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Li/SF6燃烧反应路径及机理研究

温伯尧 王起源 孙成珍 宗潇 骆政园 白博峰

温伯尧, 王起源, 孙成珍, 等. Li/SF6燃烧反应路径及机理研究[J]. 水下无人系统学报, 2023, 31(6): 856-863 doi: 10.11993/j.issn.2096-3920.2023-0012
引用本文: 温伯尧, 王起源, 孙成珍, 等. Li/SF6燃烧反应路径及机理研究[J]. 水下无人系统学报, 2023, 31(6): 856-863 doi: 10.11993/j.issn.2096-3920.2023-0012
WEN Boyao, WANG Qiyuan, SUN Chengzhen, ZONG Xiao, LUO Zhengyuan, BAI Bofeng. Reaction Path and Mechanisms of Li/SF6 Combustion[J]. Journal of Unmanned Undersea Systems, 2023, 31(6): 856-863. doi: 10.11993/j.issn.2096-3920.2023-0012
Citation: WEN Boyao, WANG Qiyuan, SUN Chengzhen, ZONG Xiao, LUO Zhengyuan, BAI Bofeng. Reaction Path and Mechanisms of Li/SF6 Combustion[J]. Journal of Unmanned Undersea Systems, 2023, 31(6): 856-863. doi: 10.11993/j.issn.2096-3920.2023-0012

Li/SF6燃烧反应路径及机理研究

doi: 10.11993/j.issn.2096-3920.2023-0012
基金项目: 基础加强计划项目资助(No. 202******D)
详细信息
    作者简介:

    温伯尧(1991-), 男, 博士, 助理教授, 主要研究方向为反应分子模拟

    通讯作者:

    白博峰(1971-), 男, 博士, 教授, 主要研究方向为多相流动与传热

  • 中图分类号: TJ630.32; U677

Reaction Path and Mechanisms of Li/SF6 Combustion

  • 摘要: 揭示Li/SF6燃烧反应机理是构建燃烧动力学模型、高效组织燃烧过程的关键基础, 但是现有实验测试以及宏观模拟方法难以揭示Li/SF6燃烧的分步反应机理。文中结合ReaxFF反应分子模拟和第一性原理计算方法研究了Li和SF6的微观反应过程, 分析了反应物和产物组分的动态演化特性, 获得了主要反应路径及其反应热。研究发现, 反应的起始过程为SF6分子S-F键的断裂, LiF是反应初始时刻的主要产物; 随着反应的进行, 多余的Li形成Li2并与S成键形成Li2S; 反应后期, 2个LiF分子结合反应形成Li2F2。基于反应物浓度变化获得了Li和SF6的总反应速率, 结果表明, 总反应速率与反应物浓度、反应物比例呈正相关关系, 这是因为反应物浓度或比例的增大均会导致反应物分子之间碰撞概率的增加; 初始温度对总反应速率的影响则相对较小。结合第一性原理得到的反应物焓值, 计算各个分步反应的放热量, 进而得到Li/SF6的反应热为−2216.7 kJ/mol, 与理论值及实验值均接近。研究结果为复杂燃烧反应的分步反应机理揭示和反应热计算提供了有效途径。

     

  • 图  1  Li/SF6反应的分子动力学仿真模型

    Figure  1.  Molecular dynamics simulation model of Li/SF6 reaction

    图  2  Li/SF6反应前后系统构象及体系中组分分子数随时间变化情况

    Figure  2.  Conformation of Li/SF6 system before and after reaction and variation of molecule number with time

    图  3  不同初始温度下Li和LiF分子数随仿真时间变化情况

    Figure  3.  Variation of Li and LiF molecule number with simulation time under different initial temperatures

    图  4  不同反应物浓度下Li、F和LiF分子数比例随时间变化情况

    Figure  4.  Variation of proportion of Li, F, and LiF molecule number with time under different reactant con- centrations

    图  5  不同反应物比例下Li和LiF分子数占比随时间变化情况

    Figure  5.  Variation of proportion of Li and LiF molecule number with time under different reactant pro- portions

    图  6  不同反应条件下反应速率随时间变化情况

    Figure  6.  Variation of reaction rate with time under different reaction conditions

    图  7  反应过程中反应物的能量折线图及分子示意图

    Figure  7.  Energy line diagram and molecular diagram of reactants in reaction process

    表  1  Li/SF6反应仿真工况

    Table  1.   Simulation conditions of Li/SF6 reaction

    控制变量变量值
    Li/SF6分子数64/8
    128/16
    256/32
    Li/SF6比例
    (SF6分子数为32)
    Li∶SF6=1∶1
    Li∶SF6=2∶1
    Li∶SF6=8∶1
    Li∶SF6=16∶1
    反应初始温度/K500
    600
    700
    800
    900
    下载: 导出CSV

    表  2  Li/SF6反应过程中反应物/产物焓值计算结果

    Table  2.   Calculation results of reactant/product enthalpy value during Li/SF6 reaction

    反应物
    /产物
    Etotal
    /(kcal/mol)
    Htotal/(kcal/mol)H=Etotal+Htotal
    /(kcal/mol)
    T=500 K
    SF6−625904.8622.10−625882.90
    LiF−67435.934.96−67435.93
    2Li−9400.094.54−9395.07
    Li2S−259359.057.48−259352.77
    2LiF−134872.489.89−134863.07
    Li2F2−134931.4611.00−134920.80
    下载: 导出CSV
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出版历程
  • 收稿日期:  2023-02-08
  • 修回日期:  2023-03-13
  • 录用日期:  2023-11-15
  • 网络出版日期:  2023-11-20

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