Damage mechanism of dissolved manganese ions from cathode to silicon anode in lithium ion batteries

doi:10.21203/rs.3.rs-4508605/v1

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Damage mechanism of dissolved manganese ions from cathode to silicon anode in lithium ion batteries

https://doi.org/10.21203/rs.3.rs-4508605/v1

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published 06 Aug, 2024

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It is still unknown how dissolved manganese ions affect the silicon anode's electrochemical performance in the lithium-ion batteries (LIBs). In this study, the damage mechanism of Mn²⁺ to silicon electrode in LIBs was studied by adding Mn²⁺ into electrolyte system to simulate the electrochemical environment.Through the comparison between full cell and half cell, the mechanism of the capacity fading of silicon electrode is revealed. In order to compare the amount of SEI growth of silicon anode during cycling, the heat flux of SEi was analyzed by DSC. Experiments shows that Mn²⁺ could make SEI more fragile, more easily break, and then accelerates the SEI thickening. So Mn2 + could reduce the coulomb efficiency and electrochemical capacity of the silicon-based electrode. The galvanostatic cycle current is 300 mA.g^− 1. The half cell's coulomb efficiency exceeds 97%, whereas the whole cell's coulomb efficiency is only 32% after 100 cycles. In addition to the damage of the Mn²⁺ to silicon anode, the depletion of active lithium ion source in full cell is also an important reason for the rapid decline of electrochemical capacity.

silicon anode

dissolved manganese ions

lithium ion batteries

Capacity fade

Coulomb efficiency

With the increasing requirement for the high energy density of traction battery, although the existing graphite negative electrode (NE) material has the advantages of low cost, stable structure, long cycle life, etc., its specific capacity is no longer able to meet the demands of the new generation of electric vehicles [1]. The energy density of lithium-ion batteries has to be higher than 300wh.kg^− 1 before they can be used as traction battery in next generation electric vehicles [2–4]. In current potential NE system, only silicon-based NE battery is capable of meeting this requirement [5–7]. Theoretically, silicon material has very high theoretical specific capacity, about 10 times of graphite material. Its low working potential of silicon material makes Li will not be precipitated on the surface of electrode, further improve the security [8]. Moreover, the world-wide silicon sources help reduces the cost of mass production. Therefore, silicon is considered to be one of the most important materials for the high capacity NE of the next generation of lithium-ion batteries [9].

However, in the process of charge-discharge cycle, the volume of silicon particles will expand by about 300%, which leads to three serious problems: (1) the silicon particles are easy to crack and pulverize, then electrode collapses; (2) the silicon particles peel off from electrode and lose the electronic connection; (3) the solid electrolyte interface (SEI) of the silicon particles continuously breaks and grows rapidly, which decrease the electrochemical capacity of silicon NE rapidly. Such phenomenon seriously hinders the application and development of silicon materials [10–13].

At present, the solution to the problem of silicon particle's fragility has been proposed: keeping the silicon particle size below 150nm to maintain its integrity [14–15]. However, even if the circular solid silicon particles are controlled at nanometer scale, because the SEI on its surface is easy to crack, the coulomb efficiency is too low to be put into actual use [16–19]. By improving the structure of silicon particles to accommodate its volume expansion, for example, hollow nano silicon is able to alleviate the SEI membrane breaking. That is to say, it can inhibit the growth of SEI membrane and provide effective measures of solving the electrochemical capacity degradation of silicon negative materials. Qiu's team designed and synthesized the hollow structure silicon material, which used to hold the volume expansion of silicon particles and inhibit the excessive growth of SEI membrane [14]. Good results was achieved: the reversible capacity of silicon-based negative electrode could still reach 1650 mAh/g after 100 cycles at the current density of 100mA/g, and the coulomb efficiency could reach 99.5%. Furthermore, hollow SnO₂@Si composites with high energy density were synthesized by further modifying hollow structural silicon [15]. After 500 cycles at 300mAh/g current density, the volumetric capacity is 1030 mAh/cm³, the reversible capacity is 800mA/g, and the coulomb efficiency is 99.5%. In addition, an effective way to improve the coulomb efficiency of silicon negative electrode is coating a layer of flexible polymer on the surface of silicon particles to isolate the direct contact between the electrolyte and the surface of silicon particles that lead to electrochemical decomposition.

