WO2022016554A1 - 金属碳化物催化剂及其制备方法与在锂氧气电池中的应用 - Google Patents

金属碳化物催化剂及其制备方法与在锂氧气电池中的应用 Download PDF

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WO2022016554A1
WO2022016554A1 PCT/CN2020/104636 CN2020104636W WO2022016554A1 WO 2022016554 A1 WO2022016554 A1 WO 2022016554A1 CN 2020104636 W CN2020104636 W CN 2020104636W WO 2022016554 A1 WO2022016554 A1 WO 2022016554A1
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metal carbide
catalyst
lithium
oxygen battery
carbide catalyst
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杨瑞枝
孙志辉
金超
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Suzhou University
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Suzhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • the present invention is in the field of organic lithium battery technology oxygen systems, specifically discloses the preparation of a reconstituted plasma-surface metal carbide Mo 2 C catalysts and their use in lithium-oxygen batteries.
  • the present invention discloses a metal carbide catalyst and preparation method and application of oxygen in the lithium battery, the oxygen electrode thus prepared architecture comprises sufficient ORR / OER active site, an electronic / ionic transport and diffusion of O 2 good interconnecting channels and for storing the insoluble Li 2 O 2 was larger clearance; ORR and OER catalyst of the present invention respond to possess catalytic activity effectively, to reduce the discharge overpotential and provide a stable output performance.
  • the present invention adopts the following technical solutions.
  • the metal carbide catalyst the preparation method of which includes the following steps: electrospinning an electrospinning precursor solution composed of polyvinylpyrrolidone, polyacrylonitrile, a solvent and ammonium molybdate to obtain a fabric; then drying the fabric in sequence, calcining to obtain nitrogen-doped carbon nanofibers containing molybdenum carbide quantum dots; finally, plasma surface treatment is performed on the nitrogen-doped carbon nanofibers containing molybdenum carbide quantum dots to obtain a metal carbide catalyst.
  • the invention improves the electrocatalytic behavior of Mo 2 C quantum dots through a brand-new surface chemical treatment method, and exhibits high-efficiency catalytic performance and excellent stability in the application of lithium-oxygen batteries, the preparation process is simple, and the cost of raw materials is low. , showing a broad application prospect.
  • the dosage ratio of polyvinylpyrrolidone, polyacrylonitrile, solvent and ammonium molybdate is 0.5g:0.5g:(5-15mL):1mmol, preferably 0.5g:0.5g:10mL:1mmol;
  • calcination in nitrogen preferably, the temperature of calcination in air is 200°C for 1 hour, and the temperature of calcination in nitrogen is 800°C for 2 hours.
  • the voltage of the plasma surface treatment is 25-35KV, and the time is 50-80 seconds.
  • the invention discloses the application of the above-mentioned metal carbide catalyst in preparing a working electrode of a lithium-oxygen battery.
  • the invention discloses a lithium-oxygen battery working electrode, which is composed of a conductive substrate and an active material; the active material is composed of a metal carbide catalyst, a carbon material and a binder; the loading amount of the metal carbide catalyst on the conductive substrate is 0.6- 0.8 mg/cm 2 ; in the active material, the mass percentage of the metal carbide catalyst is 65-75%.
  • the conductive substrate is carbon paper; the carbon material is carbon black; and the adhesive is polyvinylidene fluoride.
  • the present invention utilizes simple electrospinning technology to prepare Mo2C quantum dots (5nm) in nitrogen-doped carbon nanoparticles to obtain nitrogen-doped carbon nanofibers (Mo2C@NCF) containing molybdenum carbide quantum dots.
  • Plasma (GDP) technology was used to change the surface of Mo2C@NCF, high-energy particles in the plasma can break the passivation layer of Mo2C surface, and obtain metal carbide catalysts.
  • GDP plasma
  • Figure 1 shows (a) XRD patterns of Mo 2 C@NCF and GDP-Mo 2 C@NCF, (b) SEM image of Mo 2 C@NCF, (ce) HRTEM image, (f) GDP-Mo 2 C@ SEM image of NCF, (gi) HRTEM image and (j) EDX image.
