CN113363578A - 一种硼基非亲核型可充镁电池电解液及其制备方法 - Google Patents
一种硼基非亲核型可充镁电池电解液及其制备方法 Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 80
- 239000011777 magnesium Substances 0.000 title claims abstract description 72
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 53
- 230000000269 nucleophilic effect Effects 0.000 title claims abstract description 25
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 25
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000012298 atmosphere Substances 0.000 claims abstract description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004327 boric acid Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 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 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- DIEXQJFSUBBIRP-UHFFFAOYSA-N tris(2,2,2-trifluoroethyl) borate Chemical compound FC(F)(F)COB(OCC(F)(F)F)OCC(F)(F)F DIEXQJFSUBBIRP-UHFFFAOYSA-N 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 2
- ZFMOJHVRFMOIGF-UHFFFAOYSA-N 2,4,6-trimethoxy-1,3,5,2,4,6-trioxatriborinane Chemical compound COB1OB(OC)OB(OC)O1 ZFMOJHVRFMOIGF-UHFFFAOYSA-N 0.000 claims description 2
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- SWUPLEAGZOKLNX-UHFFFAOYSA-N [4-fluoro-2-(trifluoromethyl)phenyl]boronic acid Chemical compound OB(O)C1=CC=C(F)C=C1C(F)(F)F SWUPLEAGZOKLNX-UHFFFAOYSA-N 0.000 claims description 2
- FBVALSUESDZZOF-UHFFFAOYSA-N [B].[B].C=1(O)C(O)=CC=CC1.C=1(O)C(O)=CC=CC1 Chemical compound [B].[B].C=1(O)C(O)=CC=CC1.C=1(O)C(O)=CC=CC1 FBVALSUESDZZOF-UHFFFAOYSA-N 0.000 claims description 2
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- WYPTZCBYSQFOQS-UHFFFAOYSA-N magnesium;bis(trimethylsilyl)azanide Chemical compound [Mg+2].C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C WYPTZCBYSQFOQS-UHFFFAOYSA-N 0.000 claims description 2
- BZQRBEVTLZHKEA-UHFFFAOYSA-L magnesium;trifluoromethanesulfonate Chemical compound [Mg+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F BZQRBEVTLZHKEA-UHFFFAOYSA-L 0.000 claims description 2
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
