技术领域technical field
本发明涉及一种抑制锂枝晶的铜锌合金集流体，应用于高储能金属锂电池领域。The invention relates to a copper-zinc alloy current collector suppressing lithium dendrites, which is applied to the field of high-energy storage metal lithium batteries.
背景技术Background technique
随着电动汽车、手机、笔记本电脑等行业的高速发展，人们对高能量密度、高安全性的储能电池的需求日益增长。在各类电池体系中，金属锂由于其最高的理论比能量(3860mAh g-1)及最低的氧化还原电极电势(-3.040V vs.标准氢电极)而成为下一代电池负极材料的研究热点。然而，金属锂负极在充放电过程中，易形成针状或树枝状的锂枝晶。锂枝晶的形成和生长会给电池体系带来不可逆的容量损失，甚至可能会穿过隔膜而导致电池正负极内部短路，埋下电池过热自燃等安全隐患。为解决这些问题，科研工作者们从电池结构设计、电解质体系调控等角度进行了诸多尝试，但目前还都不能完美解决金属锂负极的循环效率低、循环稳定性差、安全性低等问题。抑制金属锂枝晶的生长需要更多新的思考角度以及新的解决策略。With the rapid development of electric vehicles, mobile phones, notebook computers and other industries, people's demand for energy storage batteries with high energy density and high safety is increasing. Among various battery systems, metal lithium has become a research hotspot for the next generation of battery anode materials due to its highest theoretical specific energy (3860mAh g-1 ) and lowest redox electrode potential (-3.040V vs. standard hydrogen electrode). However, lithium metal anodes tend to form needle-like or dendritic lithium dendrites during charging and discharging. The formation and growth of lithium dendrites will bring irreversible capacity loss to the battery system, and may even pass through the separator to cause an internal short circuit between the positive and negative electrodes of the battery, burying safety hazards such as overheating and spontaneous combustion of the battery. In order to solve these problems, scientific researchers have made many attempts from the perspectives of battery structure design and electrolyte system regulation, but so far they have not been able to perfectly solve the problems of low cycle efficiency, poor cycle stability, and low safety of lithium metal anodes. Inhibiting the growth of metal lithium dendrites requires more new thinking angles and new solutions.
金属锂的前期成核生长对于金属锂的后续沉积具有重要影响，其直接关系到后续金属锂的稳定性。因此，抑制锂枝晶的关键在于能否有效控制金属锂的成核生长，尤其是控制金属锂的均匀成核。现在常用的铜箔集流体由于表面的不平整以及缺陷等，导致金属锂在成核阶段就会出现不均匀富集，进而使得锂枝晶的发生的几率大大提高。The early nucleation and growth of metallic lithium has an important impact on the subsequent deposition of metallic lithium, which is directly related to the stability of subsequent metallic lithium. Therefore, the key to inhibiting lithium dendrites lies in whether the nucleation and growth of metallic lithium can be effectively controlled, especially the uniform nucleation of metallic lithium. Due to the surface unevenness and defects of the commonly used copper foil current collectors, metal lithium will be enriched unevenly during the nucleation stage, which greatly increases the probability of lithium dendrites.
因此，寻求一种可以诱导金属锂均匀成核的集流体，对于发展金属锂负极具有重要的意义。Therefore, seeking a current collector that can induce uniform nucleation of lithium metal is of great significance for the development of lithium metal anodes.
发明内容Contents of the invention
本发明涉及一种抑制锂枝晶的铜锌合金集流体，具体是通过在基底材料上覆盖一层铜锌合金。目的是通过铜锌合金中锌原子分散金属锂沉积的成核位点，降低金属锂的成核势垒，进而起到抑制锂枝晶的效果。如图1所示。The invention relates to a copper-zinc alloy current collector that suppresses lithium dendrites, specifically covering a layer of copper-zinc alloy on a base material. The purpose is to disperse the nucleation sites of metal lithium deposition by zinc atoms in the copper-zinc alloy, reduce the nucleation barrier of metal lithium, and then achieve the effect of inhibiting lithium dendrites. As shown in Figure 1.
相对于现有技术，本发明具有以下特点：本发明的通过选择具有亲锂的锌元素作为锂成核的晶种，可以使得锂离子分布更加均匀，有利于金属锂下一步的均匀沉积生长。通过将合金覆盖在基底材料上，此方法简便易行，很容易推广。另外，这种结构须具备一定的稳定性，在金属锂的沉积溶解过程中，铜锌元素分布不会发生明显变化，能够满足电池长循环的需求。Compared with the prior art, the present invention has the following characteristics: the present invention selects a lithium-loving zinc element as the seed crystal for lithium nucleation, which can make the distribution of lithium ions more uniform, which is beneficial to the uniform deposition and growth of metal lithium in the next step. By covering the alloy on the base material, this method is simple and easy to implement, and it is easy to promote. In addition, this structure must have a certain degree of stability. During the deposition and dissolution of metal lithium, the distribution of copper and zinc elements will not change significantly, which can meet the needs of long-term battery cycles.
本发明的技术方案如下：Technical scheme of the present invention is as follows:
作为本发明一种抑制锂枝晶的铜锌合金集流体，所述的在基底材料上覆盖一层铜锌合金；铜锌合金的厚度为10nm～1μm；锌原子含量为1％～5％。As a copper-zinc alloy current collector for suppressing lithium dendrites in the present invention, a layer of copper-zinc alloy is covered on the base material; the thickness of the copper-zinc alloy is 10nm-1μm; the content of zinc atoms is 1%-5%.
