CN113707845B - Potassium metal battery cathode, preparation method and application thereof, and potassium metal battery - Google Patents
Potassium metal battery cathode, preparation method and application thereof, and potassium metal battery Download PDFInfo
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 78
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052802 copper Inorganic materials 0.000 claims abstract description 77
- 239000006260 foam Substances 0.000 claims abstract description 57
- 239000010931 gold Substances 0.000 claims abstract description 53
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 51
- 239000011591 potassium Substances 0.000 claims abstract description 51
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052737 gold Inorganic materials 0.000 claims abstract description 48
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims description 25
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- 238000002386 leaching Methods 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 3
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- 230000000052 comparative effect Effects 0.000 description 23
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 19
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- 239000002184 metal Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
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- 210000001787 dendrite Anatomy 0.000 description 4
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- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
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- XYYVDQWGDNRQDA-UHFFFAOYSA-K trichlorogold;trihydrate;hydrochloride Chemical compound O.O.O.Cl.Cl[Au](Cl)Cl XYYVDQWGDNRQDA-UHFFFAOYSA-K 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- HYTUQENVFPSZBW-UHFFFAOYSA-N O.O.O.O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O.O.O.O=C1N[ClH](=O)NC2=C1NC(=O)N2 HYTUQENVFPSZBW-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
Description
技术领域technical field
本发明涉及钾金属电池技术领域，尤其涉及一种钾金属电池负极及其制备方法和应用、钾金属电池。The invention relates to the technical field of potassium metal batteries, in particular to a negative electrode of a potassium metal battery, a preparation method and application thereof, and a potassium metal battery.
背景技术Background technique
在传统二次电池中，锂离子电池具有非常高的能量密度、工作电压高、环境友好和无记忆效应等优势，在市场中占据较大份额。但是随着不断的发展，商业锂离子电池的正极和负极已接近其理论容量，能量密度提升遇到瓶颈。而随着便携式电子设备、电动车辆和智能电网的快速发展，人们对大容量电池的需求却日益增加。因此，金属电池又回到了科学研究人员的视野。锂金属负极由于其超高的理论比容量(3860mA·h·g-1)和极低的还原电势(-3.04Vvs SHE)被认为是理想的负极材料。但是锂资源相对稀少(地球上质量百分数为0.0017％)且地域分布不均，这些因素极大地限制了其广泛应用。而与锂相比，钾含量丰富且化学性质相似。因此，金属钾适合于在电池设备中大规模应用。所以钾金属电池被认为是下一代储能设备。此外，在有机溶剂中，碱金属中K+/K氧化还原对的标准电位(相对于SHE)最低，这意味着它可以提供更高的工作电压和电流密度。Among traditional secondary batteries, lithium-ion batteries have the advantages of very high energy density, high working voltage, environmental friendliness and no memory effect, and occupy a large share in the market. However, with continuous development, the positive and negative electrodes of commercial lithium-ion batteries are close to their theoretical capacity, and the improvement of energy density has encountered a bottleneck. With the rapid development of portable electronic devices, electric vehicles and smart grids, people's demand for high-capacity batteries is increasing. Therefore, metal batteries have returned to the field of vision of scientific researchers. Li metal anode is considered as an ideal anode material due to its ultra-high theoretical specific capacity (3860mA·h·g -1 ) and extremely low reduction potential (-3.04Vvs SHE). However, lithium resources are relatively scarce (0.0017% by mass on the earth) and geographically distributed unevenly, these factors greatly limit its wide application. Potassium is abundant and chemically similar to lithium. Therefore, potassium metal is suitable for large-scale applications in battery devices. Therefore, potassium metal batteries are considered as next-generation energy storage devices. In addition, among organic solvents, alkali metals have the lowest standard potential (relative to SHE) of the K + /K redox couple, which means that it can provide higher operating voltage and current density.
然而，在钾金属负极的实际应用中仍然存在许多挑战，例如安全性和稳定性。钾金属电池系统成功的关键因素是在充电/放电过程中实现无枝晶。与大多数金属负极类似，钾离子在循环过程中沉积不均匀导致树枝状生长，是电池短路和爆炸的主要原因。而且由于没有“宿主”，因此在电镀和剥离过程中，金属钾负极的体积变化不受限制。在几个循环后，电极变得疏松、破裂，因为有大量没有电化学活性的“死钾”从电极上脱落。改善钾金属电池寿命和库仑效率的关键是抑制树枝状晶体的生长。However, there are still many challenges in the practical application of potassium metal anodes, such as safety and stability. A key factor for the success of potassium metal battery systems is to achieve dendrite-free charging/discharging. Similar to most metal anodes, the uneven deposition of potassium ions during cycling leads to dendritic growth, which is the main cause of battery short circuit and explosion. And since there is no "host", the volume change of the metal potassium anode is not limited during the plating and stripping processes. After a few cycles, the electrodes became loose and cracked as large amounts of electrochemically inactive "dead potassium" fell off the electrodes. The key to improving the lifetime and Coulombic efficiency of potassium metal batteries is to suppress the growth of dendrites.
为了抑制金属负极的树枝状生长，之前的许多报道已经提出了不同的策略。主要可以分为三种：优化电解质组成、使用固态电解质和设计负极结构。对于设计负极结构来说，目前在设计金属负极的结构时，使用三维集流体作为钾的宿主，在沉积/剥离过程中钾相对无限的体积变化受到限制。此外三维集流体可以增加电极的比表面积，减小局部有效电流并抑制树枝状钾的生长。但是由于金属钾对铜的亲和性很差，在钾沉积过程中有较大的成核过电势。因此电化学性能不能令人满意。To suppress the dendritic growth of metal anodes, many previous reports have proposed different strategies. It can be mainly divided into three types: optimizing electrolyte composition, using solid electrolyte and designing negative electrode structure. For the design of the anode structure, the current design of the structure of the metal anode uses a three-dimensional current collector as the host of potassium, which is limited by the relatively infinite volume change of potassium during the deposition/stripping process. In addition, the three-dimensional current collector can increase the specific surface area of the electrode, reduce the local effective current and inhibit the growth of dendritic potassium. However, due to the poor affinity of metal potassium to copper, there is a large nucleation overpotential during potassium deposition. Therefore, the electrochemical performance is unsatisfactory.
