WO2017124439A1 - 三维Na3V2(PO4)3纳米线网络电极材料及其制备方法和应用 - Google Patents

三维Na3V2(PO4)3纳米线网络电极材料及其制备方法和应用 Download PDF

Info

Publication number
WO2017124439A1
WO2017124439A1 PCT/CN2016/071761 CN2016071761W WO2017124439A1 WO 2017124439 A1 WO2017124439 A1 WO 2017124439A1 CN 2016071761 W CN2016071761 W CN 2016071761W WO 2017124439 A1 WO2017124439 A1 WO 2017124439A1
Authority
WO
WIPO (PCT)
Prior art keywords
dimensional
electrode material
nanowire network
network electrode
nanowire
Prior art date
Application number
PCT/CN2016/071761
Other languages
English (en)
French (fr)
Inventor
麦立强
任文皓
姚旭辉
赵云龙
徐林
Original Assignee
武汉理工大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 武汉理工大学 filed Critical 武汉理工大学
Publication of WO2017124439A1 publication Critical patent/WO2017124439A1/zh

Links

Images

Classifications

    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the field of nano materials and electrochemical technology, and particularly relates to a three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material and a preparation method and application thereof.
  • lithium-ion batteries are widely used in electrochemical energy storage devices due to their excellent performance.
  • lithium resources cannot meet the increasing demand for lithium-ion batteries.
  • sodium ion is expected to be widely used in the future electrochemical energy storage applications to replace lithium ions.
  • the energy density and cycle stability of the sodium ion battery can not fully meet the application requirements. Therefore, exploring suitable electrode materials that can solve the above problems is a prerequisite for the widespread application of sodium ion batteries.
  • Na 3 V 2 (PO 4 ) 3 is widely used as an electrode material for sodium super ion conductor (NASICON) with good ionic conductivity, high charge and discharge capacity, and excellent structural stability.
  • the Na 3 V 2 (PO 4 ) 3 electrode material has two different voltage platforms (3.3V and 1.6V), which gives the Na 3 V 2 (PO 4 ) 3 electrode material great potential in full-cell applications. .
  • the reported Na 3 V 2 (PO 4 ) 3 electrode material has undergone 200 charge and discharge cycles at a current density of 1 C. Maintaining 80%, the assembled full battery has a specific discharge capacity of only 80 mAh g -1 at a current density of 1 C.
  • the above electrochemical performance, especially the cycle stability of the whole battery is far from satisfactory. Therefore, more work on improving the electrochemical performance of Na 3 V 2 (PO 4 ) 3 electrode materials, especially rate performance and cycle stability, is urgently needed.
  • nanomaterials such as nanowires, nanorods, nanoparticles, nanosheets, etc.
  • nanowires have larger specific surface area and smaller size, which can shorten the ion diffusion path, improve the ionic conductivity of the electrode material, and effectively reduce the internal material. Stress, ultimately preventing structural collapse of the electrode material during charge and discharge.
  • the irreversible capacity of the electrode material is increased and the coulombic efficiency is lowered. Constructing a three-dimensional network structure composed of nanowires is considered to be an effective way to solve these problems.
  • nanowire materials Compared with ordinary nanomaterials, nanowire materials have the advantages of continuous ion conduction, high ionic conductivity, continuous electron conduction, effectively reduce the polarization effect at high current density, and ultimately improve the electrochemical properties of materials. performance.
  • the technical problem to be solved by the present invention is to provide a three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material, a preparation method thereof and an application thereof, which are simple and easy to use a hydrothermal combined solid phase sintering method.
  • concentration of the reactants By changing the concentration of the reactants, the morphology and size of the material can be controlled, and the obtained material has high yield, high purity, and uniform structure.
  • a three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material the nanowire electrode material has a diameter of 20-60 nm, and the morphology is uniform; the nanowires are alternately formed.
  • a three-dimensional network structure which is a product obtained by the following preparation method, comprising the following steps:
  • step 2) Dissolving sodium dihydrogen phosphate, oxalic acid, deionized water into the solution obtained in step 1), and stirring for 0.5 h;
  • the precursor is preheated in an argon atmosphere, then heated and sintered to obtain a three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material.
  • the amount of vanadium pentoxide used in the step 1) is 0.5-2 mmol
  • the amount of DMF is 20-40 ml
  • the amount of sodium dihydrogen phosphate described in the step 2) is 2-4 mmol
  • the amount of oxalic acid is 2-4 mmol.
  • the deionized water is 3-10 ml
  • the amount of glucose described in step 4) is 0.2 mmol-1.2 mmol.