作为本发明一种抑制锂枝晶的铜锌合金集流体，所述的基底材料为：铜箔、镍箔、钛箔、纳米纤维铜、泡沫铜、碳纤维或泡沫镍。As a copper-zinc alloy current collector suppressing lithium dendrites in the present invention, the base material is: copper foil, nickel foil, titanium foil, copper nanofiber, copper foam, carbon fiber or nickel foam.
作为本发明一种抑制锂枝晶的铜锌合金集流体，这种铜锌合金集流体可以通过磁控溅射的方法制备。磁控溅射中，靶材为铜锌合金，铜锌合金中锌原子含量为1％～5％。As a copper-zinc alloy current collector suppressing lithium dendrites in the present invention, the copper-zinc alloy current collector can be prepared by magnetron sputtering. In magnetron sputtering, the target material is a copper-zinc alloy, and the content of zinc atoms in the copper-zinc alloy is 1% to 5%.
作为本发明一种抑制锂枝晶的铜锌合金集流体，这种铜锌合金集流体可以采用电沉积方法制备，其镀液工艺配方及操作条件为：酒石酸钾钠80～100g/L、硫酸铜25～40g/L、硫酸锌10～15g/L、柠檬酸钾20～30g/L、磷酸二氢钾20～25g/L、氢氧化钠20～30g/L、适量光亮剂、PH值12～12.4、施镀温度为30～40℃、阴极电流密度为0.005μA cm-2～100mA cm-2，持续时间为1s～24h，机械搅拌，工作电极为基底材料，对电极为铂片，通过施加电压电沉积。As a copper-zinc alloy current collector that suppresses lithium dendrites in the present invention, this copper-zinc alloy current collector can be prepared by electrodeposition, and its plating solution process formula and operating conditions are: potassium sodium tartrate 80-100g/L, sulfuric acid Copper 25-40g/L, zinc sulfate 10-15g/L, potassium citrate 20-30g/L, potassium dihydrogen phosphate 20-25g/L, sodium hydroxide 20-30g/L, proper amount of brightener, PH value 12 ～12.4, the plating temperature is 30～40℃, the cathode current density is 0.005μA cm-2 ～100mA cm-2 , the duration is 1s～24h, mechanical stirring, the working electrode is the base material, and the counter electrode is platinum sheet. Apply voltage for electrodeposition.
作为本发明一种抑制锂枝晶的铜锌合金集流体，所述铜锌合金集流体可以应用到锂-磷酸铁锂电池。As a copper-zinc alloy current collector that suppresses lithium dendrites in the present invention, the copper-zinc alloy current collector can be applied to lithium-lithium iron phosphate batteries.
作为本发明一种抑制锂枝晶的铜锌合金集流体的拓展，这种合金元素也可以是铜硅合金、铜锗合金。As an extension of the copper-zinc alloy current collector that suppresses lithium dendrites in the present invention, the alloy element may also be a copper-silicon alloy or a copper-germanium alloy.
作为本发明一种抑制锂枝晶的铜锌合金集流体的拓展应用，这种铜锌合金集流体也可以应用到其他金属锂电池中(如锂氧电池、锂硫电池)。As an expanded application of the copper-zinc alloy current collector that suppresses lithium dendrites of the present invention, this copper-zinc alloy current collector can also be applied to other metal lithium batteries (such as lithium-oxygen batteries, lithium-sulfur batteries).
通过在常规集流体上覆盖一层铜锌合金，可以极大地改善金属锂的沉积行为。以负载有金属锂的合金集流体或普通铜箔作为负极，采用Celgard 2325隔膜，金属锂作为参比电极和对电极，在充满氩气的手套箱内装成扣式电池。用蓝电进行沉积/溶解实验。电流密度为：0.5mA cm-2，相比铜箔电极仅仅循环了520小时后，电压滞明显增大，铜锌合金负极在循环1000小时后，仍然保持着较小的电压滞。另外，我们将这种集流体应用到锂-磷酸铁锂全电池上，相比采用普通集流体材料的金属锂负极，电池的电化学性能同样有了明显的改善和提高。The deposition behavior of metallic lithium can be greatly improved by covering a conventional current collector with a layer of copper-zinc alloy. The alloy current collector or ordinary copper foil loaded with lithium metal is used as the negative electrode, the Celgard 2325 separator is used, the lithium metal is used as the reference electrode and the counter electrode, and a button battery is installed in a glove box filled with argon. Deposition/dissolution experiments were performed with Blue Electron. The current density is: 0.5mA cm-2 . Compared with the copper foil electrode, the voltage hysteresis increases significantly after only 520 hours of cycling, and the copper-zinc alloy negative electrode still maintains a small voltage hysteresis after 1000 hours of cycling. In addition, we applied this current collector to a lithium-iron phosphate full battery. Compared with the metal lithium anode using common current collector materials, the electrochemical performance of the battery has also been significantly improved and improved.
附图说明Description of drawings
图1铜锌合金集流体通过锌作为晶种诱导锂沉积示意图。Fig. 1 Schematic diagram of copper-zinc alloy current collectors using zinc as a seed to induce lithium deposition.
图2(a)普通铜箔和(b)覆盖有铜锌合金的铜箔浸入熔体锂后照片。Fig. 2 (a) normal copper foil and (b) copper foil covered with copper-zinc alloy after immersion in molten lithium.
图3为(a)普通铜箔和(b)覆盖有铜锌合金的铜箔以0.5mAcm-2电流密度，沉积0.5mAh cm-2的锂。Figure 3 shows (a) common copper foil and (b) copper foil covered with copper-zinc alloy at a current density of 0.5mAcm-2 , depositing 0.5mAh cm-2 of lithium.