发明内容Contents of the invention
本发明的目的在于提供了一种钾金属电池负极及其制备方法和应用、钾金属电池，所述钾金属电池负极可以提升钾金属电池的循环性能。The object of the present invention is to provide a potassium metal battery negative electrode, its preparation method and application, and a potassium metal battery. The potassium metal battery negative electrode can improve the cycle performance of the potassium metal battery.
为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:
本发明提供了一种钾金属电池负极，包括金负载的泡沫铜集流体和钾片；The invention provides a negative electrode of a potassium metal battery, comprising a gold-loaded copper foam current collector and a potassium sheet;
所述钾片镶嵌在所述金负载泡沫铜集流体的孔隙结构中。The potassium flakes are embedded in the pore structure of the gold-loaded copper foam current collector.
本发明还提供了上述技术方案所述钾金属电池负极的制备方法，包括以下步骤：The present invention also provides a method for preparing the negative electrode of the potassium metal battery described in the above technical solution, comprising the following steps:
将泡沫铜在氯金酸溶液中进行浸渍，得到金负载的泡沫铜集流体；Immersing foamed copper in a chloroauric acid solution to obtain a gold-loaded foamed copper current collector;
将所述金负载的泡沫铜集流体和钾片进行压合，得到所述钾金属电池负极。The gold-loaded copper foam current collector and the potassium sheet are pressed together to obtain the negative electrode of the potassium metal battery.
优选的，所述氯金酸溶液的浓度为0.0085～0.0105mol/L。Preferably, the concentration of the chloroauric acid solution is 0.0085˜0.0105 mol/L.
优选的，所述泡沫铜的质量与所述氯金酸溶液的体积比为1g：4～6mL。Preferably, the mass ratio of the copper foam to the volume ratio of the chloroauric acid solution is 1g:4-6mL.
优选的，所述浸渍的温度为室温，时间为1～1.5min。Preferably, the impregnating temperature is room temperature, and the time is 1-1.5 min.
优选的，所述金负载的泡沫铜集流体的厚度与所述钾片的厚度比为1:0.4。Preferably, the ratio of the thickness of the gold-loaded copper foam current collector to the thickness of the potassium sheet is 1:0.4.
优选的，所述压合的压力为100～300psi，保压时间为30～40s。Preferably, the pressing pressure is 100-300 psi, and the holding time is 30-40s.
优选的，将泡沫铜在氯金酸溶液中进行浸渍前，还包括将所述泡沫铜进行酸浸。Preferably, before immersing the copper foam in the chloroauric acid solution, acid leaching the copper foam is also included.
本发明还提供了上述技术方案所述钾金属电池负极或上述技术方案所述制备方法制备得到的钾金属电池负极在钾金属电池中的应用。The present invention also provides the application of the negative electrode of the potassium metal battery described in the above technical solution or the negative electrode of the potassium metal battery prepared by the preparation method described in the above technical solution in a potassium metal battery.
本发明还提供了一种钾金属电池，包括负极、隔膜、电解质和正极，所述负极为上述技术方案所述钾金属电池负极或由上述技术方案所述制备方法制备得到的钾金属电池负极。The present invention also provides a potassium metal battery, including a negative electrode, a separator, an electrolyte and a positive electrode, the negative electrode being the negative electrode of the potassium metal battery described in the above technical solution or the negative electrode of the potassium metal battery prepared by the preparation method described in the above technical solution.
本发明提供了一种钾金属电池负极，包括金负载的泡沫铜集流体和钾片；所述钾片镶嵌在所述金负载泡沫铜集流体的孔隙结构中。本发明中，所述泡沫铜集流体中的三维多孔结构限制了循环过程中钾负极的体积膨胀；金具有较低的成核过电位，是电池循环过程中钾离子的优先沉积位点，能够使钾金属沉积更加均匀，从而抑制了枝晶的生长。因此，所述钾金属电池负极能够显著减小循环过程中钾金属的体积膨胀和抑制枝晶的生长，实现较高的库伦效率、较长的循环寿命和优秀的倍率性能。The invention provides a negative electrode of a potassium metal battery, comprising a gold-loaded copper foam collector and a potassium sheet; the potassium sheet is embedded in the pore structure of the gold-loaded foam copper collector. In the present invention, the three-dimensional porous structure in the foamed copper current collector limits the volume expansion of the potassium negative electrode during cycling; gold has a lower nucleation overpotential and is the preferential deposition site for potassium ions during battery cycling, which can Make potassium metal deposition more uniform, thereby inhibiting the growth of dendrites. Therefore, the negative electrode of the potassium metal battery can significantly reduce the volume expansion of the potassium metal and inhibit the growth of dendrites during cycling, and achieve higher Coulombic efficiency, longer cycle life and excellent rate performance.