  • Figure 2 shows the CV curves in the potential range of 2.2-4.4 V at a scan rate of 0.1 mV s -1.
  • Figure 3 shows the full charge-discharge curves of LOBs at 100 mA g -1 based on GDP-Mo 2 C@NCF and Mo 2 C@NCF, respectively.
  • Figure 4 shows the discharge/charge cycling stability with a cut-off capacity of 1000 mAh g - 1 at a current density of 100 mA g -1.
  • Figure 5 is the rate performance at different discharge/charge current densities.
  • Figure 6 shows the performance comparison of GDP-Mo 2 C@NCF and existing electrocatalysts.
  • the raw materials involved in the present invention are all conventional commercially available raw materials in the battery field, and the specific preparation and testing processes involved are all conventional methods.
  • Figure 1a shows that after glow plasma treatment, all characteristic peaks of GDP-Mo 2 C@NCF become stronger due to the high energy of the plasma.
  • FIG. 1b c SEM and TEM images show fibrillar structures of Mo 2 C @ NCF, smooth surface, an average diameter of about 100 nm.
  • HRTEM images show the distribution of Mo 2 C quantum dots with an average particle size of 3–4 nm in carbon fibers even without lattice fringes ( Figures 1d and e).
  • FIG. 1a shows that after glow plasma treatment, all characteristic peaks of GDP-Mo 2 C@NCF become stronger due to the high energy of the plasma.
  • FIG. 1b c SEM and TEM images show fibrillar structures of Mo 2 C @ NCF, smooth surface, an average diameter of about 100 nm.
  • HRTEM images show the distribution of Mo 2 C quantum dots with an average particle size of 3–4 nm in carbon fibers even without lattice fringes ( Figures 1d and e).
  • Embodiment 2 Type 2032 LOBs were routinely assembled to evaluate the activity of catalysts after glow discharge plasma treatment.
  • the electrocatalyst (GDP-Mo2C@NCF), carbon black (super P) and polyvinylidene fluoride binder of Example 1 were mixed in a weight ratio of 70:20:10 and then coated on carbon paper to conventionally prepare a working electrode, Among them, the electrocatalyst loading on the carbon paper is 0.6-0.8 mg/cm2; the electrolyte is 1M lithium bis(carbon trioxide)sulfonimide (LiTFSI) in dimethyl sulfoxide; 2032 type battery LOBs, including lithium Metal anode (15 mm diameter), glass fiber separator (gfc, 19 mm diameter) soaked in electrolyte, and cathode (working electrode, 14 mm diameter), were assembled in a glove box with high-purity argon gas.
  • LiTFSI lithium bis(carbon trioxide)sulfonimi
  • the electrochemical performance of the assembled cells was routinely tested in a high-purity oxygen-sealed container, constant-current discharge-charge tests were performed on a LAND BT 2000 battery test system, and cyclic voltammetry (cv) was performed on a CHI 604B electrochemical workstation. and electrochemical impedance spectroscopy (eis) tests; all current densities and characteristic capacities of the cells were normalized against the actual loading of the active material.
  • a 2032-type LOB was assembled to evaluate the activity of the catalyst after glow discharge plasma treatment. 2 can be seen in FIG ORR onset potential GDP-Mo 2 C @ NCF oxygen electrode is 2.83 V, the peak voltage of 2.44 V, Mo 2 C @ NCF above oxygen electrode (2.80 V and 2.28 V), indicating that ORR higher electrocatalytic performance. In addition, there is a slight peak at 3.2 ⁇ 3.6 V anode, the discharge product on behalf of Li 2 O 2 was decomposed. CV an enlarged view (in FIG. 2 illustration), can be seen GDP-Mo 2 C @ NCF having a relatively low larger anodic peak onset potential and the OER, OER its electrocatalytic activity indicate better.
  • Figure 3 shows the full charge-discharge curves of the as-prepared LOBs at a current density of 100 mA g-1.
