CN113540395B - 一种可充镁电池负极表面人工sei膜的成膜液及制备方法 - Google Patents
一种可充镁电池负极表面人工sei膜的成膜液及制备方法 Download PDFInfo
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000011777 magnesium Substances 0.000 title claims abstract description 48
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000007788 liquid Substances 0.000 title description 4
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 21
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000467 phytic acid Substances 0.000 claims abstract description 19
- 229940068041 phytic acid Drugs 0.000 claims abstract description 19
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 11
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 10
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 230000008021 deposition Effects 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- -1 amino tricarboxylic acid Chemical class 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 235000015424 sodium Nutrition 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 239000001433 sodium tartrate Substances 0.000 claims description 2
- 229960002167 sodium tartrate Drugs 0.000 claims description 2
- 235000011004 sodium tartrates Nutrition 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 238000002161 passivation Methods 0.000 abstract description 10
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 16
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 8
- 229910001425 magnesium ion Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
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- 239000000126 substance Substances 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
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- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
本发明公开了一种可充镁电池负极表面人工SEI膜的制备方法,将金属镁在用于构建人工SEI膜的成膜液中浸泡5~30min,取出、洗涤、干燥,在镁电极表面形成人工SEI膜,所述用于构建人工SEI膜的成膜液按重量百分比计包括如下组分:0.01~10%的植酸,0.001~10%的无机盐成膜剂,0.01~5%的络合剂,0.001~2%的中和剂。其能够在金属镁表面形成紧密有序的人工SEI膜,能够有效的避免金属镁负极与电解液界面的钝化问题,环境友好,成本低廉,适合工业化生产,具有很高的实际应用价值。
Description
技术领域
本发明涉及电极材料的处理,具体涉及可充镁电池负极表面人工SEI膜的成膜液及制备方法。
背景技术