附图说明Description of drawings
图1为实施例1所述泡沫铜和制备得到的金负载的泡沫铜集流体的SEM图；Fig. 1 is the SEM figure of the copper foam current collector of the gold load described in
图2为实施例1和对比例1所述钾金属电池的首圈充放电电压-比容量曲线；Fig. 2 is the first cycle charge and discharge voltage-specific capacity curve of potassium metal battery described in
图3为实施例1和对比例1所述钾金属电池的循环库伦效率曲线；Fig. 3 is the cycle coulombic efficiency curve of potassium metal battery described in
图4为实施例1和对比例1所述钾金属电池的倍率性能曲线；Fig. 4 is the rate performance curve of the potassium metal battery described in
图5为实施例2和对比例2所述钾金属电池的首圈充放电电压-比容量曲线；Fig. 5 is the first cycle charge and discharge voltage-specific capacity curve of potassium metal battery described in embodiment 2 and comparative example 2;
图6为本发明所述钾金属电池负极的制备流程示意图。Fig. 6 is a schematic diagram of the preparation process of the negative electrode of the potassium metal battery according to the present invention.
具体实施方式detailed description
本发明提供了一种钾金属电池负极，包括金负载的泡沫铜集流体和钾片；The invention provides a negative electrode of a potassium metal battery, comprising a gold-loaded copper foam current collector and a potassium sheet;
所述钾片镶嵌在所述金负载泡沫铜集流体的孔隙结构中。The potassium flakes are embedded in the pore structure of the gold-loaded copper foam current collector.
在本发明中，所述金负载的泡沫铜集流体中金的粒径优选为80～140nm，更优选为120nm。In the present invention, the particle size of gold in the gold-supported foamed copper current collector is preferably 80-140 nm, more preferably 120 nm.
在本发明中，所述钾金属电池负极由金负载的泡沫铜集流体和钾片经过压合制备得到；所述金负载的泡沫铜集流体的厚度与所述钾片的厚度比优选为1:0.4。在本发明中，所述金负载的泡沫铜集流体和钾片的平面尺寸相同。In the present invention, the negative electrode of the potassium metal battery is prepared by pressing a gold-loaded copper foam current collector and a potassium sheet; the ratio of the thickness of the gold-loaded copper foam current collector to the thickness of the potassium sheet is preferably 1 :0.4. In the present invention, the planar dimensions of the gold-loaded copper foam current collector and the potassium sheet are the same.
如图6所示，本发明还提供了上述技术方案所述钾金属电池负极的制备方法，包括以下步骤：As shown in Figure 6, the present invention also provides a method for preparing the negative electrode of the potassium metal battery described in the above technical solution, comprising the following steps:
将泡沫铜在氯金酸溶液中进行浸渍，得到金负载的泡沫铜集流体；Immersing foamed copper in a chloroauric acid solution to obtain a gold-loaded foamed copper current collector;
将所述金负载的泡沫铜集流体和钾片进行压合，得到所述钾金属电池负极；Pressing the gold-loaded copper foam current collector and the potassium sheet to obtain the negative electrode of the potassium metal battery;
所述金负载的泡沫铜集流体和钾片的尺寸相同。The gold-loaded copper foam current collector and potassium flakes were of the same size.
在本发明中，若无特殊说明，所有制备原料均为本领域技术人员熟知的市售产品。In the present invention, unless otherwise specified, all preparation materials are commercially available products well known to those skilled in the art.
本发明将泡沫铜在氯金酸溶液中进行浸渍，得到金负载的泡沫铜集流体。In the invention, the copper foam is impregnated in a chloroauric acid solution to obtain a gold-loaded copper foam current collector.
在本发明中，所述氯金酸溶液的浓度优选为0.0085～0.0105mol/L，更优选为0.009～0.01mol/L。In the present invention, the concentration of the chloroauric acid solution is preferably 0.0085-0.0105 mol/L, more preferably 0.009-0.01 mol/L.
在本发明中，所述氯金酸溶液优选通过制备得到；所述氯金酸溶液的制备方法优选通过将氯金酸和水混合得到；在本发明中，所述氯金酸优选为三水合氯金酸；所述水优选为去离子水；所述混合优选在搅拌的条件下进行；本发明对所述搅拌的条件没有任何特殊的限定，采用本领域技术人员熟知的条件进行即可。In the present invention, the chloroauric acid solution is preferably prepared; the preparation method of the chloroauric acid solution is preferably obtained by mixing chloroauric acid and water; in the present invention, the chloroauric acid is preferably trihydrate Chlorauric acid; the water is preferably deionized water; the mixing is preferably carried out under stirring conditions; the present invention does not have any special restrictions on the stirring conditions, and can be carried out using conditions well known to those skilled in the art.
本发明对所述泡沫铜没有任何特殊的限定，采用本领域技术人员熟知的种类即可。The present invention does not have any special limitation on the copper foam, and the types well known to those skilled in the art can be used.
进行浸渍前，本发明优选将所述泡沫铜进行酸浸；所述酸浸采用的酸液优选为1mol/L的盐酸溶液。本发明对所述酸浸的时间没有任何特殊的限定，能够保证去除所述泡沫铜表面的氧化物即可。Before dipping, the present invention preferably pickles the foamed copper; the acid solution used in the pickling is preferably 1 mol/L hydrochloric acid solution. The present invention does not have any special limitation on the acid leaching time, as long as the oxide on the surface of the foamed copper can be ensured to be removed.
所述酸浸完成后，本发明还优选包括依次进行的洗涤和干燥；所述洗涤优选为依次采用去离子水和无水乙醇进行洗涤。本发明对所述干燥的过程没有任何特殊的限定，采用本领域技术人员熟知的过程进行即可。After the acid leaching is completed, the present invention also preferably includes sequential washing and drying; the washing is preferably sequentially using deionized water and absolute ethanol for washing. The present invention does not have any special limitation on the drying process, and it can be carried out by a process well known to those skilled in the art.
在本发明中，所述泡沫铜的质量与所述氯金酸溶液的体积比优选为1g：4～6mL，更优选为1g：6mL。In the present invention, the volume ratio of the mass of the foamed copper to the chloroauric acid solution is preferably 1 g: 4-6 mL, more preferably 1 g: 6 mL.