Such studies have greatly promoted the application of silicon negative materials, however, in which these excellent performances of silicon negative electrodes are all tested under the situation of lithium-metal half cell. The knowledge of the performance of silicon electrode combined with manganese based positive electrode in full cell is still limited [20–23]. Manganese oxides have become the most important positive electrode materials for lithium-ion batteries, but the dissolution of manganese as transition metal limits its intensive application [24–28]. The dissolution of the positive transition metal in the electrolyte will not only cause the loss of active substances then give rise to loss of positive capacity, but the damage of the full cell system. Some researches show that the dissolved Mn²⁺ will block the exchange channel for lithium ion on SEI, result as capacity degradation [29–33]. Mn²⁺ will catalyze the decomposition of the electrolyte at the location of SEI rupture, where SEI grows rapidly, result as coulomb efficiency reduction [34–38]. Whether the problems faced by manganese oxides will happen similarly on silicon negative electrode has become a key problem in the industrialization of silicon materials [39–44].

In this paper, silicon-based negative electrode of lithium-ion battery was taken as research object. By adding Mn²⁺ to simulate electrochemical environment in actual use, the damage mechanism of the dissolved Mn²⁺ on the performance of silicon negative electrode is explored. Through the comparison between the full cell and half-cell, the mechanism of capacity fading in full cell with silicon electrode in application is revealed. The results show that unlike the condition under half cell, besides the negative effect introduced by the existence of Mn²⁺, the attenuation characteristics of silicon electrode in full cell also caused by the fast consumption of active lithium ions.

Assembly of silicon half cell. The type 2025 coin cells were assembled with lithium foil as counter electrode. Non-aqueous solution of 1 mol/L LiPF₆ with ethylene carbonate/dimethyl carbonate/ethylmethyl carbonate (EC/DMC/EMC) in volume ratio of 1:1:1 was adopted as electrolyte. To be specific, silicon based NE were prepared by coating slurry consisting of nano silicon (60 wt %), Super P Li (20 wt %), and polyacrylic acid (PAA) as binder (20 wt %) on copper foil. Lithium manganese oxide (LMO) cathode were prepared by coating slurry consisting of LMO (80 wt %), Super P Li (10 wt %), and polyvinylidene fluoride (PVDF) as binder (10 wt %) on aluminum foil. All batteries were assembled in an Ar-filled glove box.

Electrochemistry test. Silicon/Li half cells galvanostatic curves were drawn on a Neware battery test system with constant current density of 100 mA/g between 0 V and 1.2 V vs. Li/Li⁺. LMO/Si full cells use the same test system with constant current density of 100 mA/g between 3 V and 4.3 V.

Material characterization. Morphologies of the as-prepared samples were portrayed by scanning electron microscopy (SEM, Zeiss Merlin). Thermal gravimetric analysis (TGA) was performed by using a METTLER TOLEDO TGA instrument with STAR system. Temperature range was set from 25 ℃ to 1000 ℃ with a scanning rate of 2 ℃/min. Mettler-Toledo calorimeter was employed for the Differential Scanning Calorimetric (DSC) analysis of SEI. Electrode materials were scratched from the copper foil in the Ar-filled glove box and sealed into high-pressure stainless steel crucibles (gold plated, Mettler-Toledo) for DSC tests. Temperature range was controlled from 30 ℃ to 300 ℃ at heating rate of 5 ℃/min. X-ray photoelectron spectroscopy (XPS) measurements were conducted on a PHI Quantera SXM spectrometer equipped with a focused and monochromatized Al Kα radiation, the binding energy scale was calibrated using the C 1s peak at 284.8 eV.

Part 1. Research on silicon-based half-cell simulating manganese environment.

Nano silicon particles, a kind of commercial silicon material with uniform structure, stable performance and low cost was chose as silicon source in this study to reduce the influence of material defects on battery performance and improve the accuracy of comparison. Figure 1 shows the characterization of nano silicon particles. Figure 1a is the result of TGA and DSC simultaneous analysis of nano silicon particles. The blue curve in the figure shows that the mass of silicon material remains stable during the process of increasing the temperature from room temperature to about 600 ℃. As temperature continuously rising, it can be found that the mass of nano silicon particles start increasing. At 1000 ℃, total mass has increased to 151%. At the same time, in the heat flow curve, it can be observed that a wide range of exothermic process appears. The highest exothermic point (about 50MW) was fixed at 600 ℃. Judging from the gas composition of thermal analysis, mass rise and exothermic process of nano silicon particles was caused by oxidation reaction. To analyze the change of surface element of nano silicon particles further, X-ray photoelectron (XPS) spectroscopy was carried out. The XPS spectra of Si 2p orbit is displayed in Fig. 1b. The main 3/2 − 1/2 doublet (the spin-orbit splitting is 0.6 eV and the intensity ratio is 3:1), located at 99.1–99.7 eV corresponds to Si⁰ (~ 58% content), the lower peak, located at 98.2-107.1 eV corresponds to silicon oxide (~ 37% content), indicating that surface of nano silicon is partly oxidized.

