Hard carbon is regarded as one of the most promising anode materials for sodium-ion battery. However, the ash content of the hard carbon anode inherited from the precursor have several negative impacts on the electrochemical performance of hard carbon. The traditional method utilizes strong inorganic acid washing to reduce the ash content of hard carbon. However, this method results in heavy environment pressure and safety hazards. Therefore, it’s necessary to exploring an alternative ash content removal method which is safer and environment friendly. This project develops an environmentally friendly approach to remove ash from hard carbon by using acetic acid. This approach effectively reduces the ash content and enhances the electrochemical performance of the hard carbon anode. The ash content of hard carbon decrease from 1.57 wt% to 0.655 wt% after the 4 mol /L acetic acid treatment. The two-step treatment process also studied in this project and shows a better ash removal ability than one-step treatment process. The ash content of 4 mol /L acetic acid and 20 wt% KOH only 0.28 wt%. Furthermore, the electrochemical performance of the two- step treated hard carbon exhibits notable improvements, including enhanced initial Columbic efficiency (from 84.53% to 88.11%), reversible capacity (from 244.2 mAh g-1 to 280.8 mAh g-1). The long cycle performance of chemical treated hard carbon anode need further investigations in future studies. / Hårt kol anses vara ett av de mest lovande anodmaterialen för natriumjonbatterier. Askhalten i den hårda kolanoden som ärvts från prekursorn har dock flera negativa effekter på den elektrokemiska prestandan hos hårt kol. Den traditionella metoden använder stark oorganisk syratvättning för att minska askhalten av hårt kol. Denna metod resulterar dock i hög miljöbelastning och säkerhetsrisker. Därför är det nödvändigt att utforska en alternativ metod för borttagning av askinnehåll som är säkrare och miljövänligare. Detta projekt utvecklar ett miljövänligt tillvägagångssätt för att ta bort aska från hårt kol genom att använda ättiksyra. Detta tillvägagångssätt reducerar effektivt askinnehållet och förbättrar den elektrokemiska prestandan hos den hårda kolanoden. Askhalten i hårt kol minskar från 1,57 viktprocent till 0,655 viktprocent efter 4 mol/L ättiksyrabehandlingen. Tvåstegsbehandlingsprocessen studerades också i detta projekt och visar en bättre förmåga att avlägsna aska än enstegsbehandling. Askhalten av 4 mol/L ättiksyra och 20 viktprocent KOH är endast 0,28 viktprocent. Dessutom uppvisar den elektrokemiska prestandan hos det tvåstegsbehandlade hårda kolet anmärkningsvärda förbättringar, inklusive förbättrad initial Columbic effektivitet (från 84,53 % till 88,11 %), reversibel kapacitet (från 244,2 mAh g-1 till 280,8 mAh g-1). Den långa cykelprestandan hos kemiskt behandlad hård kolanod behöver ytterligare undersökningar i framtida

Ce mémoire est consacré à l’étude des composites à base de phosphates de type NASICON comme matériaux d’électrode pour batteries sodium-ion : Na1+xFexTi2-x(PO4)3/C et Na1+xFexSn2-x(PO4)3/C avec 0 ≤ x ≤ 1. Ces composites ont été synthétisés par voie solide suivie d’une pyrolyse avec le saccharose. Ils sont constitués de particules ayant une porosité élevée et enrobées par du carbone conférant à l’électrode une bonne conductivité ionique et électronique. Les mécanismes réactionnels se produisant lors des cycles de charge-décharge ont été analysés en mode operando par diffraction des rayons X, spectroscopies Mössbauer du 57Fe et de 119Sn et spectroscopie d’absorption X. Pour les composites fer-titane, ces mécanismes sont essentiellement basés sur la diffusion des ions Na+ dans les canaux des phases cristallisées avec changements d’état d’oxydation des métaux. Pour les composites fer-étain, les mécanismes sont plus complexes incluant insertion, conversion conduisant à la destruction des phases NASICON, puis formation d’alliages NaxSn. Les meilleures performances électrochimiques ont été obtenues pour Na1,5Fe0,5Ti1,5(PO4)3/C avec un potentiel de fonctionnement de 2,2 V vs Na+/Na0. Même si ces deux familles de matériaux peuvent être utilisées à plus bas potentiel, les performances doivent être améliorées pour envisager leur application comme électrode négative. / This thesis is devoted to the study of phosphate based composites with NASICON type structure, that are used as electrode materials for sodium-ion batteries: Na1+xFexTi2-x (PO4)3/C et Na1+xFexSn2-x(PO4)3/C with 0 ≤ x ≤ 1. These composites were synthesized by solid state route followed by a pyrolysis reaction with sucrose. They consist of particles having high porosity and coated with carbon giving to the electrode good ionic and electronic conductivity. The reaction mechanisms occurring during charge-discharge cycles were analyzed in operando mode, by X-ray diffraction, 57Fe and 119Sn Mössbauer spectroscopies and X-ray absorption spectroscopy. For the iron-titanium composites, the mechanisms are essentially based on the diffusion of Na+ in the channels of the crystalline phases with changes of transition metal oxidation state. For iron-tin composites, the mechanisms are more complex including insertion, conversion leading to the destruction of the NASICON phases and then reversible formation of NaxSn alloys. The best electrochemical performances were obtained for Na1,5Fe0,5Ti1,5(PO4)3/C with an operating potential of 2.2 V vs. Na+/Na0. Although these two types of materials can be used at lower potential, the performances must be improved to consider their application as the negative electrode.

This diploma thesis deals with the description of individual types of batteries. The first part is focused to primary and secondary batteries, materials for their positive and negative electrodes with a focus on lithium-ion batteries and their changes over time. The next section focuses on a more detailed description of sodium-ion batteries, used electrode materials and to their problems. Practical part is focesed to preparing of electrode materials and to completing of measuring electrochemical cell and to discribing of measuring methodes and to evaluation of measured data.

In this thesis, a Sb/C composite electrode for sodium-ion batteries isprepared by a simple high energy ball milling and calenderingmethod. The prepared Sb/C composite electrode was assembled in ahalf-cell and symmetrical cell setups in order to perform avariety of electrochemical measurements.The composite electrode showed a reversible specific capacity of595 mAh/g, at a discharge/charge current rate of 15 mA/g. Theelectrode also showed a relatively good performance (compared toprevious studies) of 95% capacity retention after more than 100cycles, at a higher discharge/charge current rate of 60 mA/g. Theelectrode furthermore showed excellent self-dischargecharacteristics, in pause tests implemented over 200 hours (overeight days), which underlined the electrode materials good shelflife properties. A series of Sb/C symmetrical cells assembledthrough-out the project, furthermore, highlighted the stability ofthe solid electrolyte interface (SEI) layer formed on the Sb/Ccomposite electrode during cycling. Scanning electron microscopy(SEM) and Energy-dispersive X-ray spectroscopy (EDS) were used tocharacterize the surface morphology and composition of the Sb/Celectrode, respectively.A non-milled and milled (12 hours) graphite electrodes were alsoprepared for reference and comparison. The milled graphite matrixelectrode provided a reversible capacity of 95 mAhg-1 and acoulombic efficiency (CE) of 99% in over 250 cycles, at a currentrate of 30 mA/g. Milled and non-milled graphite were characterizedwith SEM and Raman spectroscopy, to help have a fundamentalunderstanding of the particle size and material phase,respectively.