在本发明中，所述浸渍优选在静置的条件下进行。在本发明中，所述浸渍的温度优选为室温，时间优选为1～1.5min，更优选为1.2～1.3min。In the present invention, the impregnation is preferably performed under standing conditions. In the present invention, the soaking temperature is preferably room temperature, and the time is preferably 1-1.5 min, more preferably 1.2-1.3 min.
所述浸渍完成后，本发明还优选包括依次进行的洗涤和干燥；所述洗涤选用的洗涤液优选为去离子水；所述干燥的方式优选为真空干燥，所述真空干燥的温度优选为80℃；时间优选为9～11h，更优选为10h。After the impregnation is completed, the present invention also preferably includes sequential washing and drying; the washing liquid selected for the washing is preferably deionized water; the drying method is preferably vacuum drying, and the vacuum drying temperature is preferably 80 °C; the time is preferably 9-11 h, more preferably 10 h.
得到金负载的泡沫铜集流体后，本发明将所述金负载的泡沫铜集流体和钾片进行压合，得到所述钾金属电池负极。After the gold-loaded copper foam current collector is obtained, the present invention presses the gold-loaded copper foam current collector and the potassium sheet to obtain the negative electrode of the potassium metal battery.
在本发明中，所述金负载的泡沫铜集流体的厚度与所述钾片的厚度比优选为1:0.4。本发明对所述金负载的泡沫铜集流体和钾片的平面尺寸没有任何特殊的限定，采用本领域技术人员熟知的平面尺寸并保证金负载的泡沫铜集流体和钾片的平面尺寸相同即可即可。在本发明的具体实施例中，所述金负载的泡沫铜集流体和钾片的直径均为12mm；所述金负载的泡沫铜集流体的厚度为1mm，所述钾片的厚度为0.4mm。当所述泡沫铜和钾片的平面尺寸与所需尺寸不同时优选通过剪裁实现。In the present invention, the ratio of the thickness of the gold-loaded copper foam current collector to the thickness of the potassium sheet is preferably 1:0.4. The present invention does not have any special limitation on the planar dimensions of the gold-loaded copper foam collector and the potassium sheet, and the planar dimensions well-known to those skilled in the art are adopted and the planar dimensions of the gold-loaded copper foam collector and the potassium sheet are the same. That's it. In a specific embodiment of the present invention, the diameters of the gold-loaded copper foam collector and the potassium sheet are 12 mm; the thickness of the gold-loaded foam copper collector is 1 mm, and the thickness of the potassium sheet is 0.4 mm . When the planar size of the foamed copper and potassium sheets is different from the required size, it is preferably realized by cutting.
在本发明中，所述压合的压力优选为100～300psi，更优选为150psi；保压时间优选为30～40s，更优选为30s。在本发明中，所述压合优选在保护气氛中进行；所述保护气氛优选为氩气气氛。In the present invention, the pressing pressure is preferably 100-300 psi, more preferably 150 psi; the holding time is preferably 30-40 s, more preferably 30 s. In the present invention, the pressing is preferably performed in a protective atmosphere; the protective atmosphere is preferably an argon atmosphere.
在本发明中，将所述压合的条件控制在上述范围内可以使钾片完全嵌入到所述金负载的泡沫铜集流体的孔隙中。In the present invention, controlling the pressing conditions within the above range can completely embed the potassium flakes into the pores of the gold-loaded copper foam current collector.
本发明还提供了上述技术方案所述钾金属电池负极或上述技术方案所述制备方法制备得到的钾金属电池负极在钾金属电池中的应用。The present invention also provides the application of the negative electrode of the potassium metal battery described in the above technical solution or the negative electrode of the potassium metal battery prepared by the preparation method described in the above technical solution in a potassium metal battery.
本发明还提供了一种钾金属电池，包括负极、隔膜、电解质和正极，所述负极为上述技术方案所述钾金属电池负极或由上述技术方案所述制备方法制备得到的钾金属电池负极。The present invention also provides a potassium metal battery, including a negative electrode, a separator, an electrolyte and a positive electrode, the negative electrode being the negative electrode of the potassium metal battery described in the above technical solution or the negative electrode of the potassium metal battery prepared by the preparation method described in the above technical solution.
在本发明中，所述正极的活性材料优选为普鲁士蓝。In the present invention, the active material of the positive electrode is preferably Prussian blue.
在本发明中，所述普鲁士蓝优选通过制备得到；所述普鲁士蓝的制备优选包括以下步骤：In the present invention, the Prussian blue is preferably obtained by preparation; the preparation of the Prussian blue preferably includes the following steps:
将K4Fe(CN)6和水混合，得到A溶液；Mix K 4 Fe(CN) 6 and water to obtain A solution;
将FeCl3和水混合，得到B溶液；Mix FeCl 3 and water to obtain B solution;
将所述A溶液和B溶液混合后，进行老化，得到所述普鲁士蓝。After mixing the solutions A and B, they are aged to obtain the Prussian blue.
本发明将K4Fe(CN)6和水混合，得到A溶液。在本发明中，所述水优选为去离子水；所述K4Fe(CN)6和水的用量比优选为(2～2.5)mmol：150mL，更优选为(2.1～2.3)mmol：150mL。本发明对所述混合的过程没有任何特殊的限定，采用本领域技术人员熟知的过程进行即可。The present invention mixes K 4 Fe(CN) 6 and water to obtain A solution. In the present invention, the water is preferably deionized water; the ratio of K 4 Fe(CN) 6 to water is preferably (2-2.5) mmol: 150 mL, more preferably (2.1-2.3) mmol: 150 mL . The present invention does not have any special limitation on the mixing process, and it can be carried out by adopting a process well known to those skilled in the art.