长期以来,可充电镁电池被认为是一种理想的能源转化装置受到科学家的广泛关注。金属镁是一种理想的镁离子电池阳极材料,与普通氢电极相比,金属镁具有较低还原电位(还原电位为-2.37V)、高容量(3833 mA hr cm−3)、资源丰富、安全性高和环境友好的优点。但金属镁在电池的充放电过程中容易形成阳极-电解液界面的钝化层,阻碍了镁的溶解与沉积,使金属镁在电解液中的可逆沉积与溶解变得非常困难,从而限制了金属镁的电化学活性。
锂离子电池在充放电过程中,形成的钝化膜能够允许Li+顺利穿过,对电池的可逆性影响较小。低还原电位的金属锂可以还原电解质溶液的物种组分,从而形成电子绝缘的表面膜,该表面膜主要由锂离子化合物组成,阻止电解液成分进一步减少,这类膜在电场作用下还可以传导锂离子,由此在活性电极上表现为固态电解质界面,即SEI,Solidelectrolyte interface。与锂离子电池不同,常规电解质易被镁还原,在镁金属表面形成不溶性钝化层,镁离子电池充放电过程中生成的钝化膜是Mg2+的不良导体。因此,阳极-电解液界面成为一个极具价值的研究突破点。
为了解决这一关键技术问题,突破Mg表面形成的不溶性钝化层所带来的镁溶解与沉积的技术障碍,提供一种简单有效、成本低的方法,保证金属镁负极安全、稳定工作,是未来高性能镁离子电池技术的一个重要技术突破。表面涂层技术不仅可以调节负极表面的电化学环境,还可以提供物理保护性的界面。通过在镁金属表面构筑一层Mg2+导电但电子绝缘的人造SEI膜,有望解决金属镁负极界面钝化问题。
CN112331817A公开了一种高导电性电极材料的制备方法,其将负极成膜液体分子采用等离子喷雾的方式涂覆负极形成一层SEI膜,负极膜成膜单体分子包括碳酸亚乙烯酯(VC)、1,3-丙磺酸内酯(PS)、氟代碳酸乙烯酯(FEC)和乙腈(AN)中的一种或多种,由于需要通过等离子喷雾的方式形成SEI膜,设备复杂,限制了大规模推广应用。
发明内容
本发明的目的是提供一种可充镁电池负极表面人工SEI膜的成膜液及制备方法,其能够在金属镁表面形成紧密有序的人工SEI膜,能够有效的避免金属镁负极与电解液界面的钝化问题,使镁沉积剥离均匀化,同时具有环境友好,成本低廉,适合工业化生产的优点,具有很高的实际应用价值。
本发明所述的可充镁电池负极表面人工SEI膜的成膜液,按重量百分比计包括如下组分:0.01~10%的植酸,0.001~10%的无机盐成膜剂,0.01~5%的络合剂,0.001~2%的中和剂。
进一步,按重量百分比计包括如下组分:0.1~5%的植酸,0.01~5%的无机盐成膜剂,0.01~1%的络合剂,0.001~1%的中和剂。
进一步,所述无机盐成膜剂为硝酸锌、硝酸钙、硝酸镁、硝酸钴、硝酸铜、硝酸锆、硝酸铈、硝酸镧、钼酸钠、钼酸铵和钨酸钠中的至少一种。
进一步,所述络合剂为酒石酸、酒石酸钠、柠檬酸、柠檬酸钠、草酸钠、醋酸钠、乙二酸、氨基三羧酸、氨基三羧酸钠中的至少一种。
进一步,所述中和剂为氢氧化钠、氢氧化钾、碳酸钠、碳酸铵和三乙醇胺中的至少一种。
一种可充镁电池负极表面人工SEI膜的制备方法,将镁电极在pH为3~7的表面处理溶液中浸泡5~30min,取出、洗涤、干燥,在镁电极表面形成人工SEI膜,所述表面处理溶液为上述的可充镁电池负极表面人工SEI膜的成膜液。
本发明与现有技术相比具有如下有益效果。
1、本发明所述可充镁电池负极表面人工SEI膜的成膜液以植酸为主要成膜物质,以无机盐成膜剂、络合剂和中和剂作为辅助成膜物质,所有组分均对环境友好,成膜过程中不会产生有害物质。并且由于植酸是具有六个磷酸基和十二个羟基的多功能配体,当植酸与无机盐成膜剂中的金属离子共存时,混合溶液中即形成具有片层结构的金属植酸盐络合物,将金属镁浸入后,部分植酸先组装到金属镁表面形成底层膜层,更多的植酸以植酸盐的形式沉积到金属表面,层层组装,最终形成以植酸金属配合物为主要成分的植酸金属膜层。
2、本发明限定了各个组分的具体配比,植酸与无机盐成膜剂共存时,形成的络合物达到溶度积后会自发的沉积在金属镁表面,当络合物沉积速率大于基体的溶解速率时,即可在基体表面形成完整致密的人工SEI膜。若无机盐成膜剂的量过少,则形成的络合物浓度太低,影响金属镁表面膜层的完整性和致密性,使得形成的人工SEI膜的保护性能不够。若植酸的量过多,未络合的植酸会与金属镁基体反应,导致金属镁基体腐蚀,影响SEI膜的稳定性。
3、本发明通过将金属镁浸入成膜液中进而在镁负极表面形成人工SEI膜,原料简单易得,制备工艺简单,成本低廉,适用于大规模工业化生产。并且形成的SEI膜均匀致密,结构稳定,能够有效避免负极与电解液界面的钝化问题,明显降低了镁离子电池充放电过程中负极上的极化,从而提高镁离子电池放电的电压平台和放电比容量。
附图说明
图1是本发明实施例一制得的镁负极的金相显微组织图;
图2是本发明实施例一制得的镁负极的扫描电子显微结构图;
图3是本发明实施例一与对比例一的界面阻抗图;
