Citation: Li-Jun ZHAI, Ru TONG, Ci-Bin WANG, Meng-Jie SHI, Ya-Nan MO, Wen-Kai CHE, Yu-Lan NIU, Tuo-Ping HU. Structural Diversity and Magnetic Properties of Two Coordination Polymers Based on 6-(3, 5-Dicarboxylphenyl)nicotinic Acid[J]. Chinese Journal of Structural Chemistry, ;2021, 40(12): 1687-1695. doi: 10.14102/j.cnki.0254-5861.2011-3354 shu

Structural Diversity and Magnetic Properties of Two Coordination Polymers Based on 6-(3, 5-Dicarboxylphenyl)nicotinic Acid

  • Corresponding author: Yu-Lan NIU, niuyl@tit.edu.cn Tuo-Ping HU, hutuoping@nuc.edu.cn
  • Received Date: 6 September 2021
    Accepted Date: 8 November 2021

    Fund Project: the NSF of China 21676258the Scientific and Technologial Innovation Project of Shanxi Province 2020L0647Innovation and Entrepreneurship Project of Taiyuan Institute of Technology S202114101015

Figures(5)

  • Two new coordination polymers (Co-CPs), namely {[Co8(DCPN)4(1, 2-bimb)4(μ3-OH)4]· (CH3CN)0.5(H2O)2}n (1) and {[Co2(DCPN)(1, 3-bimb)(μ3-OH)]·H2O}n (2), where H3DCPN = 6-(3, 5-dicarboxyl-phenyl)nicotinic acid, 1, 2-bimb = 1, 2-bis(imidazole-1-methyl)benzene and 1, 3-bimb = 1, 3-bis(imidazole-1-methyl)benzene, have been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction analysis, elemental analysis (EA), infrared (IR) analysis, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). The structural analysis indicated that 1 is a 2D structure based on two different [Co4(DCPN)2(μ3-OH)2]n SBUs, and 2 is a 3D framework based on [Co4(DCPN)2(μ3-OH)2] SBUs. In addition, the magnetic measurements showed that 1 and 2 have antiferromagnetic interactions between adjacent Co(II) ions. The slight difference of magnetic properties between 1 and 2 may be attributed to their different structures formed during the assembly process.
  • Lithium-ion batteries (LIBs) have become a vital component in mobile electronic devices and electric vehicles[1]. Recently, research efforts have been devoted to developing next generation LIBs with high capacity and good cycling performance. The high price and toxicity of cobalt also increase the cost of using LiCoO2 cathode and its recovery. Therefore, researchers developed the LiNixCoyMn1-x-yO2 cathode material to overcome the disadvantages of LiCoO2[7]. LiNixCoyMn1-x-yO2 possesses the same layered structure (R-3m) as LiCoO2, but its actual capacity reaches 250 mAh·g-1. The specific capacity of LiNixCoyMn1-x-yO2 is related to its nickel content. Generally, increasing nickel content leads to higher discharge specific capacity[8, 9].

    In the LiNixCoyMn1-x-yO2 cathode family, materials with x < 0.6 have been successfully commercialized, such as NCM111 (LiNi0.33Co0.33Mn0.33O2) and NCM522 (LiNi0.5Co0.25Mn0.25O2). This is because of their simple preparation process, which does not require inert atmosphere or specially designed sintering equipment. On the other hand, the low nickel content also leads to their relatively low specific capacity (less than 180 mAh·g-1), which cannot meet the requirement of high capacity LIBs. The specific capacity of LiNixCoyMn1-x-yO2 with x > 0.6 is more than 200 mAh·g-1. However, the commercialization of nickel-rich cathode material is hindered by its complex preparation process, including strict requirements on the preparation environment and process parameters[10-12].

