阅读说明：本技术 一种用于钾离子电池的Sn4P3/Ti3C2Tx型MXene复合负极材料 (Sn for potassium ion battery4P3/Ti3C2TxMXene composite negative electrode material ) 是由 陈人杰 刘欢 屈雯洁 罗锐 黄茹玲 李丽 于 2019-08-28 设计创作，主要内容包括：本发明涉及一种用于钾离子电池的Sn_4P_3/Ti_3C_2T_x型MXene复合负极材料,属于钾离子电池负极材料技术领域。所述复合负极材料是由Sn_4P_3纳米颗粒与Ti_3C_2T_x型MXene纳米片通过静电自组装制备而成的,Ti_3C_2T_x型MXene可以改善Sn_4P_3的导电性能并缓冲Sn_4P_3储钾时的体积变化,进而使该复合负极材料具有优异的循环性能和倍率性能；另外,该复合负极材料的制备方法简单、高效、安全且成本低,有利于推广Sn_4P_3作为钾离子电池负极材料的应用。(The invention relates to Sn for a potassium ion battery 4 P 3 /Ti 3 C 2 T x A MXene composite anode material belongs to the technical field of potassium ion battery anode materials. The composite negative electrode material is composed of Sn 4 P 3 Nanoparticles and Ti 3 C 2 T x Prepared from MXene nanosheets by electrostatic self-assembly, Ti 3 C 2 T x The MXene can improve Sn 4 P 3 Conductive property and buffer Sn 4 P 3 The volume change during potassium storage, so that the composite anode material has excellent cycle performanceAnd rate capability; in addition, the preparation method of the composite negative electrode material is simple, efficient, safe and low in cost, and is beneficial to popularization of Sn 4 P 3 The material is applied as a negative electrode material of a potassium ion battery.)

1. Sn for potassium ion battery₄P₃/Ti₃C₂T_xThe type MXene composite negative electrode material is characterized in that: the composite negative electrode material is prepared by adopting the following method,

sn is added₄P₃Preparing uniformly dispersed suspension from nano particles, surfactant and water, and mixing Ti₃C₂T_xPreparing the MXene nanosheet and water into a solution; mixing the suspension and the solution, then carrying out ultrasonic treatment at 0-50 ℃ for not less than 0.5h, collecting a solid product, washing and drying to obtain Sn₄P₃/Ti₃C₂T_xA type MXene composite anode material;

wherein Sn₄P₃Nanoparticles and Ti₃C₂T_xThe mass ratio of the MXene nanosheets is (1-9): 1, and the mass of the surfactant is Sn₄P₃10-20% of the mass of the nano particles, and the surfactant is at least one of thiourea, sodium dodecyl benzene sulfonate, hexadecyl ammonium bromide, P123, Pluronic F127, Pluronic F108 and span 80.

2. Sn for potassium ion battery according to claim 1₄P₃/Ti₃C₂T_xThe type MXene composite negative electrode material is characterized in that: in the suspension, Sn₄P₃The concentration of the nano particles is 0.01 g/mL-2 g/mL; in solution, Ti₃C₂T_xThe concentration of the MXene nano-sheet is 0.1-10 mg/mL.

3. Sn for potassium ion battery according to claim 1 or 2₄P₃/Ti₃C₂T_xThe type MXene composite negative electrode material is characterized in that: sn (tin)₄P₃The particle diameter of the nano-particles is 10 nm-100 nm, and Ti₃C₂T_xThe size of the MXene nano-sheet is 100 nm-5 μm.

4. Sn for potassium ion battery according to claim 1₄P₃/Ti₃C₂T_xThe type MXene composite negative electrode material is characterized in that: the temperature of ultrasonic treatment is 25-30 ℃.

5. Sn for potassium ion battery according to claim 1₄P₃/Ti₃C₂T_xType MXene compositeAn anode material, characterized in that: when the ultrasonic frequency is 40W, the ultrasonic time is 1 h-6 h.

6. Sn for potassium ion battery according to claim 1₄P₃/Ti₃C₂T_xThe type MXene composite negative electrode material is characterized in that: the surfactant is thiourea.

Technical Field

The invention relates to Sn for a potassium ion battery₄P₃/Ti₃C₂T_xA MXene composite anode material belongs to the technical field of potassium ion battery anode materials.

Background

The potassium ions can be used as current carriers to shuttle between the positive electrode material and the negative electrode material like lithium ions or sodium ions so as to complete the conversion between chemical energy and electric energy and further perform electrochemical energy storage. The potassium element has the advantages of low standard electrode potential, high resource storage amount, wide distribution and low cost, so the potassium ion battery is a novel low-cost high-performance electrochemical energy storage technology at present.

Sn as a negative electrode material of a high-performance potassium ion battery₄P₃The method is concerned by the advantages of high theoretical capacity, abundant resource reserves, low price and the like. However, Sn₄P₃Large volume change in the potassium storage process can cause rapid decay of cycling stability, and Sn₄P₃Low conductivity results in poor potassium storage rate performance, and these problems limit Sn₄P₃The material is used as a potassium storage negative electrode material.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides Sn for a potassium ion battery₄P₃/Ti₃C₂T_xThe MXene composite negative electrode material is prepared from Sn₄P₃Nanoparticles and Ti₃C₂T_xThe MXene nanosheet is prepared by electrostatic self-assembly and has excellent performanceCycle performance and rate performance.