  • the holding temperature of the step 3) is 160-200 ° C, and the time is 10-30 h.
  • the drying temperature in the step 4) is 50-90 °C.
  • the preheating temperature in the step 5) is 400 ° C
  • the sintering temperature is 600-800 ° C
  • the time is 6-10 h
  • the heating rate is 5 ° C min -1 .
  • the preparation method of the three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material comprises the following steps:
  • step 2) Dissolving sodium dihydrogen phosphate, oxalic acid, deionized water into the solution obtained in step 1), and stirring for 0.5 h;
  • the precursor is preheated in an argon atmosphere, then heated and sintered to obtain a three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material.
  • the three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material is used as a positive electrode active material of a sodium ion battery.
  • the three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material prepared by the invention has the advantages of multi-ion channel and continuous electron conduction, and can fully exert the electrochemical performance of the material.
  • the nanowire network improves the structural integrity and effectively improves the cycle stability of the electrode material.
  • the sodium ion half-cell assembled into the nano-cell half-cell can maintain 95.9% discharge specific capacity after 100 cycles of material flow. At 100C high current density, the discharge specific capacity of the material is still 94mAh. g -1 . Therefore, the three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material has very excellent electrochemical performance and is a very promising cathode material for sodium ion batteries.
  • the invention mainly prepares a three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material by a simple hydrothermal method combined with a solid phase sintering method, and exhibits high power when used as a positive electrode active material of a sodium ion battery.
  • the cycle stability is good.
  • the process of the invention is simple, and a three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire precursor can be obtained by a simple hydrothermal method, and the precursor is dried and under an argon atmosphere.
  • Solid phase sintering gives a three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material.
  • the invention has strong feasibility, is easy to be enlarged, and conforms to the characteristics of green chemistry, and is favorable for market promotion.
  • Example 1 is an XRD pattern of a three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material of Example 1;
  • Example 2 is a SEM and EDS diagram of the three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material of Example 1;
  • Example 3 is a TEM image of the three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material of Example 1;
  • Example 4 is a CV diagram of a three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material of Example 1;
  • Example 5 is a battery magnification diagram of the three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material of Example 1;
  • Example 6 is a graph showing the long-term battery cycle performance of the three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material of Example 1.
  • Example 7 is a view showing the formation mechanism of the three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material of Example 1.
  • a method for preparing a three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network comprising the steps of:
  • V 2 O 5 vanadium pentoxide
  • step 2) taking 3mmol sodium dihydrogen phosphate (NaH 2 PO 4 ), 3mmol oxalic acid (H 2 C 2 O 4 ), 5ml deionized water dissolved in the solution obtained in step 1), stirring is continued for 0.5h;
  • the structure is determined by an X-ray diffractometer.
  • the X-ray diffraction pattern (XRD) shown in Figure 1 shows that the three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network coincides with the Na 3 V 2 (PO 4 ) 3 standard sample with card number 00-053-0018.
  • the SEM, EDS image shown in Figure 2 and the TEM image shown in Figure 3 show the three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network structure prepared by us.
  • the nanowire material has a diameter of 20-60 nm and a length of several millimeters. The size is uniform, and the nanowires are interlaced to form a three-dimensional network structure, which has good structural stability and dispersion.
  • the formation process of the three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network is divided into five stages.
  • the addition of DMF starts to nucleate and form a solid microsphere, and then increases with the reaction time.
  • the microspheres grow into micron flowers, further increasing the reaction time, and the nanoflowers surface begins to form nanowires.
  • the reaction time is extended to 20h, the nanoflowers are all converted into nanowire networks.
  • the application of the three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material obtained in this embodiment as a positive electrode active material of a sodium ion battery is as follows:
  • the preparation process of the positive electrode sheet uses three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material as the active material, acetylene black as the conductive agent, and 10 wt% polydiene (PVDF) dissolved in the appropriate amount of 1-methyl-2- Pyrrolidone (NMP) as a binder, the mass ratio of active material, acetylene black, and polydiene is 70:20:10; after the active material is fully mixed with acetylene black, it is uniformly ground and poured into the ultrasonic dispersion for 30 minutes. The resulting PVDF-NMP solution was ultrasonically dispersed for 1 h, and the resulting mixed solution was applied to an aluminum foil of about 10 ⁇ m thick.
  • PVDF polydiene
  • the coated electrode sheet was dried in an oven at 80 ° C for 24 hours, and taken out, and it was made into an electrode sheet having a diameter of 14 ⁇ m for use. Dissolved in 1 M sodium perchlorate (NaClO 4 ) in ethylene carbonate (EC) and dimethyl carbonate (DMC) as an electrolyte, and added 5% fluoroethylene carbonate (FEC) additive.
  • the sodium sheet is the negative electrode
  • the glass fiber is the separator
  • the CR2016 type stainless steel is assembled into a button type sodium ion battery for the battery casing.
  • the remaining steps of the preparation method of the sodium ion battery are the same as the usual preparation methods.
  • a three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material with a cyclic voltammetry (CV) image at a scan rate of 0.1 mV s -1 shows potential applications ranging from 2.3 V to 3.9.
  • Figure 3 shows the rate performance of three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode materials at different current densities.
  • the initial discharge specific capacity of Na 3 V 2 (PO 4 ) 3 nanowire network electrode materials can reach 113, 110, 108, 102, 98, 94 mAh, respectively.
  • g -1 The material has excellent rate performance.
  • the capacity of the material at a current density of 1 C can be restored to 113 mAh g -1 , indicating that the structural stability of the material is good.
  • the current density relative to 1 C can still maintain a specific capacity of approximately 83%, and it can be seen that the material has the potential for rapid charging performance. It can be seen in Figure 6 that the cycling stability of the material is also very prominent.
  • the discharge capacity after 1000 cycles can still be maintained as high as 95.9%.
  • the above properties indicate that the three-dimensional Na 3 V 2 (PO 4 ) 3 nanowire network electrode material has excellent electrochemical performance and is a potential cathode material for sodium ion batteries.
  • V 2 O 5 vanadium pentoxide
  • step 2) taking 1.5mmol sodium dihydrogen phosphate (NaH 2 PO 4 ), 1.5mmol oxalic acid (H 2 C 2 O 4 ), 10ml deionized water dissolved in the solution obtained in step 1), stirring is continued for 0.5h;
  • the final precursor is preheated in an argon atmosphere at 5 ° C min -1 to 400 ° C for 2 h, then heated at 5 ° C min -1 to 750 ° C for 8 h to obtain three-dimensional sodium vanadium phosphate (Na 3 V 2 ( PO 4 ) 3 ) Nanowire network electrode material.
  • the initial discharge capacity of the material is 103 mAh g -1 at a current density of 10 C, and the cycle is 1000 times.
  • the subsequent discharge capacity retention rate was 94.5%.
  • V 2 O 5 vanadium pentoxide
  • step 2) taking 3mmol sodium dihydrogen phosphate (NaH 2 PO 4 ), 3mmol oxalic acid (H 2 C 2 O 4 ), 7ml deionized water dissolved in the solution obtained in step 1), stirring is continued for 0.5h;
  • the initial discharge capacity of the material is 99 mAh g -1 at a current density of 10 C, and the cycle is 1000 times.
  • the subsequent discharge capacity retention rate was 93.1%.
  • V 2 O 5 vanadium pentoxide
  • step 2) taking 3mmol sodium dihydrogen phosphate (NaH 2 PO 4 ), 3mmol oxalic acid (H 2 C 2 O 4 ), 10ml deionized water dissolved in the solution obtained in step 1), stirring is continued for 0.5h;
  • the initial discharge capacity of the material is 108 mAh g -1 at a current density of 10 C, and the cycle is 1000 times.
  • the subsequent discharge capacity retention rate was 95.9%.
  • V 2 O 5 vanadium pentoxide
  • step 2) taking 3mmol sodium dihydrogen phosphate (NaH 2 PO 4 ), 3mmol oxalic acid (H 2 C 2 O 4 ), 5ml deionized water dissolved in the solution obtained in step 1), stirring is continued for 0.5h;
  • the initial discharge capacity of the material is 105 mAh g -1 at a current density of 10 C, and the cycle is 1000 times.
  • the subsequent discharge capacity retention rate was 94.9%.
  • V 2 O 5 vanadium pentoxide
  • step 2) taking 3mmol sodium dihydrogen phosphate (NaH 2 PO 4 ), 3mmol oxalic acid (H 2 C 2 O 4 ), 5ml deionized water dissolved in the solution obtained in step 1), stirring is continued for 0.5h;
  • the initial discharge capacity of the material is 97 mAh g -1 at a current density of 10 C, and the cycle is 1000 times.
  • the subsequent discharge capacity retention rate was 93.1%.

