CN113830774A - 一种基于溶胶-凝胶法的利用钛铁矿制备碳复合硅酸亚铁锂的方法 - Google Patents
一种基于溶胶-凝胶法的利用钛铁矿制备碳复合硅酸亚铁锂的方法 Download PDFInfo
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 33
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 28
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 15
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229940062993 ferrous oxalate Drugs 0.000 claims abstract description 18
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 18
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- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
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- -1 iron ions Chemical class 0.000 claims abstract description 4
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
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- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229930003268 Vitamin C Natural products 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
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- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 10
- 239000010406 cathode material Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
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- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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Abstract
本发明属于锂离子电池及其制造的技术领域，提供一种基于溶胶‑凝胶法的利用钛铁矿(FeTiO3)制备锂离子电池聚阴离子型正极材料碳复合硅酸亚铁锂(Li2FeSiO4/C)的制备方法。该方法将钛铁矿粉碎后加入盐酸进行提取，获得富含铁离子的浸取液；向浸取液中加入过量草酸，获得沉淀物，加热煮沸至干燥，获得草酸亚铁前驱体；添加锂源、硅源、碳源，采用加热回流溶胶‑凝胶法制备凝胶前驱体，干燥后在保护气氛下烧结得到碳复合硅酸亚铁锂材料。钛铁矿是富含亚铁离子的铁源，来源丰富且廉价，溶胶‑凝胶法制备工艺简单、成本低。
Description
技术领域
本发明属于锂离子电池及其制造的技术领域，具体为一种基于溶胶-凝胶法的利用钛铁矿(FeTiO3)制备锂离子电池正极材料碳复合硅酸亚铁锂(Li2FeSiO4/C)的制备方法，能有效降低原料成本。
背景技术
聚阴离子型正极材料硅酸亚铁锂(Li2FeSiO4)具有高理论容量330mAh/g，原料资源储藏丰富，工作电压稳定，Si-O键具有出色的热稳定性以及材料的环保、低成本等优点，在高能量锂电池中成为引人注目的正极材料之一。目前制备硅酸亚铁锂的铁源(如草酸亚铁、硝酸铁、乙酸亚铁等)大多是由含铁矿石经复杂的提纯工艺制得，而在制备硅酸亚铁锂时，为提高其电化学性能又需掺杂金属元素，比如Ti、Mn元素，但这些掺杂金属元素多在含铁矿石中存在。因此，利用含铁矿石制备锂离子电池正极材料硅酸亚铁锂是降低其成本的有效方法。