具体实施方式Detailed ways
本发明提供的一种抑制锂枝晶的铜锌合金集流体，其特征在于在常规集流体(基底)上覆盖一层铜锌合金，进而起到抑制锂枝晶的效果。The present invention provides a copper-zinc alloy current collector for suppressing lithium dendrites, which is characterized in that a conventional current collector (substrate) is covered with a layer of copper-zinc alloy, thereby achieving the effect of suppressing lithium dendrites.
下面结合具体实例对本发明作进一步说明。The present invention will be further described below in conjunction with specific examples.
实例1Example 1
在本实例中铜锌合金集流体是通过磁控溅射法制备的，定制溅射/电子束/ICP-CVD(基础压力<1E-6托，ICP-CVD腔室)。典型的沉积条件：等离子体气体流量为100sccm，等离子体功率为200W，基底为铜箔，CuZn合金靶材中锌含量为1％，最终在普通铜箔上沉积10nm铜锌合金。In this example, the copper-zinc alloy current collector is prepared by magnetron sputtering, custom sputtering/electron beam/ICP-CVD (base pressure<1E-6 Torr, ICP-CVD chamber). Typical deposition conditions: the plasma gas flow rate is 100sccm, the plasma power is 200W, the substrate is copper foil, the zinc content in the CuZn alloy target is 1%, and finally 10nm copper-zinc alloy is deposited on the common copper foil.
实例2Example 2
在本实例中铜锌合金集流体是通过磁控溅射法法制备的，基底为镍箔，CuZn合金靶材中锌含量为3％，在普通铜箔上沉积200nm铜锌合金。其他条件与实例1相同。In this example, the copper-zinc alloy current collector is prepared by magnetron sputtering, the substrate is nickel foil, the zinc content in the CuZn alloy target is 3%, and 200nm copper-zinc alloy is deposited on the common copper foil. Other conditions are the same as Example 1.
实例3Example 3
在本实例中铜锌合金集流体是通过磁控溅射法法制备的，基底为钛箔，CuZn合金靶材中锌含量为5％，在普通铜箔上沉积1000nm铜锌合金。其他条件与实例1相同。In this example, the copper-zinc alloy current collector is prepared by magnetron sputtering method, the substrate is titanium foil, the zinc content in the CuZn alloy target is 5%, and 1000nm copper-zinc alloy is deposited on the common copper foil. Other conditions are the same as Example 1.
实例4Example 4
在本实例中铜锌合金集流体是通过磁控溅射法法制备的，基底为泡沫铜，CuZn合金靶材中锌含量为1％，在普通铜箔上沉积500nm铜锌合金。其他条件与实例1相同。In this example, the copper-zinc alloy current collector is prepared by magnetron sputtering method, the substrate is copper foam, the zinc content in the CuZn alloy target is 1%, and 500nm copper-zinc alloy is deposited on the common copper foil. Other conditions are the same as Example 1.
实例5Example 5
在本实例中铜锌合金集流体是通过磁控溅射法制备的，基底为碳纤维，CuZn合金靶材中锌含量为2％，在普通铜箔上沉积500nm铜锌合金。其他条件与实例1相同。In this example, the copper-zinc alloy current collector is prepared by magnetron sputtering, the substrate is carbon fiber, the zinc content in the CuZn alloy target is 2%, and 500nm copper-zinc alloy is deposited on the common copper foil. Other conditions are the same as Example 1.
实例6Example 6
在本实例中铜锌合金集流体是通过磁控溅射法法制备的，基底为纳米纤维铜，CuZn合金靶材中锌含量为5％，在普通铜箔上沉积500nm铜锌合金。其他条件与实例1相同。In this example, the copper-zinc alloy current collector is prepared by the magnetron sputtering method, the substrate is copper nanofiber, the zinc content in the CuZn alloy target is 5%, and 500nm copper-zinc alloy is deposited on the common copper foil. Other conditions are the same as Example 1.
实例7Example 7
在本实例中铜锌合金集流体是通过磁控溅射法法制备的，基底为泡沫镍，CuZn合金靶材中锌含量为2％，在普通铜箔上沉积500nm铜锌合金。其他条件与实例1相同。实例8In this example, the copper-zinc alloy current collector is prepared by magnetron sputtering method, the substrate is nickel foam, the zinc content in the CuZn alloy target is 2%, and 500nm copper-zinc alloy is deposited on the common copper foil. Other conditions are the same as Example 1. Example 8
在本实例中铜锌合金集流体是通过电沉积制备的，其工艺配方及操作条件为：酒石酸钾钠100g/L、硫酸铜40g/L、硫酸锌15g/L、柠檬酸钾20g/L、磷酸二氢钾25g/L、氢氧化钠20/L、适量光亮剂、pH值12.4、施镀温度为30℃、阴极电流密度为30mA cm-2，持续时间为1s，机械搅拌，工作电极为铜箔，对电极为铂片，通过施加电压电沉积。所得铜锌合金镀层为30nm，铜锌含量为2％。In this example, the copper-zinc alloy current collector is prepared by electrodeposition, and its process formula and operating conditions are: potassium sodium tartrate 100g/L, copper sulfate 40g/L, zinc sulfate 15g/L, potassium citrate 20g/L, Potassium dihydrogen phosphate 25g/L, sodium hydroxide 20/L, appropriate amount of brightener, pH value 12.4, plating temperature 30°C, cathode current density 30mA cm-2 , duration 1s, mechanical stirring, working electrode Copper foil, counter electrode is a platinum sheet, electrodeposited by applying a voltage. The obtained copper-zinc alloy plating layer is 30nm, and the copper-zinc content is 2%.