本发明将FeCl3和水混合，得到B溶液。在本发明中，所述水优选为去离子水；所述FeCl3和水的用量比优选为4mmol:50mL。本发明对所述混合的过程没有任何特殊的限定，采用本领域技术人员熟知的过程进行即可。The present invention mixes FeCl 3 and water to obtain B solution. In the present invention, the water is preferably deionized water; the FeCl and water ratio is preferably 4mmol:50mL. The present invention does not have any special limitation on the mixing process, and it can be carried out by adopting a process well known to those skilled in the art.
得到A溶液和B溶液后，本发明将所述A溶液和B溶液混合后，进行老化，得到所述普鲁士蓝。After the A solution and the B solution are obtained, the present invention mixes the A solution and the B solution, and performs aging to obtain the Prussian blue.
在本发明中，所述A溶液中的K4Fe(CN)6和B溶液中的FeCl3的摩尔比优选为1:2或5:8。In the present invention, the molar ratio of K 4 Fe(CN) 6 in solution A to FeCl 3 in solution B is preferably 1:2 or 5:8.
在本发明中，所述混合优选为在搅拌的条件下将所述B溶液逐滴滴加到所述A溶液中；本发明对所述搅拌的条件没有任何特殊的限定，采用本领域技术人员熟知的条件进行即可。所述滴加完成后，本发明还优选包括继续搅拌2h。在本发明中，所述老化的温度优选为室温；所述老化的时间优选为12h。所述老化完成后，本发明还优选包括依次进行的过滤、洗涤和干燥；本发明对所述过滤没有任何特殊的限定，采用本领域技术人员熟知的过程进行即可。所述洗涤优选为依次采用水和乙醇对所述过滤得到的沉淀进行洗涤。在本发明中，所述干燥优选为真空干燥；所述真空干燥的温度优选为80℃，时间优选为12h。In the present invention, the mixing is preferably adding the B solution dropwise to the A solution under stirring conditions; the present invention does not have any special restrictions on the stirring conditions, and it is adopted by those skilled in the art Familiar conditions can be carried out. After the dropwise addition is completed, the present invention also preferably includes continuing to stir for 2 h. In the present invention, the aging temperature is preferably room temperature; the aging time is preferably 12 hours. After the aging is completed, the present invention also preferably includes successively filtering, washing and drying; the present invention does not have any special limitation on the filtering, and it can be carried out by a process well known to those skilled in the art. The washing is preferably to wash the precipitate obtained by the filtration with water and ethanol in sequence. In the present invention, the drying is preferably vacuum drying; the temperature of the vacuum drying is preferably 80° C., and the time is preferably 12 hours.
在本发明中，所述正极优选为普鲁士蓝电极；所述普鲁士蓝电极优选通过制备得到；所述普鲁士蓝电极的制备优选包括：将上述技术方案所述的普鲁士蓝、炭黑、聚偏氟乙烯和N-甲基吡咯烷酮混合后均匀涂覆在铝箔上，干燥，得到所述普鲁士蓝电极。In the present invention, the positive electrode is preferably a Prussian blue electrode; the Prussian blue electrode is preferably prepared; the preparation of the Prussian blue electrode preferably includes: Prussian blue, carbon black, polylidene fluoride described in the above technical scheme Ethylene and N-methylpyrrolidone are mixed and uniformly coated on an aluminum foil and dried to obtain the Prussian blue electrode.
在本发明中，所述普鲁士蓝、炭黑和聚偏氟乙烯的质量比优选为6:3:1或8:1:1，本发明对所述N-甲基吡咯烷酮的用量没有任何特殊的限定，采用本领域技术人员熟知的制备正极过程中的使用量使得所述混合后形成膏状浆料即可。In the present invention, the mass ratio of the Prussian blue, carbon black and polyvinylidene fluoride is preferably 6:3:1 or 8:1:1, and the present invention does not have any special restrictions on the amount of N-methylpyrrolidone As a limitation, it is sufficient to use the amount used in the process of preparing the positive electrode well-known to those skilled in the art so that the paste-like slurry is formed after the mixing.
在本发明中，所述混合优选在搅拌的条件下进行；本发明对所述搅拌的过程没有任何特殊的限定，采用本领域技术人员熟知的过程进行即可。In the present invention, the mixing is preferably carried out under the condition of stirring; the present invention does not have any special limitation on the process of stirring, and it can be carried out by a process well known to those skilled in the art.
本发明对所述涂覆的过程没有任何特殊的限定，采用本领域技术人员熟知的正极制备过程中的涂覆过程即可。The present invention does not have any special limitation on the coating process, and the coating process in the positive electrode preparation process well known to those skilled in the art can be used.
在本发明中，所述干燥优选为真空干燥；所述真空干燥的温度优选为80℃，时间优选为12h。In the present invention, the drying is preferably vacuum drying; the temperature of the vacuum drying is preferably 80° C., and the time is preferably 12 hours.
所述干燥完成后，本发明还优选包括剪裁的过程，本发明对所述剪裁的过程没有任何特殊的限定，采用本领域技术人员熟知的过程得到直径为10mm的圆片即可。After the drying is completed, the present invention preferably also includes a cutting process. The present invention does not have any special limitation on the cutting process, and a disc with a diameter of 10 mm can be obtained by using a process well known to those skilled in the art.
在本发明中，所述隔膜的材质优选为玻璃纤维。在本发明的实施例中，所述隔膜的型号具体为CATNO.1820-090。In the present invention, the material of the separator is preferably glass fiber. In an embodiment of the present invention, the model of the diaphragm is specifically CAT NO.1820-090.