Abstract

本发明属纳米材料与电化学技术领域，具体涉及三维Na3V2(PO4)3纳米线网络电极材料及其制备方法和应用，该纳米线电极材料直径20-60nm，形貌均一；纳米线相互交错形成三维网络状结构，结构稳定。本发明主要是通过简单易行的水热法结合固相烧结法制备了三维Na3V2(PO4)3纳米线网络电极材料，其作为钠离子电池正极活性材料时，表现出功率高、循环稳定性好的特点；其次，本发明工艺简单，通过简单易行的水热法即可得到三维Na3V2(PO4)3纳米线前驱体，对前驱体进行干燥和氩气气氛下固相烧结即可得到三维Na3V2(PO4)3纳米线网络电极材料，其可行性强，易于放大化，符合绿色化学的特点，利于市场化推广。

Description

三维Na3V2(PO4)3纳米线网络电极材料及其制备方法和应用 技术领域
本发明属于纳米材料与电化学技术领域，具体涉及三维Na3V2(PO4)3纳米线网络电极材料及其制备方法和应用。
背景技术
如今，锂离子电池由于其出色的性能在电化学能量存储器件领域得到广泛应用，然而锂资源已不能满足越来越多对锂离子电池的需求。钠离子作为一种与锂离子具有相似电化学性能，并且储量更丰富，售价更低廉的原材料，有希望在未来的电化学储能应用中取代锂离子从而受到广泛的关注。然而，由于钠离子较大的离子半径
Figure PCTCN2016071761-appb-000001
和在嵌入、脱嵌中较大的体积变化，导致钠离子电池的能量密度和循环稳定性还不能完全满足应用要求。因此，探索合适的可以解决上述问题的电极材料是钠离子电池广泛应用的前提。
Na3V2(PO4)3作为一种钠超离子导体(NASICON)的电极材料，具有良好的离子电导率、高的充放电容量以及优异的结构稳定性从而受到广泛的关注；除此之外，Na3V2(PO4)3电极材料存在两个不同的电压平台(3.3V和1.6V)，赋予了Na3V2(PO4)3电极材料在全电池应用中极大的潜力。然而至今关于磷酸钒钠在钠离子全电池方面的探索还远远不够，目前报道的Na3V2(PO4)3电极材料在1C的电流密度下经过200次的充放电循环，容量只能保持80％，组装的全电池在1C的电流密度下放电比容量只有80mAh g-1，上述电化学性能尤其是全电池的循环稳定性方面还远远不能满足应用的要求。因此，更多关于提高Na3V2(PO4)3电极材料的电化学性能特别是倍率性能和循环稳定性的工作亟待研究。
研究表明，纳米材料(如纳米线、纳米棒、纳米颗粒、纳米片等)的比表面积较大且尺寸较小，可以缩短离子的扩散路径，提高电极材料的离子电导率，同时有效减少材料内部应力，最终防止电极材料在充放电过程中的结构崩塌。然而，由于纳米材料所形成不稳定的SEI数量较多，使电极材料的不可逆容量增加且库伦效率降低。构筑由纳米线组成的三维空间网络结构被认为是解决这些问题的有效途径。与普通纳米材料相比，纳米线材料除了具有短的离子扩散路径、高的离子电导率外，更具有连续的电子传导优点，有效减少大电流密度下的极化效应，最终提高材料的电化学性能。
发明内容
本发明所要解决的技术问题是针对上述现有技术而提出一种三维Na3V2(PO4)3纳米线网络电极材料及其制备方法和应用，其采用水热结合固相烧结法简单易行，通过改变反应物的 浓度可控制材料的形貌和尺寸大小，且制得的材料产量高、纯度高、结构均一。
本发明解决上述技术问题所采用的技术方案是：一种三维Na3V2(PO4)3纳米线网络电极材料，该纳米线电极材料直径20-60nm，形貌均一；纳米线相互交错形成三维网络状结构，其为下述制备方法所得产物，包括以下步骤：
1)首先取五氧化二钒溶于DMF中，水浴搅拌使其分散均匀；
2)把磷酸二氢钠、草酸、去离子水溶入步骤1)所得溶液中，继续搅拌0.5h；
3)将溶液转移至聚四氟乙烯不锈钢高压反应釜中，在烘箱中保温；
4)取出产物，然后将葡萄糖加入溶液中，继续搅拌0.5h后烘干得到前驱体产物；
5)将前驱体在氩气气氛中先升温预热，然后升温并烧结，即得到三维Na3V2(PO4)3纳米线网络电极材料。
按上述方案，步骤1)所述的五氧化二钒的用量为0.5-2mmol，DMF用量为20-40ml，步骤2)所述的磷酸二氢钠用量为2-4mmol，草酸用量为2-4mmol，去离子水为3-10ml，步骤4)所述的葡萄糖用量为0.2mmol-1.2mmol。
按上述方案，步骤3)所述保温温度为160-200℃，时间为10-30h。
按上述方案，步骤4)所述烘干温度为50-90℃。
按上述方案，步骤5)所述的预热温度为400℃，烧结温度为600-800℃，时间为6-10h，升温速率为5℃ min-1。
所述的三维Na3V2(PO4)3纳米线网络电极材料的制备方法，包括以下步骤：
1)首先取五氧化二钒溶于DMF中，水浴搅拌使其分散均匀；
2)把磷酸二氢钠、草酸、去离子水溶入步骤1)所得溶液中，继续搅拌0.5h；
3)将溶液转移至聚四氟乙烯不锈钢高压反应釜中，在烘箱中保温；
4)取出产物，然后将葡萄糖加入溶液中，继续搅拌0.5h后烘干得到前驱体产物；
5)将前驱体在氩气气氛中先升温预热，然后升温并烧结，即得到三维Na3V2(PO4)3纳米线网络电极材料。
