CN110380027A - 一种含碳双金属氧化物的制备方法 - Google Patents
一种含碳双金属氧化物的制备方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
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- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 7
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- DAPUDVOJPZKTSI-UHFFFAOYSA-L ammonium nickel sulfate Chemical compound [NH4+].[NH4+].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DAPUDVOJPZKTSI-UHFFFAOYSA-L 0.000 claims description 2
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- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 2
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims description 2
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- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 2
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- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 claims 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910017163 MnFe2O4 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
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- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
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- 150000002632 lipids Chemical class 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 235000021081 unsaturated fats Nutrition 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
本发明涉及一种含碳双金属氧化物的制备方法，用高锰酸钾与铁、钴或镍过渡金属氧化物前驱体及不饱和长链脂肪酸反应，直接合成嵌入在碳基质中的纳米级双金属氧化物材料。通过微乳化技术结合Baeyer试剂反应路线，精确调变金属盐种类及其比例、长链不饱和脂肪酸的种类和比例、加热方法、焙烧气氛、焙烧温度，直接将双金属氧化物嵌入到碳基质中，获得一种结构、组分含量、组分种类可控的含碳的纳米级双金属复合氧化物。
Description
技术领域
本发明涉及领域化工应用技术领域，尤其涉及一种双金属复合氧化物及其制备方法。
背景技术
双金属过渡金属氧化物复合材料由于不同金属之间的协同效应，相较于单一金属氧化物可表现出更好的电源、光学、磁学性能。纳米化的双金属氧化物具有小尺寸效应、表面效应、量子尺寸效应和宏观量子轨道效应，可使材料具有更高的活性。另一方面，将碳与双金属复合氧化物复合可使材料的稳定性、导电性等方面得到有效提升。这种含有碳的纳米双金属氧化物在反应催化、物理化学吸附、精细陶瓷、磁性材料、超级电容器、在锂离子电池负极材料等领域有重要应用前景。
