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[资源] Polyanionic Frameworks as Electrode Materials for Rechargeable Batteries

1. Introduction: From Oxides to Ionically Conducting Polyanionic Frameworks as Positive Electrodes in Li Batteries
2. The Early Days: The NASICON and Anti-NASICON Structures Used as Model Frameworks2.1. Structural Considerations
2.2. The Inductive Effect: Tuning the Mn+/M(n–1)+ Redox Couple in the NASICON Structure by Changing the Chemical Nature of the XO4n– Groups
2.3. Relative Positions of Various Mn+/M(n–1)+ Redox Couples (M = Fe, Ti, V, Nb) in NASICON-type Phosphates2.3.1. Position of the Ti4+/Ti3+ Couple versus Li+/Li or Na+/Na
2.3.2. Position of the Fe3+/Fe2+ Couple versus Li+/Li or Na+/Na
2.3.3. Position of the Vn+/V(n–1)+ Couples versus Li+/Li or Na+/Na

2.4. Complex Redox Phenomena in Anti-NASICON Compositions LixM2(PO4)3 (0 < x < 5 ; M = Fe, V)2.4.1. Li+ Insertion into Monoclinic Fe2(SO4)3, Li3Fe2(PO4)3, and Li3Fe2(AsO4)3
2.4.2. Li+ Insertion/Extraction into Monoclinic Li3V2(PO4)3

3. LiMPO4 Compositions Based on the Olivine Structure: Fifteen Years of Great Achievements3.1. The Early Days: From an Academic Curiosity to First Industrial Realizations
3.2. A Myriad of Synthesis Routes Developed for Optimal Electrochemical Response of LiMPO4 Powders, Industrial Process Ability, and Cost Reduction3.2.1. Solid-State Syntheses
3.2.2. Solution-Based Syntheses
3.2.3. Carbon Coating and Purity Control of LiFePO4

3.3. The Highly Insulating LiMnPO4
3.4. Substitutions of Mn and/or Co for Fe in LiFePO4
3.5. Intrinsic Physicochemical Properties of LiFePO4 and Mechanism of Li+ Extraction3.5.1. Crystal Structure, Defects, e– Transport, Li+ Diffusion
3.5.2. Reactivity with Moisture and/or Air
3.5.3. Mechanism

4. Alternative Polyanionic Structures and Compositions: Hydrated Phosphates, Diphosphates, Alluaudites, Silicates, and Borates4.1. Fe3+/Fe2+ Couple in Amorphous or Crystalline Iron Phosphates: FePO4·nH2O
4.2. V4+/V3+, Ti4+/Ti3+, and Fe3+/Fe2+ Redox Couples in Diphosphates and Diarsenates LixMX2O7 (M = Fe, V, Ti; X = P, As) and Fe4(P2O7)3·nH2O
4.3. Transition Metal Silicates Li2MSiO4 (M = Fe, Mn, Co)
4.4. Na3Fe3(PO4)4 and Alluaudite Phases
4.5. Lithiated Transition Metal Borates

5. Oxy-, Hydroxy-, Fluoro-phosphates and -sulfates: New Promising Electrode Materials5.1. V5+/V4+ and V4+/V3+ Couples in LixVOXO4 (X = P, As)
5.2. The Nb5+/Nb4+ and Ti4+/Ti3+ Couples in LixMOXO4 (X = S, P, Si)
5.3. V4+/V3+ and V3+/V2+ Couples in NaxVPO4F and LixVPO4F
5.4. Fe3+/Fe2+ and Ti4+/Ti3+ Couples in LiFeIIIPO4F and LiTiIIIPO4F
5.5. Fe3+/Fe2+ Couple in A2MPO4F (A = Li, Na; M = Fe, Mn)
5.6. V3+/V4+ Redox Couple in A3V2(PO4)2F3 and A5V(PO4)2F2
5.7. Fe3+/Fe2+ in Tavorite-like LiFeIISO4F and LiFeIIIPO4OH. Extension to the Triplite Family

6. Conclusions and Future Outlook

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附件 1 : Polyanionic_(Phosphates,_Silicates,_Sulfates)_Frameworks_as_Electrode_Materials_for_Rechargeable_Li_(or_Na)_Batteries.pdf

2013-06-07 20:23:02, 28.4 M