CN109461899A - 一种同时回收利用过期碳酸锂药片和硫酸亚铁药片的方法 - Google Patents
一种同时回收利用过期碳酸锂药片和硫酸亚铁药片的方法 Download PDFInfo
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- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 73
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 71
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 title claims abstract description 57
- 229910000359 iron(II) sulfate Inorganic materials 0.000 title claims abstract description 57
- 239000011790 ferrous sulphate Substances 0.000 title claims abstract description 56
- 235000003891 ferrous sulphate Nutrition 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000004064 recycling Methods 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052493 LiFePO4 Inorganic materials 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 29
- 235000019441 ethanol Nutrition 0.000 claims abstract description 25
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000000227 grinding Methods 0.000 claims abstract description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000000470 constituent Substances 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 239000003814 drug Substances 0.000 abstract description 11
- 229940079593 drug Drugs 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- 239000011777 magnesium Substances 0.000 description 11
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000004088 simulation Methods 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 5
- 235000019359 magnesium stearate Nutrition 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 208000007502 anemia Diseases 0.000 description 4
- 239000000546 pharmaceutical excipient Substances 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 208000017194 Affective disease Diseases 0.000 description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PNEFIWYZWIQKEK-UHFFFAOYSA-N carbonic acid;lithium Chemical compound [Li].OC(O)=O PNEFIWYZWIQKEK-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