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- 238000004090 dissolution Methods 0.000 abstract description 15
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
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- 238000002484 cyclic voltammetry Methods 0.000 description 3
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- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
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- 229910006400 μ-Cl Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
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- -1 magnesium bis (trifluoromethanesulfonate) imide Chemical class 0.000 description 2
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- UWKKBEQZACDEBT-UHFFFAOYSA-N CCCC[Mg] Chemical compound CCCC[Mg] UWKKBEQZACDEBT-UHFFFAOYSA-N 0.000 description 1
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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Abstract
本发明提供一种硼基非亲核型可充镁电池电解液及其制备方法。本发明制备电解液以镁盐、有机硼酸及其衍生物、催化剂、除水剂和无水无氧有机溶剂为原料；制备方法是在惰性气氛下，将上述原料中的镁盐、有机硼酸及其衍生物、催化剂、除水剂加入到无水无氧有机溶剂中，室温磁力搅拌24 h~48 h，过滤，所得滤液即为可充镁电池电解液。本发明电解液采用一步原位合成，原料成本低廉、制备工艺简单、易于大规模工业化生产；电解液电导率大、过电位小、电化学窗口宽、镁沉积‑溶出效率高、与Mg阳极及高压阴极的相容性好、循环稳定性好，具有很大的推广应用价值。
Description
技术领域
本发明属于可充镁电池技术领域，具体涉及一种硼基非亲核型可充镁电池电解液及其制备方法。
背景技术
近年来，可充金属电池的发展受到很多关注。与锂相比，镁在地壳中的储量要大的多，价格也远低于锂；镁具有双价性，可提供比锂金属(2062mAh·cm-3)更大的理论体积容量(3832mAh·cm-3)；与锂阳极易形成枝晶不同，镁阳极不受枝晶形成的困扰，暴露于空气中相对较稳定，安全性高。因此，可充镁电池被认为是一种非常有前途的储能和转换技术。
电解液被称为电池的“血液”，是电池的重要组成部分，对于电池的性能具有重要影响。可充镁电池的发展历史基本取决于电解液的发展。可充镁电池电解液的发展经历了如下三个主要阶段：第一阶段的电解液是有机格氏试剂基电解液Mg(AlCl2BuEt)2/THF(DCC)，也被称为“第一代”电解液，这类电解液电化学稳定窗口窄，无法与大多数阴极材料互配，只用于可充镁电池原型系统。第二阶段是使用苯基氯化镁取代丁基镁合成的“第二代”电解液PhMgCl/AlCl3/THF(APC)，其电化学稳定窗口显著增加；但由于其亲核性，所以无法与高容量亲电阴极兼容且容易腐蚀集流体。第三阶段是对各类非亲核型电解液的探索，如六甲基二硅胺烷基电解液(HMDS)2Mg/AlCl3/THF、无机氯化镁基电解液MgCl2/AlCl3/Mg/DME(MACC)、双(三氟甲磺酸基)酰亚胺镁Mg(TFSI)2/THF和硼基非亲核电解液，其中硼基非亲核型电解液具有过电位小、电化学窗口宽、镁沉积-溶出效率高、与Mg阳极及高压阴极的相容性好、循环稳定性好等优点，被认为是最具发展前景的电解液之一。然而，硼基非亲核型电解液的商品化应用受到原料成本高、制备工艺复杂等因素的限制，因此，研究和开发成本低廉、制备工艺简单、易于大规模工业化生产的具有优异电化学性能的硼基非亲核型电解液极为必要和迫切。
发明内容
针对现有技术存在的上述不足，本发明的目的是提供一种成本低廉、具有优异电化学性能的硼基非亲核型可充镁电池电解液。
本发明还提供所述硼基非亲核型可充镁电池电解液的制备方法，解决现有技术制备工艺复杂、不易规模化生产等问题。
实现上述目的，本发明采用如下技术方案：