    As a new preparation technology, spray drying has been widely applied in materials synthesis for fuel cell[13], photocatalyst[14], sensors, and biological imaging[15, 16]. Recently, researchers have found that spray drying technology has unique advantages in synthesizing electrode materials[17]. This is mainly because of three reasons: (1) the spray drying method can mix different reaction precursors homogeneously; (2) the void space of secondary particles can be controlled to provide high rate charge/discharge capabilities; (3) the spray drying method can precisely control the size of product particles while is capable of producing hollow particles. These advantages are highly desirable for tuning the electrochemical performance of electrode materials. Moreover, spray drying is a continuous synthetic technology, which can be adopted in mass production with relatively simple equipment. In recent years, spray drying technology has been gradually adopted in producing the nickel-rich LiNixCoyMn1-x-yO2 cathode materials. It is likely that the processing parameters of spray drying processes have a decisive influence on the performance of cathode materials. Herein, we study the effect of spray drying flow-rate on the structural and electrochemical properties of LiNi0.8Co0.1Mn0.1O2 (NCM811) LIB cathode material and determined the optimal flow-rate based on our synthetic system. We seek to provide guidance for other researchers who are using spray drying method to produce the nickel-rich NCM811 cathode materials.

    The spray drying precursor was produced by mixing Ni0.8Co0.1Mn0.1(OH)2 (Beijing Dangsheng Materials) powder with LiOH (Aladdin Reagent Co., 5 wt% excess from the stoichiometric amount) by ball milling. The mixture was then sprayed to form a dry powder at the flow-rate of 200, 250, 300, and 400 mL·min-1. The spray drying temperature was set to 200 ℃. The obtained powder sample was sintered in a muffle furnace under 550 ℃ for 5 h and then under 750 ℃ for 10 h. The sintering process was done in air. The prepared samples were named as 200NCM811, 250NCM811, 300NCM811 and 400NCM811, with the first three digits representing the spray drying flow-rate in mL·min-1.

    The contents of Ni, Co, and Mn in different samples were determined by inductive coupled plasma emission spectrometer (ICP, Ultima 2). The crystal structure of the samples was identified by powder X-ray diffraction (XRD) in the 2θ range from 10° to 80° with a scan rate of 5 º·min-1 on a Rigaku MiniFlex 600 diffractometer equipped with Cu- radiation. The oxidation state and composition of surface elements were determined by X-ray photoelectron spectroscopy (XPS, ESCALAB 250Xi). The morphology of the obtained samples was characterized by scanning electron microscopy (SEM, SU-8010).

    The electrochemical performance of the electrode materials was characterized using CR2025 coin-type cells. The preparation process of electrode is as follows: 80 wt.% active material, 10 wt.% super-P, and 10 wt.% polyvinylidene fluoride (PVDF) were mixed with N-methyl-2-pyrrolidone (as solvent) to form a homogeneous slurry. The slurry was coated on a piece of aluminum foil using doctor blade method and dried at 120 ℃ for 12 h in vacuum. After drying, the electrode was cut into circular shape and pressed under 10-MPa pressure. The coin-type cells were assembled in an Ar filled glove box with a lithium metal plate as the counterelectrode and LBC3033 (Shenzhen Xinyubang Science and Technology) as the electrolyte solution.

    The constant current charge-discharge test and cycling performance test were done on a Neware battery test system at different current densities in the voltage range of 3.0~4.3 V. The cyclic voltammetry (CV, 3.0~4.3 V vs. Li+/Li, 0.2 mV·s-1) and electrochemical impedance spectroscopy (EIS, 0.01~10, 000 Hz, 5 mV) were carried out with a Princeton electrochemical workstation.