Figure 2 is a morphological study of nano silicon and the prepared silicon electrode. Figure 2a is an SEM image of nano silicon particles. It can be observed that the nano silicon particles with regular spherical shape in particle size of 70-100nm. Figure 2b is the SEM image of the prepared nano silicon electrode (Preparation method is detailed in the test section). The electrode was coated on one side, and the upper part of SEM image is active material, which is composed of nano silicon particles, conductive agent and binder with total thickness of about 11.2µm; the lower part of SEM image is copper current collector with thickness of about 12.2µm. The coating material was uniformly covered on electrode, closely connected with the current collector.

To study the effect of Mn²⁺ existing in electrochemical environment on the performance of silicon electrode, the coin cell with and without MnF₂ in electrolyte was prepared, and galvanostatic charge-discharge cycle test at current density of 100mA/g was carried out. The charge-discharge capacity and coulomb efficiency of the silicon-based half-cell in 100 cycles are shown in Fig. 3. Obviously the discharge capacity of both batteries in first cycle is much higher than that in second cycle, because of the formation of SEI membrane on the particle surface during the first lithium insertion in nano silicon particles. This irreversible reaction will increase the discharge capacity in the first cycle and reduce the first coulomb efficiency. Specifically, the first cycle coulomb efficiency of cell without MnF₂ is 36.8%, and that of cell with MnF₂ is 29.7%. In the 2nd to 5th cycles, the discharge capacity of the two batteries increased slowly, because of the high volume expansion rate of nano silicon in electrochemical reaction. In the first few cycles, the electrode expanded gradually then reached the best electrochemical state, so that the capacity will rise slowly. From the 6th cycle, the battery capacity showed a slow downward trend. When it came to the 100th cycle, the discharge specific capacity ofcell without MnF₂ is 758mAh/g, 62.1% of the 6th cycle, while the discharge specific capacity of cell with MnF₂ is 514mAh / g, 49.4% of the 6th cycle. As a conclusion, when MnF₂ was added to the nano silicon particle half-cell, the first cycle coulomb efficiency and cycle stability of the battery decreased significantly. It can be considered that, the decrease of coulomb efficiency in the first cycle is mainly because more SEI generated during the first lithium insertion process. On the other hand, even in the same state, the decrease of cycle stability is also due to the lower coulomb efficiency of each cycle, that’s to say, in the battery with MnF₂, there will be more irreversible reactions consuming lithium source. It can be inferred that Mn²⁺ is the dominate factor affecting the cycle stability of silicon-based half-cell.

To figure out the growth of SEI membrane of silicon-based negative electrode after 100th cycles, the cycled battery was adjusted to delithiation state, and then being disassembled in the argon glove box. After washing the residual electrolyte with dimethyl carbonate (DMC), the electrode was observed by SEM. Figures 4a and 4b are images of silicon negative electrode without MnF₂, and Figs. 4c and 4d are electrode with MnF₂. Overall, larger cracks appeared in the negative electrode with MnF₂ after cycling. The generation of cracks will make part of the electrode materials lose their electrochemical activity as dropping off from the collector, which to some extent will impede nano silicon particles to become fully effective. Judging from the surface morphological pattern of silicon particles, floccules layer can be observed on the surface of silicon particles of the two electrodes, which is the SEI membrane generated on the surface of silicon particles. The growth of SEI with MnF₂ is more serious than that without MnF₂.

To obtain the direct evidence of the growth of SEI membrane on silicon-based NE, differential scanning calorimetry (DSC) was used to test the cycled battery in delithiation state, and fresh silicon NE as comparison. The results of DSC test are shown in Fig. 5. It can be seen from the figure that a significant exothermic peak between 100–200 ℃ representing decomposition reaction of SEI membrane on the negative electrode surface, according to previous research, appeared in cycled battery while not in new battery. The peak value0.54 W/g of exothermic peak is at about 162℃.

The difference of SEI thickness between with and without Mn²⁺ environment is shown in Fig. 6, then the damage mechanism of Mn²⁺ on the silicon anode in lithium-ion batteries is also explained. The SEI excessive growth is mainly caused by the large volume change of the silicon particles during charge /discharge cycling. By the way, Mn²⁺ makes SEI more fragile, lets SEI more easily break, results silicon particles more electrochemical reaction interface, and then accelerates the SEI thickening.

Part 2 Research on capacity fading mechanism on silicon/LMO full cell.

