Figure
1.
Schematic of the processes of the battery assembly.
| Citation: |
Chenxi Zheng, Shijun Tang, Fangmei Wen, Jinxue Peng, Wu Yang, Zhongwei Lv, Yongmin Wu, Weiping Tang, Zhengliang Gong, Yong Yang. Reinforced cathode-garnet interface for high-capacity all-solid-state batteries[J]. Materials Futures, 2022, 1(4): 045103. DOI: 10.1088/2752-5724/aca110
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Garnet-type solid-state electrolyte (SSE) is considered as a prospective candidate for building all-solid-state batteries (ASSBs) owing to its high ionic conductivity, wide electrochemical window and high stability against lithium (Li) metal and air [1-3], which enable it to fit high-voltage cathode materials and Li metal anode (3860 mAh g-1 and -3.040 V versus the standard hydrogen electrode) for higher energy density [4, 5]. However, the practical application of garnet-based ASSBs is restricted by the large interfacial resistance between the electrolytes and electrodes. Many attempts have been made to ameliorate the interfacial contact between the garnet SSE and Li anode, including introducing interface coatings (e.g. C, Mg, Al2O3, g-C3N4, LiF, Cu3N) [6-12], and removing the Li2CO3 from the garnet by surface treatment (e.g. HCI, H3PO4, NH4F, H3BO3-HF) [13-16], which have effectively reduced the interfacial resistance and improved the performance of Li symmetric batteries. Nevertheless, building an intimate cathode/garnet SSE interface is still limited by the following challenges. (a) High-temperature sintering may give rise to unexpected side reactions between the cathode active material (CAM) and the electrolyte in the composite cathode, while low-temperature sintering leads to poor contact between CAM and the electrolyte, and between the composite cathode layer and the electrolyte layer [17-19]; (b) non-negligible volume change in CAM during cycling may cause particle fracture and interface delamination [20, 21]; (c) electrochemical reactions may occur between CAM and the electrolyte [22, 23]. All the above ultimately results in low cathode loading and poor cyclic performance of garnet-based ASSBs.
Recent studies have made extensive efforts to reduce the resistance of the cathode/garnet SSE interface, where LiCoO2 (LCO) is extensively studied as CAM due to its high electronic conductivity, high thermal stability and similar thermal expansion coefficient to garnet SSEs [24-27]. Among them, three main approaches have been highlighted. (a) Depositing LCO on the garnet pellet directly to form a thin film [28-30]. However, the loading of the cathode film, which is typically hundreds of nanometers thick, is extremely low. (b) Casting the composite cathode slurry on the top surface of garnet pellets followed by sintering [31-38]. To improve the contact of LCO and garnet, sintering additives such as Li3BO3 (LBO) and its derivatives are added to the composite cathode slurry. Despite all this, most cells fabricated by this method still suffer from low operating current density and areal loading, which cannot meet the requirements of high-energy bulk-type Li batteries. (c) Co-sintering the electrolyte and the composite cathode into a dual-layer by simultaneous pressurization and heating, such as spark plasma sintering (SPS) [22, 39-41], and hot-press sintering [42]. The significant merit of the co-sintering process is to construct a cathode/SSE interface directly from each specific powder rather than rigid pellets under applied pressure, which can easily attain tight interface bonding and high-capacity cathodes (>1 mAh cm-2). Generally, a lower sintering temperature (700 C) is usually chosen to avert side reactions between LCO and garnet, yet leading to poor interfacial contact and high interfacial impedance. Moreover, degradation may occur at the LCO/garnet interface during electrochemical cycling [22], both resulting in poor cycling stability. Therefore, in terms of the state-of-the-art garnet-based ASSBs, there is still much scope for improvement to reach the desired target, and it remains a major challenge to enhance the stability of cathode/garnet interface.
Herein, we report a reinforced cathode/garnet interface constructed by the SPS method, which achieves an intimate contact between high-capacity cathode and garnet SSE. The electrolyte is composed of Li6.5La3Zr1.5Ta0.5O12 (LLZTO) and LBO, and the composite cathode is composed of LCO, LLZTO and LBO (figure 1). LBO is served as a sintering additive with a room-temperature Li-ion conductivity of 2 10-6 S cm-1 and melts at 700 C, which can wet the particles and accelerates the interdiffusion of atoms in liquid phase, beneficial to the enhancement of densification and Li+ conductivity [43, 44]. Profiting from the SPS and LBO strategies, the composite cathode with conductive network structure is firmly bonded to the LLZTO layer, thereby reducing its interfacial impedance to as low as 3.9 cm2 at 100 C. Thus, the bulk-type Li|LLZTO|LCO-LLZTO ASSB with an areal loading of 0.73 mAh cm-2 exhibits superior cycling stability with a capacity retention of 81.7% after 50 cycles at 100
LLZTO and LBO were both synthesized via solid-state reaction methods. The starting materials of LLZTO, LiOH·H2O (99%, Aladdin), La2O3 (99.99%, Aladdin), ZrO2 (99.99%, Aladdin), Ta2O5 (99.5%, Aladdin), were ball milled in stoichiometric amounts with 2-propanol as dispersant and 10 wt% excess LiOH·H2O was added to compensate for Li loss during subsequent sintering. The mixed powder was then dried and transferred to a muffle furnace for calcining at 900 C for 12 h. The sintered powder was finally sieved into a uniform fine powder with a 200-mesh sieve. For LBO synthesis, LiOH·H2O (99%, Aladdin) and B2O3 (98%, Aladdin) were mixed in a mole ratio of 6:1 and then calcined at 600 C for 4 h.
