CN116601793A - 掺杂的钠阳极、具有掺杂的钠阳极的电池及其使用方法 - Google Patents
掺杂的钠阳极、具有掺杂的钠阳极的电池及其使用方法 Download PDFInfo
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- CN116601793A CN116601793A CN202180073614.0A CN202180073614A CN116601793A CN 116601793 A CN116601793 A CN 116601793A CN 202180073614 A CN202180073614 A CN 202180073614A CN 116601793 A CN116601793 A CN 116601793A
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- Prior art keywords
- anode
- battery
- dopant
- cathode
- sodium
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- 239000011734 sodium Substances 0.000 title claims abstract description 115
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 24
- 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 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims description 31
- 239000002019 doping agent Substances 0.000 claims abstract description 44
- 239000003792 electrolyte Substances 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims description 21
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- 239000000203 mixture Substances 0.000 claims description 9
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- 230000002441 reversible effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 1
- IKULXUCKGDPJMZ-UHFFFAOYSA-N sodium manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Na+] IKULXUCKGDPJMZ-UHFFFAOYSA-N 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 1
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 description 1
- HEVWJXJIIXJVKU-UHFFFAOYSA-K sodium;manganese(2+);phosphate Chemical compound [Na+].[Mn+2].[O-]P([O-])([O-])=O HEVWJXJIIXJVKU-UHFFFAOYSA-K 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 230000004222 uncontrolled growth Effects 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- H01—ELECTRIC ELEMENTS