一种硼基非亲核型可充镁电池电解液，其特征在于，以镁盐、有机硼酸及其衍生物、催化剂、除水剂和无水无氧有机溶剂为原料；
所述镁盐为氯化镁、氟化镁、溴化镁、双(六甲基二硅叠氮)镁、双(三氟甲磺酰基)酰亚胺镁和三氟甲基磺酸镁中的一种或几种；
所述有机硼酸及其衍生物为硼酸三(三氟乙基)酯、三氟化硼、4-氟-2-三氟甲基苯硼酸、2,4,6-三甲氧基硼氧六环、双(邻苯二酚)二硼或和双(频哪醇合)二硼中的一种或几种；
所述催化剂为氯化铬、氯化锂、氯化钛、氯化钪和氯化钇中一种或几种；
所述除水剂为金属镁、金属锂和金属钠中一种或几种；
所述无水无氧有机溶剂为四氢呋喃、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚和四乙二醇二甲醚中的一种或几种。
进一步，所述镁盐、有机硼酸及其衍生物、催化剂三者的摩尔质量比为1:0.5～4:0.05～0.1；所述无水无氧有机溶剂的加入量满足镁盐摩尔浓度为0.1mol/L～0.5mol/L；所述除水剂的加入量与镁盐加入量的摩尔质量比为1～4:1。
本发明还提供一种硼基非亲核型可充镁电池电解液的制备方法，包括以下步骤：
按上述电解液组分，取镁盐、有机硼酸及其衍生物、催化剂、除水剂加入到无水无氧有机溶剂中，室温磁力搅拌反应24h～48h，过滤，所得滤液即为电解液。
进一步，反应在惰性气氛下进行，水、氧含量均低于0.01ppm。
进一步，其中无水无氧有机溶剂先作预处理，包括以下步骤：
将有机溶剂加入到蒸馏装置中，然后按每升有机溶剂中加入30～50g金属钠的比例加入金属钠，以二苯甲酮为指示剂，在惰性气氛下重蒸；蒸出的溶剂中加入经过350℃高温活化8～20h的4A型分子筛，密封并置于惰性气氛下保存。
相比现有技术，本发明具有如下有益效果：
1、本发明硼基非亲核型可充镁电池电解液以镁盐、有机硼酸及其衍生物、催化剂、除水剂和无水无氧有机溶剂为原料，具有成本低的特点。其中，镁盐是电解液中Mg2+的提供者，是电解液实现镁可逆沉积-溶解的关键成分；催化剂可有效促进Mg2+的溶解，形成有效的活性阳离子，增大电解液的电导率，提升电解液镁的可逆沉积-溶解性能，降低过电位；除水剂可有效消除溶剂中所含的微量水，增强电解液的耐水能力，抑制镁盐在镁阳极表面形成钝化层，提升电解液的循环稳定性；有机硼酸及其衍生物可与溶剂分子形成阴离子配合物，该配合物可与电解液中镁盐二聚体阳离子配合物发生相互作用，从而提高电解质镁盐在有机溶剂中的溶解度(>0.5mol/L)，增大电解液的电导率，降低过电位，其具体作用机理如下(以氯化镁和硼酸三(三氟乙基)酯在有机溶剂乙二醇二甲醚中为例)：
电解质镁盐与溶剂乙二醇二甲醚形成二聚体阳离子配合物[Mg2(μ-Cl)2(DME)4]2+，硼酸三(2,2,2-三氟乙基)酯会形成大体积弱配位的阴离子[B(TFE)4]-，上述两种阴阳离子相互作用达到平衡并形成配合物[Mg2(μ-Cl)2(DME)4][B(TFE)4]，从而增加电解质镁盐在有机溶剂中的溶解度。[Mg2(μ-Cl)2(DME)4][B(TFE)4]的结构式如下：
2、本发明硼基非亲核型可充镁电池电解液的制备方法，采用一步原位合成，原料成本低廉、制备工艺简单、易于大规模工业化生产。
3、本发明制备的电解液属于硼基非亲核型电解液，各成分之间的相互协同作用赋予该电解液电导率大、过电位小、电化学窗口宽、镁沉积-溶出效率高、与Mg阳极及高压阴极的相容性好、循环稳定性好的优异性能，具有很好的商业应用前景。
附图说明
图1为本发明实施例1所制备的电解液以铜箔为工作电极的循环伏安曲线。
图2为本发明实施例1所制备的电解液在不同工作电极上的线性扫描伏安曲线。
图3为本发明实施例1所制备的电解液以铜箔为工作电极在0.5mA·cm-2电流密度下的可逆镁沉积-溶出循环曲线和库伦效率。
图4为采用本发明实施例1所制备的电解液组装的Mg/Mg对称电池在0.1mA·cm-2电流密度下长期极化性能曲线。
图5为采用本发明实施例1所制备的电解液组装的Mg/Mg对称电池在不同电流密度下的倍率极化性能曲线。
具体实施方式
下面结合具体实施例对本发明作进一步的详细说明。
实施例1：
一种硼基非亲核型可充镁电池电解液，其制备原料及方法具体包括：
(1)溶剂的预处理：量取有机溶剂乙二醇二甲醚500mL加入到蒸馏装置中，再加入25g金属钠，以二苯甲酮为指示剂，在惰性气氛下重蒸；蒸出的溶剂中加入经过350℃高温活化8h的4A型分子筛，密封并置于惰性气氛下保存。
(2)电解液的制备：所有反应均在惰性气氛下进行，水、氧含量均低于0.01ppm。取2.5g氯化镁溶于经过上述预处理的100mL乙二醇二甲醚溶剂中，然后再缓慢加入15.5g硼酸三(三氟乙基)酯和0.35g无水氯化铬，最后加入2.5g镁粉，室温磁力搅拌反应24h。过滤，所得滤液即为电解液。
电解液的性能测试方法如下(其他实施例测试方法相同)：
a.电导率测试