  • the GDP-Mo 2 C@NCF oxygen electrode also has a relatively low charging voltage plateau.
  • the charge voltage of GDP-Mo 2 C@NCF is 3.92 V , which is about 120 mV lower than that of Mo 2 C@NCF oxygen electrode (4.04 V), which has It is beneficial to improve the cycle efficiency and reduce the decomposition of the electrolyte.
  • GDP-Mo 2 C@NCF exhibits lower charge-discharge voltage polarization at all operating current densities.
  • a detailed comparison with the LOB of the existing reported TMCs electrocatalysts on some key parameters was made (the same test), as shown in Fig. 6 , GDP-Mo 2 C@NCF shows quite excellent performance. All of the above results strongly indicate that, GDP-Mo 2 C @ NCF oxygen electrode having high electrocatalytic activity and excellent charge-discharge reversibility.
  • the present invention discloses a brand-new surface chemical treatment method, which can not only destroy the surface passivation layer of the material, but also significantly improve the ionic interaction within the material, so as to optimize the surface chemical properties of the electrode material for lithium-oxygen battery. Improving the electrochemical performance of electrode materials opens up a promising avenue.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inert Electrodes (AREA)
  • Catalysts (AREA)

Abstract

本发明属于有机体系锂氧气电池技术领域，具体公开了金属碳化物催化剂及其制备方法与在锂氧气电池中的应用。通过静电纺丝制备出掺有碳化钼量子点的氮掺杂的碳纳米纤维（Mo 2C@NCF），之后通过辉光放电等离子体技术（GDP）对催化剂的表面进行处理，不仅能破坏其Mo 2C表面钝化层（MoO x）,而且引入了Mo-N化合键。本发明公布的锂氧气电池正极催化剂的优点是：破坏了催化剂表面钝化层的包覆，更多的活性位点得以暴露；增强了离子间的相互作用，提高了催化剂的性能；过电势显著降低，倍率性能优异，循环稳定性大大提升。我们的发明主要通过简便的辉光放电等离子体工艺来优化锂氧气电池电极材料的表面化学性质，为改善电极材料的电化学性能开辟了一条有前景的途径。

Description

金属碳化物催化剂及其制备方法与在锂氧气电池中的应用 技术领域
