储氢材料07-Hydrogen Storage materials.PPT

Tel: 0571- 8795 1152 Email: lxchen@ Laboratory of Hydrogen Storage Materials Institute of Metallic Materials Zhejiang University Hydrogen Storage Materials Dr. Li-xin Chen Thermodynamics of Hydrogen Storage Alloys Lecture VI 1.1 Introduction 1) P-C-T curves ( P-C isotherms) Pressure ①②③There are three regions: ①region : solid solution; I . Equilibrium of M-H systems ②( + ) region: double phases －plateau; ③region: hydride phase. Composition Temperature 2) Gibbs phase rule F = C P + 2 Where : F is the freeness of system; C is the component number of system (M and H); P is the phase number. For ①region: F = C P + 2 = 2 2 + 2 = 2, so, at fixed T, all of P and C are variable; For ②( + ) region: F = C P + 2 = 2 3 + 2 = 1, so, at fixed T, only C is variable and P is invariable; For ③region: F = C P + 2 = 2 2 + 2 = 2, so, at fixed T, all of P and C are variable; I . Equilibrium of M-H systems 1.2 (or ) solid solution region Assuming that the system is ideal, and at equilibrium: I . Equilibrium of M-H systems There is a direct proportion between the solid solubility [H]s.s. and PH2 Mono-phase solid solution region is unimportant for hydrogen storage system. 1.2 (or ) solid solution region 1.3 ( + ) region 1) Van’t-Hoff equation The saturated solid solution phase absorb hydrogen and form phase hydride through phase transformation: I . Equilibrium of M-H systems 1.3 ( + ) region 1.3 ( + ) region Where : PH2 is the hydrogen equilibrium pressure (atm); ΔH is the formation enthalpy of hydride; ΔS is the entropy of a transformation; R is the gas constant ( R = 8.31441 J/mol.K ). There is a precondition: AssumeΔG ,ΔH andΔS are invariable in ( + ) region. slope ΔH As 1/T 0, intercept ΔS 1.3 ( + ) region 0 Relations between desorption pressure and temperature of various metal hydrides 1.3 ( + ) region 2) Some key factors: (i) ΔS : It is fairly independent of many metals or compounds. 1.3 ( + ) region Commonly, ΔS = –125 25 J/mol.K = –30 6 cal/mol.K 1.3 ( + )