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- 231100000225 lethality Toxicity 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种同时回收利用过期碳酸锂药片和硫酸亚铁药片的方法,属于新能源材料技术领域。将过期碳酸锂药片、过期硫酸亚铁药片、(NH4)2HPO4置于乙醇中混合并研磨2~4h得到研磨物料;在氮气气氛中,将得到的研磨物料在温度为650~750℃煅烧8~10h,得到黑色Mg2+/LiFePO4/C粉末。本发明首次提供了一种同时回收利用过期碳酸锂药片和硫酸亚铁药片的方法,具体主要是利用过期碳酸锂药片和硫酸亚铁药片为原料,制得黑色的Mg2+/LiFePO4/C粉末,并将其应用于锂离子电池的正极材料,充分利用了废弃药品中的非医疗价值。
Description
技术领域
本发明涉及一种同时回收利用过期碳酸锂药片和硫酸亚铁药片的方法,属于新能源材料技术领域。
背景技术
双相情感性精神障碍是一种严重的精神疾病,兼有躁狂与抑郁两种表现,具有高患病率、高致残率和高致死率等危害。碳酸锂片是由碳酸锂和赋形剂共同组成的专门治疗双相情感性精神障碍的对症药品,其中碳酸锂是活性成分,具有预防和治疗双相情感性精神障碍的作用,主要通过稳定钙和血清素来稳定情绪,赋形剂则具有赋形、充当载体、提高稳定性的作用。未被及时使用完的碳酸锂药片很容易被遗忘并过期,不可避免地导致过期碳酸锂药片的产生。众所周知,碳酸锂一种常见的用于合成锂离子电池正极材料和含锂电解液的原材料。一旦过期,如果不能充分探索过期碳酸锂片的非医疗价值,将会造成锂资源的浪费,同时稀有且不可再生的锂源将被消耗制备碳酸锂,并可能造成二次污染。此外,缺铁性贫血也是一种常见疾病。当机体对铁的需求与供给失衡,导致体内贮存铁耗尽,继而红细胞内铁缺乏,最终引起缺铁性贫血。硫酸亚铁片是由硫酸亚铁、赋形剂以及硬脂酸镁组成的治疗缺铁性贫血的药品,其中的硫酸亚铁是活性成分,具有预防和治疗缺铁性贫血的作用;作为药品辅料的赋形剂则具有赋形、充当载体、提高稳定性的作用,硬脂酸镁为疏水性润滑剂,易与颗粒混匀,压片后片面光洁美观。与碳酸锂片一样,未被使用完全的硫酸亚铁药片也容易会被遗忘并过期。目前对过期医疗药品的处置方式主要是由相关部门收集后统一进行焚烧或填埋,这不仅是对资源的浪费,同时也有可能会造成环境污染。因此开展对过期药品的回收及利用迫在眉睫。
LiFePO4被广泛认为是一种具有开发和应用潜力的新一代锂离子动力电池的正极材料。然而批量LiFePO4的生产需要消耗大量的锂源和铁源。鉴于此,本发明采用简单的固相反应以Mg2+/LiFePO4/C黑色粉末的形式将过期碳酸锂药片和硫酸亚铁药片同时进行回收,其中碳酸锂作为锂源,硫酸亚铁作为Fe2+源,硬脂酸镁作为Mg2+源,从而构建过期碳酸锂片和硫酸亚铁片与锂离子电池的新型关联。不仅减少了对环境的污染,同时变废为宝,有利于促进循环经济和可持续战略的发展,具有重要的环保意义。
发明内容
针对上述现有技术存在的问题及不足,本发明提供一种同时回收利用过期碳酸锂药片和硫酸亚铁药片的方法。本发明首次提供了一种同时回收利用过期碳酸锂药片和硫酸亚铁药片的方法,具体主要是利用过期碳酸锂药片和硫酸亚铁药片为原料,制得黑色的Mg2 +/LiFePO4/C粉末,并将其应用于锂离子电池的正极材料,充分利用了废弃药品中的非医疗价值。本发明通过以下技术方案实现。
一种同时回收利用过期碳酸锂药片和硫酸亚铁药片的方法,其具体步骤如下:
步骤1、将过期碳酸锂药片、过期硫酸亚铁药片、(NH4)2HPO4置于乙醇中混合并研磨2~4h得到研磨物料;
步骤2、在氮气气氛中,将步骤1得到的研磨物料在温度为650~750℃煅烧8~10h,得到黑色Mg2+/LiFePO4/C粉末。
所述步骤1中过期碳酸锂药片、过期硫酸亚铁药片、(NH4)2HPO4按照过期碳酸锂药片中活性成分Li2CO3、过期硫酸亚铁药片中活性成分FeSO4∙7H2O、 (NH4)2HPO4的摩尔比为1:2:2置于乙醇中。
所述步骤1中过期碳酸锂药片中活性成分Li2CO3的摩尔量与乙醇体积比为1:8~20mol/mL。
所述步骤2氮气气氛中氮气流量为0.1~0.5 L/min。
上述过期硫酸亚铁药片中含有活性成分FeSO4∙7H2O以及硬脂酸镁。
上述过期碳酸锂药片Li2CO3作为锂源,过期硫酸亚铁药片中活性成分FeSO4∙7H2O作为Fe2+源,过期硫酸亚铁药片中硬脂酸镁作为Mg2+源。
本发明的有益效果是:
