Is the pyrolysis of tetrachloroaluminate(III) anion possible? Wikipedia says that lithium tetrafluoroborate decomposes to lithium fluoride and boron trifluoride when heated. Does the same hold for sodium tetrachloroaluminate (all anhydrous) as well?
Unlike lithium tetrafluoroborate $\ce{LiBF4},$ sodium tetrachloroaluminate $\ce{NaAlCl4}$ doesn't decompose upon melting, and doesn't show any signs of decomposition or phase transition up to approx. $\pu{800 °C}$ [1, p. 688]:


FIGURE 3. Calculated $(\ce{NaCl + AlCl3})$ phase diagram at $\pu{0.1 MPa}$ (dotted lines are liquid–liquid miscibility gap boundary and monotectic at $P &gt; \pu{0.1 MPa}).$

Molten sodium tetrachloroaluminate is used as electrolyte in ZEBRA batteries with normal operating temperature range of $\pu{270–350 °C}.$
References

Robelin, C.; Chartrand, P.; Pelton, A. D. Thermodynamic Evaluation and Optimization of the $(\ce{NaCl + KCl + AlCl3})$ System. The Journal of Chemical Thermodynamics 2004, 36 (8), 683–699. https://doi.org/10.1016/j.jct.2004.04.011.