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Abstract
电池的阳极包括钠金属和在所述钠金属中的掺杂物。阳极具有至多80μm的厚度,并且掺杂物为电负性大于钠的金属。电池包括阳极、与阳极接触的阳极电荷收集元件、阴极、与阴极接触的阴极电荷收集元件、与阳极和阴极接触的电解质,以及封装阳极、阳极电荷收集单元、阴极、阴极电荷收集单元和电解质的壳体。电池中的阳极包括掺杂有掺杂物的钠金属,并且掺杂物以0.01至1.0原子%的量存在。
Description
背景技术
大规模储能系统在运输和智能电网应用中的快速增长要求与现有技术的钠离子电池(LIB)相比更便宜且更稳健的电池。1金属阳极(诸如Li、Na和Mg)具有与典型的嵌入阳极(诸如石墨)相比高多倍的比容量,并且被广泛认为是下一代电池的理想材料。2在它们当中,Na金属储量丰富,并且具有低电化学电位(相对于标准氢电极为-2.714V)和1166mAh g-1的高理论容量的组合优势,并且是最有前景的阳极候选者之一。3例如,Na金属阳极与转换型阴极的耦合将提供具有比LIB高多倍的能量密度的低成本电池,诸如对于Na-S电池为1274Wh kg-1并且对于Na-O2电池为1605Wh kg-1。4,5Na金属电池的实际部署需要具有理想地100%的镀覆-剥离库仑效率的无枝晶Na阳极。6不幸的是,Na金属具有强烈的化学反应性,且这带来了多个严重阻碍其商业化的主要挑战。Na金属在几乎所有液体和固体电解质中天然地不稳定,并自发形成不稳定的固体电解质界面(SEI),这在Na镀覆期间对界面Na离子传输产生显著的扰动,并加速不安全枝晶的生长。7这种自发反应不可逆地消耗新鲜的Na和电池电解质二者,导致松散但厚的非活性苔藓状(mossy)Na的积聚,和伴随容量迅速衰减的过早电池故障。8为了实现真正可逆的Na金属阳极,需要在合理的材料和界面上的实质性开发。9
近年来已经提出了在各种条件下保护Na金属的许多策略。一些值得注意的策略包括使用促进原位形成更强SEI层的新型电解质,诸如通过纳入氟化的电解质添加剂、10浓缩盐11和替代溶剂。7,12人造SEI层在Na金属表面上的应用也已被证明减少枝晶生长并提高循环效率。13-17除了表面保护外,三维(3D)功能宿主(主体,host)由于其“无宿主(无主体)”的性质和无限的体积变化而在重复的(反复的)剥离和镀覆循环期间对稳定Na金属起重要作用。5正如在Li金属阳极中广泛证明的那样,这些宿主不仅在结构上减轻(mitigate)了Na金属的巨大体积变化,而且降低了有效表面电流密度,并且因此改善了高倍率性能和循环稳定性,正如最近用柔性碳毡、多孔碳和Ag纳米线网所证明的那样。3,18,19
发明内容
在第一方面,本发明为包括钠金属和掺杂物(掺杂剂)的阳极。所述阳极具有至多80μm的厚度,并且所述掺杂物为电负性大于钠的金属。优选地,所述掺杂物包括锡。
在第二方面,本发明为电池,其包括阳极、阳极电荷收集元件、阴极、阴极电荷收集元件、电解质和壳体。阳极包括掺杂有掺杂物的钠。
在第三方面,本发明为制备掺杂的钠阳极的方法,包括:将钠金属熔融,将掺杂物金属引入到所述钠金属中以形成熔融的掺杂的钠金属,固化所述掺杂的钠金属,以及将所述掺杂的钠金属形成为具有至多450μm厚度的箔。
在第四方面,本发明为从上述电池产生电力的方法,包括:将电池的阳极和阴极连接到外部载荷(load)以完成电路。
在第五方面,本发明为对上述电池进行再充电的方法,包括:将电池连接到电源。
定义
“单元电池”是含有电极、隔板和电解质的基本电化学单元。
“电池”被定义为单元电池或单元电池组件的集合,具有壳体、电连接件和用于保护或控制的任选地另外的元件。
“掺杂物”是指以所使用的量不与主要金属形成金属间化合物的任意金属添加剂。
“阳极”是指在放电循环期间发生氧化反应的电极。阳极可为一个连续体,或者它可包括附接到电流收集元件的多于一个的薄膜。
“阴极”是指在放电循环期间发生还原反应的电极。阴极可为一个连续体,或者它可包括附接到电流收集元件的多于一个的薄膜。
“隔板”是指阴极和阳极之间的屏障,以防止它们接触。如果电解质是固体,则不需要隔板来避免阳极和阴极之间的接触。
“电解质”是指含有溶剂和离子的溶液,其传导离子但对电子是绝缘体。电解质可为液体、固体或凝胶。