本发明属于有机体系锂氧气电池技术领域，具体公开了一种经等离子体表面重构的金属碳化物Mo 2C催化剂的制备及其在锂氧气电池的应用。
背景技术
由于其具有极高的理论能量密度（约3500 Wh kg -1），锂氧气电池（LOB）作为下一代最有前景的能量存储体系正受到越来越多的关注。然而，较差的充放电循环耐久性和较高的极化电势严重阻碍了它们的实际应用，这主要是由于阴极的动力学比较缓慢，其中包括放电过程中的氧还原反应（ORR）和充电过程中的氧析出反应（OER），氧电极中不溶性放电产物（例如，不导电的Li 2O 2）的过多堆积等。适当的氧电极体系结构设计和有效的双功能电催化剂的开发是解决上述挑战的两种主要策略。其中，Mo 2C被誉为用于析氢反应（HER），烃类转化和LOBs的ORR/OER中具有竞争性的双功能催化剂，但在充放电过程中Mo 2C的长期不稳定性仍然是一个很大的挑战。
技术问题
本发明公开了金属碳化物催化剂及其制备方法与在锂氧气电池中的应用，由此制备的氧电极体系结构包括足够的ORR/OER活性位点，用于电子/离子传输和O 2扩散的良好互连的通道以及用于存储不溶性Li 2O 2的较大空隙；本发明催化剂应对ORR和OER均具备有效的催化活性，以降低放电过电势并提供稳定的输出性能。
技术解决方案
本发明采用如下技术方案。
金属碳化物催化剂，其制备方法包括以下步骤，将聚乙烯吡咯烷酮、聚丙烯腈、溶剂、钼酸铵组成的电纺丝前体溶液进行静电纺丝，得到织物；再将织物依次进行烘干、煅烧，得到包含碳化钼量子点的氮掺杂碳纳米纤维；最后将包含碳化钼量子点的氮掺杂碳纳米纤维进行等离子体表面处理，得到金属碳化物催化剂。本发明通过一个全新的表面化学处理方法，来提高Mo 2C量子点的电催化行为，并在锂氧气电池应用中表现出高效的催化性能和优异的稳定性，该制备工艺简单，原材料成本低廉，展现出了广阔的应用前景。
本发明中，聚乙烯吡咯烷酮、聚丙烯腈、溶剂、钼酸铵的用量比为0.5g∶0.5g∶（5～15mL）∶1mmol ，优选0.5g∶0.5g∶10mL∶1mmol；煅烧为空气中煅烧后氮气中煅烧，优选的，空气中煅烧的温度为200℃，时间为1小时，氮气中煅烧的温度为800℃，时间为2小时。
本发明中，等离子体表面处理的电压为25～35KV，时间为50～80秒。
本发明公开了上述金属碳化物催化剂在制备锂氧气电池工作电极中的应用。
本发明公开了一种锂氧气电池工作电极，由导电基底、活性材料组成；活性材料由金属碳化物催化剂、碳材料、粘接剂组成；金属碳化物催化剂在导电基底上的负载量为0.6～0.8mg/cm 2；活性材料中，金属碳化物催化剂的质量百分数为65～75%。
进一步的，导电基底为碳纸；碳材料为炭黑；粘接剂为聚偏氟乙烯。
本发明利用简单的静电纺丝技术，在氮掺杂的碳纳米粒子中制备了Mo2C量子点(5nm)得到含碳化钼量子点的氮掺杂碳纳米纤维(Mo2C@NCF)，采用辉光放电等离子体(GDP)技术来改变Mo2C@NCF的表面，等离子体中的高能粒子可以打破Mo2C表面钝化层，得到金属碳化物催化剂。当用作氧电极时，可获得低过电位、优异的速率容量和优异的稳定性；本发明为催化剂表面化学的工程化提供了一个有效的方案，这是传统合成方法所不能提供的。
 附图说明
图1 为(a) Mo 2C@NCF和GDP-Mo 2C@NCF的XRD图谱，(b) Mo 2C@NCF的SEM图像，（c-e）HRTEM图像，（f）GDP-Mo 2C@NCF的SEM图像，（g-i）HRTEM图像和（j）EDX图像。
图2为在扫描速率为0.1 mV s -1时，2.2-4.4 V的电势范围内的CV曲线。
图3为分别基于GDP-Mo 2C@NCF和Mo 2C@NCF的LOB在100 mA g -1时的全充放电曲线。
图4为在100 mA g -1的电流密度下截止容量为1000 mAh g -1的的放电/充电循环稳定性。
图5为在不同的放电/充电电流密度下的速率性能。
图6为基于GDP-Mo 2C@NCF和现有电催化剂的性能对比。
本发明的实施方式
本发明涉及的原料都是电池领域常规市售原料，涉及的具体制备以及测试过程都是常规方法。