The purpose of the invention is realized by the following technical scheme.

Sn for potassium ion battery₄P₃/Ti₃C₂T_xThe MXene composite negative electrode material is prepared by adopting an electrostatic self-assembly method, and the specific method comprises the following steps:

sn is added₄P₃Preparing uniformly dispersed suspension from nano particles, surfactant and water, and mixing Ti₃C₂T_xPreparing the MXene nanosheet and water into a solution; mixing the suspension and the solution, and then carrying out ultrasonic treatment at 0-50 ℃ for not less than 0.5h, wherein Sn is generated in the process₄P₃Assembly of nanoparticles to Ti by electrostatic interaction₃C₂T_xCollecting solid product on MXene nanosheet, washing and drying to obtain Sn₄P₃/Ti₃C₂T_xThe type MXene composite anode material.

Wherein Sn₄P₃Nanoparticles and Ti₃C₂T_xThe mass ratio of the MXene nanosheets is (1-9): 1, and the mass of the surfactant is Sn₄P₃10-20% of the mass of the nano particles, and the surfactant is at least one of thiourea, sodium dodecyl benzene sulfonate, hexadecyl ammonium bromide, P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer), Pluronic F127, Pluronic F108 and span 80.

Further, Sn is contained in the suspension₄P₃The concentration of the nano particles is 0.01 g/mL-2 g/mL; in solution, Ti₃C₂T_xThe concentration of the MXene nano-sheet is 0.1-10 mg/mL.

Further, Sn₄P₃The particle diameter of the nano-particles is 10 nm-100 nm, and Ti₃C₂T_xThe size of the MXene nano-sheet is 100 nm-5 μm.

Further, the temperature of the ultrasonic treatment is 25 ℃ to 30 ℃.

Furthermore, when the ultrasonic frequency is 40W, the ultrasonic time is 1 h-6 h.

Further, the surfactant is preferably thiourea.

Has the advantages that:

(1) sn according to the invention₄P₃/Ti₃C₂T_xIn the MXene composite anode material, Ti₃C₂T_xThe MXene can improve Sn₄P₃Conductive property and buffer Sn₄P₃Volume change during potassium storage, thereby increasing Sn₄P₃Cycle performance and rate performance during potassium storage;

(2)Ti₃C₂T_xthe MXene is easily oxidized under the heating condition to produce titanium dioxide so as to reduce the electrochemical performance, and the surfactant is adopted as the stabilizer in the application, and the Sn is mixed by simple ultrasonic₄P₃Nanoparticles and Ti₃C₂T_xSn prepared by electrostatic self-assembly of MXene nanosheets₄P₃The method has the advantages of simple operation, high efficiency, safety and low cost, and is favorable for popularizing Sn₄P₃The material is applied as a negative electrode material of a potassium ion battery.

Drawings

FIG. 1 is Sn prepared using example 2₄P₃/Ti₃C₂T_xAnd the rate performance diagram of the potassium ion battery assembled by the MXene composite negative electrode material.

FIG. 2 is Sn prepared using example 2₄P₃/Ti₃C₂T_xAnd (3) a cycle performance diagram of a potassium ion battery assembled by the MXene composite negative electrode material.

Detailed Description

The present invention is further illustrated by the following detailed description, wherein the processes are conventional unless otherwise specified, and the starting materials are commercially available from a public perspective unless otherwise specified.

In the following examples:

the potassium ion battery is assembled by the following steps: sn prepared in the example₄P₃/Ti₃C₂T_xUniformly mixing the MXene composite negative electrode material, the conductive agent Super P and the binder CMC (carboxymethyl cellulose) according to the mass ratio of 8:1:1, taking water as a solvent to prepare a mixture, mixing the mixture into slurry, coating the slurry on a copper foil, and drying and cutting the pieces to obtain a working electrode; assembling a CR2025 type button half-cell by using 1M KFSI EC/PC (1:1) as electrolyte, potassium metal as a counter electrode and a reference electrode and glass fiber as a diaphragm;

Sn₄P₃reference to nanoparticles (Sn)_4+xP₃@ Amorphous Sn-P compositions as antibodies for Sodium-Ion Batteries with Low Cost, High Capacity, Long Life, and Superior RateCapability, Weijie Li, Shu-Lei Chou, Jia-ZHao Wang, Jung Ho Kim, Hua-Kun Liu, and Shi-Xue Dou, adv.Mater.,2014,26, 4037-4042), and adjusting the Sn by controlling the ball milling time₄P₃The particle size of the nanoparticles;

Ti₃C₂T_xthe MXene Nanosheets were prepared by methods reported in the reference literature (Self-Assembly of transformation Metal Oxide Nanosheets for Fast and Stable Lithium Storage, Yi-TaoLiu, Peng Zhang, Ning Sun, Babak Anasori, Qi-ZHen Zhu, Huang Liu, Yury Gogotsi, andBi Xu, adv. Mater.,2018,1707334) and Ti of different sizes was obtained by varying the ultrasound time₃C₂T_xMXene nanosheets.