本发明旨在开发过期废药的非医疗价值,将过期碳酸锂药片和硫酸亚铁药片以具有高经济附加值的Mg2+/LiFePO4/C黑色粉末的形式同时回收,并考察其电化学储锂性能,不仅变废为宝、缓解过期废药对生态环境造成的负面影响,而且充分发挥废弃资源的有用价值。
附图说明
图1是本发明实物图,其中(a)过期碳酸锂药片、(b)过期硫酸亚铁药片、(c)实施例1制备得到的Mg2+/LiFePO4/C黑色粉末的照片;
图2是本发明实施例1制备得到的Mg2+/LiFePO4/C黑色粉末SEM图;
图3是本发明实施例2制备得到的Mg2+/LiFePO4/C黑色粉末EDX谱图;
图4是本发明实施例3制备得到的Mg2+/LiFePO4/C黑色粉末XRD谱图;
图5是本发明实施例4制备得到的Mg2+/LiFePO4/C黑色粉末组装的模拟锂离子电池的充/放电曲线;
图6是本发明实施例5制备得到的Mg2+/LiFePO4/C黑色粉末组装的模拟锂离子电池的循环稳定曲线;
图7是本发明实施例6制备得到的Mg2+/LiFePO4/C黑色粉末组装的模拟锂离子电池的循环伏安曲线。
具体实施方式
下面结合附图和具体实施方式,对本发明作进一步说明。
实施例1
该同时回收利用过期碳酸锂药片和硫酸亚铁药片的方法,其具体步骤如下:
步骤1、将过期碳酸锂药片(照片图如图1(a)所示)、过期硫酸亚铁药片(照片图如图1(b)所示)、(NH4)2HPO4置于乙醇中混合并研磨2h得到研磨物料;其中过期碳酸锂药片、过期硫酸亚铁药片、(NH4)2HPO4按照过期碳酸锂药片中活性成分Li2CO3、过期硫酸亚铁药片中活性成分FeSO4∙7H2O、(NH4)2HPO4的摩尔比为1:2:2置于乙醇中;过期碳酸锂药片中活性成分Li2CO3的摩尔量与乙醇体积比为1:10mol/mL;
步骤2、在氮气气氛中(氮气气氛中氮气流量为0.5L/min),将步骤1得到的研磨物料在温度为650℃煅烧8h,得到黑色Mg2+/LiFePO4/C粉末。
本实施例制备得到黑色Mg2+/LiFePO4/C粉末照片如图1(c)所示,SEM图如图2所示,从图2可知黑色Mg2+/LiFePO4/C粉末呈现无规则的纳米颗粒形貌,粒径大小为200-500nm。
实施例2
该同时回收利用过期碳酸锂药片和硫酸亚铁药片的方法,其具体步骤如下:
步骤1、将过期碳酸锂药片、过期硫酸亚铁药片、(NH4)2HPO4置于乙醇中混合并研磨3h得到研磨物料;其中过期碳酸锂药片、过期硫酸亚铁药片、(NH4)2HPO4按照过期碳酸锂药片中活性成分Li2CO3、过期硫酸亚铁药片中活性成分FeSO4∙7H2O、(NH4)2HPO4的摩尔比为1:2:2置于乙醇中;过期碳酸锂药片中活性成分Li2CO3的摩尔量与乙醇体积比为1:15mol/mL;
步骤2、在氮气气氛中(氮气气氛中氮气流量为0.5L/min),将步骤1得到的研磨物料在温度为700℃煅烧9h,得到黑色Mg2+/LiFePO4/C粉末。
本实施例制备得到黑色Mg2+/LiFePO4/C粉末EDX谱图如图3所示,从图3可知黑色Mg2+/LiFePO4/C粉末主要含有C、Fe、O、P和Mg元素,且无其它杂质元素,表明Mg2+成功掺杂到LiFePO4/C中。
实施例3
该同时回收利用过期碳酸锂药片和硫酸亚铁药片的方法,其具体步骤如下:
步骤1、将过期碳酸锂药片、过期硫酸亚铁药片、(NH4)2HPO4置于乙醇中混合并研磨4h得到研磨物料;其中过期碳酸锂药片、过期硫酸亚铁药片、(NH4)2HPO4按照过期碳酸锂药片中活性成分Li2CO3、过期硫酸亚铁药片中活性成分FeSO4∙7H2O、(NH4)2HPO4的摩尔比为1:2:2置于乙醇中;过期碳酸锂药片中活性成分Li2CO3的摩尔量与乙醇体积比为1:8mol/mL;
步骤2、在氮气气氛中(氮气气氛中氮气流量为0.5L/min),将步骤1得到的研磨物料在温度为750℃煅烧9h,得到黑色Mg2+/LiFePO4/C粉末。
本实施例制备得到黑色Mg2+/LiFePO4/C粉末XRD谱图如图4所示,从图4可知衍射峰强而尖锐,与XRD标准图谱对应,无杂质峰出现,表明Mg2+掺杂没有改变LiFePO4的橄榄石结构,且结晶度较好。
实施例4
该同时回收利用过期碳酸锂药片和硫酸亚铁药片的方法,其具体步骤如下:
步骤1、将过期碳酸锂药片、过期硫酸亚铁药片、(NH4)2HPO4置于乙醇中混合并研磨3h得到研磨物料;其中过期碳酸锂药片、过期硫酸亚铁药片、(NH4)2HPO4按照过期碳酸锂药片中活性成分Li2CO3、过期硫酸亚铁药片中活性成分FeSO4∙7H2O、(NH4)2HPO4的摩尔比为1:2:2置于乙醇中;过期碳酸锂药片中活性成分Li2CO3的摩尔量与乙醇体积比为1:20mol/mL;