“循环”是指对可再充电电池充电并根据需要将其放电到载荷中的过程。该术语通常用于指定电池的预期寿命,因为充电循环的次数对寿命的影响比仅时间流逝的影响更大。
除非另有说明,否则所有的百分比都指原子百分比。在没有指定掺杂物百分比的情况下,掺杂物的原子百分比为0.1%。
附图说明
图1A是掺杂物结构的示意图。
图1B是Sn-Na的相图。
图2显示了具有阴极、阳极和隔板的电池。
图3示出了钠离子电池的示意图。
图4是纳入了掺杂的钠电极的钠电池的示意图。
图5是0.2原子%Sn掺杂的Na阳极的扫描电子显微镜(SEM)图像。
图6是未掺杂的Na和0.2原子%Sn掺杂的Na的X射线衍射图案的图。
图7A是掺杂的Na电极在干燥空气中暴露7天后的照片。
图7B是未掺杂的Na电极在干燥空气中暴露7天后的照片。
图7C是掺杂的Na电极在干燥空气中暴露7天后的能量色散X射线光谱(EDS)。
图7D是未掺杂的Na电极在干燥空气中暴露7天后的能量色散X射线光谱(EDS)。
图8A是掺杂的Na在干燥空气中暴露2天后的扫描电子显微镜图像。
图8B是未掺杂的Na在干燥空气中暴露2天后的扫描电子显微镜图像。
图9是比较掺杂和未掺杂的Na在干燥空气中暴露不同天后的电荷转移电阻的图。
图10是由未掺杂的Na和0.2原子%Sn掺杂的Na组装的对称钮扣电池在0.5mAcm-2下循环并且每次循环持续30分钟的电压分布图。
图11是由未掺杂的Na和0.2原子%Sn掺杂的Na组装的对称钮扣电池在0.5mAcm-2下循环并且每次循环持续1小时的电压分布图。
图12是显示用具有不同Sn掺杂浓度的Na阳极组装的原型Na电池的循环稳定性的图。
图13A是在全电池中循环之后掺杂的Na的SEM图像。
图13B是在全电池中循环之后未掺杂的Na的SEM图像。
具体实施方式
尽管在保护钠金属方面取得了巨大进展,但对调节金属Na的固有物理化学性质的努力却很少,这从根本上限制了性能改善。因此,探索专门设计来操纵Na金属的基本行为的方法具有极大的兴趣和实际意义。添加掺杂物作为痕量杂质是用于改变基底的电学或光学性质的有力方法,并且已经在领域诸如固态电子学和激光中广泛证明。本发明描述了掺杂有痕量掺杂物(诸如锑、铟、铅、铋、铊或锡)的钠金属阳极。掺杂的金属表现出增强的化学稳定性和好得多的电化学反应性。掺杂物原子以原子形式分散在Na晶体中(图1)。掺杂物具有比钠原子更高的电负性,并强烈吸引其附近的电子,这增加了功函数并降低了Na金属的反应性,导致在干燥空气中更稳定的掺杂电极。掺杂物原子与Na原子具有更强的结合,并引导均匀的Na镀覆,这从根本上减轻了不安全枝晶的生长。这些益处的组合促进了在碳酸酯电解质中循环期间产生更薄但更强的SEI层,并实现了对称电池和全电池二者中的高容量和持久的电池循环。
图1A示出了包括钠金属102和掺杂物104的掺杂的钠阳极100的晶体结构。图1B示出了Sn-Na相图,Sn掺杂的Na电极可如下合成:通过向熔融的Na添加少于1.0原子%的Sn,随后快速猝灭(通常通过在室温下将熔融混合物倾倒在大型不锈钢板上)。
掺杂物可为电负性大于钠的电负性的任意金属。掺杂物可为铍、镁、铝、钙、钪、钛、钒、铬、锰、铁、镍、钴、铜、锌、镓、锗、钇、锆、铌、钼、钌、铑、钯、银、镉、铟、锡、锑、镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥、铪、钽、钨、铼、锇、铱、铂、金、汞、铅、铋、锕、镤、钍、镎、铀、镅、钚和锔。优选地,掺杂物为锑、铟、铅、铋、铊或锡,最优选锡。
本发明的阳极包括掺杂有掺杂物的钠金属。掺杂物可以0.01-2.0原子%的量存在,包括0.02、0.03、0.04、0.05、0.06、0.07、0.08、0.09、0.1、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1.0、1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8和1.9。优选地,掺杂物以0.05–0.5原子%的量存在。优选地,掺杂物不形成金属间相,并且以间隙形式存在、或取代钠晶体结构中的钠原子。