在本发明中，所述电解质优选为3mol/L的双氟磺酰亚胺钾的二甲基醚溶液(KFSI-DME)。In the present invention, the electrolyte is preferably a 3 mol/L potassium bisfluorosulfonimide solution in dimethyl ether (KFSI-DME).
本发明对所述钾金属电池的制备过程没有任何特殊的限定，采用本领域技术人员熟知的过程进行即可。In the present invention, there is no special limitation on the preparation process of the potassium metal battery, and the process well known to those skilled in the art can be used.
下面结合实施例对本发明提供的钾金属电池负极及其制备方法和应用、钾金属电池进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。The negative electrode of the potassium metal battery provided by the present invention, its preparation method and application, and the potassium metal battery will be described in detail below in conjunction with the examples, but they should not be understood as limiting the protection scope of the present invention.
实施例1Example 1
将200mg三水合氯金酸和60mL去离子混合，搅拌均匀，得到氯金酸溶液；Mix 200mg of chloroauric acid trihydrate with 60mL of deionized, and stir evenly to obtain a chloroauric acid solution;
将泡沫铜(厚度为1mm)置于1mol/L的盐酸溶液中5min，去除表面的氧化物，然后依次用去离子水和无水乙醇洗涤，干燥，得到预处理的泡沫铜；Foam copper (thickness is 1mm) is placed in the hydrochloric acid solution of 1mol/L 5min, removes the oxide on the surface, then washes with deionized water and absolute ethanol successively, dries, obtains the pretreated foam copper;
将15g预处理的泡沫铜在60mL所述氯金酸溶液中在静置的条件下浸渍1min后，用去离子水洗涤，在80℃的条件下真空干燥9h，得到金负载的泡沫铜集流体；After immersing 15g of pretreated foamed copper in 60mL of the chloroauric acid solution under static conditions for 1min, wash with deionized water, and vacuum-dry at 80°C for 9h to obtain a gold-loaded copper foam current collector ;
在氩气气氛下，将所述金负载的泡沫铜集流体与钾片(厚度为0.4mm)剪裁成直径为12mm的圆形，然后层叠设置，并采用压片机进行压合，所述压合的压力为150psi，保压时间为30s，使所述钾片完全嵌入所述金负载的泡沫铜集流体的孔隙中，得到所述钾金属电池负极；Under an argon atmosphere, the gold-loaded copper foam current collector and the potassium sheet (0.4 mm in thickness) were cut into a circle with a diameter of 12 mm, then stacked and laminated, and pressed using a tablet press. The combined pressure is 150psi, and the holding time is 30s, so that the potassium sheet is completely embedded in the pores of the gold-loaded copper foam current collector to obtain the negative electrode of the potassium metal battery;
将2mmol K4Fe(CN)6和150mL去离子水混合，得到A溶液；Mix 2mmol K 4 Fe(CN) 6 and 150mL deionized water to obtain A solution;
将4mmol FeCl3和50mL去离子水混合，得到B溶液；Mix 4mmol FeCl 3 and 50mL deionized water to obtain B solution;
在搅拌的条件下，将所述B溶液逐滴滴加A溶液中，继续搅拌2h后，老化12h，过滤，依次用水和乙醇洗涤，在80℃的条件下真空干燥12h，得到普鲁士蓝；Under the condition of stirring, the B solution was added dropwise to the A solution, and after continuing to stir for 2 hours, aged for 12 hours, filtered, washed with water and ethanol in sequence, and vacuum-dried at 80°C for 12 hours to obtain Prussian blue;
按照6:3:1的质量比，将所述普鲁士蓝、炭黑和聚偏氟乙烯混合后，加入N-甲基吡咯烷酮，并搅拌至呈膏状浆料；According to the mass ratio of 6:3:1, after mixing the Prussian blue, carbon black and polyvinylidene fluoride, add N-methylpyrrolidone, and stir until it is a paste slurry;
将所述膏状浆料涂覆在铝箔上，80℃真空干燥12h，剪裁成直径为10mm的圆片，得到普鲁士蓝电极；Coat the paste-like slurry on an aluminum foil, dry it in vacuum at 80°C for 12 hours, and cut it into a disc with a diameter of 10mm to obtain a Prussian blue electrode;
以所述钾金属电池负极为负极，以所述普鲁士蓝电极为正极，以CAT NO.1820-090的玻璃纤维作为隔膜，以3mol/L的KFSI-DME为电解质，组装成型号为CR2032的钾金属电池。The negative electrode of the potassium metal battery is the negative electrode, the Prussian blue electrode is the positive electrode, the glass fiber of CAT No.1820-090 is used as the separator, and the KFSI-DME of 3mol/L is used as the electrolyte, and the potassium battery model CR2032 is assembled. metal battery.
将所述泡沫铜(Cu)和制备得到的金负载的泡沫铜集流体(Au@Cu)进行SEM测试，测试结果如图1所示，由图1可知，泡沫铜具有三维结构，表面光滑，金负载的泡沫铜集流体中，在泡沫铜表面有很多金颗粒。The copper foam (Cu) and the prepared gold-loaded copper foam current collector (Au@Cu) are subjected to SEM testing, and the test results are shown in Figure 1. It can be seen from Figure 1 that the copper foam has a three-dimensional structure and a smooth surface. In the gold-loaded copper foam current collector, there are many gold particles on the surface of the copper foam.