实例9Example 9
在本实例中铜锌合金集流体是通过电沉积制备的，其工艺配方及操作条件为：酒石酸钾钠80g/L、硫酸铜25g/L、硫酸锌10g/L、柠檬酸钾30g/L、磷酸二氢钾20g/L、氢氧化钠30/L、适量光亮剂、PH值12、施镀温度为40℃、阴极电流密度为100mA cm-2，持续时间为24h，机械搅拌，工作电极为泡沫铜，对电极为铂片，通过施加电压电沉积。所得铜锌合金镀层为200nm，铜锌含量为1％。In this example, the copper-zinc alloy current collector is prepared by electrodeposition, and its process formula and operating conditions are: potassium sodium tartrate 80g/L, copper sulfate 25g/L, zinc sulfate 10g/L, potassium citrate 30g/L, Potassium dihydrogen phosphate 20g/L, sodium hydroxide 30/L, appropriate amount of brightener, pH value 12, plating temperature 40℃, cathode current density 100mA cm-2 , duration 24h, mechanical stirring, working electrode Copper foam with a platinum sheet as the counter electrode, electrodeposited by applying a voltage. The obtained copper-zinc alloy plating layer is 200nm, and the copper-zinc content is 1%.
实例10Example 10
在本实例中铜锌合金集流体是通过电沉积制备的，其工艺配方及操作条件为：酒石酸钾钠90g/L、硫酸铜30g/L、硫酸锌15g/L、柠檬酸钾25g/L、磷酸二氢钾25g/L、氢氧化钠30/L、适量光亮剂、PH值12、施镀温度为40℃、阴极电流密度为0.05μA cm-2，持续时间为24h，机械搅拌，工作电极为碳纤维，对电极为铂片，通过施加电压电沉积。所得铜锌合金镀层为1000nm，铜锌含量为5％。In this example, the copper-zinc alloy current collector is prepared by electrodeposition, and its process formula and operating conditions are: potassium sodium tartrate 90g/L, copper sulfate 30g/L, zinc sulfate 15g/L, potassium citrate 25g/L, Potassium dihydrogen phosphate 25g/L, sodium hydroxide 30/L, appropriate amount of brightener, pH value 12, plating temperature 40℃, cathode current density 0.05μA cm-2 , duration 24h, mechanical stirring, working electrode It is a carbon fiber, and the counter electrode is a platinum sheet, which is electrodeposited by applying a voltage. The obtained copper-zinc alloy plating layer is 1000nm, and the copper-zinc content is 5%.
实例11Example 11
在充满氩气的手套箱内，将铜锌合金集流体或普通铜箔集流体浸入熔体锂中60秒后取出，如图2所示。In a glove box filled with argon, the copper-zinc alloy current collector or common copper foil current collector was immersed in molten lithium for 60 seconds and then taken out, as shown in Figure 2.
实例12Example 12
在充满氩气的手套箱内，以铜锌合金集流体或普通铜箔作为负极，采用Celgard2325隔膜，金属锂作为参比电极和对电极，装成扣式电池。铜锌合金的厚度为100nm，铜锌合金中，锌含量为2％。本发明中所用电解液包含一定浓度的锂盐和有机溶剂。锂盐分别为六氟磷酸锂(LiPF6)，溶剂碳酸乙烯酯(EC)和碳酸二乙酯(DEC)(EC/DEC,v/v＝1:1)。用蓝电进行沉积/溶解实验。实验电流密度为：0.5mA cm-2。相比铜箔电极仅仅能循环30圈，铜锌合金集流体负极(基底为铜箔)可以循环在循环300圈后库伦效率仍然保持在98％左右。In a glove box filled with argon gas, a copper-zinc alloy current collector or ordinary copper foil is used as the negative electrode, a Celgard2325 separator is used, and metal lithium is used as the reference electrode and the counter electrode to form a button battery. The thickness of the copper-zinc alloy is 100nm, and the zinc content in the copper-zinc alloy is 2%. The electrolytic solution used in the present invention contains a certain concentration of lithium salt and organic solvent. Lithium salts are lithium hexafluorophosphate (LiPF6 ), solvent ethylene carbonate (EC) and diethyl carbonate (DEC) (EC/DEC, v/v=1:1). Deposition/dissolution experiments were performed with Blue Electron. The experimental current density is: 0.5mA cm-2 . Compared with the copper foil electrode, which can only cycle 30 times, the copper-zinc alloy current collector negative electrode (the substrate is copper foil) can be cycled after 300 cycles, and the Coulombic efficiency still remains at about 98%.
实例13Example 13
在充满氩气的手套箱内，以铜锌合金集流体或普通铜箔作为负极，采用Celgard2400隔膜，金属锂作为参比电极和对电极，装成扣式电池。纸团状石墨烯的厚度为80nm，铜锌合金中，锌含量为3％。本发明中所用电解液包含一定浓度的锂盐和有机溶剂。锂盐分别为二(三氟甲磺酰)亚胺锂(LiTFSI)、溶剂是二甘醇二甲醚(DME)和1,3-二氧戊烷(DOL)(DOL/DME,v/v＝1:1)。用蓝电进行沉积/溶解实验。实验电流密度为：10mA cm-2。相比铜箔电极仅仅能循环15圈，铜锌合金集流体负极(基底为泡沫铜)可以循环在循环100圈后库伦效率仍然保持在97％左右。In a glove box filled with argon gas, a copper-zinc alloy current collector or ordinary copper foil is used as the negative electrode, a Celgard2400 separator is used, and metal lithium is used as the reference electrode and the counter electrode to form a button battery. The thickness of the paper-like graphene is 80nm, and in the copper-zinc alloy, the zinc content is 3%. The electrolytic solution used in the present invention contains a certain concentration of lithium salt and organic solvent. The lithium salt is lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), the solvent is diglyme (DME) and 1,3-dioxolane (DOL) (DOL/DME, v/v =1:1). Deposition/dissolution experiments were performed with Blue Electron. The experimental current density is: 10mA cm-2 . Compared with the copper foil electrode, which can only cycle 15 times, the copper-zinc alloy current collector negative electrode (the substrate is copper foam) can be cycled after 100 cycles, and the Coulombic efficiency still remains at about 97%.