掺杂的钠可被压制成具有1至450μm厚度的箔。优选地,所述箔具有小于80μm的厚度,包括5、10、15、20、25、30、35、40、45、50、55、60、65、70和75μm。最优选地,所述箔具有至多30μm的厚度。
优选地,掺杂的阳极在干燥空气中是稳定的。可通过测量掺杂和未掺杂的钠阳极的Rct(电荷转移电阻)来测量掺杂和未掺杂的电极在干燥空气中的表面腐蚀。掺杂的阳极优选通过电阻稳定性测试,所述测试要求当使用对称钮扣电池(用掺杂和未掺杂的钠阳极组装、用在碳酸亚乙酯/碳酸亚丙酯(EC/PC)(1:1体积)中的1.0M NaPF6溶液作为电解质)的电化学阻抗谱(EIS)分析来测量阳极的电阻时,掺杂的阳极在干燥空气中暴露7天后测量的电阻为未掺杂的钠阳极的电阻的1/10或更少。
任选地,阳极可纳入到具有阴极、电解质和壳体的电池中。所述电池还可包括在阳极和阴极上的电荷收集元件以聚集或分配(分布)电子。电荷收集元件可连接到外部电路,所述外部电路任选地连接到载荷或再充电电源。
图2示出了电池200。电池具有阳极202和阴极204。阳极和阴极被卷起,并且隔板206在阴极和阳极之间。电池具有正极端子208和负极端子210。电池被封装(enclosed)在壳体212中。图3示出了电池300的示意图。电池具有阴极302,其作为薄膜条示出,附接到阴极电荷收集元件304。阳极306附接到阳极电荷收集元件305。隔板308位于阳极和阴极之间。电解质310与阳极和阴极接触,并允许离子312在阳极和阴极之间移动。图4示出了电池单元电池400的示意图。电池具有阳极402、阴极404和电解质410。阳极包括钠406和掺杂物408。
在钠离子电池中,钠离子在放电期间从阳极移动到阴极,并且在再充电期间沿相反的方向移动。电解质携带带正电荷的钠离子从阳极通过隔板到阴极,且反之亦然。钠离子的移动在阳极中产生自由电子,自由电子在阳极电流收集元件处产生电荷。然后,电流从阴极上的集流体通过载荷(正被供电的装置)流到阳极上的电流收集元件。当电池被再充电时,电子和离子沿相反的方向流动。
优选地,在200至1000次循环后,电池保持电池初始容量的至少50%的容量。在200次循环后,电池可保留电池初始容量的55%、60%、65%、70%、75%、80%、85%、90%、95%和100%的容量。最优选地,对于100、120、140、160、180、200、220、240、260、280、300、320、340、360、380、400、420、440、460、480、500、520、540、560、580、600、620、640、660、680、700、720、740、760、780或800次循环,电池保持初始容量的至少70%的容量。
阴极材料可为氧化物,诸如钠钴氧化物、钠锰氧化物、钠镍锰氧化物(NaNixMn1-xO2(x在0和1之间))、钠镍锰钴氧化物、钠铁锰氧化物、磷酸铁钠、磷酸锰钠、磷酸钒钠、Na2/ 3Fe1/2Mn1/2O2氧化物、混合的P3/P2/O3型Na0.76Mn0.5Ni0.3Fe0.1Mg0.1O2氧化物、或O3型NaNi1/ 4Na1/6Mn2/12Ti4/12Sn1/12O2氧化物。阴极可包括Mo6S8,其是非常稳定的阴极材料。普鲁士蓝类似物(PBA)对于钠阴极也可能是合乎需要的。PBA包括斜方六面体NaxMn[Fe(CN)6]、NaxCo[Fe(CN)6]和斜方六面体普鲁士白NaxFe[Fe(CN)6]·0.18(9)H2O(x在0至10的范围内)(美国专利号9,099,718和Brant等人,"Selective Control of Composition in Prussian Whitefor Enhanced Material Properties",Chemistry of Materials,第31卷,第18期,第7203–7211页(2019))。还可使用Komaba等人"P2-type Nax[Fe1/2Mn1/2]O2 made from earth-abundant elements for rechargeable Na batteries"Nature Materials,第11卷,第6期,第512–517页的阴极。
感兴趣的其它阴极材料为硫和氧。因为它们的较高的能量密度和来自使用硫而降低的成本,钠-硫和钠-氧电池比钠离子单元电池具有优点。硫具有低电导率,因此硫阴极也可与高导电材料配对以改善电导率。可使用碳涂层来提供缺失的导电性。硫基电极包括共聚硫、硫-石墨烯氧化物和硫/硫化钠。