实施例2Example 2
将200mg三水合氯金酸和60mL去离子混合，搅拌均匀，得到氯金酸溶液；Mix 200mg of chloroauric acid trihydrate with 60mL of deionized, and stir evenly to obtain a chloroauric acid solution;
将泡沫铜(厚度为1mm)置于1mol/L的盐酸溶液中5min，去除表面的氧化物，然后依次用去离子水和无水乙醇洗涤，干燥，得到预处理的泡沫铜；Foam copper (thickness is 1mm) is placed in the hydrochloric acid solution of 1mol/L 5min, removes the oxide on the surface, then washes with deionized water and absolute ethanol successively, dries, obtains the pretreated foam copper;
将10g预处理的泡沫铜在60mL所述氯金酸溶液中在静置的条件下浸渍1.5min后，用去离子水洗涤，在80℃的条件下真空干燥11h，得到金负载的泡沫铜集流体；After immersing 10 g of pretreated foamed copper in 60 mL of the chloroauric acid solution under static conditions for 1.5 min, wash it with deionized water, and dry it in vacuum at 80 ° C for 11 h to obtain a gold-loaded foamed copper aggregate. fluid;
在氩气气氛下，将所述金负载的泡沫铜集流体与钾片(厚度为0.4mm)剪裁成直径为12mm的圆形，然后层叠设置，并采用压片机进行压合，所述压合的压力为150psi，保压时间为30s，使所述钾片完全嵌入所述金负载的泡沫铜集流体的孔隙中，得到所述钾金属电池负极；Under an argon atmosphere, the gold-loaded copper foam current collector and the potassium sheet (0.4 mm in thickness) were cut into a circle with a diameter of 12 mm, then stacked and laminated, and pressed using a tablet press. The combined pressure is 150psi, and the holding time is 30s, so that the potassium sheet is completely embedded in the pores of the gold-loaded copper foam current collector to obtain the negative electrode of the potassium metal battery;
将2mmol K4Fe(CN)6和150mL去离子水混合，得到A溶液；Mix 2mmol K 4 Fe(CN) 6 and 150mL deionized water to obtain A solution;
将4mmol FeCl3和50mL去离子水混合，得到B溶液；Mix 4mmol FeCl 3 and 50mL deionized water to obtain B solution;
在搅拌的条件下，将所述B溶液逐滴滴加A溶液中，继续搅拌2h后，老化12h，过滤，依次用水和乙醇洗涤，在80℃的条件下真空干燥12h，得到普鲁士蓝；Under the condition of stirring, the B solution was added dropwise to the A solution, and after continuing to stir for 2 hours, aged for 12 hours, filtered, washed with water and ethanol in sequence, and vacuum-dried at 80°C for 12 hours to obtain Prussian blue;
按照8:1:1的质量比，将所述普鲁士蓝、炭黑和聚偏氟乙烯混合后，加入N-甲基吡咯烷酮，并搅拌至呈膏状浆料；According to the mass ratio of 8:1:1, after mixing the Prussian blue, carbon black and polyvinylidene fluoride, add N-methylpyrrolidone, and stir until it is a paste slurry;
将所述膏状浆料涂覆在铝箔上，80℃真空干燥12h，剪裁成直径为10mm的圆片，得到普鲁士蓝电极；Coat the paste-like slurry on an aluminum foil, dry it in vacuum at 80°C for 12 hours, and cut it into a disc with a diameter of 10mm to obtain a Prussian blue electrode;
以所述钾金属电池负极为负极，以所述普鲁士蓝电极为正极，以CAT NO.1820-090的玻璃纤维作为隔膜，以3mol/L的KFSI-DME为电解质，组装成型号为CR2032的钾金属电池。The negative electrode of the potassium metal battery is the negative electrode, the Prussian blue electrode is the positive electrode, the glass fiber of CAT No.1820-090 is used as the separator, and the KFSI-DME of 3mol/L is used as the electrolyte, and the potassium battery model CR2032 is assembled. metal battery.
对比例1Comparative example 1
将泡沫铜(厚度为1mm)置于1mol/L的盐酸溶液中5min，去除表面的氧化物，然后依次用去离子水和无水乙醇洗涤，干燥，得到预处理的泡沫铜；Foam copper (thickness is 1mm) is placed in the hydrochloric acid solution of 1mol/L 5min, removes the oxide on the surface, then washes with deionized water and absolute ethanol successively, dries, obtains the pretreated foam copper;
在氩气气氛下，将所述预处理的泡沫铜与钾片(厚度为0.4mm)剪裁成直径为12mm的圆形，然后层叠设置，并采用压片机进行压合，所述压合的压力为150psi，保压时间为30s，使所述钾片完全嵌入所述预处理的泡沫铜的孔隙中，得到所述钾金属电池负极；Under an argon atmosphere, the pretreated copper foam and potassium sheet (0.4 mm in thickness) were cut into a circular shape with a diameter of 12 mm, then stacked and laminated, and pressed using a tablet press. The pressure is 150psi, and the holding time is 30s, so that the potassium sheet is completely embedded in the pores of the pretreated foamed copper to obtain the negative electrode of the potassium metal battery;
制备型号为CR2032的钾金属电池的过程参考实施例1。Refer to Example 1 for the process of preparing the potassium metal battery model CR2032.
对比例2Comparative example 2
制备钾金属电池负极的过程参考对比例1；Refer to Comparative Example 1 for the process of preparing the negative electrode of the potassium metal battery;
制备型号为CR2032的钾金属电池的过程参考实施例2。Refer to Example 2 for the process of preparing the potassium metal battery model CR2032.