实例14Example 14
在充满氩气的手套箱内，以铜锌合金集流体或普通铜箔作为负极，采用Celgard2325隔膜，金属锂作为参比电极和对电极，装成扣式电池。铜锌合金的厚度为200nm，铜锌合金中，锌含量为1％。本发明中所用电解液包含一定浓度的锂盐和有机溶剂。锂盐为LiTFSI，溶剂是DOL/DME(v/v＝1:1)，添加1％LiNO3。用蓝电进行沉积/溶解实验。实验电流密度为：0.5mA cm-2。相比铜箔电极仅仅能循环20圈，铜锌合金集流体(基底为碳纤维)在循环150圈后库伦效率仍然保持在97％左右。In a glove box filled with argon gas, a copper-zinc alloy current collector or ordinary copper foil is used as the negative electrode, a Celgard2325 separator is used, and metal lithium is used as the reference electrode and the counter electrode to form a button battery. The thickness of the copper-zinc alloy is 200nm, and the zinc content in the copper-zinc alloy is 1%. The electrolytic solution used in the present invention contains a certain concentration of lithium salt and organic solvent. The lithium salt is LiTFSI, the solvent is DOL/DME (v/v=1:1), and 1% LiNO3 is added. Deposition/dissolution experiments were performed with Blue Electron. The experimental current density is: 0.5mA cm-2 . Compared with the copper foil electrode, which can only cycle 20 times, the copper-zinc alloy current collector (the base is carbon fiber) still maintains a coulombic efficiency of about 97% after 150 cycles.
实例15Example 15
在充满氩气的手套箱内，以铜锌合金集流体或普通铜箔作为负极，采用Celgard2325隔膜，金属锂作为参比电极和对电极，装成扣式电池。铜锌合金的厚度为100nm，铜锌合金锌含量为3％。本发明中所用电解液包含一定浓度的锂盐和有机溶剂。锂盐为LiTFSI，溶剂是DME/DOL(v/v＝1:1)。用蓝电进行沉积/溶解实验。实验电流密度为：0.5mA cm-2。循环1圈后，将沉积完锂或多次循环后的电池，在手套箱内拆开，对负极进行冲洗晾干处理，用冷场发射扫描电子显微镜(SEM)观察金属锂沉积形貌，如图3所示。相比普通铜箔集流体，铜锌合金集流体(基底为高分子纤维)锂沉积明显改善，沉积更加均匀。In a glove box filled with argon gas, a copper-zinc alloy current collector or ordinary copper foil is used as the negative electrode, a Celgard2325 separator is used, and metal lithium is used as the reference electrode and the counter electrode to form a button battery. The thickness of the copper-zinc alloy is 100nm, and the zinc content of the copper-zinc alloy is 3%. The electrolytic solution used in the present invention contains a certain concentration of lithium salt and organic solvent. The lithium salt is LiTFSI, and the solvent is DME/DOL (v/v=1:1). Deposition/dissolution experiments were performed with Blue Electron. The experimental current density is: 0.5mA cm-2 . After 1 cycle, the battery that has deposited lithium or has been cycled for many times is disassembled in the glove box, and the negative electrode is rinsed and dried, and the deposition morphology of metallic lithium is observed with a cold field emission scanning electron microscope (SEM), as shown in the figure 3 shown. Compared with ordinary copper foil current collectors, the lithium deposition of copper-zinc alloy current collectors (based on polymer fibers) is significantly improved and the deposition is more uniform.
实例16Example 16
将沉积一定量锂金属的电池在手套箱中拆开，与LiFePO4正极，组装成扣式电池进行全电池测试，正负极容量按一定比例匹配，所用电解液锂盐为LiPF6，溶剂为EC/DEC(v/v＝1:1)。采用铜锌合金集流体(基底为铜箔)的电池负极稳定性得到了明显改善，相比普通铜箔电池寿命得到极大地改善。The battery deposited with a certain amount of lithium metal was disassembled in the glove box and assembled into a button battery with LiFePO4 positive electrode for full battery testing. The capacity of the positiveand negative electrodes was matched according to a certain ratio. EC/DEC (v/v=1:1). The stability of the negative electrode of the battery using the copper-zinc alloy current collector (the base is copper foil) has been significantly improved, and the life of the battery has been greatly improved compared with ordinary copper foil batteries.
实例17Example 17
将沉积一定量锂金属的电池在手套箱中拆开，与super P空气电极正极，组装成扣式锂氧电池进行全电池测试，正负极容量按一定比例匹配，所用电解液锂盐为三氟甲基磺酸锂(LiCFSO3)，溶剂为四乙二醇二甲醚(TEGDME)。采用铜锌合金集流体(基底为铜箔)的电池负极稳定性得到了明显改善，相比普通铜箔电池寿命得到极大地改善。The battery deposited with a certain amount of lithium metal was disassembled in the glove box, and the positive electrode of the super P air electrode was assembled into a button lithium oxygen battery for full battery testing. The capacity of the positive and negative electrodes was matched in a certain ratio, and the electrolyte lithium salt used was three Lithium fluoromethanesulfonate (LiCFSO3 ), the solvent is tetraethylene glycol dimethyl ether (TEGDME). The stability of the negative electrode of the battery using the copper-zinc alloy current collector (the base is copper foil) has been significantly improved, and the life of the battery has been greatly improved compared with ordinary copper foil batteries.