电解液的电导率由解析电化学阻抗谱而得到。电化学阻抗谱测试在惰性气氛手套箱中进行，利用Autolab PGSTAT302N电化学工作站完成。采用三电极体系，以清洁的不锈钢箔(14mm厚)电极为参比电极、工作电极和对电极，所加激励信号为5mV，测试频率范围为105Hz～0.01Hz，测试温度为25℃。
b.可逆镁溶解-沉积性能和氧化稳定性测试
电解液的可逆镁溶解-沉积性能和氧化稳定性分别通过循环伏安法和线性扫描伏安法测试，利用Autolab PGSTAT302N电化学工作站完成。采用两电极体系，以清洁的镁片(14mm厚)电极为参比电极和对电极、不同集流体(12mm厚)电极为工作电极。对于循环伏安测试，电位范围为-0.8～1.8V，扫速为25mV/s。对于线性扫描伏安测试，电位范围为开路电压～4.0V，扫速为1mV/s。
c.镁可逆沉积-溶出库伦效率测试
镁在电解液中的可逆沉积-溶出库伦效率及充放电特征等通过组装CR2032扣式电池进行测试。在惰性气氛手套箱中进行组装，水、氧含量均小于0.01ppm。工作电极分别为清洁的不锈钢(SS)、石墨箔(GF)、铂片(Pt)，对电极采用清洁的镁片(同时作为参比电极)、隔膜采用GF/A膜、与自制的电解液一起组装成CR2032型扣式电池。电池组装好后在室温下静置12小时后再进行测量。整个测试过程在武汉蓝电(Land)充放电测试系统上进行。放电时(1小时)工作电极上发生的是镁的电化学沉积反应，电流密度为0.1～0.5mA cm-2；充电过程则是对应沉积在工作电极上的镁的溶出反应，电流密度为0.1～0.5mAcm-2，采用电压控制(充电至0.8Vvs.Mg RE)。
d.极化性能测试
镁在电解液中的长期及倍率极化性能等通过组装CR2032扣式电池来进行测试。在惰性气氛手套箱中进行组装，水、氧含量均小于0.01ppm。对电极采用清洁的镁片(同时作为参比电极))、隔膜采用GF/A膜、与自制的电解液一起组装成CR2032型扣式电池。电池组装好后在室温下静置12小时后再进行测量。整个测试过程在武汉蓝电(Land)充放电测试系统上进行。放电时工作电极上发生的是镁的电化学沉积反应，电流密度为0.05～1mAcm-2，采用时间控制(放电30min)；充电过程则是对应沉积在工作电极上的镁的溶出反应，电流密度为0.05～1mAcm-2，采用时间控制(充电30min)。
利用上述方法对实施例1所制备的电解液性能进行测试，测试结果如下：电解液的电导率为3.79mS·cm-1；以铜箔为工作电极，电解液循环50圈后沉积过电位为-196mV，溶出过电位为-57mV，总的过电位为139mV(参见图1)；电解液在不锈钢、石墨箔、铂电极上的氧化稳定电位(vs.Mg/Mg2+)分别为2.7V、2.8V和3.4V(参见图2)；电解液在长期循环(500圈)中的镁可逆沉积-溶出(铜箔基底上)的库伦效率一直保持在97％(参见图3)；在电流密度为0.1mA·cm-2时，初始极化电位为0.15V，随着循环时间的增加，极化电位稳定在0.068V，且稳定循环500小时，极化电位没有明显增加(参见图4)；当电流密度从0.05mAcm-2增加到1mAcm-2，极化电位缓慢增大稳定在0.12V(参见图5)。上述性能测试结果表明，本发明电解液具有电导率大、过电位小、电化学窗口宽、镁沉积-溶出效率高、与Mg阳极及高压阴极的相容性好、循环稳定性好等优异性能。
实施例2-5的制备原料及其用量如下：
实施例2-5中无水无氧有机溶剂的预处理条件及电解液制备需要的反应时间如下：
制备硼基非亲核型可充镁电池电解液，采用与实施例1相同的方法，即包括以下步骤：
在惰性气氛下(水、氧含量均低于0.01ppm)，按上述电解液组分，取镁盐、有机硼酸及其衍生物、催化剂、除水剂加入到无水无氧有机溶剂中，室温磁力搅拌反应一定时间，过滤，所得滤液即为电解液。
其中，溶剂的预处理方法为：量取有机溶剂加入到蒸馏装置中，再加入上述质量的金属钠，以二苯甲酮为指示剂，在惰性气氛下重蒸；蒸出的溶剂中加入经过350℃高温活化一定时间的4A型分子筛，密封并置于惰性气氛下保存。
最后，采用与实施例1相同方法进行性能测试，结果如下表所示。可以看出，本发明电解液具有电导率大、过电位小、电化学窗口宽、镁沉积-溶出效率高、循环稳定性好等优异性能。
综上，本发明采用一步原位合成硼基非亲核型可充镁电池电解液，原料成本低廉，各成分之间的相互协同作用赋予该电解液电导率大、过电位小、电化学窗口宽、镁沉积-溶出效率高、与Mg阳极及高压阴极的相容性好、循环稳定性好的优异性能，具有很好的商业应用前景。并且，本发明具有制备工艺简单、易于大规模工业化生产的特点。
最后需要说明的是，以上实施例仅用以说明本发明的技术方案而非限制技术方案，本领域的普通技术人员应当理解，那些对本发明的技术方案进行修改或者等同替换，而不脱离本技术方案的宗旨和范围，均应涵盖在本发明的权利要求范围当中。
Claims (7)
1.一种硼基非亲核型可充镁电池电解液，其特征在于，以镁盐、有机硼酸及其衍生物、催化剂、除水剂和无水无氧有机溶剂为原料；
所述镁盐为氯化镁、氟化镁、溴化镁、双(六甲基二硅叠氮)镁、双（三氟甲磺酰基）酰亚胺镁和三氟甲基磺酸镁中的一种或几种；