LCO-LLZTO/LLZTO half cells were sintered using a LABOX-212 SPS system. LCO (Canrd, China), LLZTO, LBO were mixed in a mass ratio of 50:50-x:x (x = 0, 2, 5, 10) as the composite cathode. LLZTO, LBO were mixed in a mass ratio of 100-x:x (x = 0, 2, 5, 10) as the electrolyte. The two powders were layered into a graphite mold with an inner diameter of 10 mm, and sintered at 80 MPa and 690 C for 1 h at high vacuum. Then the LCO-LLZTO/LLZTO half cells were transferred to a tube furnace and annealed at 875 C for 2 h in O2 flow. The as-sintered pellets were firstly polished, where the LLZTO layers were about 800
The phase structure was analyzed by x-ray diffraction (XRD), using a Rigaku Ultima IV x-ray Diffractometer, which operated at 40 kV and 30 mA over the range of 10 90 (2
Galvanostatic charge and discharge tests of Li|LLZTO|LCO-LLZTO ASSBs were conducted between 3.0 and 4.05 V at different current density, and collected with a Land CT-2001A (Wuhan, China). The electrochemical impedance spectroscopy (EIS) tests were performed in an Auto Lab workstation, in the frequency range from 1 MHz to 0.01 Hz and with an amplitude of 10 mV. The full cells were charged to 4.05 V and held at 4.05 V for 12 h, then rest at open circuit voltage for 2 h before EIS testing.
As shown in figure S1, no discernible impurities are detected in the as-synthesized LLZTO and LBO by XRD, and the diffraction peaks of LLZTO are well indexed to cubic phase. Previous studies have reported that LCO and LLZTO would gradually set off a heat-induced reaction from 700 C [18, 45], thus we selected 690 C as the heating temperature. Owing to the relatively low temperature, the density of pellets can be improved by prolonging the dwell time, in contrast to that of other previous reports (10 min) [39, 41]. The Li-ion conductivity of the electrolyte pellets with various dwell time of 15 min, 30 min, 1 h, and 1.5 h were tested by EIS at room temperature (figure S2, table S1). The results indicate that the Li-ion conductivity increases with the prolongation of the dwell time within 1 h, and when the dwell time reaches 1.5 h, the excessive volatilization of Li leads to the formation of La2Zr2O7 impurity phase (figure S3), resulting in a slight decrease in ionic conductivity, and thus 1 h is selected as the dwell time.
During sintering above 600 C, LCO in the composite cathode is reduced to CoO due to direct contact with graphite molds [25, 41, 46], but interestingly, this change can be reversed by annealing in O2 flow, confirmed by both XRD, Raman spectroscopy, and XPS, as shown in figure 2. From XRD and Raman results (figures 2(a) and (b)), the patterns show explicitly that the CoO in the composite cathode is oxidized back to LCO after annealing. From XPS results (figure 2(c)), Co2p spectrum shows spin orbit splitting into 2p1/2 (at the high binding energy) and 2p3/2 (at the low binding energy) intensity peaks which contain the same chemical information. For the sample of composite cathode before annealing, the 2p3/2 peak locates at 781.1 eV can be assigned to Co2+, with a corresponding satellite peak at 786.8 eV, consistent with the previous report [47]. For the sample of composite cathode after annealing, the 2p3/2 component can be well fitted into an intensive main peak at 779.4 eV assigned to Co3+ and a weak peak at 781.3 eV assigned to Co2+, accompanied by a satellite peak at 788.4 eV [48], which indicates that most Co2+ is converted to Co3+. By contrast, the cubic phase structure of LLZTO is well maintained during the sintering process, implying that LLZTO does not occur any chemical reaction with LCO or graphite at the current experimental conditions (figure S4).