隔板是液体电解质电池中的优选部件。在液体电解质的情况下,隔板为用电解质浸泡并保持其在适当位置的多孔材料。隔板需要是电子绝缘体,同时具有最小的电解质电阻、最大的机械稳定性和在高度电化学活性的环境中对降解(劣化)的化学耐受性。另外,隔板经常具有称为“热关断(thermal shutdown)”的安全特征,其在升高的温度下熔化或关闭其孔以关断钠离子传输而不损失其机械稳定性。隔板或者以片材合成并与电极组装在一起,或者原位沉积在一个电极上。隔板一般包括形成多微孔层的聚合物膜。隔板可由以下制成:非织造纤维,诸如棉、尼龙、聚酯、玻璃;聚合物膜,诸如聚乙烯、聚丙烯、聚(四氟乙烯)、聚氯乙烯;陶瓷;和天然存在的物质,诸如橡胶、石棉或木材。也可使用在Arora,P.等人,Battery Separators Chemical Reviews 2004 104(10),第4419-4462页中描述的隔板材料。
电解质提供了用于将钠离子从阴极传输到阳极且反之亦然的介质。电解质的类型包括液体、聚合物和固态电解质。钠离子电池中的液体电解质包括:盐,诸如NaFSI、NaTFSI、NaPF6、NaBF4和NaClO4;和溶剂,诸如碳酸亚乙酯、碳酸亚丙酯、碳酸二甲酯、碳酸二乙酯、二甲氧基乙烷、二甘醇二甲醚、三甘醇二甲醚和四甘醇二甲醚、或其混合物。电解质的选择可受阴极材料的选择的影响。本领域技术人员将基于阴极材料、隔板材料、阳极材料和单元电池设计来选择合适的电解质、合适的电解质体积和合适的电解质浓度。电解质的浓度可为0.1M至10.0M,包括0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1.0、2.0、3.0、4.0、5.0、6.0、7.0、8.0和9.0M。优选地,电解质的浓度为0.5-2.0M。优选地,电解质为NaPF6在碳酸亚乙酯/碳酸二甲酯(EC/DMC)中的溶液或NaPF6在碳酸亚乙酯/碳酸亚丙酯(EC/PC)中的溶液。碳酸亚乙酯对碳酸亚丙酯的比例优选为按体积1:1。
电解质可为固体或半固体诸如陶瓷。固体电解质避免了泄漏的风险,并且由于固体电解质防止阳极和阴极之间的接触,因此隔板不是必需的。固体陶瓷电解质主要为钠金属氧化物或硫化物。常见的陶瓷电解质为钠超离子导体(NASICON)、β″-Al2O3固体电解质(BASE)或磷酸铝钛钠(“NATP”)。也可使用在Wang等人,“Development of solid-stateelectrolytes for sodium-ion battery–Ashort review”,第1卷,第91-100页(2019)中描述的固体电解质。
在电子进入外部电路之前,电流收集元件在放电期间收集来自阳极的电子。阴极上的电流收集元件将把电子分配到阴极材料。在再充电期间,电子沿相反的方向移动。电流收集元件可包括铝、铜、钢或其它导电材料。电荷收集元件包括柔性碳毡、多孔碳和银纳米线网,它们可为钠提供“宿主”。
壳体封装电池并防止电解质泄漏。壳体可包括金属或塑料。壳体可为刚性的或柔性的。柔性壳体材料允许单元电池在再充电期间膨胀,或允许通过电池内部的气体形成造成的膨胀。也可使用在Schroder等人,“Comparatively assessing different shapes oflitihium-ion battery cells”,ScienceDirect Procedia Manufacturing,第8卷,第104–111页(2017)中描述的电池结构和制造技术。
电池形状和设计可选自各种形状以优化电池并避免过热、增加能量密度或减少自放电。常见的电池设计包括小圆柱体(没有端子的固体主体,诸如在较老的膝上型电脑电池中使用的那些)、纽扣电池、棱柱形电池、大圆柱体(具有大螺纹端子的固体主体)、袋(柔软、扁平主体,诸如在手机和较新的膝上型电脑中使用的那些;也称为Na离子聚合物或钠聚合物电池)和具有大螺纹端子的刚性塑料盒(诸如在电动车辆中)。
实施例
实施例1
材料合成:
本实施例侧重于Sn作为掺杂物,但相同的原理可用于生产Sb、In、Pb、Bi、Tl等掺杂的Na电极,只要掺杂物金属可溶于熔融的Na。Sn的原子浓度可在0.01%至1%之间变化以确保完全的溶剂化而不形成结晶化合物,如从Sn-Na相图所确定的(图1B)。在氩气填充的手套箱中进行掺杂,其中氧气和水分水平均为<0.5ppm。通常,将2.0g Na金属(99.9%,Sigma-Aldrich)添加到10ml坩埚中,使用加热罩将其缓慢加热至200℃。然后加入适量的Sn箔,并且一般在几秒内将其溶解在熔融的Na中。将熔融混合物在200℃下保持2小时以确保Sn完全溶剂化。将熔融混合物猝灭至室温,并且得到掺杂的Na(图5)。使用辊压机将固化的Sn掺杂的Na块压制成厚度为400、80或30μm的箔。将这些箔切割成16mm的圆盘用于研究它们的物理化学性质和电化学行为。使用相同的程序在不添加掺杂物的情况下制备未掺杂的Na电极以确保结果是可比较的。
电化学测量:
所有的电池研究都使用在Ar填充的手套箱中组装的2025型钮扣电池进行(图4)。使用CH Instruments恒电位仪记录循环伏安图。使用Neware型CT-4008电池分析仪评估电池循环行为。在室温下以0.02Hz至100kHz的频率范围获得电化学阻抗谱。使用相同组成的Na金属阳极组装对称钮扣电池,并且电解质为在碳酸亚乙酯/碳酸亚丙酯(EC/PC,1:1体积)中的1.0MNaPF6溶液。除非另有说明,否则电解质体积为70μl。用非常稳定的Mo6S8阴极组装全电池(图4)。将Mo6S8涂覆在面积容量为~1.5mAh cm-2的Al箔上,将其冲压成圆盘,并在使用前在75℃下真空干燥过夜。
结果:
图6比较了未掺杂的和0.2原子%Sn掺杂的Na金属电极的X射线衍射图案。两个电极都表现出衍射峰,所述衍射峰可唯一地指示金属Na的体心立方(BCC)结构,并且没有识别到结晶金属间Na-Sn化合物。增强的(200)衍射峰是掺杂的Na电极的重要特征,这可通过Sn掺杂物在如图1A中所示的Na晶体结构中的空的面心位点上的选择性占据和/或Sn掺杂导致的优选结晶取向来贡献。
比较了Na电极在有或没有Sn掺杂的情况下在相对湿度<5%的干燥空气中的表面稳定性。未掺杂的Na电极表现出典型的强烈化学反应性,并且几乎立即产生淡灰色的失去光泽的层(图7A、7B、8A和8B)。另一方面,0.2原子%Sn掺杂的Na表现出显著改善的稳定性,并在几天内保持光泽。掺杂的Na电极的表面保持平坦和密实,而未掺杂的Na形成了伴随广泛腐蚀坑的明显孔隙率(图8A和8B)。另外,还评估了表面腐蚀对电化学活性(Na+/Na氧化还原动力学)的影响。这是通过在干燥空气中暴露不同天数后,用未掺杂或掺杂的Na电极组装的对称钮扣电池的EIS分析来进行的。在图9中对结果进行了比较,并揭示,Sn掺杂的Na电极的Rct(电荷转移电阻)在暴露7天后略有增加(51至110Ωcm-2),这显著地好于在仅两天内未掺杂的Na电极的Rct的多于20倍的增加。这些结果表明,由于Sn掺杂,Na金属的干燥空气稳定性显著提高,这可使它们在基于干燥室的工业制造设施中直接集成,而无昂贵的表面保护处理。
首先使用对称纽扣电池配置评估掺杂的Na电极在电池中的稳定性,该对称纽扣电池配置使用具有相同组成的两个Na电极组装。这些电池以0.5mA cm-2或4.0mAcm-2循环,每次循环的容量为2.0mAh cm-2。Sn掺杂的Na电极在两种测试条件下都表现出优异的稳定性(图10-12)。在整个测试中,与Na镀覆和剥离相关的过电位保持相对平坦,表明均匀的Na镀覆而在表面构造(architecture)中没有显著扰动。尽管确实观察到了一些随机的异常电压尖峰,但这种现象主要与高电流下表面Na离子的耗尽有关,并且一般很快消失。另一方面,未掺杂的Na阳极表现出具有大尖峰的显著电压波动,这是苔藓状非活性表面层不可控生长的特征。另外,由于碳酸酯电解质中未掺杂的Na的不稳定性质,在4.0mAcm-2下测试~100小时后,由于电解质的消耗,单元电池也表现出过电位快速增加的故障。相反,掺杂的Na电极直到在相同条件下循环600小时才表现出这种故障,并且因此,Sn掺杂的阳极表现出大约六倍的改善的耐久性。