所述有机硼酸及其衍生物为硼酸三(三氟乙基)酯、三氟化硼、4-氟-2-三氟甲基苯硼酸、2,4,6-三甲氧基硼氧六环、双(邻苯二酚)二硼或和双(频哪醇合)二硼中的一种或几种；
所述催化剂为氯化铬、氯化锂、氯化钛、氯化钪和氯化钇中一种或几种；
所述除水剂为金属镁、金属锂和金属钠中一种或几种；
所述无水无氧有机溶剂为四氢呋喃、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚和四乙二醇二甲醚中的一种或几种。
2.根据权利要求1所述的一种硼基非亲核型可充镁电池电解液，其特征在于，所述镁盐、有机硼酸及其衍生物、催化剂三者的摩尔质量比为1:0.5~4:0.05~0.1。
3.根据权利要求1所述的一种硼基非亲核型可充镁电池电解液，其特征在于，所述无水无氧有机溶剂的加入量满足镁盐摩尔浓度为0.1mol/L~0.5mol/L。
4.根据权利要求1所述的一种硼基非亲核型可充镁电池电解液，其特征在于，所述除水剂的加入量与镁盐加入量的摩尔质量比为1~4:1。
5.一种硼基非亲核型可充镁电池电解液的制备方法，其特征在于，包括以下步骤：
按权利要求1~4任一种硼基非亲核型可充镁电池电解液组分，取镁盐、有机硼酸及其衍生物、催化剂、除水剂加入到无水无氧有机溶剂中，室温磁力搅拌反应24h~48h，过滤，所得滤液即为电解液。
6.根据权利要求5所述硼基非亲核型可充镁电池电解液的制备方法，其特征在于，反应在惰性气氛下进行，水、氧含量均低于0.01ppm。
7.根据权利要求5所述硼基非亲核型可充镁电池电解液的制备方法，其特征在于，所述无水无氧有机溶剂先作预处理，包括以下步骤：
将有机溶剂加入到蒸馏装置中，然后按每升有机溶剂中加入30~50g金属钠的比例加入金属钠，以二苯甲酮为指示剂，在惰性气氛下重蒸；蒸出的溶剂中加入经过350℃高温活化8～20h的4A型分子筛，密封并置于惰性气氛下保存。
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110159381A1 (en) * | 2011-03-08 | 2011-06-30 | Pellion Technologies, Inc. | Rechargeable magnesium ion cell components and assembly |
| CN102916220A (zh) * | 2011-08-05 | 2013-02-06 | 丰田自动车株式会社 | 镁电池电解液 |
| CN103155235A (zh) * | 2010-05-25 | 2013-06-12 | 佩里昂技术公司 | 用于镁电池的电极材料 |
| US20140220450A1 (en) * | 2011-12-22 | 2014-08-07 | Pellion Technologies, Inc. | Non-aqueous electrolyte for rechargeable magnesium ion cell |
| US20140302403A1 (en) * | 2011-12-22 | 2014-10-09 | Pellion Technologies Inc. | Non-aqueous electrolyte for rechargeable magnesium ion cell |
| US20150140422A1 (en) * | 2013-11-19 | 2015-05-21 | Battelle Memorial Institute | Mixed electrolytes for hybrid magnesium-alkali metal ion batteries |
| CN105047987A (zh) * | 2014-04-28 | 2015-11-11 | 丰田自动车工程及制造北美公司 | 用于镁蓄电池的不含氯化物的电解质和将镁电解质转化为不含氯化物的电解质的方法 |
| US20160028117A1 (en) * | 2014-07-25 | 2016-01-28 | Korea Institute Of Science And Technology | Electrolyte for magnesium rechargeable battery and preparation method thereof |
| US20170033359A1 (en) * | 2013-12-26 | 2017-02-02 | Kyoto University | Secondary battery |
| US20180316059A1 (en) * | 2015-12-28 | 2018-11-01 | Suzhou Institute of Nano-tech and Nano-bionics, Chinese Academy of Sciences | Mono-Nuclei Cationized Magnesium Salt, Preparation Method and Applications Thereof |