所述的三维Na3V2(PO4)3纳米线网络电极材料作为钠离子电池正极活性材料的应用。
本发明制备的三维Na3V2(PO4)3纳米线网络电极材料具有多离子通道、连续的电子传导优势，可以充分发挥材料的电化学性能。另外，纳米线网络提高了结构的完整性，有效改善电极材料的循环稳定性。最终实现将其组装成的钠离子半电池，在10C的电流密度下，材料循环100次后的放电比容量仍能保持95.9％，在100C的高电流密度下，材料的放电比容量仍 为94mAh g-1。从而使三维Na3V2(PO4)3纳米线网络电极材料具有非常优异的电化学性能，是一种非常有潜力的钠离子电池正极材料。
本发明的有益效果：
本发明主要是通过简单易行的水热法结合固相烧结法制备了三维Na3V2(PO4)3纳米线网络电极材料，其作为钠离子电池正极活性材料时，表现出功率高、循环稳定性好的特点；其次，本发明工艺简单，通过简单易行的水热法即可得到三维Na3V2(PO4)3纳米线前驱体，对前驱体进行干燥和氩气气氛下固相烧结即可得到三维Na3V2(PO4)3纳米线网络电极材料。本发明可行性强，易于放大化，符合绿色化学的特点，利于市场化推广。
附图说明
图1为实施例1的三维Na3V2(PO4)3纳米线网络电极材料的XRD图；
图2为实施例1的三维Na3V2(PO4)3纳米线网络电极材料的SEM和EDS图；
图3为实施例1的三维Na3V2(PO4)3纳米线网络电极材料的TEM图；
图4为实施例1的三维Na3V2(PO4)3纳米线网络电极材料的CV图；
图5为实施例1的三维Na3V2(PO4)3纳米线网络电极材料的电池倍率图；
图6为实施例1的三维Na3V2(PO4)3纳米线网络电极材料的长期电池循环性能图。
图7为实施例1的三维Na3V2(PO4)3纳米线网络电极材料的形成机理图。
具体实施方式
下面结合实施例进一步阐释本发明的技术方案，但不作为对本发明保护范围的限制。
实施例1
三维Na3V2(PO4)3纳米线网络的制备方法，它包括如下步骤：
1)取1mmol五氧化二钒(V2O5)溶于30mL DMF(N,N-二甲基甲酰胺)中，水浴搅拌使其分散均匀；
2)取3mmol磷酸二氢钠(NaH2PO4)、3mmol草酸(H2C2O4)、5ml去离子水溶入步骤1)所得溶液中，继续搅拌0.5h；
3)将溶液转移至聚四氟乙烯不锈钢高压反应釜中，在180℃烘箱中保温20h；
4)取出产物，然后将1mmol葡萄糖加入溶液中，继续搅拌0.5h后烘干得到前驱体产物；
5)最后前驱体在氩气气氛中先经过5℃ min-1升温至400℃预热4h，然后以5℃ min-1升温至700℃烧结8h，得到三维磷酸钒钠(Na3V2(PO4)3)纳米线网络电极材料。
以本实施例产物三维Na3V2(PO4)3纳米线网络电极材料为例，其结构由X射线衍射仪确 定。附图1所示X射线衍射图谱(XRD)表明，三维Na3V2(PO4)3纳米线网络与卡片号为00-053-0018的Na3V2(PO4)3标准样品吻合。
附图2所示SEM、EDS图像和附图3所示TEM图像表明我们所制备的三维Na3V2(PO4)3纳米线网络结构，纳米线材料直径20-60nm、长度达几毫米，大小均一，纳米线相互交错形成三维网络状结构，具有很好的结构稳定性、分散性。
附图7所示，三维Na3V2(PO4)3纳米线网络的形成过程分为5个阶段，首先是DMF的加入使其开始成核并形成实心微米球，然后随着反应时间增加到3h，微米球生长成为微米花，进一步增加反应时间，纳米花表面开始形成纳米线，当反应时间延长至20h时，纳米花全部转换为纳米线网络。
本实施例所得三维Na3V2(PO4)3纳米线网络电极材料作为钠离子电池正极活性材料的应用如下：
正极片的制备过程采用三维Na3V2(PO4)3纳米线网络电极材料作为活性材料，乙炔黑作为导电剂，10wt％聚乙二烯(PVDF)溶于适量1-甲基-2-吡咯烷酮(NMP)作为粘结剂，活性材料、乙炔黑、聚乙二烯的质量比为70:20:10；将活性物质与乙炔黑按比例充分混合后，研磨均匀，倒入已经超声分散30min后的PVDF-NMP溶液，超声分散1h，将所得混合溶液涂于约10μm厚的铝箔上。将涂布后的电极片置于80℃的烘箱干燥24h后取出，将其制成直径为14μm的电极片备用。以1M的高氯酸钠(NaClO4)溶解于乙烯碳酸酯(EC)和碳酸二甲酯(DMC)中作为电解液，并加入5％的氟代碳酸乙烯酯(FEC)添加剂。钠片为负极，玻璃纤维为隔膜，CR2016型不锈钢为电池外壳组装成扣式钠离子电池。钠离子电池的制备方法其余步骤与通常的制备方法相同。
附图4中所示，三维Na3V2(PO4)3纳米线网络电极材料以0.1mV s-1扫描速率的循环伏安法(CV)图像，显示潜在的应用范围在2.3V与3.9V之间；附图5所示三维Na3V2(PO4)3纳米线网络电极材料在不同电流密度下的倍率性能。在1、5、10、30、50和100C的电流密度下，Na3V2(PO4)3纳米线网络电极材料的首次放电比容量可以分别达到113、110、108、102、98、94mAh g-1。材料的倍率性能优异，在经历1～100C不同电流密度下的充放电后，材料在1C的电流密度下的容量可以恢复到113mAh g-1，说明材料的结构稳定性好。此外，在100C的大电流密度下相对于1C的电流密度仍可保持接近83％的比容量，可以看出材料具有快速充电性能的潜力。附图6中可以看出材料的循环稳定性也非常突出，在10C的电流密度下，循环1000次后的放电容量仍可保持高达95.9％。上述性能表明，三维Na3V2(PO4)3纳米线网络电极材料 具有非常优异的电化学性能，是一种潜在的钠离子电池正极材料。