图4是本发明实施例一与对比例一的恒流极化曲线图。
图5是本发明对比例一制得的镁负极在电流密度为5mAcm-1下放电一小时的表面形貌;
图6是本发明对比例一制得的镁负极在电流密度为5mAcm-1下充电一小时的表面形貌;
图7是本发明实施例一制得的镁负极在电流密度为5mAcm-1下放电一小时的表面形貌;
图8是本发明实施例一制得的镁负极在电流密度为5mAcm-1下充电一小时的表面形貌。
具体实施方式
下面结合附图对本申请作详细说明。
实施例一,一种可充镁电池负极表面人工SEI膜的制备方法,其包括如下步骤:
步骤一,将纯度为99.98%的轧制态金属镁进行机械加工,冲压成直径为14mm的圆片形,打磨、抛光至表面平整光亮,得到金属镁电极片。
步骤二,配制成膜液,该成膜液按重量百分比计包括如下组分:1%的植酸,0.05%的硝酸铜,0.01%的柠檬酸,0.02%的中和剂。
步骤三,将金属镁电极片在pH为4成膜液中浸泡10min,取出、洗涤、干燥,在镁负极表面形成SEI膜。
分别采用采用金相显微镜和扫描电子显微镜观察制得的金属镁电极片的表面形貌,参见图1和图2,能够看出金属镁电极片表面的SEI膜均匀致密。
在水值、氧值小于1ppm的氩气手套箱中,以实施例一制得的带有SEI膜的金属镁电极片作为正极和负极,隔膜采用GF/D玻璃纤维隔膜,在隔膜上滴加120μL的APC电解液,组装成CR2032扣式电池。在温度为25℃的条件下采用新威电池测试系统对电池进行恒流充放电测试,电流密度为0.2mA/cm2,充放电各60min。对比例一采用未作表面处理的金属镁作为正极和负极。
进行阻抗性能测试,结果参见图3,相较于对比例一,带有SEI膜的金属镁对称电池的界面电阻明显减小,表明了SEI膜对镁离子在界面上的扩散起到了积极作用。
进行电池循环效率测试,结果参见图4,经过多次循环的活化过程后,带有SEI膜的金属镁对称电池的极化稳定在0.04V左右,表明了带有SEI膜的金属镁电极在该有机电解液中不会发生严重的钝化。
采用扫描电子显微镜观察镁负极在电流密度为5mAcm-1下充电或放电一小时的表面形貌,参见图5至图8,相较于对比例一,带有SEI膜的金属镁电极的剥离沉积行为更为均匀。
实施例二,一种可充镁电池负极表面人工SEI膜的制备方法,其包括如下步骤:
步骤一,将纯度为99.98%的轧制态金属镁进行机械加工,冲压成直径为14mm的圆片形,打磨、抛光至表面平整光亮,得到金属镁电极片。
步骤二,配制成膜液,该成膜液按重量百分比计包括如下组分:5%的植酸,0.01%的硝酸铜,0.05%的柠檬酸,0.5%的中和剂。
步骤三,将金属镁电极片在pH为5成膜液中浸泡20min,取出、洗涤、干燥,在镁负极表面形成SEI膜。该SEI膜均匀致密,能够有效避免负极与电解液界面的钝化问题,降低了镁离子电池充放电过程中负极上的极化。
实施例三,一种可充镁电池负极表面人工SEI膜的制备方法,其包括如下步骤:
步骤一,将纯度为99.98%的轧制态金属镁进行机械加工,冲压成直径为14mm的圆片形,打磨、抛光至表面平整光亮,得到金属镁电极片。
步骤二,配制成膜液,该成膜液按重量百分比计包括如下组分:0.1%的植酸,5%的硝酸铜,0.1%的柠檬酸,0.01%的中和剂。步骤三,将金属镁电极片在pH为6成膜液中浸泡5min,取出、洗涤、干燥,在镁负极表面形成SEI膜。能够有效避免负极与电解液界面的钝化问题,降低了镁离子电池充放电过程中负极上的极化。
以上所述仅为本申请的较佳实施例而已,并不用以限制本申请,凡在本申请的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本申请的保护范围之内。
Claims (2)
1.一种可充镁电池负极表面人工SEI膜的成膜液,其特征在于,按重量百分比计包括如下组分:0.01~10%的植酸,0.001~10%的无机盐成膜剂,0.01~5%的络合剂,0.001~2%的中和剂;
所述无机盐成膜剂为硝酸锌、硝酸钙、硝酸镁、硝酸钴、硝酸铜、硝酸锆、硝酸铈、硝酸镧、钼酸钠、钼酸铵和钨酸钠中的至少一种;
所述络合剂为酒石酸、酒石酸钠、柠檬酸、柠檬酸钠、草酸钠、醋酸钠、乙二酸、氨基三羧酸、氨基三羧酸钠中的至少一种;
所述中和剂为氢氧化钠、氢氧化钾、碳酸钠、碳酸铵和三乙醇胺中的至少一种;
可充镁电池负极表面人工SEI膜的制备具体为:将镁电极在pH为3~7的表面处理溶液中浸泡5~30min,取出、洗涤、干燥,在镁电极表面形成人工SEI膜,所述表面处理溶液为所述的可充镁电池负极表面人工SEI膜的成膜液。
2.根据权利要求1所述的可充镁电池负极表面人工SEI膜的成膜液,其特征在于,按重量百分比计包括如下组分:0.1~5%的植酸,0.01~5%的无机盐成膜剂,0.01~1%的络合剂,0.001~1%的中和剂。
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