目前，纳米双金属复合氧化物的制备方法主要可以分为物理法和化学法。物理法采用高能耗的激光溅射法、球磨法、电弧法等方式“强制”将材料细化，该法产量低、设备投入大、纳米化效果差，成本高。化学法主要有沉淀法、水热法、相转移法、界面合成法、溶胶-凝胶法，化学法合成的纳米材料均匀、可大量生产、设备投入小。纳米双金属氧化物的化学合成法也存在一些问题，如合成路线复杂、原料昂贵、反应条件苛刻、反应时间过长、合成产物产量低、组分难控制、纳米化效果不佳等。现有技术制备含碳的纳米级双金属混合氧化物还比较困难，亟需一种成本更低、合成路线更合理高效的合成技术来合成一种结构、组分含量、组分种类可控的含碳双金属复合氧化物。
发明内容
为实现上述目的，本发明采用如下技术方案：用价格低、来源丰富的高锰酸钾与铁、钴或镍过渡金属氧化物前驱体及不饱和长链脂肪酸反应，直接合成嵌入在碳基质中的纳米级双金属氧化物材料。通过微乳化技术结合Baeyer试剂反应路线，精确调变金属盐种类及其比例、长链不饱和脂肪酸的种类和比例、加热方法、焙烧气氛、焙烧温度，直接将双金属氧化物嵌入到碳基质中，获得一种结构、组分含量、组分种类可控的含碳的纳米级双金属复合氧化物。具体制备过程如下：
S1.由NaOH水溶液、长链不饱和脂肪酸和乙醇在不低于60 ℃水浴条件下制得微乳液A；
S2.将过渡金属T（T=Ni、Fe或Co）莫尔盐用纯水溶解配置成溶液B，再将B溶液与微乳液A溶液混合后在不低于60 ℃温度下搅拌不少于2h得到溶液C；
S3.向溶液C中加入高锰酸钾溶液使其发生Baeyer试剂反应，在60-220℃的温度下搅拌不少于2 h得到D；
S4.对D进行固液分离得到固体E，依次用乙醇和水对E进行洗涤后干燥处理；
S5.将E移至管式炉或马弗炉中在单一气体的气氛中升温至400-1000℃一定温度，恒温不少于2h后自然冷却至室温，得到含碳双金属复合氧化物。
进一步的，步骤S1中长链不饱和脂肪酸为巴豆酸、肉桂酸、油酸或蓖麻油酸等中的一种或几种混合。
进一步的，步骤S2中过渡金属T莫尔盐为硫酸亚铁铵、硫酸铁铵、硫酸钴铵、硫酸镍铵中的一种或几种混合。
进一步的，步骤S3中的高锰酸钾溶液中高锰酸钾的物质的量与过渡金属T莫尔盐的摩尔比为0.01-1：1。
进一步的，步骤S3中反应温度为60℃、150℃、180℃或210℃。若反应温度为60℃，优选的采用恒温水浴；若反应温度为150℃、180℃或210℃，优选的采用水热反应釜加热。
进一步的，步骤S5中单一气体的气氛可为氧气或者氮气，升温速率可为 1-10℃/min。
进一步的，步骤S5中得到的中含碳的双金属氧化物结构式为：(TO)x(MnO)1-x、TMn2O4、(TxMn1-x)O3或MnO-T，其中x=0.001-1。
本发明的工作原理为：由过渡金属T的莫尔盐出发（T= Fe、Co或Ni），在“不饱和脂肪酸-醇-水溶液”微乳液体系中，加入高锰酸钾，使其不饱和双键发生Baeyer试剂反应，再结合焙烧手段在不同气氛中使不饱和脂肪酸缓慢分解生成碳，同时，控制不同的反应条件使KMnO4还原成低价态的MnO，直接将TO-MnO嵌入碳基质中制得含碳的纳米级双金属氧化物。
本发明的有益效果为：采用本发明的技术方案，控制反应条件可直接将纳米级的TO-MnO氧化物嵌入碳基质中制得含碳的双金属氧化物，这种材料含有两种金属氧化物组分，并且含碳，可显著提高材料的导电性与电化学性能。
通过该法制得的含碳的双金属氧化物的结构丰富，可为(TxMn1-x)O3、TMn2O4、(TO)x(MnO)1-x或MnO-T（其中T=Ni、Fe、Co, B=Mn，x=0.001-1）中的一种，如MnFe2O4, CoMn2O4,(FeO)0.25(MnO)0.75, , (NiO)0.25(MnO)0.75, MnO-Fe，MnO-Ni，MnO-Co等。
通过该方法可以控制合成分散度好、结晶度高、稳定性好的一系列双金属氧化物。与现有技术相比，这种方法反应原料价格低、资源丰富，反应条件温和、高效、产率高。本发明制得的含碳的双金属氧化物材料可作为负极材料应用锂离子电池或超级电容器等领域。
附图说明
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。
图1为本发明中实施例1-5制备的不同结构的含碳的双金属氧化物的XRD谱图。
图2为本发明实施例1中制得的含碳的低价态铁锰双金属氧化物的HRTEM图。
具体实施方式
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。
实施例1
在恒温60℃水浴条件下，将1 g 氢氧化钠、10 mL无水乙醇、10 mL油酸配制成微乳液，再加入溶解在100 mL硫酸亚铁铵莫尔盐溶液（0.1 mol/L），搅拌2h，再将150 mL（0.04 mol/L）高锰酸钾溶液加入到上述溶液中使其发生Baeyer试剂反应，60℃继续反应2h获得沉淀物，用乙醇和纯水分别洗涤沉淀物质并在60℃下干燥12h。再转移到氮气下800℃下焙烧2h可以得到含碳的铁锰双金属氧化物(FeO)0198(MnO)0.802 ，其XRD谱图如图1中的（1）所示，其HRTEM图如图2所示，图2中颜色较深部分为FeO-MnO双金属氧化物，较浅部分为碳材料。