实例18Example 18
将沉积一定量锂金属的电池在手套箱中拆开，与硫正极，组装成扣式锂硫电池进行全电池测试，正负极容量按一定比例匹配，所用电解液为1M LiTFSI in DME/DOL(v/v＝1:1)添加1％LiNO3。采用铜锌合金集流体(基底为铜箔)的电池负极稳定性得到了明显改善，相比普通铜箔电池寿命得到极大地改善。Disassemble the battery deposited with a certain amount of lithium metal in the glove box, assemble it with the sulfur positive electrode, and assemble it into a button-type lithium-sulfur battery for full battery testing. The capacity of the positive and negative electrodes is matched according to a certain ratio, and the electrolyte used is 1M LiTFSI in DME/DOL (v/v=1:1) 1% LiNO3 was added. The stability of the negative electrode of the battery using the copper-zinc alloy current collector (the base is copper foil) has been significantly improved, and the life of the battery has been greatly improved compared with ordinary copper foil batteries.
实例19Example 19
将沉积一定量锂金属的电池在手套箱中拆开，与硫正极，组装成扣式锂硫电池进行全电池测试，正负极容量按一定比例匹配，所用电解液锂盐为LiTFSI，溶剂为DOL/DME(v/v＝1:1)。采用铜锌合金集流体(基底为铜箔)的电池负极稳定性得到了明显改善，相比普通铜箔电池寿命得到极大地改善。The battery deposited with a certain amount of lithium metal was disassembled in the glove box and assembled with the sulfur positive electrode to form a button-type lithium-sulfur battery for full battery testing. The capacity of the positive and negative electrodes was matched according to a certain ratio. DOL/DME (v/v=1:1). The stability of the negative electrode of the battery using the copper-zinc alloy current collector (the base is copper foil) has been significantly improved, and the life of the battery has been greatly improved compared with ordinary copper foil batteries.
实例20Example 20
在充满氩气的手套箱内，以铜硅合金集流体或普通铜箔作为负极，采用Celgard2325隔膜，金属锂作为参比电极和对电极，装成扣式电池。铜硅合金的厚度为100nm，铜硅合金中，硅含量为1％。本发明中所用电解液包含一定浓度的锂盐和有机溶剂。锂盐为LiTFSI，溶剂为DOL/DME(v/v＝1:1)，添加1％LiNO3。用蓝电进行沉积/溶解实验。实验电流密度为：2.0mA cm-2。相比铜箔电极仅仅能循环30圈，铜硅合金集流体负极(基底为铜箔)可以循环在循环200圈后库伦效率仍然保持在98％左右。In a glove box filled with argon gas, a copper-silicon alloy current collector or ordinary copper foil is used as the negative electrode, Celgard2325 separator is used, and metal lithium is used as the reference electrode and the counter electrode to form a button cell. The thickness of the copper-silicon alloy is 100 nm, and the silicon content in the copper-silicon alloy is 1%. The electrolytic solution used in the present invention contains a certain concentration of lithium salt and organic solvent. The lithium salt is LiTFSI, the solvent is DOL/DME (v/v=1:1), and 1% LiNO3 is added. Deposition/dissolution experiments were performed with Blue Electron. The experimental current density is: 2.0mA cm-2 . Compared with the copper foil electrode, which can only be cycled 30 times, the copper-silicon alloy current collector negative electrode (the substrate is copper foil) can be cycled for 200 cycles and the Coulombic efficiency still remains at about 98%.
实例21Example 21
将沉积一定量锂金属的电池在手套箱中拆开，与硫正极，组装成扣式锂硫电池进行全电池测试，正负极容量按一定比例匹配，所用电解液锂盐为LiTFSI，溶剂为DOL/DME(v/v＝1:1)。采用铜锡合金集流体(基底为铜箔)的电池负极稳定性得到了明显改善，相比普通铜箔电池寿命得到极大地改善。The battery deposited with a certain amount of lithium metal was disassembled in the glove box and assembled with the sulfur positive electrode to form a button-type lithium-sulfur battery for full battery testing. The capacity of the positive and negative electrodes was matched according to a certain ratio. The electrolyte lithium salt used was LiTFSI, and the solvent was DOL/DME (v/v=1:1). The stability of the negative electrode of the battery using the copper-tin alloy current collector (the base is copper foil) has been significantly improved, and the battery life has been greatly improved compared with ordinary copper foil batteries.
综上所述，采用铜锌合金集流体，可以显著改善金属锂的沉积问题，防止锂枝晶的生成，提高金属锂负极的循环稳定性。该方法简单可行，成本低，适于大规模应用。In summary, the use of copper-zinc alloy current collectors can significantly improve the deposition of lithium metal, prevent the formation of lithium dendrites, and improve the cycle stability of lithium metal anodes. The method is simple, feasible, low in cost and suitable for large-scale application.
