| Cite this article as: |
Zhen Zhang, Pan Luo, Yan Zhang, Yuhan Wang, Li Liao, Bo Yu, Mingshan Wang, Junchen Chen, Bingshu Guo, and Xing Li, Effects of conductive agent type on lithium extraction from salt lake brine with LiFePO4 electrodes, Int. J. Miner. Metall. Mater., 31(2024), No. 4, pp.678-687. https://dx.doi.org/10.1007/s12613-023-2750-2
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The scarcity of conventional fossil fuels and growing environmental concerns have driven the exploration of new clean energy sources [1–2]. Consequently, the development of electrochemical energy storage systems has remarkably surged [3]. Notably, lithium-ion batteries (LIBs) have garnered considerable research attention due to their high energy density and long-term cycle life [4–5]. The demand for LIBs is experiencing rapid growth, which is primarily driven by the swift expansion of the global electric vehicle market, the need for large-scale grid power storage, and the increasing demand for portable energy storage devices [6–7]. The surge in demand for lithium resources [8–9] has consequently led to a sharp rise in the price of lithium [10]. Therefore, obtaining sufficient lithium resources is crucial for the sustainable development of electrochemical energy storage on the premise of protecting the environment and controlling costs [11]. High-grade lithium ores and brines serve as the principal sources of lithium for industrial production. Although hard rock deposits were initially the most extensively mined lithium resources due to their considerable lithium concentrations, they now comprise less than 40% of the total known lithium resources [12]. More than 59% of lithium resources in the world are distributed in salt lakes [13]. Salt lake brine is a concentrated salt solution containing lithium cations and a large number of other metal cations (cocations), such as Na+, K+, and Mg2+ [14]. Although the technology for lithium extraction from ores is well-established, the necessity of lithium extraction from salt lake brine has arisen due to the high production costs and severe environmental pollution associated with ore-based extraction methods [15]. Therefore, the development of technologies for lithium extraction from salt lake brine has received increasing attention [16].
The main technologies for lithium extraction from salt lake brine include precipitation, adsorption [17], extraction [18], membrane [19], and electrodialysis [20] methods. These methods possess distinct characteristics that make them suitable for lithium extraction from various salt lakes. Nevertheless, they also present several challenges, including limitations in working environments, extended lithium extraction durations, diminished lithium recovery rates, and considerable environmental pollution [21]. In 1993, Kanoh et al. [22] proposed extracting Li+ from aqueous solutions by using the electrochemical method for the first time. This approach provided a new research direction for lithium extraction from salt lake brine. Electrochemical lithium extraction materials mainly include positive and negative electrode materials that are similar to those in LIBs. The working mechanism of lithium extraction is similar to that of rechargeable LIBs, specifically, the movement of Li+ from positive to negative through an electrolyte during charging and then vice versa during discharging. By controlling the working potential of electrodes in salt lake brine, Li+ can be embedded into electrodes and extracted from salt lake brine [22]. The common electrode materials used for lithium extraction can be mainly divided into two types: (1) LiFePO4 (LFP) [23] and (2) LiMn2O4 [22]. Zhao et al. [24–25] proposed an electrochemical lithium extraction system based on rocking-chair batteries. During charging and discharging, Li+ is selectively absorbed by an electrode from the salt lake brine in a cathode chamber. This phenomenon is accompanied by Li+ deintercalation/intercalation from/into the electrode. In the corresponding anode chamber, Li+ is extracted from the electrode and enriched in the anode chamber solution. However, the active material loading capacity used in electrochemical deintercalation is considerably higher than that of electrodes in LIBs to ensure the productivity of electrodes per unit area. This situation would cause the slow transfer of Li+ in electrodes, affecting the actual lithium extraction efficiency. Additionally, electrodes need to work at heavy current densities to ensure lithium extraction capacity.