中国钛铁矿(FeTiO3)储量约有2亿吨，占全球储量的28％。钛铁矿中含有铁、钛、锰、钒等元素，为减少资源浪费和环境污染，发展综合利用矿物中各种元素的新技术和新工艺是必然趋势。目前，利用钛铁矿制备锂离子电池电极材料的报道较少。专利CN201310285093.2公布了由钛铁矿制备草酸亚铁的技术方案，但未给出由草酸亚铁进一步制备碳复合硅酸亚铁锂的技术方案；专利CN201310285095.1利用钛铁矿采用火法冶金和高温固相反应结合的技术方案制备硅酸亚铁锂；专利CN201310148769.3先采用碱性SiO2加入草酸和硫酸亚铁，形成草酸亚铁包覆壳核材料，再加入锂源和碳源化合物烧结得到硅酸亚铁锂复合材料；专利CN201410627330.3采用先将柠檬酸、氢氧化锂和草酸亚铁在水中混合后进行油浴，再加入纳米二氧化硅制备凝胶，再将凝胶干燥烧结得到碳复合硅酸亚铁锂正极材料。迄今为止，直接利用钛铁矿制备草酸亚铁，并一步添加锂源、硅源、碳源通过溶胶-凝胶法制备碳复合硅酸亚铁锂正极材料的未见公开报道。
发明内容
(一)要解决的技术问题
本发明的目的是提供基于溶胶-凝胶法的利用钛铁矿制备碳复合硅酸亚铁锂的方法，要解决的技术问题是利用储量丰富、价格低廉的钛铁矿为原料，制备草酸亚铁作为铁源，再添加锂源、硅源、碳源化合物一步制备凝胶，干燥烧结后即可得到碳复合硅酸亚铁锂材料，简化生产工艺，降低成本。
(二)技术方案
本发明的技术方案是：
一种利用钛铁矿制备碳复合硅酸亚铁锂材料的制备方法，包括以下步骤：
步骤1、将钛铁矿粉碎，加入盐酸常压下加热回流酸浸，反应结束后得到富含亚铁离子的浸出液；
步骤2、向浸出液中加入还原剂，加热并反应结束后，过滤去除沉淀物，得到富Fe2+浸出液；
步骤3、向富Fe2+浸出液加入过量草酸，反应后将所得沉淀物洗涤、离心、烘干得到草酸亚铁前驱体；
步骤4、将草酸亚铁前驱体并添加化学计量比的乙酸锂、硅酸四乙酯、葡萄糖，溶解到乙醇水溶液中，向溶液中添加适量的聚乙二醇和乙酸；聚乙二醇作为表面活性剂，乙酸用于调节pH值；
步骤5、将溶液在120℃下加热回流5h，反应结束后加热蒸干溶剂得到凝胶前驱体；
步骤6、将凝胶前驱体在氮气氛围中，按程序升温至700℃保温12h，得到碳复合硅酸亚铁锂材料；
所述步骤4中，草酸亚铁、乙酸锂、硅酸四乙酯、葡萄糖的添加量按照元素摩尔比Li:Fe:Si:C＝2.1:1:1:0.5进行添加，聚乙二醇的添加量上述混合物的3～3.5wt％。
进一步的，
步骤1中，将钛铁矿球磨至d(50)＝1～6μm，盐酸的摩尔浓度为3～9mol/L，盐酸与钛铁矿的质量比为1.1～1.9：1，120～140℃温度下浸出0.5～24h；
步骤2中，所述还原剂为维生素C、Fe粉、Mg粉中的一种或几种，加热至40～80℃并反应0.5～5h。
优选的，
步骤1中，所述盐酸的摩尔浓度为7mol/L，盐酸与钛铁矿的质量比为1.5:1；
步骤4中，所述聚乙二醇具体为聚乙二醇-10000。
(三)有益效果
本发明相对于现有技术，具有以下有益效果：
1、本发明采用储量丰富、价格低廉的钛铁矿为原料，并可利用其中的Ti、Mn元素作为掺杂元素，同时采用可循环利用的盐酸作为浸出钛铁矿的介质，减小污染，环境友好；2、采用廉价的草酸作为沉淀剂处理富铁浸出液来制备金属离子掺杂的草酸亚铁前驱体，并将其作为铁源制备硅酸亚铁锂正极材料，最终掺杂金属元素均匀地分布在硅酸亚铁锂正极材料中，解决了掺杂金属元素难以混均的问题，可提高硅酸亚铁锂正极材料的电导率，进而提高其电化学性能；3、由草酸亚铁前驱体并添加化学计量比的乙酸锂、硅酸四乙酯、葡萄糖，再乙醇水溶液中加热回流，一步得到凝胶前驱体，简化了工艺，缩短了制备时间；4、向溶液中添加适量的聚乙二醇可作为造孔剂，配合硅酸四乙酯的水解缩合形成凝胶，烧结过程中形成三维网络结构，降低了离子再晶格重组时迁移的距离和所需活化能，有利于降低反应温度、缩短反应时间，也增加了材料的比表面积。
附图说明
图1是实施例1的碳复合硅酸亚铁锂材料的XRD图；
图2是实施例1的碳复合硅酸亚铁锂材料的扫描电镜图(SEM)；
图3是实施例1的碳复合硅酸亚铁锂材料的EDS能谱图；