    The XRD patterns of the NCM811 materials prepared at different spray drying flow-rates are presented in Fig. 1. The unit cell parameters are calculated and summarized in Table 1, which indicate that all samples possess typical α-NaFeO2 layer structure. The splitting of (108)/(110) and (006)/(012) diffraction peaks shows that the obtained materials belong to the typical hexagonal layered structure[18-20]. In Table 1, the a-axis of the four unit cells appears to be the same (2.87 ± 0.01 Å), but the c-axis is quite different (varying from 14.1960 to 14.3644 Å). This may be caused by the fact that the ionic radius of Ni2+ (0.69 Å) is similar to that of Li+ (0.76 Å) and therefore the Li+ site in the structure may be occupied by Ni2+, resulting in the mixed occupancy of two cations at the lithium site[21, 22]. The increasing cation mixing could decrease the structure stability of NCM811, which is typically reflected by the capacity decay during charge-discharge cycles[8]. The I(003)/I(104) ratio from the XRD spectra is often used as an indicator of the degree of cation mixing in NCM811. Higher value of I(003)/I(104) points to the lower cation mixing in the NCM811 materials. Based on Fig. 1, we observe that the I(003)/I(104) of 250NCM811 is the largest[23, 24], indicating that 250NCM811 has the lowest level of cation mixing in all four samples. Therefore, the lattice structure of 250NCM811 is likely the most stable, and it may exhibit better electrochemical properties. The elemental composition of Ni, Co and Mn in different NCM811 cathode materials was characterized by ICP elemental analysis. The results (Table 2) reveal that the ratio between Ni, Co and Mn in the four NCM811 materials varies little from 8:1:1. This indicates that the different spray drying flow-rates do not have a significant effect on the contents of Ni, Co, and Mn, which ensures the consistent elemental composition in all samples.

    Figure 1

    Figure 1.  X-ray diffraction patterns of different NCM811 materials prepared at different spray drying flow-rates

    Table 1

    Table 1.  Lattice Parameters of Different NCM811 Materials Prepared at Different Spray Drying Flow-rates
    DownLoad: CSV
    Samples a (Å) c (Å) c/a I(003)/I(104)
    200 NCM811 2.8712 14.1960 4.944274 0.977
    250 NCM811 2.8684 14.1639 4.937910 1.000
    300 NCM811 2.8690 14.3644 5.006762 0.876
    400 NCM811 2.8708 14.1394 4.925247 0.867

    Table 2

    Table 2.  Ni, Co, and Mn Contents of Different NCM811 Materials Prepared at Different Spray Flow-rates
    DownLoad: CSV
    Samples Ni (wt.%) Co (wt.%) Mn (wt.%)
    200 NCM811 50.35 6.26 5.35
    250 NCM811 49.84 6.38 5.27
    300 NCM811 49.23 6.21 5.18
    400 NCM811 50.66 5.98 5.32

    In Fig. 2, the SEM images of 200 NCM811 (Fig. 2a and 2b), 250NCM811 (Fig. 2c and 2d), 300NCM811 (Fig. 2e and 2f) and 400NCM811 (Fig. 2g and 2h) are shown at different magnifications. As shown in Fig. 2a, 2c, 2e, and 2g, the four samples consist of spherical particles with the diameters ranging from 2 to 5 μm. Fig. 2b, 2d, 2f, and 2h show that these secondary particles are formed by primary particles of 200~600 nm in size. The diameter of secondary particles in 200NCM811 and 250NCM811 are about 5 μm in size, while the secondary particles in 300NCM811 and 400NCM811 are smaller than 3 μm. This indicates that the increasing spray drying flow-rate will reduce the particle size because of the decreasing droplet size during spraying. On the other hand, the effect of flow-rate on the size of primary particle is not significant. The primary particle size is likely dictated by the solid state synthetic conditions.

    Figure 2

    Figure 2.  SEM images of different NCM811 materials prepared at different spray drying flow-rates: (a, b) 200NCM811, (c, d) 250NCM811, (e, f) 300NCM811, and (g, h) 400NCM811

    X-ray photoelectron spectroscopy (XPS) is a characterization method for determining the oxidation state and elemental composition at the surface of materials. Although the ICP analysis results confirm that the ratio of nickel, cobalt, and manganese is 8:1:1 in all four samples, the valence of these transition metals could change because of the different preparation conditions. In the NCM811 system, the oxidation state of Co and Mn are stable as III and IV, respectively, but the oxidation state of Ni is unstable. The Ni3+ in the structure can be easily changed to Ni2+ under the influence of external factors[25]. As a result, the possibility of cation mixing will increase when a large number of Ni2+ with radius similar to Li+ presents in the lattice[26, 27]. Fig. 3 shows the fitting results of the Ni2p2/3 spectra of 200NCM811, 250NCM811, 300NCM811, and 400NCM811. It shows that the Ni2+ content of 250NCM811 is the lowest, while that of 200NCM811 is the highest. Because of the lowest Ni2+ content, 250NCM811 may have the least cation mixing and therefore its crystal structure is probably the most stable among all four materials.