-
2021
- 2021-06-08 CN CN202110637090.5A patent/CN113363578B/zh active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103155235A (zh) * | 2010-05-25 | 2013-06-12 | 佩里昂技术公司 | 用于镁电池的电极材料 |
| US20110159381A1 (en) * | 2011-03-08 | 2011-06-30 | Pellion Technologies, Inc. | Rechargeable magnesium ion cell components and assembly |
| CN102916220A (zh) * | 2011-08-05 | 2013-02-06 | 丰田自动车株式会社 | 镁电池电解液 |
| US20140220450A1 (en) * | 2011-12-22 | 2014-08-07 | Pellion Technologies, Inc. | Non-aqueous electrolyte for rechargeable magnesium ion cell |
| US20140302403A1 (en) * | 2011-12-22 | 2014-10-09 | Pellion Technologies Inc. | Non-aqueous electrolyte for rechargeable magnesium ion cell |
| US20150140422A1 (en) * | 2013-11-19 | 2015-05-21 | Battelle Memorial Institute | Mixed electrolytes for hybrid magnesium-alkali metal ion batteries |
| US20170033359A1 (en) * | 2013-12-26 | 2017-02-02 | Kyoto University | Secondary battery |
| CN105047987A (zh) * | 2014-04-28 | 2015-11-11 | 丰田自动车工程及制造北美公司 | 用于镁蓄电池的不含氯化物的电解质和将镁电解质转化为不含氯化物的电解质的方法 |
| US20160028117A1 (en) * | 2014-07-25 | 2016-01-28 | Korea Institute Of Science And Technology | Electrolyte for magnesium rechargeable battery and preparation method thereof |
| US20180316059A1 (en) * | 2015-12-28 | 2018-11-01 | Suzhou Institute of Nano-tech and Nano-bionics, Chinese Academy of Sciences | Mono-Nuclei Cationized Magnesium Salt, Preparation Method and Applications Thereof |
Non-Patent Citations (2)
| Title |
|---|
| DU AOBING等: "An efficient organic magnesium borate based electrolyte with non-nucleophilic characteristic for magnesium sulfur battery", 《ENERGY&ENVIRONMENTAL SCIENCE》 * |
| 赵青松等: "可充镁电池电解液", 《化学进展》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115347230A (zh) * | 2022-09-14 | 2022-11-15 | 哈尔滨工业大学 | 一种原位生成镁盐的镁二次电池非亲核电解液及其制备方法与应用 |
| CN115692845A (zh) * | 2022-10-31 | 2023-02-03 | 重庆大学 | 一种无卤素可充镁电池电解液及其制备方法和应用 |
| CN115692845B (zh) * | 2022-10-31 | 2024-02-02 | 重庆大学 | 一种不含氟以外卤素可充镁电池电解液及其制备方法和应用 |
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