Toward all organic Li-ion batteries Study of by chd21292

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									                                                    Toward all organic Li-ion batteries
                                                     Study of polycarbonyl materials
                                                   J. Geng, M. Armand, J-P. Bonnet, J-M. Tarascon, F. Dolhem, P. Poizot

                                                 Laboratoire de Réactivité et Chimie des Solides, UMR 6007 & Laboratoire des Glucides, UMR 6219,
                                                            Université de Picardie Jules Verne, 33 rue Saint-Leu, 80039 Amiens, France.


                                                                                  joaquin.geng@u-picardie.fr
Main goal :                               Synthesis, characterization and study of the electrochemical properties of
                                          organic compounds, able to act as electrodes for Li-ion batteries.

                                Load                          Energy storage (using batteries) constitutes one of the main columns to renewable energies
                                                           and make part of our well-being (portable electronic devices, hybrid electric vehicules (HEV) and
                    Non-aqueous
  +               Liquid electrolyte               -       electric vehicules.(EV)
                                    Li+                       Li-ion batteries constitute an attractive technology for electricity storage. However they are
                                                           based on the use of non renewable electroactive materials (e.g. LiCoO2, LiNiO2, LiFePO4).
                                    Li+                       The life cycle analysis of such inorganic-based electrode materials (extraction, processing and
                                                           recycling) shows a negative impact on the environment.
                                                              A more “sustainable” Li-ion battery could be foreseen in the synthesis of new active
   Positive                                 Negative
  electrode                                 electrode      materials produced from organic renewable resources and via eco-efficient processes1,2 .


                                          Piperazine tetrones                                                               Diquinoxalino phenazine
  Use of carbonyl (C=O) groups as RedOx centers and                                                                       Use of pyrazine ring as a RedOx center.
influence by the incorporation of nitrogen atom in the ring.
                                                                                                                                                           3.2
  Synthesis of diallyl-piperazine tetrone3 (AP) and oligomer
(p-AP) via Acyclic Diene Metahetsis (ADMET).                                                                                                                    3


                                                                                                                            N
                              AP                                           p-AP                                                                            2.8
                                                                                                                                      0
                                                                                                                                       E / V vs. Li /Li




           O                        O                                  O      O
                                                                                                                  N               N
                                                                                                                                                           2.6
                                                                                                                                      +




                                                    [M]                                                                                                    2.4
           N                        N                                  N      N             + C 2H4
                                                                                                                  N               N
                                                                                                                                                           2.2
                                                                       O      O         n                                   N
           O                        O
                                                                                                                                                                2
[M] : Grubbs 1st generation; Grubbs 2nd generation; Hoveyda Grubbs 2nd generation;
WCl6/SnBu4/AcOPr. Conditions : inert atmosphere; anhydrous solvents (1,2-DCE;                                                                              1.8
toluene;1,2,4-TCB); Temparature (60-110°C); time of reaction (4 – 24h); 2 – 5%mol/mol                                                                               0   20        40           60     80     100
catalyst / substrate.                                                                                                                                                              Q (mA.h/g)
                              3.2                                                                       POE cell type : Li metal disc as negative electrode, a POE/LiClO4 as separator, Powder
                                                                                                        hand milled: 50%active material + 10%carbon Ketjen Black + 40%POE(100000 Mw).       5-
                               3                                                                        15 of active material is used. Electron exchange rate 1e- /10h.


                              2.8
           0
            E/ V vs. Li /Li




                                                                                                               Tetrahydroxy-1,4-quinone derivatives
           +




                              2.6


                              2.4                                                                               Use of carbonyl (C=O) groups as RedOx centers.
                                                                                                                                                           4
                              2.2


                               2
                                                                                                                      O
                                          AP                                                                                                              3.5
                                          p-AP
                                                                                                                                      0




                                                                                                       MeO                      OMe
                                                                                                                                       E / V vs. Li /Li




                              1.8
                                                                                                                                      +




                                    0        50            100       150          200
                                                                                                                                                           3
                                                        Q (mA.h/g)
      Swagelock type cell : Li metal disc as negative electrode, a Whatmann GF/D as
                                                                                                       MeO                      OMe
      separator, saturated in LP30 as electrolyte . Powder hand milled: active material +                                                                 2.5
       50%(w/w) carbon SP. 10-12 of powder is used. Electron exchange rate 1e- /10h.
                                                                                                                      O

                                                                                                                                                           2
Conclusions and perspectives                                                                                                                                    0            50
                                                                                                                                                                                  Q (mA.h/g)
                                                                                                                                                                                                100        150

  Carbonyl RedOx potential can be tuned.                                                               Swagelock type cell : Li metal disc as negative electrode, a Whatmann GF/D as
  Materials tested display low polarization and good average                                           separator, saturated in LP30 as electrolyte . Powder hand milled: active material +
                                                                                                       50%(w/w) carbon SP. 10-12 of powder is used. Electron exchange rate 1e- /10h.
potential.
  Main drawback of organic compounds is the solubility in the
electrolyte, but it can be solved by increasing the molecular                                         1.H. Chen, M. Armand, G. Demailly, F. Dolhem, P. Poizot,
weight (polymers) or increasing the negative charge (lithium                                          J-M. Tarascon, ChemSusChem, 4, 2008, 348-355.
salts).                                                                                               2. H. Chen, et al. J. Am. Chem. Soc., 2009, 131 (25), pp 8984–8988
                                                                                                      3.T. Umemoto; US 6737193 B3 ; May 2004.

								
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