At present, carbon black conductive agents, such as acetylene black (AB) and super P, are the most widely used conductive agents of electrode materials for electrochemical salt lake lithium extraction. However, carbon black cannot effectively form conductive networks upon contact with active materials owing to its low conductivity, which is typically 1 × 103–1.5 × 103 S/m. Therefore, carbon black cannot meet the requirements for establishing an efficient conductive network and high electronic and Li+ conductivities in electrodes for salt lake lithium extraction. Multiwalled carbon nanotubes (MWCNTs) have a conductivity of approximately 5 × 107 S/m at room temperature, an aspect ratio of more than 1000, axial dimensions on the micron scale, and longitudinal dimensions on the nanoscale [26]. Moreover, MWCNTs exhibit large specific surface areas [27] and excellent mechanical and chemical properties. As conductive agents, MWCNTs and active substances generally make full contact in a line-to-point manner [28], forming efficient conductive networks with good conductivity [29]. Yang et al. [30] studied the modification of Li1.2Ni0.13Co0.13Mn0.54O2 electrodes by adding MWCNTs with a mass fraction of 1.5% and found that the Coulombic efficiency and specific charge–discharge capacity of the electrodes greatly improved. Sheem et al. [31] demonstrated that electrodes containing super P exhibited noticeable cracking compared with those containing MWCNTs. This difference is due to the superior conductive network and mechanical properties established by MWCNTs within the electrodes. Ning et al. [32] showed that mixing AB with a small amount of MWCNTs greatly improved the cycling performance, specific capacity, and rate performance of LFP electrodes and considerably reduced impedance.
All the above information indicates that MWCNTs have better conductivity and mechanical strength than AB and that adding an appropriate amount of MWCNTs would help build a good conductive network and improve electrode performance. Studies on the modification of LFP electrodes for lithium extraction from salt lake brine mainly focused on surface coating and bulk doping [23,33] and works on the effect of conductive agents on the performance of LFP electrodes in lithium extraction from salt lake brine are scarce. In this work, LFP electrodes with a single conductive agent (AB or MWCNTs) and mixed conductive agent (AB/MWCNTs) were prepared, and the effect of conductive agents on their lithium extraction efficiency and performance in salt lake brine was systematically investigated. Through the optimization of the conductive agent, an efficient conductive network was established in LFP electrodes, enhancing their cycling performance and lithium extraction capacity.
This study used commercially available LFP (Guangdong Canrd New Energy Technology Co., Ltd.), AB (Guangdong Canrd New Energy Technology Co., Ltd.), MWCNTs (Suzhou Carbon Rich Graphene Technology Co., Ltd.), polyvinylidene difluoride (PVDF, HSV900), N-methyl pyrrolidone (NMP, Chengdu Kelong Chemical Co., Ltd.), anion-exchange membrane (AEM8040, Hangzhou Huamembrane Technology Co., Ltd.), carbon fiber cloth (W0S1011, Carbon Energy Technology (Beijing) Co., Ltd.), 600 µm-thick lithium metal chips (diameter: 16 mm, China Energy Lithium Co., Ltd.), and diaphragms (Celgard2400, Celgard Company).
For the preparation of LFP electrodes, the LFP active material, single conductive agent AB, and PVDF binder (dissolved in NMP) were first fully mixed at the mass ratio of 8:1:1 and ground to obtain a well-mixed slurry. The slurry was then coated onto carbon fiber cloth. The LFP loading capacity was 15 mg⋅cm−2. Finally, the electrode was dried in a vacuum box at 80°C for 12 h. The obtained electrode was called LFP-AB. LFP electrodes prepared by using the single conductive agent of MWCNTs and mixed conductive agent of AB/MWCNTs were named LFP-MWCNTs and LFP-AB/MWCNTs, respectively.
FePO4 electrodes were obtained by removing lithium from the prepared LFP electrodes (including LFP-AB, LFP-MWCNTs, and LFP-AB/MWCNTs). The prepared LFP electrodes were used as anodes, and a foam nickel electrode was applied as a cathode. Anion film was utilized to separate the cathode and anode. The electrolyte solution was 0.5 M NaCl solution. FePO4 electrodes were obtained by applying a voltage of 1 V at both electrodes for electrolytic lithium removal until the current was less than 2 A⋅m−2.