测试例1
将实施例1和对比例1所述钾金属电池在0.5mA/g的电流密度下进行恒流充放电测试，电压范围设置为2～4V；The potassium metal batteries described in Example 1 and Comparative Example 1 were subjected to a constant current charge and discharge test at a current density of 0.5mA/g, and the voltage range was set to 2-4V;
其中，图2为实施例1和对比例1所述钾金属电池的首圈充放电电压-比容量曲线，其中，Cu-K对应的为对比例1所述钾金属电池，Au@Cu-K对应的为实施例1所述钾金属电池，由图2可知，在第一圈充放电过程中，实施例1所述的钾金属电池表现出较高的质量比容量，为65mA·h/g，而对比例1所述的钾金属电池只有48mA·h/g；Wherein, Fig. 2 is the first cycle charge and discharge voltage-specific capacity curve of the potassium metal battery described in Example 1 and Comparative Example 1, wherein, Cu-K corresponds to the potassium metal battery described in Comparative Example 1, Au@Cu-K Corresponding to the potassium metal battery described in Example 1, it can be seen from Figure 2 that during the first round of charging and discharging, the potassium metal battery described in Example 1 exhibits a relatively high mass specific capacity, which is 65 mA h/g , while the potassium metal battery described in Comparative Example 1 has only 48mA h/g;
图3为实施例1和对比例1所述钾金属电池的循环库伦效率曲线，其中Cufoam-K对应的为对比例1所述钾金属电池，Au@Cufoam-K对应的为实施例1所述钾金属电池，由图3可知，实施例1所述的钾金属电池在循环250圈后，库伦效率依旧高达93％，表现出了良好的循环性能；而对比例1所述钾金属电池在循环150圈后，库伦效率只有59％；Fig. 3 is the cycle coulombic efficiency curve of the potassium metal battery described in Example 1 and Comparative Example 1, wherein Cufoam-K corresponds to the potassium metal battery described in Comparative Example 1, and Au@Cufoam-K corresponds to the one described in Example 1 Potassium metal battery, as can be seen from Figure 3, after 250 cycles of the potassium metal battery described in Example 1, the Coulombic efficiency is still as high as 93%, showing a good cycle performance; while the potassium metal battery described in Comparative Example 1 is cycled After 150 cycles, the Coulombic efficiency is only 59%;
将实施例1和对比例1所述钾金属电池进行倍率性能测试，电流密度依次为0.1、0.2、0.5、1、3和5A/g，测试结果如图4所示，其中，Cu-K对应的为对比例1所述钾金属电池，Au@Cu-K对应的为实施例1所述钾金属电池，由图4可知，实施例1所述钾金属电池的倍率性能优于对比例1所述钾金属电池的性能，当电流密度从0.1A/g逐渐增加至5A/g，比容量均有所下降，但实施例1所述钾金属电池的比容量较为稳定，没有出现类似于对比例1所述钾金属电池的波动情况，此外比容量也明显高于对比例1。由此可见，通过对泡沫铜的表面进行改性(负载金)，能够降低钾沉积过电位，这使得钾沉积过程更加均匀，有助于形成较为均匀稳定的SEI膜，抑制了钾的枝晶状生长以及电解质消耗，此外泡沫铜的三维骨架结构限制了钾沉积过程中严重的体积膨胀，从而延长了电池的循环寿命，提高了安全性能。The potassium metal batteries described in Example 1 and Comparative Example 1 were tested for rate performance, and the current densities were successively 0.1, 0.2, 0.5, 1, 3 and 5A/g. The test results are shown in Figure 4, wherein Cu-K corresponds to is the potassium metal battery described in Comparative Example 1, and Au@Cu-K corresponds to the potassium metal battery described in Example 1. It can be seen from Figure 4 that the rate performance of the potassium metal battery described in Example 1 is better than that described in Comparative Example 1. The performance of the potassium metal battery described above, when the current density gradually increased from 0.1A/g to 5A/g, the specific capacity all decreased, but the specific capacity of the potassium metal battery described in Example 1 was relatively stable, and there was no such thing as a comparative example. The fluctuation situation of the potassium metal battery described in 1, in addition specific capacity is also obviously higher than comparative example 1. It can be seen that by modifying the surface of foam copper (supporting gold), the overpotential of potassium deposition can be reduced, which makes the potassium deposition process more uniform, helps to form a more uniform and stable SEI film, and inhibits the dendrite of potassium. In addition, the three-dimensional framework structure of copper foam limits the severe volume expansion during potassium deposition, thereby prolonging the cycle life of the battery and improving safety performance.
测试例2test case 2
将实施例2和对比例2所述钾金属电池在0.5mA/g的电流密度下进行恒流充放电测试，电压范围设置为2～4V；The potassium metal batteries described in Example 2 and Comparative Example 2 were subjected to a constant current charge and discharge test at a current density of 0.5mA/g, and the voltage range was set to 2-4V;
其中，图5为实施例2和对比例2所述钾金属电池的首圈充放电电压-比容量曲线，其中，Cu-K对应的为对比例2所述钾金属电池，Au@Cu-K对应的为实施例2所述钾金属电池，由图5可知，在第一圈充放电过程中，实施例1所述的钾金属电池表现出较高的质量比容量，为73mA·h/g，而对比例1所述的钾金属电池只有50mA·h/g。Wherein, Fig. 5 is the first cycle charge and discharge voltage-specific capacity curve of the potassium metal battery described in Example 2 and Comparative Example 2, wherein Cu-K corresponds to the potassium metal battery described in Comparative Example 2, Au@Cu-K Corresponding to the potassium metal battery described in Example 2, it can be seen from Figure 5 that during the first round of charging and discharging, the potassium metal battery described in Example 1 exhibits a relatively high mass specific capacity, which is 73mA·h/g , while the potassium metal battery described in Comparative Example 1 has only 50mA·h/g.
综上可知，本发明所述的钾金属电池负极可以提高钾金属电池的比容量、库伦效率和优异的倍率性能，提升了钾金属电池的循环稳定性及安全性，延长了电池的使用寿命。In summary, the negative electrode of the potassium metal battery of the present invention can improve the specific capacity, coulombic efficiency and excellent rate performance of the potassium metal battery, improve the cycle stability and safety of the potassium metal battery, and prolong the service life of the battery.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.
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