The experiments of simulating the electrochemical environment of Mn²⁺ show that Mn²⁺ has a serious impact on the coulomb efficiency and cycle performance of the negative electrode. In order to deeply explore the mechanism and influence of such effect in practical application of silicon-based batteries, full cell with LMO as positive electrode (PE) and nano silicon particle as NE were assembled to analyze their electrochemical behavior and capacity degradation trend.

Figure 7 shows SEM images of positive and negative electrodes used to prepare the full cell. Figure 7a shows the surface morphological image of LiMn₂O₄ electrode. It is clear that the coating is uniform and there are no obvious defects. Figure 7b is the detailed morphological pattern of LiMn₂O₄ particles whose particle size is about 500nm. The particles with size lower than 100 nm are uniformly distributed around the LiMn₂O₄ particles, which are the binders and conductive agents of the electrode. Figure 7c and 7d are the surface morphological image of nano silicon particle electrode. The distribution of silicon particles in the electrode is as uniform as half-cell.

Figure 8 shows galvanostatic charge and discharge test results of LMO/Si full cell, the results of silicon-based half-cell are also shown in the figure for comparison. The charge capacity of the 1st cycle and the 2nd cycle of full cell are 2820mAh / g and 3010mAh/g, respectively, and then reduced gradually in every next cycles. At 100th cycle, the capacity has decayed to 170mAh/g, 6% of original capacity. The battery can be considered as being failure at this time. In aspect of coulomb efficiency, the first and second cycle coulomb efficiency is 30.2% and 36.4%, respectively. As cycles increasing, the coulomb efficiency went down first and then went up inversely. At 100th cycle, the coulomb efficiency is 41.1%. Compared with the silicon based half-cell, full cell shows a serious downward trend of capacity: the coulomb efficiency of half-cell can be stably maintained at more than 90%, while the full cell was less than 40% in the first 90 cycles. Judging from the experiment of the electrochemical performance of full cell, it can be concluded that the capacity of LMO/Si full cell has a serious decline in the process of cyclic charging and discharging, and the low coulomb efficiency is the main factor for this rapid decline. In principle, low coulomb efficiency will lead to more irreversible reactions then generate more SEI membrane.

To study the growth of SEI membrane of silicon NE in full cell, the batteries after 100 cycles were disassembled in an argon atmosphere glove box, and then washed the negative electrode with DMC to remove the residual electrolyte, finally observed by SEM, as shown in Fig. 9. From Fig. 9a, it can be seen that not only serious cracks appeared on the surface of electrode, but white mottled traces came out. Figure 9b provides more details of silicon particles: silicon particles are almost invisible, instead by lots of floccule. This phenomenon is led by the excessive growth of SEI membrane coating on silicon particles. Compared with the SEM images of 100 cycles half-cell in Fig. 4, more SEI film grew on silicon NE in the full cell indirectly explains the faster decline of capacity than that of half-cell.

In this paper, the problem of whether the dissolution of Mn²⁺ in manganese based positive electrode will affect the properties of silicon based negative electrode is investigated on the level of electrochemical properties and material structure. The electrochemical test of half-cell by simulating the electrochemical environment with Mn²⁺, shows that Mn²⁺ did affect the capacity retention rate and coulomb efficiency of silicon-based negative electrode, also verified the excessive growth of SEI membrane on the surface of silicon-based negative electrode by DSC. Further, through the electrochemical analysis of LMO/Si full cell, it is found that Mn²⁺ has more significant degradation effect on the silicon-based negative electrode in full cell whose lithium source is limited. Under such condition, more SEI membrane generated then consumed the limited lithium source in the LMO positive electrode, which leading to the rapid degradation of battery performance. The research in this paper proves that the dissolution of Mn²⁺ of positive electrode affecting silicon-based negative electrode must be considered particularly in actual application. An optimization on material level is necessary to deal with this problem.

I have read and understood the publishing policy, and submit this manuscript in accordance with this policy.

I declare that the authors have no competing interests as defined by Springer, or other interests that might be perceived to influence the results and/or discussion reported in this paper.

Data availability

Yingying Zeng and Haihui Chen wrote the main manuscript text, Xiuguang Yi prepared figures 1-5. Limin Liu prepared figures 6-9. All authors reviewed the manuscript.

ACKNOWLEGEMENTS

This work was supported by the Natural Science Foundation of China (Nos. 21865014 and 22168018), the Natural Science Foundation of Jiangxi Province of China (20202BABL203003,20232BAB203048),the Natural Science Foundation from Education Department of JiangXi Province (GJJ2201607).the Ji’an Multioly Science and Technology Project（20222-171754，20222-181740）.

DATA ACCESSIBILTY

The data used to support the findings of this study are available from the corresponding author on reasonable request.

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Damage mechanism of dissolved manganese ions from cathode to silicon anode in lithium ion batteries

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