The surface morphologies of LFP, AB, MWCNTs, and LFP electrodes were investigated through scanning electron microscopy (ZEISS Demini 300) at an acceleration voltage of 3 kV. X-ray diffraction tests were conducted by using a Rigaku Ultima IV system with a copper X-ray source (Cu Kα, 40 kV, 40 mA).
Electrochemical impedance spectroscopy (EIS) was conducted on LFP electrodes with different conductive agent systems by using a CR2032 coin-type cell with LFP-AB, LFP-MWCNTs, or LFP-AB/MWCNTs as the cathode and lithium metal disc (thickness: 600 µm; diameter: 16 mm) as the anode. A polypropylene separator with a thickness of 25 µm (Clegard 2500) was used. An electrolyte of 1.2 M LiPF6 in ethyl carbonate (EC) and ethyl methyl carbonate at a volume ratio of 3:7 was prepared, and 70 µL of this electrolyte was employed for each coin-type cell. Cells were assembled in an argon-filled glove box (Dellix Industry Co., Ltd., China) with H2O and O2 contents of less than 0.1 ppm.
The electrochemical behavior of LFP electrodes with different conductive agent systems was studied in a three-electrode system by using LFP-AB, LFP-MWCNTs, or LFP-AB/MWCNTs as the working electrode; a platinum electrode as the counter electrode; a glycerol electrode as the reference electrode. In this work, 0.5 M LiCl, 0.5 M NaCl, 0.5 M MgCl2, or 0.5 M KCl were used as single-salt electrolytes. A mixture of 0.1 M MClx (M = Li, Na, Mg, and K) was used as the mixed-salt electrolyte. The potential window was −1–1 V, and the scanning rate was 0.1–1.0 mV⋅s−1.
All experiments were conducted at room temperature. All electrochemical tests were performed with a CHI 760E electrochemical workstation.
Given the low conductivity of LFP, conductive agents must be added to enhance electrode conductivity. The commonly used conductive agents are AB and super P. Compared to LFP nanoparticles (Fig. S1(a)), AB exhibits smaller and more uniform nanoparticle sizes of 20–40 nm (Fig. S1(b)). AB forms conductive bridges between active materials, thus enhancing the conductivity of electrodes through the percolation mechanism [34]. However, AB conductive agents typically exhibit low conductivity due to their small particle surface and limited contact area with active materials. During electrode cycling, the conductive bridges formed by AB are susceptible to breakage, thereby increasing electrode resistivity (Fig. 1(a)). MWCNTs exhibit a wire-like morphology, a high aspect ratio (1:1000), superior mechanical strength, and exceptional electronic conductivity that help construct continuous conductive networks for rapid electron transfer. The large aspect ratio of MWCNTs helps sustain the integrity of conductive networks after electrode cycling, enabling simultaneous contact between MWCNTs and multiple active particles. Excessive amounts of MWCNTs tend to aggregate [35], whereas small amounts of MWCNTs can not establish an effective conductive network (Fig. 1(b)). The synergistic effect between AB and MWCNTs can maximize the activation of the overall conductive path of electrodes and improve electrochemical performance (Fig. 1(c)). During electrode cycling, AB prevents the aggregation of MWCNTs, and then the conductive agent is evenly dispersed and contact with the active materials adequately, resulting in the formation of a good conductive network.
Fig. 2 shows the surface morphology images of the LFP electrodes with single AB conductive agent (Fig. 2(a), (d), and (g)), single MWCNT conductive agent (Fig. 2(b), (e), and (h)), and mixed conductive agent with the mass ratio of AB to MWCNTs of 1:1 (Fig. 2(c), (f), and (i)). Fig. 2(a), (d), and (g) illustrates that the surfaces of these electrodes remained intact and exhibited a dense structure. Fig. 2(g) shows that small AB particles easily fell into the gaps between large LFP particles and that the formation of connections with LFP particles was difficult [36], preventing the connection of some active materials by conductive pathways. Fig. 2(h) depicts that although the long wire-like MWCNTs could come into contact with multiple LFP particles simultaneously, an excessive amount of MWCNTs caused aggregation, which is unconducive to the formation of complete conductive networks. Fig. 2(i) presents the surface morphology of the LFP electrode with the mixed conductive agent AB/MWCNTs. MWCNTs and AB were uniformly dispersed, ensuring ample contact with LFP particles for the establishment of an effective conductive network.