实施例一： 将0.5 g 聚乙烯吡咯烷酮（PVP）和0.5 g 聚丙烯腈（PAN，MW=150000）溶解在10 ml N,N-二甲基甲酰胺（DMF）中，然后加入1.0 mmol 钼酸铵（H 8MoN 2O 4），搅拌获得电纺丝前体溶液；将制备的前驱体溶液吸入带有不锈钢喷嘴（内径为0.4 mm）的塑料注射器中（10ml）进行静电纺丝，在静电纺丝制备过程中，在针头的尖端与铝箔收集器之间施加12-15 kV的高压，同时控制尖端与接收器之间的距离为10 cm，注射器的注射速度为0.05 mm· min -1，纺丝完成后，将获得的织物从收集器中取出，并转移到保持在60 ℃的真空烘箱中放置12 h，接着将干燥的纺丝织物先在200℃的空气中稳定煅烧1h，然后在高纯度N 2作为保护气的的管式炉中在800 ℃的高温下煅烧2h，其升温速率为5 ℃ min -1；煅烧后，最终获得了包含碳化钼量子点的氮掺杂碳纳米纤维（Mo 2C@NCF）；再使用辉光放电等离子体处理设备来对Mo 2C@NCF进行表面处理，其中包括CTP-2000K电源和20 kHz频率调制器，在空气中以30 kV的施加电压对Mo 2C@NCF进行辉光放电等离子辐射1min；等离子体处理后即可得到表面重构的碳化钼量子点的氮掺杂碳纳米纤维电催化剂（GDP-Mo 2C@NCF），为本发明金属碳化物催化剂。
图1a 可以看出辉光等离子体处理后，由于等离子体的高能量，GDP-Mo 2C@NCF所有特征峰都变得更强。如图1b和c所示，SEM和TEM图像显示Mo 2C@NCF的原纤维结构，表面光滑，平均直径约为100 nm。HRTEM图像显示，即使没有晶格条纹，碳纤维中平均粒径为3～4 nm的Mo 2C量子点的分布（图1d和e）。图1f和g表明GDP-Mo 2C@NCF具有相似的原纤维特征，但是，除了Mo 2C@NCF以外，在辉光等离子体处理过程中，纤维的表面还受到高能粒子的侵蚀和刻蚀，Mo 2C量子点变得粗糙同时也暴露了更多内部的Mo 2C量子点。这种结构的变化有助于提供较大的电极-电解液接触面积，以确保催化活性位的高可用性。 HRTEM图像清楚地显示了Mo 2C量子点的存在，并且观察到的晶格条纹间距为0.24nm，对应于Mo 2C的（101）平面（图1h和i）；EDX还确认了碳纤维上Mo、C、N元素，表明Mo 2C量子点是均匀分布在碳纤维上（图1j）。
实施例二： 常规组装2032型LOB以评估辉光放电等离子体处理后催化剂的活性。将实施例一的电催化剂(GDP-Mo2C@NCF)、炭黑(super P)和聚偏氟乙烯粘合剂按重量比70∶20∶10混合后涂覆在碳纸上常规制备工作电极，其中碳纸上的电催化剂负载量为0.6～0.8mg/cm2；电解质为1M锂双(三氧化碳)磺酰亚胺（LiTFSI），在二甲基亚砜中；2032型电池LOBs，包括锂金属阳极(直径15毫米)、玻璃纤维隔膜(gfc，直径19毫米)浸过电解液，和阴极(工作电极，直径14毫米)，在一个带有高纯氩气的手套箱里组装。
在高纯氧气密封容器中常规测试了组装电池的电化学性能，在LAND BT 2000型蓄电池测试系统上进行了恒流放电充电试验，在CHI 604B电化学工作站上进行了循环伏安法(cv)和电化学阻抗谱(eis)测试；以活性材料的实际负载量为标准，对电池的所有电流密度和特性容量进行了标准化。
组装了2032型LOB以评估辉光放电等离子体处理后催化剂的活性。图2中可以看到 GDP-Mo 2C@NCF氧电极的ORR起始电位为2.83 V，峰值电压为2.44 V，高于Mo 2C@NCF氧电极（2.80 V和2.28 V），表明其ORR的电催化性能更高。此外，在3.2〜3.6 V中有一个微小的阳极峰，代表放电产物Li 2O 2的分解。根据放大的CV图（图2中的插图），可以看到GDP-Mo 2C@NCF具有相对较低的OER起始电势和的更大的阳极峰，表明其OER的电催化活性更好。图3显示了在100 mA g -1的电流密度下所制备的LOB的全充放曲线。显然，与Mo 2C@NCF的6730 mAh g -1相比，GDP-Mo 2C@NCF氧电极放电容量更高，为7437 mAh g -1。