
近年来，熔盐电解转化二氧化碳制备无定形的纳米碳被认为是一种有效的纳米碳制备技术。Licht等人提出了一种将太阳能和太阳光辐射热结合加热熔盐的方法捕集利用二氧化碳(J.Physical.Chem.C.2011,115(23):11803-11821)。Groult等人在熔盐碳酸盐中采用恒电位电解的方法转化二氧化碳为纳米级的碳(J.Electrochem.Soc.2002,149(5):D72-D78)。中国专利CN102895847A报道了一种CO2捕集资源化的方法，该方法采用Li2CO3-Na2CO3-K2CO3三元碳酸盐作为熔盐电解质，通过恒槽压电解的方法制备了无定形的纳米级别碳。
这些方法制备的产品均为纯的纳米级别碳，如何使用熔盐电化学电解制备性能更优异的硫掺杂纳米碳是一项新的技术挑战。
发明内容
为了制备硫掺杂的纳米碳，本发明提供了一种熔盐电解制备硫掺杂纳米碳及其方法，该硫掺杂纳米碳可作为超级电容器用储能材料、锂离子电池正极材料、电催化材料以及有效吸附水体中及空气中污染物。
本发明所采用的技术方案是：一种硫掺杂纳米碳电化学制备方法，其使用碱金属碳酸盐作为熔盐电解质体系；采用惰性材料为阳极，以金属或非金属材料为阴极；采用电化学反应装置；将含有CO2和SO2的火电厂、水泥厂、化工厂除尘脱硫后的工业烟气通入熔盐电解质中，在350-900℃的温度范围内，进行电解，制得硫掺杂纳米碳。
一种硫掺杂纳米碳电化学制备方法，其使用碱金属碳酸盐与碱金属硫酸盐的混合体作为熔盐电解质体系；采用惰性材料为阳极，以金属或非金属材料为阴极；采用电化学反应装置；将CO2或者含有CO2和SO2的火电厂、水泥厂、化工厂除尘脱硫后的工业烟气通入熔盐电解质中，在350-900℃的温度范围内，进行电解，制得硫掺杂纳米碳。
按上述方案，所述的碱金属碳酸盐为Li2CO3、Na2CO3和K2CO3中的任意一种或者多种的混合。
按上述方案，所述的碱金属硫酸盐为Li2SO4、Na2SO4和K2SO4中的任意一种或者多种的混合。
按上述方案，所述阳极为二氧化锡陶瓷电极、石墨电极以及钛电极、金电极、铂电极、铱电极、钯电极及其合金电极中的任意一种；所述的阴极为石墨电极以及镍电极、铜电极、钼电极、钛电极、铝电极、银电极、金电极、铂电极及其合金电极中的任意一种。
按上述方案，控制电化学反应装置的电解槽压在2.8V-6V之间。
按上述方案，所述的电化学反应装置分为阴极区和阳极区，采用全封闭或者半封闭的隔膜将阴极区和阳极区分开，防止阳极区产生的氧气扩散至阴极区，避免阴极区得到的硫掺杂碳材料被二次氧化。
上述任意一项制备方法所得的硫掺杂纳米碳。
按上述方案，所述的硫掺杂纳米碳的形貌为蜂窝状，其粒径为200-250nm，所述的硫掺杂纳米碳中硫主要以C-S-C的成键方式形成。
所述的硫掺杂纳米碳作为超级电容器用储能材料、锂离子电池正极材料、电催化材料以及有效吸附水体中及空气中的污染物的材料的应用。
本发明的反应机理：当施加一定的电压在上述碳酸盐熔盐中时，碳酸盐发生分解，生成单质碳和金属氧化物，以Li2CO3-Na2CO3-K2CO3(摩尔比Li2CO3:Na2CO3:K2CO3＝43.5:31.5:25)掺杂不同浓度的Li2SO4的为例，介绍反应机理如下：
根据热力学计算，三元碳酸盐Li2CO3、Na2CO3、K2CO3中，首先发生的分解反应为Li2CO3的分解。
Li2CO3＝Li2O+C+O2(g)[1a]
当通入的气体为纯二氧化碳，熔盐中含有Li2SO4时，反应[1a]生成的C与Li2SO4发生反应生成硫掺杂的碳，反应[1a]生成的Li2O与二氧化碳反应生成Li2CO3以保持熔盐的稳定，反应式如下：
C+Li2SO4→C-S-C+S(g)+Li+Li2SO3[1b]
Li2O+CO2＝Li2CO3[1c]