The working environment of electrodes in lithium extraction from salt lake brine is different from that of LIB in traditional electrolytes (LiPF6 in the mixture of EC, diethyl carbonate, and dimethyl carbonate) and aqueous solutions (pure lithium salt solution, such as LiNO3, Li2SO4, and LiCl) [37]. In addition to Li+, salt lake brine contains high concentrations of impurity cations, such as Na+, K+, and Mg2+. Therefore, LFP electrodes must extract Li+ selectively. Fig. 3 shows the cyclic voltammograms of LFP electrodes with different conductive agent systems in single-salt electrolytes (0.5 M LiCl, NaCl, MgCl2, or KCl) and LFP electrodes with different conductive agent systems in mixed-ion solutions of 0.1 M MClx (M = Li, Na, Mg, K)) obtained over the voltage range of −1–1 V vs. saturated calomel electrode (SCE) and scanning rate of 0.5 mV⋅s−1. Fig. 3(a)–(c) shows that the LFP electrodes with different conductive agent systems exhibited only a pair of redox peaks at 0.3 and 0 V in 0.5 M LiCl solution. These peaks sepectively corresponded to the deintercalation/intercalation of Li+ from/into the spinel LFP/FePO4 structure. Other redox peaks reflecting the deintercalation/intercalation of Na+ from/into the NaFePO4/FePO4 structure could be observed in the cyclic voltammograms obtained in 0.5 M NaCl solution in addition to the oxidation peak at 0.38 V corresponded to the deintercalation of Li+ from the LFP structure during the first segment and the weak oxidation peak in the second segment between 0 and 0.2 V corresponding to the intercalation of Na+ into the FePO4 structure. In the cyclic voltammograms obtained in 0.5 M KCl solution, the strong oxidation peak in the first segment and the weak oxidation peak in the third segment corresponded to the deintercalation of Li+ from the LFP structure. In addition, no peaks corresponding to K+ deintercalation and intercalation were found. In the cyclic voltammograms acquired in 0.5 M MgCl2 solution, the strong oxidation peak in the first segment represented the deintercalation of Li+ from LFP, and the weak reduction peak in the second segment between 0 and 0.2 V represented the intercalation of Li+ into the FePO4 structure. Moreover, the intercalation peak of Mg2+ was found in the second segment at approximately −0.6 V, whereas the deintercalation peak of Mg2+ was absent.
As illustrated in Fig. 3(d), in the mixed solution, the blank carbon fiber cloth showed no redox peak. However, the LFP electrode with different conductive agent systems presented an oxidation peak at 0.27 V corresponded to the deintercalation of Li+ ions from the spinel LFP structure and a reduction peak at −0.05 V corresponded to the intercalation of Li+ into the spinel FePO4 structure. Although the reduction peak at −0.27 V reflected the intercalation of Na+ into the spinel FePO4 structure, peaks corresponding to K+ and Mg2+ deintercalation and intercalation were not found. Hence, the selective extraction of Li+ ions through the precise control of the electrode operating voltage is possible. Fig. 3(d) shows that in the mixed solution, the redox peak of the electrode with the mixed conductive agent (AB/MWCNTs) was stronger than that of the electrode with the single conductive agent. This result indicates that the lithium intercalation capacity of the mixed conductive agent electrode system was greater than that of the single AB or MWCNT electrode system and proves that the mixed conductive agent electrode had high lithium extraction efficiency.