实施例2
在恒温60℃水浴条件下，将1 g 氢氧化钠、10 mL无水乙醇、10 mL油酸配制成微乳液，再加入溶解在100 mL硫酸镍铵莫尔盐溶液（0.1 mol/L），搅拌2 h，再将150 mL（0.02 mol/L）高锰酸钾溶液加入到上述溶液中使其发生Baeyer试剂反应，60 ℃继续反应2h获得沉淀物，用乙醇和纯水分别洗涤沉淀物质并在60 ℃下干燥12 h。再转移到氮气下400℃下焙烧2h可以得到含碳的镍锰双金属氧化物(NiO)0.25(MnO)0.75，其XRD谱图如图1中的（2）所示。
实施例3
在恒温60℃水浴条件下，将1.3 g 氢氧化钠、13 mL无水乙醇、13 mL油酸配制成微乳液，再加入溶解在25 mL硫酸亚铁铵莫尔盐溶液（0.1 mol/L），搅拌2h，再将60 mL（0.02mol/L）高锰酸钾溶液加入到上述溶液中使其发生Baeyer试剂反应，将上述混合溶液转移到水热反应釜中加热至150℃，以1000 rpm转速搅拌，继续反应10 h获得沉淀物，用乙醇和纯水分别洗涤沉淀物质并在60 ℃下干燥12 h。再转移到氮气下500℃下焙烧2 h可以得到含碳的铁锰双金属氧化物MnFe2O4，其XRD谱图如图1中的（7）所示。
实施例4
在恒温60 ℃水浴条件下，将1 g 氢氧化钠、10 mL无水乙醇、10 mL油酸配制成微乳液，再加入溶解在100 mL硫酸亚铁铵莫尔盐溶液（0.1 mol/L），搅拌2 h，再将150 mL（0.02mol/L）高锰酸钾溶液加入到上述溶液中使其发生Baeyer试剂反应，将上述混合溶液转移到水热反应釜中加热至180℃继续反应2 h获得沉淀物，用乙醇和纯水分别洗涤沉淀物质并在60 ℃下干燥12 h。再转移到氧气下1000 ℃下焙烧2 h可以得到含碳的双金属氧化物(Mn0.37Fe0.63)2O3，其XRD谱图如图1中的（8）所示。
实施例5
在恒温60℃水浴条件下，将1 g 氢氧化钠、10 mL无水乙醇、10 mL油酸配制成微乳液，再加入溶解在100 mL硫酸钴铵莫尔盐溶液（0.1 mol/L），搅拌2h，再将150 mL（0.04 mol/L）高锰酸钾溶液加入到上述溶液中使其发生Baeyer试剂反应，将上述混合溶液转移到水热反应釜中加热至210℃继续反应2h获得沉淀物，用乙醇和纯水分别洗涤沉淀物质并在60 ℃下干燥12 h。再转移到氮气下600 ℃下焙烧2 h可以得到含碳的钴锰双金属氧化物MnO-Co，其XRD谱图如图1中的（5）所示。
Claims (7)
1.一种含碳双金属氧化物的制备方法，包括如下步骤：
由NaOH水溶液、长链不饱和脂肪酸和乙醇在不低于60 ℃水浴条件下制得微乳液A；
将过渡金属T莫尔盐用纯水溶解配置成溶液B，再将B溶液与微乳液A混合后在不低于60℃温度下搅拌不少于2h得到溶液C；
向溶液C中加入高锰酸钾溶液使其发生Baeyer试剂反应，在60-220℃的温度下搅拌不少于2 h得到D；
对D进行固液分离得到固体E，依次用乙醇和水对E进行洗涤后干燥处理；
将E移至管式炉或马弗炉中在单一气体的气氛中升温至400-1000℃，恒温不少于2h后自然冷却至室温，得到含碳双金属复合氧化物。
2.根据权利要求1所述制备方法，其特征在于：所述步骤S1中所述长链不饱和脂肪酸为巴豆酸、肉桂酸、油酸或蓖麻油酸中的一种或几种混合。
3.根据权利要求2所述制备方法，其特征在于：所述步骤S2中所述过渡金属T莫尔盐为硫酸亚铁铵、硫酸铁铵、硫酸钴铵、硫酸镍铵中的一种或几种混合。
4.根据权利要求3所述制备方法，其特征在于：所述步骤S3中所述的高锰酸钾溶液中高锰酸钾的物质的量与过渡金属T莫尔盐的摩尔比为0.01-1：1。
5.根据权利要求4所述制备方法，其特征在于：所述步骤S3中反应温度为60℃、150℃、180℃或210℃。
6.根据权利要求5所述制备方法，其特征在于：所述步骤S5中所述单一气体的气氛可为氧气或者氮气，升温速率可为 1-10℃/min。
7.根据权利要求6所述制备方法，其特征在于：所述步骤S5中得到的中含碳的双金属氧化物结构式为：(TO)x(MnO)1-x、TMn2O4、(Tx Mn1-x)O3或MnO-T，其中T=Ni、Fe或Co，x=0.001-1。
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