而且，GDP-Mo 2C@NCF氧电极也具有相对较低的充电电压平台。例如，在2000 mAh g -1的特定充电容量下，GDP-Mo 2C@NCF的充电电压为3.92 V，比Mo 2C@NCF氧电极的充电电压（4.04 V）低约120 mV，这有利于改善循环效率并减轻电解液的分解。在100 mA g -1的电流密度和1000 mAh g -1的固定比容量下评估了所制备的LOB的充放电耐久性，如图4所示，GDP-Mo 2C@NCF氧电极成功运行了105个循环，而放电和充电容量没有任何衰减，并保持了约0.95 V的相对稳定的电压差；相比之下，Mo 2C@NCF氧电极仅能维持少于59个循环。图5显示了在不同的电流密度（100、200、500和1000 mA g -1）下制备的LOB的倍率性能（限容为1000 mAh g -1）。GDP-Mo 2C@NCF和Mo 2C@NCF在循环后均显示出出色的恢复能力。同时还可以观察到，在所有工作电流密度下，GDP-Mo 2C@NCF都具有较低的充放电电压极化。为了全面了解基于GDP-Mo 2C@NCF氧电极的LOB的性能，进一步与现有报道的TMCs电催化剂的LOB在一些关键参数上做了详细的对比（同样的测试），如图6所示，GDP-Mo 2C@NCF表现出相当优异的表现。以上所有结果充分表明，GDP-Mo 2C@NCF氧电极具有高效的电催化活性和优异的充放电可逆性。
总体来说，本发明公开了一个全新的表面化学处理方法，不仅能够破坏材料的表面钝化层，而且可以显著提高材料内的离子相互作用，来优化锂氧气电池电极材料的表面化学性质，为改善电极材料的电化学性能开辟了一条有前景的途径。

Claims (10)

  1. 金属碳化物催化剂，其特征在于，所述金属碳化物催化剂的制备方法包括以下步骤，将聚乙烯吡咯烷酮、聚丙烯腈、溶剂、钼酸铵组成的电纺丝前体溶液进行静电纺丝，得到织物；再将织物依次进行烘干、煅烧，得到包含碳化钼量子点的氮掺杂碳纳米纤维；最后将包含碳化钼量子点的氮掺杂碳纳米纤维进行等离子体表面处理，得到金属碳化物催化剂。
  2. 根据权利要求1所述金属碳化物催化剂，其特征在于，聚乙烯吡咯烷酮、聚丙烯腈、溶剂、钼酸铵的用量比为0.5g∶0.5g∶（5～15mL）∶1mmol。
  3. 根据权利要求1所述金属碳化物催化剂，其特征在于，煅烧为空气中煅烧后氮气中煅烧。
  4. 根据权利要求3所述金属碳化物催化剂，其特征在于，空气中煅烧的温度低于氮气中煅烧的温度。
  5. 根据权利要求1所述金属碳化物催化剂，其特征在于，等离子体表面处理的电压为25～35KV，时间为50～80秒。
  6. 权利要求1所述金属碳化物催化剂在制备锂氧气电池工作电极中的应用。
  7. 一种锂氧气电池工作电极，其特征在于，所述锂氧气电池工作电极由导电基底、活性材料组成；活性材料由权利要求1所述金属碳化物催化剂、碳材料、粘接剂组成。
  8. 根据权利要求7所述锂氧气电池工作电极，其特征在于，金属碳化物催化剂在导电基底上的负载量为0.6～0.8mg/cm 2；活性材料中，金属碳化物催化剂的质量百分数为65～75%。
  9. 根据权利要求7所述锂氧气电池工作电极，其特征在于，导电基底为碳纸；碳材料为炭黑；粘接剂为聚偏氟乙烯。
  10. 一种锂氧气电池，其特征在于，所述锂氧气电池的工作电极包括权利要求1所述金属碳化物催化剂。
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CN116377489A (zh) * 2023-02-16 2023-07-04 中国科学院福建物质结构研究所 一种通过水系可充电金属-催化剂电池高效分离制氢的方法
CN119517986A (zh) * 2024-09-25 2025-02-25 中国科学院重庆绿色智能技术研究院 一种zif-67/氮掺杂碳化钼异质结电催化剂及其制备方法和应用

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