Comparing the intercalation behaviors of Li+, Na+, K+, and Mg2+ revealed that K+ exhibited minimal intercalation into the FePO4 structure. Additionally, Mg2+ and Na+ experienced greater difficulty in intercalating into the FePO4 structure than Li+. Therefore, Li+ ions can be selectively extracted by carefully controlling the operating voltage.
Fig. 4 shows the EIS test results and the curve-fitted equivalent circuit models. Specific parameters are given in Table 1. The Nyquist diagram of each sample presented a semicircle in the high-frequency region and a diagonal line in the low-frequency region. The constant phase angle element (CPE) responds to the time constant distribution of the interfacial process. The semicircle in the high-frequency region and Z′ with the impedance represent the ohmic impedance of the cell under test (Re). The semicircle in the medium-frequency region represents Li+ charge transfer sresistance (RCT), and the diagonal line in the low-frequency region represents the Li+ diffusion impedance Warburg impedance in the solid phase of the electrode (W1). The RCT of the mixed conductive agent electrode (LFP-AB/MWCNTs) was 53.73 Ω, that of the single AB conductive agent electrode (LFP-AB) and the single MWCNTs conductive agent electrode (LFP-MWCNTs) were 95.14 Ω and 76.56 Ω, respectively. Among the electrodes, the mixed conductive agent electrode (LFP-AB/MWCNTs) had the lowest RCT because the mixed conductive agent (AB/MWCNTs) can establish a more efficient conductive network in LFP electrodes than a single conductive agent (AB or MWCNTs), offering improved conditions for the transportation of Li+ and electrons.
| Electrode | Re / Ω | RCT / Ω |
| LFP-AB | 1.99 | 95.14 |
| LFP-MWCNTs | 1.73 | 76.56 |
| LFP-AB/MWCNTs | 7.43 | 53.73 |
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The cyclic voltammograms of LFP-AB, LFP-MWCNTs, and LFP-AB/MWCNTs electrodes in 0.5 M LiCl aqueous solution over the voltage range of −1–1 V vs. SCE at a scanning rate of 0.1–1.0 mV⋅s−1 are shown in Fig. 5(a)–(c). Each curve had a pair of redox peaks that corresponded to Li+ deintercalation and intercalation. The results illustrates that LFP electrodes with different conductive additive materials has the same reaction mechanism during charge and discharge. The peak current of LFP-AB/MWCNTs was higher than that of LFP-AB and LFP-MWCNTs. This result indicates that the lithium storage capacity of LFP-AB/MWCNTs was higher than that of LFP-AB and LFP-MWCNTs electrodes because MWCNTs have a large specific surface area and high conductivity due to their high aspect ratio. However, individual MWCNTs would tangle with each other, hindering the uniform distribution of active materials and decreasing electrode performance. The synergy between AB and MWCNTs improves conductivity. As a result, the transfer rate of Li+ and electrons is promoted, and the capacity of the LFP cathode effectively improved due to the synergistic effect of the three-dimensional conductive network constructed by AB and MWCNTs. With the increase in scanning rate, the potentials of the oxidation and reduction peaks moved to positive and negative directions, respectively, and the absolute values of the anode and cathode currents of each pair of redox peaks differed, indicating that the system is a quasi-reversible electrochemical system. Fig. 5(d) shows the fitted curve of the peak current and the square root of the scanning rate (v1/2). The good linear relationship between the peak current (Ip) and square root of the scanning rate indicates that the deintercalation/intercalation of Li+ in the LFP electrode is mainly a diffusion-controlled process [38].
Table 2 lists the diffusion and average diffusion coefficients of Li+ in each redox process in LFP-AB, LFP-MWCNTs, and LFP-AB/MWCNTs electrodes. DLi-O is the diffusion coefficient of Li+ during oxidation, and DLi-R is the diffusion coefficient of Li+ during reduction. The average diffusion coefficient of LFP-AB/MWCNTs was 4.21 × 10−9 cm2⋅s−1, which was higher than that of LFP-AB (2.35 × 10−9 cm2⋅s−1) and LFP-MWCNTs (1.77 × 10−9 cm2⋅s−1). The high diffusion coefficient of the LFP-AB/MWCNT electrode indicates that it has good electrochemical kinetics in Li+ intercalation and deintercalation. MWCNTs with linear shapes and high specific surface areas are helpful for building continuous conductive networks that enable rapid electron transfer. Meanwhile, AB can inhibit the agglomeration of MWCNTs, thus helping construct an effective conductive network. This effect is beneficial for further enhancing the diffusion rate of Li+ and thus improving the performance of electrochemical lithium extraction.