    Figure 3

    Figure 3.  The fitting curve of Ni2p2/3 XPS spectra of different NCM811 materials prepared at different flow-rates: (a) 200NCM811, (b) 250NCM811, (c) 300NCM811, and (d) 400NCM811

    The electrochemical properties of the obtained NCM811 samples are first characterized by CV measurement. Fig. 4 exhibits the CV curves of 200NCM811, 250NCM811, 300NCM811, and 400NCM811 electrodes. The potential window is 3.0~4.3 V vs. Li+/Li and the scan rate is 0.2 mV·s-1. The oxidation peaks of all four samples occur at 3.9~4.1 V vs. Li+/Li, which corresponds to the process of Ni2+ oxidization to Ni3+ and then Ni4+; the reduction peaks occur at 3.6~3.7 V vs. Li+/Li, corresponding to the process of Ni4+ reduction first to Ni3+ and then to Ni2+[28, 29]. Comparing the CV curves of the first three cycles, we found that the oxidation peak potential of the first cycle is significantly higher than that of the second and third cycles. This is mainly because of the irreversible chemical reactions during the first CV cycle, such as the formation of solid electrolyte interface (SEI) caused by electrolyte decomposition. It is noteworthy that the current variation between the second and third cycles of 250NCM811 material is noticeably smaller than that of the other three materials. Again, this could indicate that the lattice structure of 250NCM811 experiences less change during later cycles, which is beneficial for the long-term cycling stability of batteries.

    Figure 4

    Figure 4.  CV curves of different NCM811 materials prepared at different spray flow-rates: (a) 200NCM811, (b) 250NCM811, (c) 300NCM811, and (d) 400NCM811

    Further electrochemical properties are characterized by constant current charge-discharge test. Fig. 5a~5d shows the charge-discharge curves of all four NCM811 cathode materials at 0.2 C to 2 C (1 C = 280 mA·g-1). The first cycle coulombic efficiency values are all above 85% at 0.2 C for the 200NCM811, 250NCM811, 300NCM811, and 400NCM811 electrodes. The specific discharge capacity of four NCM811 samples at different current density (0.2~10 C) is shown in Fig. 5e. We find that 250NCM811 has the best rate performances, followed by 300NCM811 and 400NCM811, while 200NCM811 has the worst rate performances. In particular, the specific capacity of 250NCM811 at 0.2 C is 210 mAh·g-1, 27.3% higher than that of 300NCM811 (165 mAh·g-1). At 10 C, the specific capacity of 250NCM811 remains 113.7 mAh·g-1, which is 65.5% higher than that of 300NCM811 (68.7 mAh·g-1), showing excellent high-rate performance. The result for cycling stability evaluation is shown in Fig. 5f. Coin-type cells consisting of four NCM811 cathodes are cycled for 100 times at 1C after completing the rate capacity test. After 100 cycles, the capacity retention ratios of 200NCM811, 250NCM811, 300NCM811, and 400NCM811 are 93.8%, 94.1%, 92.10%, and 92.07%, respectively, which are consistent with the order of I(003)/I(104) ratios in Table 1. We can see that 250NCM811 has a more stable layer structure and less degree of cation mixing, which effectively suppresses the capacity decay, leading to the improved cycling stability.

    Figure 5

    Figure 5.  Electrochemical performances of different NCM811 materials prepared at different spray drying flow-rates: (a~d) the constant current charge-discharge profiles of 200NCM811, 250NCM811, 300NCM811, and 400NCM811; (e) Rate performances of 200NCM811, 250NCM811, 300NCM811, and 400NCM811; (f) Cycling stability performance of 200NCM811, 250NCM811, 300NCM811, and 400NCM811