除了对称电池外,在Na金属全电池中也证实了掺杂的Na电极改善的稳定性。用原型Mo6S8阴极(实际容量为1.5mAh cm-2)组装这些全电池。选择Mo6S8进行此演示,因为它是一种非常稳定的材料,并且任意观察到的降解都可归因于阳极侧的故障(未掺杂的Na相对掺杂的Na)。制备并检查具有不同浓度的Sn掺杂物的Na电极,并将结果在图12中进行比较。配备有未掺杂Na的阳极的电池的容量在500次循环后衰减到少于初始容量的50%,由于Na金属侧的故障和在循环中形成非活性苔藓状Na,这对于未掺杂的Na来说是典型的。值得注意的是,与未掺杂的Na相比,所有配备有掺杂的Na的电池都表现出显著改善的稳定性。在1000次循环后的总容量保持率为~70%。对于配备有0.2原子%Sn掺杂的阳极的电池,观察到最佳稳定性,其中在1000次循环后观察到~80%的显著保持率。
然后将循环的电池拆开,并使用扫描电子显微镜分析钠阳极(图13A和13B)。Sn掺杂的阳极的表面保持相对平坦,没有太多多孔构造。另一方面,未掺杂的Na阳极表现出显著的多孔和苔藓状结构,导致电池在几百次循环内失效。
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Claims (23)
1.阳极,包括:
钠金属,和
掺杂物,所述掺杂物在所述钠金属中,
其中所述阳极具有至多80μm的厚度,并且
所述掺杂物为电负性大于钠的金属。
2.制造权利要求1所述的阳极的方法,包括:
将钠金属熔融,
将掺杂物金属引入到所述钠金属中以形成熔融的掺杂的钠金属,
固化所述掺杂的钠金属,以及
将所述掺杂的钠金属形成为具有至多450μm厚度的箔。
3.电池,包括:
阳极,
与所述阳极接触的阳极电荷收集元件,
阴极,
与所述阴极接触的阴极电荷收集元件,
与所述阳极和所述阴极接触的电解质,以及
封装所述阳极、阳极电荷收集元件、阴极、阴极电荷收集元件和电解质的壳体,
其中所述阳极包括掺杂有掺杂物的钠金属,并且所述掺杂物以0.01至1.0原子%的量存在。
4.用权利要求3所述的电池产生电力的方法,包括:将所述电池的阳极和阴极连接到外部载荷以完成电路。
5.前述权利要求任一项所述的阳极、电池或方法,其中所述掺杂物以0.01至2.0原子%的量存在。
6.前述权利要求任一项所述的阳极、电池或方法,其中所述掺杂物以至多1.0原子%的量存在。
7.前述权利要求任一项所述的阳极、电池或方法,其中所述掺杂物以0.1至0.3原子%的量存在。
8.前述权利要求任一项所述的阳极、电池或方法,其中所述阳极具有至多30μm的厚度。
9.前述权利要求任一项所述的阳极、电池或方法,其中所述掺杂物包括至少一种选自以下的金属:锑、铟、铅、铋、铊、和锡。
10.前述权利要求任一项所述的阳极、电池或方法,其中所述掺杂物包括锡。
11.前述权利要求任一项所述的阳极、电池或方法,其中所述阳极通过电阻稳定性测试。
12.前述权利要求任一项所述的阳极、电池或方法,其中所述阳极具有体心立方晶体结构。
13.前述权利要求任一项所述的阳极、电池或方法,进一步包括在壳体中的隔板。
14.前述权利要求任一项所述的阳极、电池或方法,其中电解质为液体。
15.前述权利要求任一项所述的阳极、电池或方法,其中所述掺杂物以0.1-0.4原子%的量存在。
16.前述权利要求任一项所述的阳极、电池或方法,其中电解质包括
盐,其选自:NaPF6、NaBF4、NaClO4及其混合物,和
溶剂,其选自碳酸酯、醚及其混合物。
17.前述权利要求任一项所述的阳极、电池或方法,其中隔板包括选自以下的材料:棉、尼龙、聚酯、玻璃、聚合物膜、陶瓷、橡胶、石棉和木材。
18.前述权利要求任一项所述的阳极、电池或方法,其中阳极电荷收集元件和阴极电荷收集元件包括独立地选自以下的材料:铜、铝、钢及其组合。
19.前述权利要求任一项所述的阳极、电池或方法,其中所述阳极具有至多15μm的厚度。
20.前述权利要求任一项所述的阳极、电池或方法,其中盐包括NaPF6,
溶剂包括碳酸亚乙酯和碳酸亚丙酯,并且
阴极包括Mo6S8。
21.前述权利要求任一项所述的阳极、电池或方法,其中电池在800次循环后保持至少70%的容量。
22.前述权利要求任一项所述的阳极、电池或方法,其中在干燥空气中组装电池。
23.前述权利要求任一项所述的阳极、电池或方法,进一步包括将电池连接到电源。
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