实施例2
1)取0.5mmol五氧化二钒(V2O5)溶于40mL DMF(N,N-二甲基甲酰胺)中，水浴搅拌使其分散均匀；
2)取1.5mmol磷酸二氢钠(NaH2PO4)、1.5mmol草酸(H2C2O4)、10ml去离子水溶入步骤1)所得溶液中，继续搅拌0.5h；
3)将溶液转移至聚四氟乙烯不锈钢高压反应釜中，在180℃烘箱中保温15h；
4)取出产物，然后将1mmol葡萄糖加入溶液中，继续搅拌0.5h后烘干得到前驱体产物；
5)最后前驱体在氩气气氛中先经过5℃ min-1升温至400℃预热2h，然后以5℃ min-1升温至750℃烧结8h，得到三维磷酸钒钠(Na3V2(PO4)3)纳米线网络电极材料。
以本实施例所得的三维磷酸钒钠(Na3V2(PO4)3)纳米线网络电极材料为例，在10C的电流密度下，材料的初始放电容量为103mAh g-1，循环1000次后的放电容量保持率为94.5％。
实施例3
1)取1mmol五氧化二钒(V2O5)溶于30mL DMF(N,N-二甲基甲酰胺)中，水浴搅拌使其分散均匀；
2)取3mmol磷酸二氢钠(NaH2PO4)、3mmol草酸(H2C2O4)、7ml去离子水溶入步骤1)所得溶液中，继续搅拌0.5h；
3)将溶液转移至聚四氟乙烯不锈钢高压反应釜中，在180℃烘箱中保温20h；
4)取出产物，然后将1mmol葡萄糖加入溶液中，继续搅拌0.5h后烘干得到前驱体产物；
5)最后前驱体在氩气气氛中先经过5℃ min-1升温至400℃预热4h，然后以5℃ min-1升温至700℃烧结8h，得到三维磷酸钒钠(Na3V2(PO4)3)纳米线网络电极材料。
以本实施例所得的三维磷酸钒钠(Na3V2(PO4)3)纳米线网络电极材料为例，在10C的电流密度下，材料的初始放电容量为99mAh g-1，循环1000次后的放电容量保持率为93.1％。
实施例4
1)取1mmol五氧化二钒(V2O5)溶于30mL DMF(N,N-二甲基甲酰胺)中，水浴搅拌使其分散均匀；
2)取3mmol磷酸二氢钠(NaH2PO4)、3mmol草酸(H2C2O4)、10ml去离子水溶入步骤1)所得溶液中，继续搅拌0.5h；
3)将溶液转移至聚四氟乙烯不锈钢高压反应釜中，在180℃烘箱中保温20h；
4)取出产物，然后将1mmol葡萄糖加入溶液中，继续搅拌0.5h后烘干得到前驱体产物；
5)最后前驱体在氩气气氛中先经过5℃ min-1升温至400℃预热4h，然后以5℃ min-1升温至700℃烧结8h，得到三维磷酸钒钠(Na3V2(PO4)3)纳米线网络电极材料。
以本实施例所得的三维磷酸钒钠(Na3V2(PO4)3)纳米线网络电极材料为例，在10C的电流密度下，材料的初始放电容量为108mAh g-1，循环1000次后的放电容量保持率为95.9％。
实施例5
1)取1mmol五氧化二钒(V2O5)溶于30mL DMF(N,N-二甲基甲酰胺)中，水浴搅拌使其分散均匀；
2)取3mmol磷酸二氢钠(NaH2PO4)、3mmol草酸(H2C2O4)、5ml去离子水溶入步骤1)所得溶液中，继续搅拌0.5h；
3)将溶液转移至聚四氟乙烯不锈钢高压反应釜中，在180℃烘箱中保温30h；
4)取出产物，然后将1mmol葡萄糖加入溶液中，继续搅拌0.5h后烘干得到前驱体产物；
5)最后前驱体在氩气气氛中先经过5℃ min-1升温至400℃预热4h，然后以5℃ min-1升温至700℃烧结8h，得到三维磷酸钒钠(Na3V2(PO4)3)纳米线网络电极材料。
以本实施例所得的三维磷酸钒钠(Na3V2(PO4)3)纳米线网络电极材料为例，在10C的电流密度下，材料的初始放电容量为105mAh g-1，循环1000次后的放电容量保持率为94.9％。
实施例6
1)取1mmol五氧化二钒(V2O5)溶于30mL DMF(N,N-二甲基甲酰胺)中，水浴搅拌使其分散均匀；
2)取3mmol磷酸二氢钠(NaH2PO4)、3mmol草酸(H2C2O4)、5ml去离子水溶入步骤1)所得溶液中，继续搅拌0.5h；
3)将溶液转移至聚四氟乙烯不锈钢高压反应釜中，在180℃烘箱中保温20h；
4)取出产物，然后将1mmol葡萄糖加入溶液中，继续搅拌0.5h后烘干得到前驱体产物；
5)最后前驱体在氩气气氛中先经过5℃ min-1升温至400℃预热4h，然后以5℃ min-1 升温至750℃烧结8h，得到三维磷酸钒钠(Na3V2(PO4)3)纳米线网络电极材料。
以本实施例所得的三维磷酸钒钠(Na3V2(PO4)3)纳米线网络电极材料为例，在10C的电流密度下，材料的初始放电容量为97mAh g-1，循环1000次后的放电容量保持率为93.1％。