当通入的气体为除尘脱硫后含少量二氧化硫和大量二氧化碳的烟气，熔盐中不含硫酸盐时，反应[1a]生成的Li2O与二氧化碳发生反应[1c]生成Li2CO3以保持熔盐的稳定，反应[1a]生成的Li2O和O2与烟气中的SO2发生反应[1d]生成Li2SO4，反应[1d]生成的Li2SO4与C发生[1b]的反应生成硫掺杂的碳，反应[1d]如下：
2Li2O+2SO2+O2＝2Li2SO4[1d]
本发明阴极碳材料中硫的含量可控。硫在阴极碳材料中主要以C-S-C的成键方式形成。通过本发明制得的硫掺杂的纳米碳，可作为超级电容器用储能材料、锂离子电池正极材料、电催化材料以及有效吸附水体中及空气中的污染物。
与现有技术相比，本发明的有益效果是：提出了一种新的硫掺杂纳米碳的制备方法。该方法工艺简单，制备的硫掺杂纳米碳硫含量可控、碳材料的形貌可控。该硫掺杂的纳米碳相对于单纯的纳米碳粉，表现出更广泛及优异的应用性能，可作为超级电容器用储能材料、锂离子电池正极材料、电催化材料以及吸附水体中及空气中的污染物。
附图说明
图1.反应装置示意图；
图2.某一槽压电解阴极得到的硫掺杂碳材料SEM图；
图3.某一槽压电解阴极得到的硫掺杂碳材料XPS图；
图4.某一槽压电解阴极得到的硫掺杂碳材料在H2SO4溶液中的充放电测试图。
具体实施方式
下面结合附图对本发明进一步说明，其在于进一步描述而非限制本发明。
实施例1：
以Li2CO3-Na2CO3-K2CO3(摩尔比Li2CO3:Na2CO3:K2CO3＝43.5:31.5:25)掺杂不同浓度的Li2SO4(Li2SO4％＝1.45mol％,4mol％,8mol％)熔盐作为电解质，475℃条件下，二氧化锡陶瓷电极做阳极，镍片做阴极，两电极体系，阴极区电极用两端开口的氧化铝管套住，防止阳极区产生的氧气扩散至阴极区，避免阴极区硫掺杂的碳材料被二次氧化(图1)。选定4.5V、5V以及5.5V槽压，恒槽压电解，电解的过程中不间断通入含二氧化硫和二氧化碳混合气体的烟气，不同槽压下阴极镍片上制得不同形貌不同含量硫掺杂的纳米碳。
图2为某一槽压电解阴极得到的硫掺杂碳材料SEM图，如图2所示，阴极碳材料的形貌为蜂窝状，粒径为200-250nm。
图3为某一槽压电解阴极得到的硫掺杂碳材料XPS图，如图3所示，硫在阴极碳材料中主要以C-S-C的成键方式形成。
实施例2：
以不同配比的Li2CO3-Na2CO3-K2CO3三元混合盐作为电解质，在温度为350℃-900℃范围内，二氧化锡陶瓷电极做阳极，镍片做阴极，两电极体系，阴极区电极用两端开口的氧化铝管套住，防止阳极区产生的氧气扩散至阴极区，避免阴极区硫掺杂的碳材料被二次氧化(图1)。以一定的槽压电解，电解的过程中不间断通入含二氧化硫和二氧化碳的烟气，不同槽压下阴极镍片上制得不同形貌不同含量硫掺杂的纳米碳。由此说明该硫掺杂的纳米碳中硫源可来自烟气中的二氧化硫。
实施例3：
以不同配比的Li2CO3-Na2CO3-K2CO3三元混合盐掺杂不同浓度的Li2SO4作为电解质，在温度为350℃-900℃范围内，二氧化锡陶瓷电极做阳极，镍片做阴极，两电极体系，阴极区电极用两端开口的氧化铝管套住，防止阳极区产生的氧气扩散至阴极区，避免阴极区硫掺杂的碳材料被二次氧化(图1)。以一定的槽压电解，电解的过程中不间断通入纯的二氧化碳气体，不同槽压下阴极镍片上制得不同形貌不同含量硫掺杂的纳米碳。由此说明该硫掺杂的纳米碳中硫源可来自盐中掺杂的Li2SO4。
实施例4：
以不同配比的Li2CO3-K2CO3二元混合碳酸盐掺杂不同浓度的硫酸盐作为电解质，在温度为350℃-900℃范围内，二氧化锡陶瓷电极做阳极，镍片做阴极，两电极体系，阴极区电极用两端开口的氧化铝管套住，防止阳极区产生的氧气扩散至阴极区，避免阴极区硫掺杂的碳材料被二次氧化(图1)。以一定的槽压电解，电解的过程中不间断通入含二氧化硫和二氧化碳的烟气，不同槽压下阴极镍片上制得不同形貌不同含量硫掺杂的纳米碳。
实施例5：
