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Nanomaterials 2022, 12, 3018 as a sodium-ion battery cathode material under constant current 13 mAg−1, voltage win- dow 1.5–4.3 V test conditions. Figure 4a is a constant current cycle curve of the thin film deposited under different oxygen partial pressures. The first discharge-specific capacities of the 35 Pa, 50 Pa, and 65 Pa thin film electrodes were 163.9 mAh g−1, 171.1 mAh g−1, and 175.3 mAh g−1, respectively. It can be seen that, for the samples grown under 35 Pa and 50 5 of 7 creases. After 30 cycles, the capacity retention rate was only 48% (78.2 mAh g−1) and 63% (108.0 mAh g−1) of the initial values, respectively. It may be that under the lower oxygen opxyregsesnurper, ethsseucrey,sthalelincritystoafltlihneitfyilmofisthneotfiplmerfiescnt,otxpygerefnecdte,foicxieyngceyncdanefifcoiremncsytrucacntufroalrm stdruefcetcutrsa,lthdefpeacrttsi,cltehseapraeritrircelegsualarre,iarnredgtuhleari,natenrdfatcheeisinbtelurrfarecde,isrebslulrtirnegd,inresluolwtinsgodiniusmlow soiodniukmineiotincsk. iWnehteincst.hWe ohxeyngtehneporxeyssguerne pgreasdsuarlelygirnacdreuaslelys tionc6r5eaPsae, sthtoe o6x5yPgae,nthdefoexctyigsen dienfhecibtitsedin,htihbeitecrdy,stthaellicnriytystaislliennithyaniscedn,htahnececdry,sthtaelcprlyasntealsplacniengspiascincgreisasiendcr,eansdedt,haend ththeitchkinceksnseossf othfethseodsoiudmiumioniolnaylaeryeisr iaslsaolsioncinrecareseadse,dw,hwichhicchancaennehnahnacnectehethdeedbelobclokcinkging Pa, the discharge-specific capacitance decreases rapidly when the number of cycles in- kinetics of sodium ions. The specific capacity retention rate of the 65 Pa thin film electrode kinetics of sodium ions. The specific capacity retention rate of the 65 Pa thin film electrode is 91%, which is much higher than that of the 35 Pa and 50 Pa thin film electrodes, showing is 91%, which is much higher than that of the 35 Pa and 50 Pa thin film electrodes, showing excellent cycle stability. excellent cycle stability. Figure 4. (a) cycling curves of NNMO thin film electrode materials at different oxygen pressures; Figure 4. (a) cycling curves of NNMO thin film electrode materials at different oxygen pressures; −1 (b) first charge/discharge curves (constant current 13 mA g −, v1oltage window 1.5–4.3 V). (b) first charge/discharge curves (constant current 13 mA g , voltage window 1.5–4.3 V). The first charge–discharge curve of the NNMO thin film electrode is shown in Figure The first charge–discharge curve of the NNMO thin film electrode is shown in Figure 4b. 4b. When the partial pressure of oxygen is 35 Pa and 50 Pa, the curve is smooth and sloped, When the partial pressure of oxygen is 35 Pa and 50 Pa, the curve is smooth and sloped, and and the voltage platform is almost invisible. It may be that the hypoxia and incomplete the voltage platform is almost invisible. It may be that the hypoxia and incomplete crystalline crystalline state of the thin film material under low oxygen pressure make it difficult to state of the thin film material under low oxygen pressure make it difficult to react redox or react redox or phase change during charge–discharge so that no charge–discharge plat- phase change during charge–discharge so that no charge–discharge platform appears. With form appears. With the increase of oxygen partial pressure, it can replenish the oxygen the increase of oxygen partial pressure, it can replenish the oxygen content that is missing due content that is missing due to high temperature sputtering during film growth, and the to high temperature sputtering during film growth, and the crystallinity is also improved. crystallinity is also improved. When the partial pressure of oxygen is increased to 65 Pa, When the partial pressure of oxygen is increased to 65 Pa, three obvious voltage platforms three obvious voltage platforms appear on the charge–discharge curve, located around appear on the charge–discharge curve, located around 4.0 V, 3.5 V, and 2.0 V, respectively. 4.0 V, 3.5 V, and 2.0 V, respectively. The voltage platform at 4.0 V here is caused by the The voltage platform at 4.0 V here is caused by the P2-O2 phase transition, and the voltage P2-O2 phase transition, and the voltage platform at 3.5 V and 2.0 indicates that the two platform at 3.5 V and 2.0 indicates that the two pairs of redox reactions12 have occurred, pairs of redox reactions12 have occurred, Ni2+/Ni4+ and Mn3+/Mn4+, respectively [20,21]. Ni2+/Ni4+ and Mn3+/Mn4+, respectively [20,21]. Figure 5 compares the discharge rate characteristics of the NNMO thin film electrode Figure 5 compares the discharge rate characteristics of the NNMO thin film electrode under different oxygen partial pressures, and the charge and discharge voltage range and under different oxygen partial pressures, and the charge and discharge voltage range and charging current density are the same as the previous parameter settings. Obviously, in a charging current density are the same as the previous parameter settings. Obviously, in a lower lower oxygen partial pressure environment (35 Pa and 50 Pa), the thin film material is in oxygen partial pressure environment (35 Pa and 50 Pa), the thin film material is in a mixed a mixed state of crystalline and amorphous state, and this incomplete crystallization state of crystalline and amorphous state, and this incomplete crystallization during charge– discharge will hinder the diffusion and migration rate of sodium ions and electrons, so the first discharge specific capacity is low, and the decay is faster with the increase of discharge current density. When the partial pressure of oxygen is increased to 65 Pa, the crystallinity of the thin film material is improved, the particle size is uniform, and the discharge-specific capacity and capacity retention rate are improved. Although it also shows rapid decay at higher current densities above 520 mA g−1, when the current density is restored to 130 mA g−1, its discharge-specific capacity can be maintained at about 70%, indicating that the thin film cathode material can withstand high current charge and discharge.PDF Image | xcimer Laser-Deposited Na Film Cathode Sodium-Ion Battery
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