Claims (10)

  1. 一种三维Na3V2(PO4)3纳米线网络电极材料，该纳米线电极材料直径20-60nm，形貌均一；纳米线相互交错形成三维网络状结构，其为下述制备方法所得产物，包括以下步骤：
    1)首先取五氧化二钒溶于DMF中，水浴搅拌使其分散均匀；
    2)把磷酸二氢钠、草酸、去离子水溶入步骤1)所得溶液中，继续搅拌0.5h；
    3)将溶液转移至聚四氟乙烯不锈钢高压反应釜中，在烘箱中保温；
    4)取出产物，然后将葡萄糖加入溶液中，继续搅拌0.5h后烘干得到前驱体产物；
    5)将前驱体在氩气气氛中先升温预热，然后升温并烧结，即得到三维Na3V2(PO4)3纳米线网络电极材料。
  2. 如权利要求1所述的三维Na3V2(PO4)3纳米线网络电极材料，其特征在于，步骤1)所述的五氧化二钒的用量为0.5-2mmol，DMF用量为20-40ml，步骤2)所述的磷酸二氢钠用量为2-4mmol，草酸用量为2-4mmol，去离子水为3-10ml，步骤4)所述的葡萄糖用量为0.2mmol-1.2mmol。
  3. 如权利要求1所述的三维Na3V2(PO4)3纳米线网络电极材料，其特征在于，步骤3)所述保温温度为160-200℃，时间为10-30h。
  4. 如权利要求1所述的三维Na3V2(PO4)3纳米线网络电极材料，其特征在于，步骤4)所述烘干温度为50-90℃。
  5. 如权利要求1所述的三维Na3V2(PO4)3纳米线网络电极材料，其特征在于，步骤5)所述的预热温度为400℃，烧结温度为600-800℃，时间为6-10h，升温速率为5℃min-1。
  6. 权利要求1所述的三维Na3V2(PO4)3纳米线网络电极材料的制备方法，包括以下步骤：
    1)首先取五氧化二钒溶于DMF中，水浴搅拌使其分散均匀；
    2)把磷酸二氢钠、草酸、去离子水溶入步骤1)所得溶液中，继续搅拌0.5h；
    3)将溶液转移至聚四氟乙烯不锈钢高压反应釜中，在烘箱中保温；
    4)取出产物，然后将葡萄糖加入溶液中，继续搅拌0.5h后烘干得到前驱体 产物；
    5)将前驱体在氩气气氛中先升温预热，然后升温并烧结，即得到三维Na3V2(PO4)3纳米线网络电极材料。
  7. 如权利要求6所述的三维Na3V2(PO4)3纳米线网络电极材料的制备方法，其特征在于，步骤1)所述的五氧化二钒的用量为0.5-2mmol，DMF用量为20-40ml，步骤2)所述的磷酸二氢钠用量为2-4mmol，草酸用量为2-4mmol，去离子水为3-10ml，步骤4)所述的葡萄糖用量为0.2mmol-1.2mmol。
  8. 如权利要求6所述的三维Na3V2(PO4)3纳米线网络电极材料的制备方法，其特征在于，步骤3)所述保温温度为160-200℃，时间为10-30h。
  9. 如权利要求6所述的三维Na3V2(PO4)3纳米线网络电极材料的制备方法，其特征在于，步骤4)烘干温度为50-90℃，步骤5)所述的预热温度为400℃，烧结温度为600-800℃，时间为6-10h，升温速率为5℃min-1。
  10. 权利要求1所述的三维Na3V2(PO4)3纳米线网络电极材料作为钠离子电池正极活性材料的应用。
PCT/CN2016/071761 2016-01-18 2016-01-22 三维Na3V2(PO4)3纳米线网络电极材料及其制备方法和应用 WO2017124439A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610032400.X 2016-01-18
CN201610032400.XA CN105680041B (zh) 2016-01-18 2016-01-18 三维Na3V2(PO4)3纳米线网络电极材料及其制备方法和应用

Publications (1)

Publication Number Publication Date
WO2017124439A1 true WO2017124439A1 (zh) 2017-07-27

Family

ID=56301334

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/071761 WO2017124439A1 (zh) 2016-01-18 2016-01-22 三维Na3V2(PO4)3纳米线网络电极材料及其制备方法和应用

Country Status (2)

Country Link
CN (1) CN105680041B (zh)
WO (1) WO2017124439A1 (zh)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111606314A (zh) * 2020-06-04 2020-09-01 哈尔滨工业大学 一种钠离子电池正极材料三氟磷酸钒钠的制备方法
CN113394365A (zh) * 2021-06-11 2021-09-14 北京化工大学 一种柔性一体化nvp/go/cnt膜电极及其制备方法
CN114031063A (zh) * 2021-11-04 2022-02-11 湖南工程学院 一种氟磷酸钒钠纳米复合材料及其制备方法
CN114725345A (zh) * 2022-04-19 2022-07-08 江苏理工学院 一种Fe3O4/NaTi2(PO4)3/C微纳复合材料的制备方法与应用
CN114864919A (zh) * 2022-04-27 2022-08-05 郑州大学 一种制备3D打印Nb2CTx/rGO复合钠金属负极的方法
CN115818611A (zh) * 2022-12-13 2023-03-21 大连融科储能集团股份有限公司 一种掺Mg磷酸钒钠、掺Mg氟磷酸钒钠、其制备方法及用途
CN116081591A (zh) * 2023-02-23 2023-05-09 武汉工程大学 一种钠离子电池负极材料的制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106450307B (zh) * 2016-12-16 2019-08-06 武汉理工力强能源有限公司 一种分级内连接碳修饰磷酸钒钠电极材料及其制备方法和应用
CN107317017B (zh) * 2017-07-10 2020-06-02 三峡大学 一种无粘结剂Na3V2(PO4)3/C复合钠离子电池正极及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102306771A (zh) * 2011-08-17 2012-01-04 中南大学 一种混合离子电池氟磷酸钒钠正极材料的制备方法
CN104617294A (zh) * 2015-01-05 2015-05-13 武汉理工大学 纳米片组装的Na3V2(PO4)3/C分级微米花电极材料及其制备方法和应用
CN104733731A (zh) * 2015-03-25 2015-06-24 天津大学 制备均匀碳包覆磷酸钒钠材料的方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101734637B (zh) * 2008-11-20 2011-08-31 中国科学院理化技术研究所 一种锂离子电池用正极材料磷酸钒锂粉体的制备方法
CN103545518B (zh) * 2013-11-01 2015-12-02 武汉理工大学 磷酸钒锂/碳异质介孔纳米线材料及其制备方法和应用
CN104466178B (zh) * 2014-12-05 2016-03-30 武汉理工大学 分级介孔钒酸钠弯折纳米线及其制备方法和应用
CN104638228B (zh) * 2015-02-04 2017-03-22 武汉理工大学 同轴碳包覆束状磷酸钒钾纳米线及其制备方法和应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102306771A (zh) * 2011-08-17 2012-01-04 中南大学 一种混合离子电池氟磷酸钒钠正极材料的制备方法
CN104617294A (zh) * 2015-01-05 2015-05-13 武汉理工大学 纳米片组装的Na3V2(PO4)3/C分级微米花电极材料及其制备方法和应用
CN104733731A (zh) * 2015-03-25 2015-06-24 天津大学 制备均匀碳包覆磷酸钒钠材料的方法