| Electrode | Scanning rates / (mV·s−1) | DLi-O | DLi-R | Average |
| LFP-AB | 0.1 | 2.94 × 10−9 | 1.65 × 10−9 | 2.35 |
| 0.5 | 3.03 × 10−9 | 1.77 × 10−9 | ||
| 1.0 | 2.96 | 1.77 × 10−9 | ||
| LFP-MWCNTs | 0.1 | 1.96 × 10−9 | 1.23 × 10−9 | 1.77 |
| 0.5 | 2.22 × 10−9 | 1.44 × 10−9 | ||
| 1.0 | 2.25 × 10−9 | 1.54 × 10−9 | ||
| LFP-AB/MWCNTs | 0.1 | 5.5 × 10−9 | 2.74 × 10−9 | 4.21 |
| 0.5 | 5.27 × 10−9 | 2.92 × 10−9 | ||
| 1.0 | 5.67 × 10−9 | 3.17 × 10−9 |
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As shown in Fig. 6, the cyclic stability of LFP electrodes with different conductive agents was further studied through the continuous constant current charge–discharge cycle test. Fig. 6(a)–(c) shows the 30-cycle charge–discharge curves of LFP-AB, LFP-MWCNTs, and LFP-AB/MWCNTs in 0.5 M LiCl solution taken over the voltage range of −1–1 V vs. SCE at the current density of 20 mA⋅g−1. The charge–discharge curves of LFP electrodes with different conductive systems presented two obvious potential plateaus in the range of −0.06–0.06 V, corresponding to the two-step redox reaction of Li+ intercalation and deintercalation. The initial discharge capacities of the single AB conductive electrode (LFP-AB), single MWCNTs conductive electrode (LFP-MWCNTs), and mixed AB/MWCNT conductive electrode (LFP-AB/MWCNTs) were 146, 142, and 152 mAh⋅g−1, respectively. After 30 cycles, the discharge capacities were 96, 105, and 126 mAh⋅g−1, respectively. The capacity retention rates were 65.8%, 73.9%, and 82.9%. The cycling performance was poor because the particle size of the AB conductive agent is considerably smaller than that of LFP, the surface contact between AB and LFP is limited, and the conductive pathway formed by AB and LFP is easily broken during cycling. Moreover, excessive MWCNTs tend to aggregate within the electrode, leading to the inability to establish a continuous conductive pathway and affecting the overall performance of the electrode. Nevertheless, owing to their wire-like shape, exceptional conductivity, and robust mechanical strength, MWCNTs exhibited a higher cycle retention rate than AB. In the mixed conductive electrode, AB and MWCNTs collaborate to construct an efficient conductive network, thus resulting in the higher Li+ adsorption capacity and better cycling stability of the mixed conductive system than those of the single conductive agent system. The discharge specific capacity of the three different conductive agent systems during the charge–discharge cycle and the lithium-ion adsorption capacity of the corresponding electrodes were calculated and are shown in Fig. 6(d).
The charge–discharge curves of different electrodes in Fig. 6(a)–(c) show that the electrode utilizing a mixed conductive agent displayed considerably lower polarization than the systems employing a single conductive agent during cycling. Here, polarization is defined as the voltage difference when the discharge capacity is 50%. The polarization voltages of the electrode with a single AB conductive agent (Fig. 6(a)) at cycles 1, 5, 15, and 30 were 0.15, 0.14, 0.22, and 0.55, respectively. The polarization voltages of the electrode with the single MWCNTs conductive agent (Fig. 6(b)) at cycles 1, 5, 15, and 30 were 0.15, 0.13, 0.21, and 0.33, respectively. The polarization voltage of the electrode with the mixed AB/MWCNTs conductive agent (Fig. 6(c)) at cycles 1, 5, 15, and 30 were 0.15, 0.13, 0.16, and 0.22, respectively. As shown in Fig. 6(d), the average lithium extraction capacity per gram of LFP electrode increased from 30.36 mg with the single conductive agent (AB) to 35.62 mg with the mixed conductive agent (AB/MWCNTs).