上述内容仅为本发明的优选实施例，并非用于限制本发明的实施方案，本领域普通技术人员根据本发明的主要构思和精神，可以十分方便地进行相应的变通或修改，因此本发明的保护范围应以权利要求书所要求的保护范围为准。The above content is only a preferred embodiment of the present invention, and is not intended to limit the implementation of the present invention. Those skilled in the art can easily make corresponding modifications or modifications according to the main idea and spirit of the present invention. Therefore, the present invention The scope of protection shall be subject to the scope of protection required by the claims.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810219640.XACN108550858A (en) | 2018-03-16 | 2018-03-16 | A kind of ormolu collector inhibiting Li dendrite |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810219640.XACN108550858A (en) | 2018-03-16 | 2018-03-16 | A kind of ormolu collector inhibiting Li dendrite |
| Publication Number | Publication Date |
|---|---|
| CN108550858Atrue CN108550858A (en) | 2018-09-18 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810219640.XAPendingCN108550858A (en) | 2018-03-16 | 2018-03-16 | A kind of ormolu collector inhibiting Li dendrite |
| Country | Link |
|---|---|
| CN (1) | CN108550858A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109585855A (en)* | 2018-12-05 | 2019-04-05 | 厦门大学 | Lithium metal supporter and the preparation method and application thereof |
| CN109950545A (en)* | 2019-03-06 | 2019-06-28 | 浙江工业大学 | A kind of preparation method of three-dimensional hierarchical porous copper-zinc composite current collector |
| CN110085871A (en)* | 2019-06-03 | 2019-08-02 | 哈尔滨工业大学 | A kind of preparation method and applications of modified metal cathode of lithium collector |
| CN110112367A (en)* | 2019-04-23 | 2019-08-09 | 南方科技大学 | Three-dimensional composite metal lithium cathode, preparation method thereof, lithium metal battery and lithium sulfur battery |
| CN110148752A (en)* | 2019-04-25 | 2019-08-20 | 西北工业大学 | A kind of negative current collector surface electropolymerization pyrroles's method of modifying |
| CN110752375A (en)* | 2019-10-31 | 2020-02-04 | 山东大学 | Lithium battery for inhibiting growth of lithium dendrite by using liquid metal and preparation method and application thereof |
| CN110911689A (en)* | 2019-10-31 | 2020-03-24 | 南方科技大学 | Current collector and preparation method thereof, electrode sheet and secondary battery |
| CN111106355A (en)* | 2018-10-25 | 2020-05-05 | 中国科学院宁波材料技术与工程研究所 | Anode multi-stage copper skeleton current collector for lithium metal battery, preparation method thereof, and battery containing the same |
| CN111224115A (en)* | 2018-11-27 | 2020-06-02 | 中国科学院大连化学物理研究所 | Zinc-based battery negative electrode and preparation and application thereof |
| CN112216809A (en)* | 2019-07-11 | 2021-01-12 | 深圳市比亚迪锂电池有限公司 | Lithium metal cathode, preparation method thereof and lithium ion battery |
| CN112349911A (en)* | 2020-07-27 | 2021-02-09 | 上海恩力动力技术有限公司 | Porous metal current collector, preparation method, negative electrode and battery |
| CN112382764A (en)* | 2020-11-12 | 2021-02-19 | 武汉理工大学 | Lithium-philic copper-nickel double-metal-layer modified three-dimensional framework material and preparation method and application thereof |
| CN112397726A (en)* | 2020-11-19 | 2021-02-23 | 中国科学院宁波材料技术与工程研究所 | Modified planar current collector, preparation method thereof, lithium electrode and lithium battery |
| WO2021173469A1 (en)* | 2020-02-27 | 2021-09-02 | ZAF Energy Systems, Incorporated | Electrode having protective and locking layers on current collector |
| CN113346041A (en)* | 2021-05-19 | 2021-09-03 | 北京化工大学 | Method for constructing flexible metal negative electrode by using positive electrode material as interface layer |
| CN113644267A (en)* | 2021-08-03 | 2021-11-12 | 西北工业大学 | Multi-element alloy induced flexible sodium metal battery substrate and preparation method thereof |
| CN114400331A (en)* | 2022-03-03 | 2022-04-26 | 电子科技大学 | A kind of preparation method of negative electrode current collector that can improve the cycle stability of metallic lithium |
| CN115224247A (en)* | 2022-07-28 | 2022-10-21 | 电子科技大学长三角研究院(衢州) | A kind of preparation method of three-dimensional porous cobalt-indium alloy electrode |
| CN116022853A (en)* | 2022-12-26 | 2023-04-28 | 国网河南省电力公司电力科学研究院 | Material for inhibiting zinc dendrite, preparation method and application |
| CN116364941A (en)* | 2023-03-31 | 2023-06-30 | 武汉中原长江科技发展有限公司 | Fast-charging negative electrode and application thereof in non-anode battery |
| CN116598617A (en)* | 2023-07-18 | 2023-08-15 | 帕瓦(长沙)新能源科技有限公司 | Lithium metal composite negative electrode, preparation method thereof and battery |
| CN117613283A (en)* | 2024-01-22 | 2024-02-27 | 中自环保科技股份有限公司 | A kind of negative electrode copper foil current collector and its preparation process and application |
| CN118919737A (en)* | 2024-10-11 | 2024-11-08 | 浙江金羽新能源科技有限公司 | Three-dimensional current collector, preparation method thereof and lithium battery |
| US12305309B2 (en) | 2022-11-18 | 2025-05-20 | Industrial Technology Research Institute | Composite metal foil |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001256968A (en)* | 2000-03-13 | 2001-09-21 | Mitsui Mining & Smelting Co Ltd | Anode material for nonaqueous electrolyte secondary battery and manufacturing method thereof |
| CN1360356A (en)* | 2002-01-24 | 2002-07-24 | 南开大学 | Foam-metal current collector of secondary battery using zinc as negative electrode and its preparing process |
| CN1599098A (en)* | 2003-09-17 | 2005-03-23 | 日立麦克赛尔株式会社 | Electrode for non-aqueous secondary battery and non-aqueous secondary battery using the same |