步骤2、在氮气气氛中(氮气气氛中氮气流量为0.4L/min),将步骤1得到的研磨物料在温度为650℃煅烧10h,得到黑色Mg2+/LiFePO4/C粉末。
本实施例制备得到黑色Mg2+/LiFePO4/C粉末进一步研磨并制成电极片,与锂箔组装成扣式模拟锂离子电池,以恒流充/放电法测试其电化学性能,如图5所示。由图5可知,在0.5 C、1 C、2 C、5 C 和 10 C的倍率下,放电比容量分别为134.8 mAh/g、132.1 mAh/g、128.1 mAh/g、115.7 mAh/g和96.9 mAh/g,表明Mg2+/LiFePO4/C正极具有良好的储锂性能以及对大的电流变化具有高的耐受性。
实施例5
该同时回收利用过期碳酸锂药片和硫酸亚铁药片的方法,其具体步骤如下:
步骤1、将过期碳酸锂药片、过期硫酸亚铁药片、(NH4)2HPO4置于乙醇中混合并研磨4h得到研磨物料;其中过期碳酸锂药片、过期硫酸亚铁药片、(NH4)2HPO4按照过期碳酸锂药片中活性成分Li2CO3、过期硫酸亚铁药片中活性成分FeSO4∙7H2O、(NH4)2HPO4的摩尔比为1:2:2置于乙醇中;过期碳酸锂药片中活性成分Li2CO3的摩尔量与乙醇体积比为1:10mol/mL;
步骤2、在氮气气氛中(氮气气氛中氮气流量为0.3L/min),将步骤1得到的研磨物料在温度为700℃煅烧8h,得到黑色Mg2+/LiFePO4/C粉末。
本实施例制备得到黑色Mg2+/LiFePO4/C粉末进一步研磨并制成电极片,与锂箔组装成扣式模拟锂离子电池,Mg2+/LiFePO4/C黑色粉末组装的模拟锂离子电池的循环稳定曲线如图6所示。由图6可知,在2C下充/放电测试循环500圈后,电池容量可以维持在124.1mAh/g,表明Mg2+/LiFePO4/C正极具有良好的循环稳定性。
实施例6
该同时回收利用过期碳酸锂药片和硫酸亚铁药片的方法,其具体步骤如下:
步骤1、将过期碳酸锂药片、过期硫酸亚铁药片、(NH4)2HPO4置于乙醇中混合并研磨3h得到研磨物料;其中过期碳酸锂药片、过期硫酸亚铁药片、(NH4)2HPO4按照过期碳酸锂药片中活性成分Li2CO3、过期硫酸亚铁药片中活性成分FeSO4∙7H2O、(NH4)2HPO4的摩尔比为1:2:2置于乙醇中;过期碳酸锂药片中活性成分Li2CO3的摩尔量与乙醇体积比为1:14mol/mL;
步骤2、在氮气气氛中(氮气气氛中氮气流量为0.1L/min),将步骤1得到的研磨物料在温度为750℃煅烧8h,得到黑色Mg2+/LiFePO4/C粉末。
本实施例制备得到黑色Mg2+/LiFePO4/C粉末进一步研磨并制成电极片,与锂箔组装成扣式模拟锂离子电池,Mg2+/LiFePO4/C黑色粉末组装的模拟锂离子电池的循环伏安曲线如图7所示。由图7可知,第一圈正向扫描过程中,在3.6 V左右出现氧化峰,第一圈负向扫描过程中,在3.3V左右出现还原峰,且随后第二圈CV曲线中的氧化/还原峰基本与第一圈重合,表明了Mg2+/LiFePO4/C正极具有良好的可逆性和循环稳定性。
以上结合附图对本发明的具体实施方式作了详细说明,但是本发明并不限于上述实施方式,在本领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。
Claims (4)
1.一种同时回收利用过期碳酸锂药片和硫酸亚铁药片的方法,其特征在于具体步骤如下:
步骤1、将过期碳酸锂药片、过期硫酸亚铁药片、(NH4)2HPO4置于乙醇中混合并研磨2~4h得到研磨物料;
步骤2、在氮气气氛中,将步骤1得到的研磨物料在温度为650~750℃煅烧8~10h,得到黑色Mg2+/LiFePO4/C粉末。
2.根据权利要求1所述的同时回收利用过期碳酸锂药片和硫酸亚铁药片的方法,其特征在于:所述步骤1中过期碳酸锂药片、过期硫酸亚铁药片、(NH4)2HPO4按照过期碳酸锂药片中活性成分Li2CO3、过期硫酸亚铁药片中活性成分FeSO4∙7H2O、 (NH4)2HPO4的摩尔比为1:2:2置于乙醇中。
3.根据权利要求1所述的同时回收利用过期碳酸锂药片和硫酸亚铁药片的方法,其特征在于:所述步骤1中过期碳酸锂药片中活性成分Li2CO3的摩尔量与乙醇体积比为1:8~20mol/mL。
4.根据权利要求1所述的同时回收利用过期碳酸锂药片和硫酸亚铁药片的方法,其特征在于:所述步骤2氮气气氛中氮气流量为0.1~0.5 L/min。
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