The cyclic stability of LFP electrodes with different amounts of conductive agent additions and active material loadings was further studied, as shown in Fig. 7. Fig. 7(a) and (b) provides the charge–discharge curves of LFP-AB, LFP-MWCNTs, and LFP-AB/MWCNTs in 0.5 M LiCl solution at −1–1 V and current density of 20 mA⋅g−1. As shown in Fig. 7(a), the electrodes prepared by different conductive agent systems but with a fixed mass ratio of LFP : conductive agents : PVDF of 8:1:1 and loading capacity of the LFP active material of 15 mg⋅cm−2 were named LFP-10wt% AB, LFP-10wt% MWCNTs, and LFP-5wt% AB/5wt% MWCNTs. The electrodes prepared after reducing the mass of the conductive agent by half but without changing other conditions were named LFP-5wt% AB, LFP-5wt% MWCNTs, and LFP-2.5wt% AB/2.5wt% MWCNTs. When the content of the conductive agent was reduced, the performance of the electrode decreased. It can be known that the Li+ adsorption capacity of per gram LFP for the LFP-2.5wt% AB/2.5wt% MWCNT electrode continued to reach 37.76 mg, which was higher than the adsorption capacity of 33.65 mg shown by the LFP-5wt%AB electrode and of 33.65 mgpresented by the LFP-5wt% MWCNTs electrode because even a small quantity of the mixed conductive agent was sufficient to establish a complete conductive network within the electrode. Moreover, the initial capacity of the LFP-10wt% AB electrode was higher than that of the LFP-10wt% MWCNTs electrode. However, when the conductive agent content reduced, the initial capacity of the LFP-5wt% MWCNTs electrode became higher than that of the LFP-5wt% AB electrode because the decrease in the content of MWCNTs weakenes the aggregation of MWCNT conductive agents and active substances in the electrode, optimizing electrode performance. Electrodes with the LFP loading capacity of 15 mg⋅cm−2 were named 15-LFP-AB, 15-LFP-MWCNTs, and 15-LFP-AB/MWCNTs. The electrodes prepared under the same conditions except with the LFP loading capacity of 40 mg⋅cm−2 were named 40-LFP-AB, 40-LFP-MWCNTs, and 40-LFP-AB/MWCNTs. As shown in Fig. 7(b), when the loading capacity increased, the Li+ adsorption capacity of per gram LFP for the electrodes significantly decreased, whereas that of the electrodes using the mixed conductive agent (AB/MWCNTs) stiil could reach 30.96 mg, which was much higher than that of elctrodes, using a single conductive agent. This result indicates that the use of mixed conductive agents can further improve the lithium extraction efficiency per unit area of electrodes and the performance of working electrodes in lithium extraction from salt lake brine.
Fig. 8(a) shows the changes in the concentration of each cation during continuous lithium extraction using the LFP (AB/MWCNT)/FePO4 (AB/MWCNT) system (Fig. S2) (simulated brine solution of 0.865 g⋅L−1 Li, 11.1 g⋅L−1 Na, 15.59 g⋅L−1 K, and 75.41 g⋅L−1 Mg). The black dots in each graph represent the ion concentration in the simulated solution before lithium extraction. The concentration of Li+ gradually decreased with the increase in cycle number, specifically from the original value of 0.865 to 0.535 g⋅L−1 after five cycles, whereas the concentrations of other cations did not change significantly. Fig. 8(b) shows that the LFP (AB/MWCNT)/FePO4 (AB/MWCNT) system for continuous lithium extraction had a lithium extraction capacity for per gram LEP of 31.06 mg in the simulated salt lake brine at the first cycle and retained an adsorption capacity of 27.12 mg at the fifth cycle, demonstrating selective lithium extraction and the high adsorption capacity of the hybrid conductive (AB/MWCNT) electrode.
