CN109384262B - 一种片状Li4Mn5O12离子筛前驱体及离子筛的制备方法 - Google Patents
一种片状Li4Mn5O12离子筛前驱体及离子筛的制备方法 Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910011981 Li4Mn5O12 Inorganic materials 0.000 claims abstract description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 31
- 150000002500 ions Chemical class 0.000 claims abstract description 28
- 239000011572 manganese Substances 0.000 claims abstract description 25
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 7
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- 239000000243 solution Substances 0.000 claims description 42
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 15
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 13
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical group [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
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- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
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- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 2
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- 150000007524 organic acids Chemical class 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
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- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 8
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- -1 hydrogen ions Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Substances OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
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- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
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- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
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Abstract
本发明涉及一种片状Li4Mn5O12离子筛前驱体及离子筛的制备方法。将锂源和锰源按锂锰摩尔比为(0.6‑2)∶1配制含锂离子和锰离子的混合盐溶液；先在140‑200℃条件下干燥活化后，得到深灰色粉末，研磨均匀后放入管式炉内于250‑400℃条件下煅烧，得到片状Li4Mn5O12离子筛前驱体。脱锂之后得到MnO2·0.3H2O离子筛，其吸附容量大，稳定性好，可用于盐湖海水提锂。
Description
技术领域
本发明涉及一种片状Li4Mn5O12离子筛前驱体及离子筛的制备方法，该方法制得的MnO2·0.3H2O离子筛及其前驱体Li4Mn5O12具有独特的片状结构，接触面积大，脱附后对锂离子吸附效果优良，稳定性好，可循环应用。
背景技术
锂是密度最轻的碱金属元素，具有硬度大、比能量高等优异性能，广泛应用于能源、航天、冶金、医疗等方面，被称为“21世纪的能源元素”。传统的锂资源获得手段主要是通过开采锂矿石，开采难度大，而且随着长年累月的连续开采，锂矿石资源日渐枯竭，使得锂盐价格越来越高。离子筛吸附法是一种发展较为成熟、吸附效果较好、成本较低的一种绿色高效的提锂方法，可以最大程度地提取盐湖或海水中的锂。Li4Mn5O12是常见的离子筛前驱体之一，相较于其他形式的离子筛前驱体，Li4Mn5O12中的Mn全部以四价形式存在，其离子筛在吸附和脱附的过程中不会发生Mn的溶损，稳定性好。Li4Mn5O12是一种富锂形式的离子筛前驱体，理论吸附量高。
目前合成Li4Mn5O12的方法主要有熔盐法、水热法、固相法等，制得的 Li4Mn5O12颗粒有球状、棒状、多边形颗粒状。Yang等煅烧以锂盐或氢氧化锂为助溶剂，混合γ-MnOOH，在400℃的氧气氛围下煅烧168h得到棒状Li4Mn5O12 (Journal of Materials Chemistry,1999,9(10):2683-2690)。中国专利公开号 CN101764224A公开了一种水热法制备Li4Mn5O12亚微米棒的方法。以 MnSO4·H2O、KMnO4、CTAB为原料，先制备γ-MnOOH，再将其与LiOH混合在高温条件(500-900℃)下煅烧得到Li4Mn5O12。许惠等通过EDTA-柠檬酸络合法以LiNO3和Mn(NO3)2·4H2O为原料制备溶胶，再与400℃条件下煅烧24h 得到球状Li4Mn5O12颗粒。以上方法合成得到的Li4Mn5O12颗粒稳定性好，但是需得到γ-MnOOH才能进行后续反应，否则制备条件苛刻，制备周期延长，步骤繁琐，需要进行二次转移。
发明内容
本发明的目的是为了改进现有技术的不足而提供一种一种片状Li4Mn5O12离子筛前驱体及离子筛的制备方法。本发明首次制备出一种片状Li4Mn5O12颗粒，以非卤素作为阴离子的锂盐、及硝酸锰为原料，通过煅烧法制备，煅烧过程只需设定加热器的温控程序即可实现一步操作，不需二次转移，不需γ-MnOOH中间体，简化了制备步骤，缩短制备时间，有利于工业化应用。片状Li4Mn5O12颗粒酸洗后得到MnO2·0.3H2O离子筛依然保持其片状结构，与吸附液接触面积大，吸附效果优异。
本发明的技术方案为：一种片状Li4Mn5O12离子筛前驱体的制备方法，其特征在于将锂源和锰源按锂锰摩尔比为(0.6-2):1配制含锂离子和锰离子的混合盐溶液；先在140-200℃条件下干燥活化后，得到深灰色粉末，研磨均匀后放入管式炉内于250-400℃条件下煅烧，得到片状Li4Mn5O12离子筛前驱体。脱锂之后得到MnO2·0.3H2O离子筛。
优选上述的锂源为可溶性的非卤素作为阴离子的锂盐；锰源采用硝酸锰，溶剂为水。经过多次试验证明该锂盐不能使用阴离子含有卤素元素，因为最终产物出现Mn8O10X13杂质。更优选上述的锂源为硝酸锂、硫酸锂、碳酸锂、乙酸锂或甲酸锂等。
优选上述的干燥活化的时间为6-10h。优选上述的煅烧时间为6-14h。
本发明还提供了一种MnO2·0.3H2O离子筛的制备方法，将上述制备得到片状Li4Mn5O12离子筛前驱体酸性溶液洗脱之后得到片状的MnO2·0.3H2O离子筛。
优选上述的酸性溶液为无机酸、有机酸或酸性盐；酸性溶液的浓度为 0.02-0.4mol/L。更优选酸性溶液为盐酸、硫酸、磷酸、亚磷酸、硝酸、亚硫酸、过硫酸钠或氯化铵。
反应原理如下：