以Li2CO3单元熔盐为电解质，升温至Li2CO3的熔点温度723℃或以上，保持熔融状态，二氧化锡陶瓷电极做阳极，镍片做阴极，两电极体系，阴极区电极用两端开口的氧化铝管套住，防止阳极区产生的氧气扩散至阴极区，避免阴极区硫掺杂的碳材料被二次氧化(图1)。以一定的槽压电解，电解的过程中不间断通入含二氧化硫和二氧化碳的烟气，不同槽压下阴极镍片上制得不同形貌不同含量硫掺杂的纳米碳。
实施例6：
将由实施例1制得的硫掺杂碳粉作为电极材料制备为超级电容器电极，在475℃，8mol％Li2SO4掺杂，4.5V恒定槽压下制得的硫掺杂碳粉，当恒流充放电电流密度为2A/g、1A/g、0.5A/g以及0.2A/g时，比电容为：346.4F/g，415F/g，489.5F/g以及712F/g(图4)。由此说明该硫掺杂的纳米碳具备优异的电容性能。
实施例7：
将由实施例1制得的硫掺杂碳粉作为锂离子电池材料，将该硫掺杂的碳粉作为锂离子电池的正极，锂片作为负极，组装成锂硫电池，将该锂硫电池进行电化学性能测试，在0.5C的下的放电比容量为967mAh/g。由此说明该硫掺杂的纳米碳具备较好的容量优势。
实施例8：
将由实施例1制得的硫掺杂碳粉作为氧还原用催化剂，在0.1M KOH溶液中测试该硫掺杂碳粉的氧还原催化性能，氧还原峰电流密度可高达4mA/cm2。由此说明该硫掺杂的纳米碳具备优良的氧还原催化效果。
实施例9：
将由实施例1制得的硫掺杂纳米碳作为吸附剂吸附水中污染物，以吸附水中阳离子染料亚甲基蓝为例，该硫掺杂的碳粉对水中亚甲基蓝的去除率高达95％以上。
实施例10：
将由实施例1制得的硫掺杂纳米碳作为空气中甲醛吸附用材料，当甲醛浓度为255ppm时，该硫掺杂的纳米碳对甲醛的吸附容量可达166.84ppm/g。由此说明该硫掺杂纳米碳可作为空气中污染物吸附用材料。
Claims (8)
1.一种硫掺杂纳米碳电化学制备方法，其使用碱金属碳酸盐作为熔盐电解质体系，所述的碱金属碳酸盐为Li2CO3、Na2CO3和K2CO3的混合；采用惰性材料为阳极，以金属或非金属材料为阴极；采用电化学反应装置，控制电化学反应装置的电解槽压在2.8V-6V之间；将含有CO2和SO2的火电厂、水泥厂、化工厂除尘脱硫后的工业烟气通入熔盐电解质中，在350-900℃的温度范围内，进行电解，制得硫掺杂纳米碳。
2.一种硫掺杂纳米碳电化学制备方法，其使用碱金属碳酸盐与碱金属硫酸盐的混合体作为熔盐电解质体系，所述的碱金属碳酸盐为Li2CO3、Na2CO3和K2CO3的混合；采用惰性材料为阳极，以金属或非金属材料为阴极；采用电化学反应装置，控制电化学反应装置的电解槽压在2.8V-6V之间；将CO2或者含有CO2和SO2的火电厂、水泥厂、化工厂除尘脱硫后的工业烟气通入熔盐电解质中，在350-900℃的温度范围内，进行电解，制得硫掺杂纳米碳。
3.根据权利要求2所述的硫掺杂纳米碳电化学制备方法，其特征在于，所述的碱金属硫酸盐为Li2SO4、Na2SO4和K2SO4中的任意一种或者多种的混合。
4.根据权利要求1或2所述的硫掺杂纳米碳电化学制备方法，其特征在于，所述阳极为二氧化锡陶瓷电极、石墨电极以及钛电极、金电极、铂电极、铱电极、钯电极及其合金电极中的任意一种；所述的阴极为石墨电极以及镍电极、铜电极、钼电极、钛电极、铝电极、银电极、金电极、铂电极及其合金电极中的任意一种。
5.根据权利要求1或2所述的硫掺杂纳米碳电化学制备方法，其特征在于：所述的电化学反应装置分为阴极区和阳极区，采用全封闭或者半封闭的隔膜将阴极区和阳极区分开，防止阳极区产生的氧气扩散至阴极区，避免阴极区得到的硫掺杂碳材料被二次氧化。
6.权利要求1-5任意一项制备方法所得的硫掺杂纳米碳。
7.根据权利要求6所述的硫掺杂纳米碳，其特征在于，所述的硫掺杂纳米碳的形貌为蜂窝状，其粒径为200-250nm，所述的硫掺杂纳米碳中硫主要以C-S-C的成键方式形成。
8.权利要求6所述的硫掺杂纳米碳作为超级电容器用储能材料、锂离子电池正极材料、电催化材料以及有效吸附水体中及空气中的污染物的材料的应用。
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