图4是实施例1的碳复合硅酸亚铁锂材料的粒径分布图；
图5是实施例的碳复合硅酸亚铁锂材料在0.1C电流下的充放电曲线。
具体实施方式
为更好地说明本发明，便于理解本发明的技术方案，本发明的典型但非限制性的实施例如下：
实施例1：
(1)将10g钛铁矿球磨至d(50)＝3.217μm，用摩尔浓度7mol/L的盐酸在常压下回流浸出钛铁矿，盐酸与钛铁矿的质量比1.5：1，130℃温度下浸出24h，反应结束后，冷冻离心洗涤得富钛渣和富铁浸出液；
(2)将步骤(1)中所得富铁浸出液中加入维生素C，加热至50℃并反应5h，反应结束后，冷却过滤去除杂质，再加入过量草酸，反应后将所得沉淀洗涤、离心、烘干得草酸亚铁前驱体；
(3)加热回流溶胶-凝胶法材料合成：①物料：3.6g草酸亚铁前驱体，添加3.5g乙酸锂、5.2g硅酸四乙酯，0.52g聚乙二醇-10000，0.4g葡萄糖，1ml乙酸；②制备凝胶前驱体：将物料投入乙醇/水体系中120℃加热回流5h，反应结束后加热蒸干溶剂得到凝胶前驱体；③烧结：氮气氛围中，按程序升温升至700℃保温12h，得纯黑色碳复合硅酸亚铁锂(Li2FeSiO4/C)粉末。
对实施例1制备的碳复合硅酸亚铁锂材料进行物理表征(物相、微观形貌、元素组成、碳含量、粒度分布、比表面积)测试，结果为：
1)XRD图(图1)显示，合成的材料物相纯，没有出现Li2SiO3杂峰；
2)SEM图(图2)显示，材料的颗粒分布均匀，在10～30μm之间；粒径分布图(图4)表明d(50)＝20.814μm；
3)EDS图谱(图3)显示，材料中，碳的含量在13％左右且碳的分布比较均匀；Fe和Si的元素比在2:1左右，局部略高。
对实施例1制备的碳复合硅酸亚铁锂材料进行电化学性能测试：按正极材料Li2FeSiO4:Super P Li:PVDF＝8:1:1(by mass)研磨混料，NMP溶解PVDF，经搅拌调浆、制膜、压片、冲片、真空烘干、称重，制备好正极电极片，在手套箱中组装扣式CR2032型半电池，搁置后进行充放电测试，结果为：
充放电曲线图(图5)表明，材料在0.1C倍率下，首圈充电比容量在192mAh/g，首圈放电比容量83mAh/g，库伦效率仅43.2％；从2圈开始，充电曲线发生明显的电压降；第4圈放电比容量90mAh/g；如果去除复合物中的C，单纯计算Li2FeSiO4/的比容量，在0.1C倍率下Li2FeSiO4的首圈充电比容量可达213mAh/g，首圈放电比容量可达93mAh/g，第4圈放电比容量100mAh/g。
Claims (5)
1.一种利用钛铁矿制备碳复合硅酸亚铁锂材料的制备方法，包括以下步骤：
步骤1、将钛铁矿粉碎，加入盐酸常压下加热回流酸浸，反应结束后得到富含亚铁离子的浸出液；
步骤2、向浸出液中加入还原剂，加热并反应结束后，过滤去除沉淀物，得到富Fe2+浸出液；
步骤3、向富Fe2+浸出液加入过量草酸，反应后将所得沉淀物洗涤、离心、烘干得到草酸亚铁前驱体；
步骤4、将草酸亚铁前驱体并添加化学计量比的乙酸锂、硅酸四乙酯、葡萄糖，溶解到乙醇水溶液中，向溶液中添加适量的聚乙二醇和乙酸；
步骤5、将溶液在120℃下加热回流5h，反应结束后加热蒸干溶剂得到凝胶前驱体；
步骤6、将凝胶前驱体在氮气氛围中，按程序升温至700℃保温12h，得到碳复合硅酸亚铁锂材料；
所述步骤4中，草酸亚铁、乙酸锂、硅酸四乙酯、葡萄糖的添加量按照元素摩尔比Li:Fe:Si:C＝2.1:1:1:0.5进行添加，聚乙二醇的添加量为上述混合物的3～3.5wt％。
2.根据权利要求1所述的制备方法，其特征在于，步骤1中，将钛铁矿球磨至d(50)＝1～6μm，盐酸的摩尔浓度为3～9mol/L，盐酸与钛铁矿的质量比为(1.1～1.9):1，120～140℃温度下浸出0.5～24h。
3.根据权利要求1所述的制备方法，其特征在于，步骤2中，所述还原剂为维生素C、Fe粉、Mg粉中的一种或几种，加热至40～80℃并反应0.5～5h。
4.根据权利要求1所述的制备方法，其特征在于，步骤4中，所述聚乙二醇具体为聚乙二醇-10000。
5.根据权利要求1所述的制备方法，其特征在于，所述盐酸的摩尔浓度为7mol/L，盐酸与钛铁矿的质量比为1.5:1。
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