在该反应体系下，硝酸锰通过加热分解最终生成MnO2，最终在高温条件下，锂原子进入Mn-O空间结构生成Li4Mn5O12，通过酸洗Li4Mn5O12中的锂离子与氢离子进行离子交得到MnO2·0.3H2O离子筛；吸附锂离子时，MnO2·0.3H2O中的氢离子与海水中的锂离子发生离子交换。
有益效果：
1、本发明通过两步煅烧法制备Li4Mn5O12离子筛前驱体，实际只是两段温控，在加热设备内可以一步完成，无需转移设备，无质量损耗，制备过程简单，周期短，易操作，易于工业化。迄今为止，无相关文献或专利报道。
2、本发明所采用的原料为金属盐，简单易得，成本低廉，无需添加其他络合剂，无需预先制备中间体。
3、本发明所制得的Li4Mn5O12离子筛前驱体为片状纳米结构，具有比表面积大，结构稳定的优点，吸附容量大，选择性高，可循环利用。
附图说明
图1为本发明实施例1所制得的Li4Mn5O12离子筛前驱体的XRD图；
图2为本发明实施例1所制得的Li4Mn5O12离子筛前驱体的SEM图。
具体实施方式
实施例1：
称取0.04mol硝酸锂加入17.895g 50％的硝酸锰溶液中(锂锰摩尔比＝0.8)，搅拌至完全溶解，将混合溶液放置在烘箱中，于200℃的温度下干燥6h。将干燥后的混合物在400℃的条件下煅烧10h后取出研磨使颗粒均匀，得到黑色粉末。对其进行XRD表征，结果如图1所示，具有Li4Mn5O12的特征峰，晶格常数为
稳定性较好。通过SEM对其表面形貌进行表征，结果如图2所示，产物具有明显的片状结构。将Li4Mn5O12用0.1mol/L的盐酸溶液酸洗得到 MnO2·0.3H2O，置于富锂溶液进行吸附实验，在不同时间间隔用ICP检测其浓度用，经计算，吸附量为35.5mg/g。
实施例2：
称取0.02mol碳酸锂加入17.895g 50％的硝酸锰溶液中(锂锰摩尔比＝0.8)，搅拌至完全溶解，将混合溶液放置在烘箱中，于140℃的温度下干燥8h。将干燥后的混合物在400℃的条件下煅烧10h后取出研磨使颗粒均匀，得到黑色粉末。对其进行XRD表征，具有Li4Mn5O12的特征峰，晶格常数为
稳定性较好。通过SEM对其表面形貌进行表征，产物具有明显的片状结构。将Li4Mn5O12用0.25mol/L的盐酸溶液酸洗得到MnO2·0.3H2O，置于富锂溶液进行吸附实验，在不同时间间隔用ICP检测其浓度用，经计算，吸附量为31.8mg/g。
实施例3：
称取0.05mol硝酸锂加入17.895g 50％的硝酸锰溶液中(锂锰摩尔比＝1.0)，搅拌至完全溶解，将混合溶液放置在烘箱中，于140℃的温度下干燥8h。将干燥后的混合物在350℃的条件下煅烧10h后取出研磨使颗粒均匀，得到黑色粉末。对其进行XRD表征，具有Li4Mn5O12的特征峰，晶格常数为
稳定性较好。通过SEM对其表面形貌进行表征，产物具有明显的片状结构。将Li4Mn5O12用0.15mol/L的硫酸溶液酸洗得到MnO2·0.3H2O，置于富锂溶液进行吸附实验，在不同时间间隔用ICP检测其浓度用，经计算，吸附量为32.5mg/g。
实施例4：
称取0.06mol醋酸锂加入17.895g 50％的硝酸锰溶液中(锂锰摩尔比＝1.2)，搅拌至完全溶解，将混合溶液放置在烘箱中，于160℃的温度下干燥10h。将干燥后的混合物在300℃的条件下煅烧8h后取出研磨使颗粒均匀，得到黑色粉末。对其进行XRD表征，具有Li4Mn5O12的特征峰，晶格常数为
稳定性较好。通过SEM对其表面形貌进行表征，产物具有明显的片状结构。将Li4Mn5O12用0.06mol/L的硝酸溶液酸洗得到MnO2·0.3H2O，置于富锂溶液进行吸附实验，在不同时间间隔用ICP检测其浓度用，经计算，吸附量为30.9mg/g。
实施例5：
称取0.06mol硫酸锂加入17.895g 50％的硝酸锰溶液中(锂锰摩尔比＝1.2)，搅拌至完全溶解，将混合溶液放置在烘箱中，于180℃的温度下干燥6h。将干燥后的混合物在300℃的条件下煅烧12h后取出研磨使颗粒均匀，得到黑色粉末。对其进行XRD表征，具有Li4Mn5O12的特征峰，晶格常数为
稳定性较好。通过SEM对其表面形貌进行表征，产物具有明显的片状结构。将Li4Mn5O12用0.3mol/L的过硫酸钠溶液酸洗得到MnO2·0.3H2O，置于富锂溶液进行吸附实验，在不同时间间隔用ICP检测其浓度用，经计算，吸附量为30.1mg/g。