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111606314A (zh) * 2020-06-04 2020-09-01 哈尔滨工业大学 一种钠离子电池正极材料三氟磷酸钒钠的制备方法
CN111606314B (zh) * 2020-06-04 2023-05-26 哈尔滨工业大学 一种钠离子电池正极材料三氟磷酸钒钠的制备方法
CN113394365A (zh) * 2021-06-11 2021-09-14 北京化工大学 一种柔性一体化nvp/go/cnt膜电极及其制备方法
CN113394365B (zh) * 2021-06-11 2023-03-21 北京化工大学 一种柔性一体化nvp/go/cnt膜电极及其制备方法
CN114031063A (zh) * 2021-11-04 2022-02-11 湖南工程学院 一种氟磷酸钒钠纳米复合材料及其制备方法
CN114031063B (zh) * 2021-11-04 2023-02-28 湖南工程学院 一种氟磷酸钒钠纳米复合材料及其制备方法
CN114725345A (zh) * 2022-04-19 2022-07-08 江苏理工学院 一种Fe3O4/NaTi2(PO4)3/C微纳复合材料的制备方法与应用
CN114864919A (zh) * 2022-04-27 2022-08-05 郑州大学 一种制备3D打印Nb2CTx/rGO复合钠金属负极的方法
CN114864919B (zh) * 2022-04-27 2023-09-15 郑州大学 一种制备3D打印Nb2CTx/rGO复合钠金属负极的方法
CN115818611A (zh) * 2022-12-13 2023-03-21 大连融科储能集团股份有限公司 一种掺Mg磷酸钒钠、掺Mg氟磷酸钒钠、其制备方法及用途
CN116081591A (zh) * 2023-02-23 2023-05-09 武汉工程大学 一种钠离子电池负极材料的制备方法

Also Published As

Publication number Publication date
CN105680041A (zh) 2016-06-15
CN105680041B (zh) 2017-12-29

Similar Documents

Publication Publication Date Title
Li et al. Sphere-like SnO2/TiO2 composites as high-performance anodes for lithium ion batteries
WO2017124439A1 (zh) 三维Na3V2(PO4)3纳米线网络电极材料及其制备方法和应用
WO2020030014A1 (zh) 磷酸钒钠正极材料、钠离子电池及其制备方法和应用
Cheng et al. CeO2 decorated graphene as separator modification material for capture and boost conversion of polysulfide in lithium-sulfur batteries
US11380881B2 (en) Anode material of lithium ion battery and non-aqueous electrolyte battery
CN105914369B (zh) 一种纳米级碳包覆硫化锂复合材料及其制备方法和应用
Liu et al. A facile synthesis of core-shell structured ZnO@ C nanosphere and their high performance for lithium ion battery anode
CN111564612B (zh) 一种高导热导电性锂电正极材料及其制备方法
Xiao et al. Research progress of nano-silicon-based materials and silicon-carbon composite anode materials for lithium-ion batteries
CN111211273A (zh) 氮化铁纳米颗粒原位生长在还原氧化石墨烯上作为修饰隔膜材料的锂硫电池及其制备方法
CN112357956B (zh) 碳/二氧化钛包覆氧化锡纳米颗粒/碳组装介孔球材料及其制备和应用
Zeng et al. Mesoscopic Ti2Nb10O29 cages comprised of nanorod units as high-rate lithium-ion battery anode
CN106450423B (zh) 一种高比能柔性一体化电极及其制备方法
Zhang et al. A review on electrode materials of fast‐charging lithium‐ion batteries
CN112174220A (zh) 二氧化钛包覆四氧化三钴蜂窝孔纳米线材料及其制备和应用
Wei et al. Towards high-performance battery systems by regulating morphology of TiO2 materials
CN110467170B (zh) 一种钾离子电池高电位正极材料及其制备方法
CN110957486A (zh) 超结构锡碳-氧化钼复合材料的制备方法及其应用于电极
Xu et al. Porous N-doped C coated gallium nitride submicron bricks/reduced graphene oxide hybrid as high-performance anode for lithium-ion batteries
CN113772718A (zh) 一种SnS-SnS2@GO异质结构复合材料及其制备方法和应用
CN113036100A (zh) 一种含刚性颗粒骨架的锂金属复合负极及其制备方法
CN109449440B (zh) 微孔超薄软碳纳米片及其制备方法和应用
CN113921812B (zh) 一种超高功率密度钠离子电池及其制备方法
CN112421027B (zh) 表面改性的多孔六边形Na3V2(PO4)2F3碳包覆微米球及其制备方法和应用
Tang et al. Electrochemically driven amorphization of (Li-) Ti-PO nanoparticles embedded in porous CNTs for superior lithium storage performance

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16885712

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16885712

Country of ref document: EP

Kind code of ref document: A1