    The electrochemical impedance spectra and the equivalent circuit models of four NCM811 samples are shown in Fig. 6a and 6b, respectively. The model consists of four parts: (1) the resistance Rs represents the equivalent ohmic resistance of the cell and corresponds to a point in the EIS spectrum, which appears in the ultrahigh frequency (UHF) region (10 kHz and above); (2) in the high frequency region, the transportation of electron through SEI film is shown as a semi-circle on EIS spectra and corresponds to the RSEI/CPESEI parallel circuit, in which RSEI represents the electronic resistance across the SEI film; (3) in the intermediate frequency region, an RCT/CPECT parallel circuit is used to represent the EIS spectrum (as another half circle), which is related to the charge transfer resistance; (4) finally, in the low frequency region, there is an straight line in the EIS spectra, which reflects the diffusion process of lithium ions in solid material and is simulated by CPEW[30]. Table 3 contains the simulation results from analyzing the EIS spectra, which shows no significant difference in the RS, RSEI, and CPEW-P values between the four NCM811 cathode materials. However, the RCT values change dramatically. The RCT of 200NCM811 is 349 Ω, which is much higher than that of the other three samples. This can also be reflected in the rate performances. As shown in Fig. 5e, the difference in discharge capacity between 200NCM811 and other materials increases with the increasing current density. On possible explanation is that the high RCT of 200NCM811 could be attributed to the high surface Ni2+ content of 200NCM811 (Fig. 3). In other words, large amount of NiO could be present on the surface of the particles[31]. Pure NiO is neither an ionic conductor nor an electronic conductor. Therefore, the de-intercalation of lithium ions and the electron conduction are both greatly hindered.

    Figure 6

    Figure 6.  (a) Nyquist plots of different NCM811 materials prepared at different spray flow-rates; (b) Equivalent circuit for fitting the EIS spectra

    Table 3

    Table 3.  Parameters Obtained by Fitting the EIS Spectra of NCM811 Materials Prepared at Different Spray Drying Flow-rates
    DownLoad: CSV
    Samples RS(Ω) RSEI(Ω) RCT(Ω) CPEW-P
    200NCM811 1.273 38.43 349.0 0.8698
    250NCM811 1.513 31.84 185.5 0.8686
    300NCM811 7.489 57.32 158.3 0.8596
    400NCM811 4.031 38.10 174.0 0.8374

    In another aspect, it is well known that the property of NCM811 is sensitive to the preparation conditions. Based on our observations, the particle size and lattice structure of NCM811 are both affected by spray drying flow-rate. The decrease of particle size is because of decreasing droplet sized caused by the increasing flow-rate during spray drying, as we discussed earlier. However, as shown in Fig. 5, small particles do not necessarily guarantee the excellent electrochemical performances. It is true that Li+ will have a long pathway during lithiation and delithiation if the radii of NCM811 particles are large[32]. But the larger specific surface area of small NCM811 particles results in more SEI films, which decreases specific capacity. Meanwhile, we hypothesized that because of the different drying rate of LiOH solution, the distribution of Li isn't uniform, which could lead to different levels of cation mixing. The abundance of Ni2+ on the surface is also an indication of this. As we know, the cation mixing of NCM811 leads to a high activation energy barrier for Li+ diffusion owing to its smaller distance between the slabs, and also a lower Li+ diffusion because of the hindrance caused by the transition metal in the lithium layer[8]. Overall, the optimal performance of 250NCM811 is mainly attributed to its appropriate particle size and the sufficient inhibition of cationic mixing.

    Although spray drying technology has been applied in the synthesis of lithium-ion battery materials, there are still few studies on the effects of spray drying parameters on the electrochemical performance of final products. In this work, nickel-rich cathode materials were prepared by different spray drying flow-rates. Their elemental composition, unit cell parameters, and morphology are characterized. The results show that the electrochemical performance of 250NCM811 prepared at the spray drying flow-rate of 250 mL·min-1 is the best. The main reasons might be as follows: (1) 250NCM811 has a suitable particle size that neither extends the Li+ transportation distance nor increases SEI film formation; (2) the uniform distribution of Li+ in NCM811 reduces the cation mixing, which can restrain the collapsing of its structure during the charging and discharging processes. Hence, 250NCM811 maintains a high discharge specific capacity, even under high rates. Cation mixing and radius of NCM811 are the key factors affecting the properties of NCM811. Regulating the spray drying flow-rate provides an effective approaching in tuning the NCM811 properties for next generation batteries.


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