| CN105655632A (en)* | 2016-03-17 | 2016-06-08 | 湖北知本信息科技有限公司 | Method for preparing lithium-air battery and prepared lithium-air battery |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001256968A (en)* | 2000-03-13 | 2001-09-21 | Mitsui Mining & Smelting Co Ltd | Anode material for nonaqueous electrolyte secondary battery and manufacturing method thereof |
| CN1360356A (en)* | 2002-01-24 | 2002-07-24 | 南开大学 | Foam-metal current collector of secondary battery using zinc as negative electrode and its preparing process |
| CN1599098A (en)* | 2003-09-17 | 2005-03-23 | 日立麦克赛尔株式会社 | Electrode for non-aqueous secondary battery and non-aqueous secondary battery using the same |
| CN105655632A (en)* | 2016-03-17 | 2016-06-08 | 湖北知本信息科技有限公司 | Method for preparing lithium-air battery and prepared lithium-air battery |
| Title |
|---|
| SHAN LIU，ET AL: "Dendrite-free Li metal anode by lowering deposition interface energy with Cu99Zn alloy coating", 《ENERGY STORAGE MATERIALS》* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111106355A (en)* | 2018-10-25 | 2020-05-05 | 中国科学院宁波材料技术与工程研究所 | Anode multi-stage copper skeleton current collector for lithium metal battery, preparation method thereof, and battery containing the same |
| CN111224115A (en)* | 2018-11-27 | 2020-06-02 | 中国科学院大连化学物理研究所 | Zinc-based battery negative electrode and preparation and application thereof |
| US12230792B2 (en) | 2018-12-05 | 2025-02-18 | Xiamen University | Supporter of lithium metal and methods thereof |
| CN109585855A (en)* | 2018-12-05 | 2019-04-05 | 厦门大学 | Lithium metal supporter and the preparation method and application thereof |
| CN109950545A (en)* | 2019-03-06 | 2019-06-28 | 浙江工业大学 | A kind of preparation method of three-dimensional hierarchical porous copper-zinc composite current collector |
| CN110112367A (en)* | 2019-04-23 | 2019-08-09 | 南方科技大学 | Three-dimensional composite metal lithium cathode, preparation method thereof, lithium metal battery and lithium sulfur battery |
| CN110112367B (en)* | 2019-04-23 | 2021-09-03 | 南方科技大学 | Three-dimensional composite metal lithium cathode, preparation method thereof, lithium metal battery and lithium sulfur battery |
| CN110148752A (en)* | 2019-04-25 | 2019-08-20 | 西北工业大学 | A kind of negative current collector surface electropolymerization pyrroles's method of modifying |
| CN110085871A (en)* | 2019-06-03 | 2019-08-02 | 哈尔滨工业大学 | A kind of preparation method and applications of modified metal cathode of lithium collector |
| CN110085871B (en)* | 2019-06-03 | 2021-12-10 | 哈尔滨工业大学 | Preparation method and application of modified metal lithium negative electrode current collector |
| CN112216809A (en)* | 2019-07-11 | 2021-01-12 | 深圳市比亚迪锂电池有限公司 | Lithium metal cathode, preparation method thereof and lithium ion battery |
| CN112216809B (en)* | 2019-07-11 | 2022-03-18 | 深圳市比亚迪锂电池有限公司 | Metal cathode, preparation method thereof and lithium ion battery |
| CN110911689A (en)* | 2019-10-31 | 2020-03-24 | 南方科技大学 | Current collector and preparation method thereof, electrode sheet and secondary battery |
| CN110752375A (en)* | 2019-10-31 | 2020-02-04 | 山东大学 | Lithium battery for inhibiting growth of lithium dendrite by using liquid metal and preparation method and application thereof |
| WO2021173469A1 (en)* | 2020-02-27 | 2021-09-02 | ZAF Energy Systems, Incorporated | Electrode having protective and locking layers on current collector |
| CN112349911A (en)* | 2020-07-27 | 2021-02-09 | 上海恩力动力技术有限公司 | Porous metal current collector, preparation method, negative electrode and battery |
| CN112382764B (en)* | 2020-11-12 | 2022-03-01 | 武汉理工大学 | Modified three-dimensional framework material with lithiophilic copper-nickel bimetallic layer and preparation method and application thereof |
| CN112382764A (en)* | 2020-11-12 | 2021-02-19 | 武汉理工大学 | Lithium-philic copper-nickel double-metal-layer modified three-dimensional framework material and preparation method and application thereof |
| CN112397726A (en)* | 2020-11-19 | 2021-02-23 | 中国科学院宁波材料技术与工程研究所 | Modified planar current collector, preparation method thereof, lithium electrode and lithium battery |
| CN113346041A (en)* | 2021-05-19 | 2021-09-03 | 北京化工大学 | Method for constructing flexible metal negative electrode by using positive electrode material as interface layer |
| CN113644267A (en)* | 2021-08-03 | 2021-11-12 | 西北工业大学 | Multi-element alloy induced flexible sodium metal battery substrate and preparation method thereof |
| CN113644267B (en)* | 2021-08-03 | 2023-09-29 | 西北工业大学 | Multi-element alloy induced flexible sodium metal battery substrate and preparation method thereof |
| CN114400331A (en)* | 2022-03-03 | 2022-04-26 | 电子科技大学 | A kind of preparation method of negative electrode current collector that can improve the cycle stability of metallic lithium |
| CN115224247A (en)* | 2022-07-28 | 2022-10-21 | 电子科技大学长三角研究院(衢州) | A kind of preparation method of three-dimensional porous cobalt-indium alloy electrode |
| US12305309B2 (en) | 2022-11-18 | 2025-05-20 | Industrial Technology Research Institute | Composite metal foil |
| CN116022853A (en)* | 2022-12-26 | 2023-04-28 | 国网河南省电力公司电力科学研究院 | Material for inhibiting zinc dendrite, preparation method and application |
| CN116364941A (en)* | 2023-03-31 | 2023-06-30 | 武汉中原长江科技发展有限公司 | Fast-charging negative electrode and application thereof in non-anode battery |
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| WD01 | Invention patent application deemed withdrawn after publication | Application publication date:20180918 |