实施例6：
称取0.06mol硝酸锂加入17.895g 50％的硝酸锰溶液中(锂锰摩尔比＝1.2)，搅拌至完全溶解，将混合溶液放置在烘箱中，于180℃的温度下干燥8h。将干燥后的混合物在250℃的条件下煅烧14h后取出研磨使颗粒均匀，得到黑色粉末。对其进行XRD表征，具有Li4Mn5O12的特征峰，晶格常数为
稳定性较好。通过SEM对其表面形貌进行表征，产物具有明显的片状结构。将Li4Mn5O12用0.2mol/L的氯化铵溶液酸洗得到MnO2·0.3H2O，置于富锂溶液进行吸附实验，在不同时间间隔用ICP检测其浓度用，经计算，吸附量为29.0mg/g。
实施例7：
称取0.04mol醋酸锂加入17.895g 50％的硝酸锰溶液中(锂锰摩尔比＝0.8)，搅拌至完全溶解，将混合溶液放置在烘箱中，于180℃的温度下干燥10h。将干燥后的混合物在400℃的条件下煅烧12h后取出研磨使颗粒均匀，得到黑色粉末。对其进行XRD表征，具有Li4Mn5O12的特征峰，晶格常数为
稳定性较好。通过SEM对其表面形貌进行表征，产物具有明显的片状结构。将Li4Mn5O12用0.08mol/L的硝酸溶液酸洗得到MnO2·0.3H2O，置于富锂溶液进行吸附实验，在不同时间间隔用ICP检测其浓度用，经计算，吸附量为34.2mg/g。
实施例8：
称取0.07mol醋酸锂加入17.895g 50％的硝酸锰溶液中(锂锰摩尔比＝1.4)，搅拌至完全溶解，将混合溶液放置在烘箱中，于160℃的温度下干燥60h。将干燥后的混合物在350℃的条件下煅烧14h后取出研磨使颗粒均匀，得到黑色粉末。对其进行XRD表征，具有Li4Mn5O12的特征峰，晶格常数为
稳定性较好。通过SEM对其表面形貌进行表征，产物具有明显的片状结构。将Li4Mn5O12用0.04mol/L的盐酸溶液酸洗得到MnO2·0.3H2O，置于富锂溶液进行吸附实验，在不同时间间隔用ICP检测其浓度用，经计算，吸附量为29.8mg/g。
实施例9：
称取0.04mol碳酸锂加入17.895g 50％的硝酸锰溶液中(锂锰摩尔比＝1.6)，搅拌至完全溶解，将混合溶液放置在烘箱中，于160℃的温度下干燥10h。将干燥后的混合物在250℃的条件下煅烧8h后取出研磨使颗粒均匀，得到黑色粉末。对其进行XRD表征，具有Li4Mn5O12的特征峰，晶格常数为
稳定性较好。通过SEM对其表面形貌进行表征，产物具有明显的片状结构。将Li4Mn5O12用0.35mol/L的甲酸溶液酸洗得到MnO2·0.3H2O，置于富锂溶液进行吸附实验，在不同时间间隔用ICP检测其浓度用，经计算，吸附量为31.4mg/g。
Claims (8)
1.一种片状Li4Mn5O12离子筛前驱体的制备方法，其特征在于将锂源和锰源按锂锰摩尔比为(0.6-2):1配制含锂离子和锰离子的混合盐溶液；先在140-200℃条件下干燥活化后，得到深灰色粉末，研磨均匀后放入管式炉内于250-400℃条件下煅烧，得到片状Li4Mn5O12离子筛前驱体，脱锂之后得到MnO2·0.3H2O离子筛；其中锂源为可溶性的非卤素作为阴离子的锂盐。
2.根据权利要求1所述的制备方法，其特征在于所述的锰源采用硝酸锰。
3.根据权利要求1所述的制备方法，其特征在于所述的锂源为硝酸锂、硫酸锂、碳酸锂、乙酸锂或甲酸锂。
4.根据权利要求1所述的制备方法，其特征在于所述的干燥活化的时间为6-10h。
5.根据权利要求1所述的制备方法，其特征在于所述的煅烧时间为6-14h。
6.一种片状MnO2·0.3H2O离子筛的制备方法，其特征在于将权利要求1制备得到片状Li4Mn5O12离子筛前驱体酸性溶液洗脱之后得到片状的MnO2·0.3H2O离子筛。
7.根据权利要求6所述的制备方法，其特征在于所述的酸性溶液为无机酸、有机酸或酸性盐；酸性溶液的浓度为0.02-0.4mol/L。
8.根据权利要求6所述的制备方法，其特征在于所述的酸性溶液为盐酸、硫酸、磷酸、亚磷酸、硝酸、亚硫酸、过硫酸钠或氯化铵。
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