In this work, the difference between the performances of LFP electrodes with a mixed conductive agent (AB/MWCNTs) or a single conductive agent (AB or MWCNTs) in electrochemical lithium extraction from salt lake brine was systematically investigated. As a result of the efficient conductive network constructed by the synergy between AB and MWCNTs and the high mechanical strength, aspect ratio, and conductivity of MWCNTs, the utilization of the mixed conductive agent exhibited a notable reduction in charge transfer resistance within the electrodes. This reduction subsequently mitigated electrode polarization during reactions, enhanced Li+ diffusion efficiency, and contributed to improving cycling performance and lithium intercalation capacity. With the change in conductive agent, the average Li+ diffusion coefficient in the LFP electrodes during electrochemical lithium extraction increased from 2.35 × 10−9 cm2⋅s−1 (LFP-AB) and 1.77 × 10−9 cm2⋅s−1 (LFP-MWCNTs) to 4.21 × 10−9 cm2⋅s−1 (LFP-AB/MWCNTs). After 30 cycles at the current density of 20 mA⋅g−1, the average lithium extraction capacity of per gram LEP for the LFP electrode increased from 30.36 mg with the single conductive agent (AB) to 35.62 mg with the mixed conductive agent (AB/MWCNTs). The results showed that changing the conductive agent type improved the lithium extraction efficiency of the electrode. After 30 cycles, the electrode with the mixed conductive agent exhibited a better capacity retention rate (82.9%) than the electrode with the single conductive agent (AB, 65.8%). When the content of the conductive agent was reduced, the LFP electrode with the mixed conductive agent showed an excellent Li+ adsorption capacity for per gram LEP of 37.76 mg. When the loading capacity of the electrodes increased, the Li+ adsorption capacity of per gram LEP for the LFP electrode with the mixed conductive agent remained at 30.96 mg. After five cycles in simulated salt lake brine, the electrode with the mixed conductive agent in the self-made continuous lithium extraction device achieved a high Li+ adsorption capacity for per gram LEP of 31.06 mg.
This work was financially supported by the National Natural Science Foundation of China (No. 52072322) and the Department of Science and Technology of Sichuan Province, China (Nos. 23GJHZ0147, 23ZDYF0262, 2022YFG0294, and 2019-GH02-00052-HZ).
All authors declare that there is no conflict of interest regarding the publication of this paper.
The online version contains supplementary material available at https://doi.org/10.1007/s12613-023-2750-2
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Figures(8) / Tables(2)
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| Electrode | Re / Ω | RCT / Ω |
| LFP-AB | 1.99 | 95.14 |
| LFP-MWCNTs | 1.73 | 76.56 |
| LFP-AB/MWCNTs | 7.43 | 53.73 |
DownLoad:
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| Electrode | Scanning rates / (mV·s−1) | DLi-O | DLi-R | Average |
| LFP-AB | 0.1 | 2.94 × 10−9 | 1.65 × 10−9 | 2.35 |
| 0.5 | 3.03 × 10−9 | 1.77 × 10−9 | ||
| 1.0 | 2.96 | 1.77 × 10−9 | ||
| LFP-MWCNTs | 0.1 | 1.96 × 10−9 | 1.23 × 10−9 | 1.77 |
| 0.5 | 2.22 × 10−9 | 1.44 × 10−9 | ||
| 1.0 | 2.25 × 10−9 | 1.54 × 10−9 | ||
| LFP-AB/MWCNTs | 0.1 | 5.5 × 10−9 | 2.74 × 10−9 | 4.21 |
| 0.5 | 5.27 × 10−9 | 2.92 × 10−9 | ||
| 1.0 | 5.67 × 10−9 | 3.17 × 10−9 |
DownLoad:
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