As mentioned above, LBO was added as a sintering additive for SPS process, which has a great influence on the microstructure of sintered products. Figures S5(a) and (d) show the SEM images of the cross section of the sintered LCO-LLZTO/LLZTO half cells with 0 wt%, 2 wt%, 5 wt% and 10 wt% LBO, respectively. Figures S5(e)-(h) show the corresponding contact state of particles inside the composite cathode at high magnification, respectively. With the increase of LBO content, the voids between the composite cathode layer and the electrolyte layer and between the particles reduce accordingly, and the sintered density increases. When the LBO content reaches 5%, the LCO-LLZTO/LLZTO half cell achieves a fairly dense state, as shown in figure 3(a). An enlarged SEM image of the interface between the LCO composite cathode and the LLZTO electrolyte (red boxed area in figure 3(a)) is shown in figure 3(b), which shows a densified sintered structure and a well-welded interface. The EDS mappings of La, Zr, Co and B (figures 3(c)-(f)) demonstrate that the LLZTO and LCO are each connected into a conductive network, which are tightly cross-linked throughout the cathode, providing composite channels to facilitate Li-ion and electron transport. LBO is evenly scattered in the LCO-LLZTO/LLZTO half cell which boosts the cementing among particles to form a reinforced dual-layer structure and mitigate the strain/stress of LCO. The EDS line scan (figure 3(g)) shows the variation trends of elements in the direction perpendicular to the LLZTO/LCO interface (the inset in figure 3(g)), where a thin interfacial layer of about 320 nm think is formed, and no additional elements are detected in the bulk of LLZTO and LCO particles, implying that there is no obvious element diffusion or chemical reactions between the bulk of two particles. Furthermore, the electrolyte pellet with LBO exhibits a higher mechanical strength, as shown in the figure 3(h) and S6. The Young’s modulus of the electrolyte pellet with 5% LBO is 6.5 GPa, while that without the additive is only 3.5 GPa. This also indicates that LBO enhances the compactness of the pellets, which conduces to improve Li-ion conductivity and restrains the growth of Li dendrite.
The optimal LBO content was explored by evaluating the impedance of the full cell. As shown in figure S7, the EIS spectra of Li|LLZTO|LCO-LLZTO ASSBs with different LBO contents at 100 C all comprise four parts. The impedance value of the real axis intercept in the high frequency can be assigned to the resistance of LLZTO electrolyte (RLLZTO), the semicircle in the high-frequency region (1 MHz-150 Hz) represents the interfacial resistance between Li and LLZTO (RLi/LLZTO), the semicircle in the mid-frequency region (150 Hz-1 Hz) represents the interfacial resistance between composite cathode and LLZTO (RLCO-LLZTO/LLZTO), and the diagonal line in the low frequency is related to the Warburg impedance attributed to the Li-ion diffusion process [31, 49]. The inserted equivalent circuit is used for simulating the electrical response of the full cells, wherein R is the resistance element, CPE is the constant phase element, W is the Warburg element. The fitting results of RLLZTO, RLi/LLZTO, and RLCO-LLZTO/LLZTO for the full cells with different LBO content are shown in table S2. It shows that each resistance component of the full cell with 5% LBO is the smallest. This can be attributed to the influences of sintering additive LBO. Wherein, moderate LBO can promote the densification, thus facilitate rapid ionic/electronic conduction. While excess addition is adverse to Li-ion transport due to the low Li-ion conductivity of LBO. Furthermore, the interfacial resistance between the cathode and LLZTO is as low as 3.9 cm2 (at 100 C, 5% LBO), confirming that the SPS and sintering additive strategies are highly effective at improving the poor solid-solid contact between the garnet and the cathode.
We then selected Li|LLZTO|LCO-LLZTO full cells with 5% LBO for electrochemical performance measurements due to their lower impedance. The full cells with different areal capacity are assembled and subjected to the galvanostatic charge-discharge test at 100 C with a current density of 100
To further explore the evolution of electrode/electrolyte interfaces of the cell during cycling, we performed ex-situ SEM tests on the same batch of high-capacity cells (1 mAh cm-2) with different cycle numbers at 60 C. For LLZTO/anode interface, the Li metal exhibits intimate contact with the LLZTO electrolyte prior to cycling (figure 5(a)). After 30 cycles, as shown in figure 5(b), there are several gaps between Li and LLZTO electrolyte, triggered by the accumulated stress due to the persistent uneven Li plating/stripping at the Li/LLZTO interface. The loss in the interface contact would accelerate the generation of an uneven electric field, causing the continuous deterioration of the Li/LLZTO interface. After 130 cycles, the Li/LLZTO interface shows severe degradation with the formation of large voids and the cell fails (figure 5(c)). In comparison, there is no obvious change observed for the LCO/LLZTO interface, which is still in intimate contact even after 130 cycles (figure 5(d)). The composite cathode layer maintains a dense state as well, where most particles show no obvious fractures (the inset of figure 5(d)). Besides, no impurity is generated in the composite cathode after 130 cycles, validated by the XRD pattern (figure S10). These results indicate that the electrochemical reaction and the resultant volume change are uniform throughout the composite cathode, and the SPS process builds a durable SSE/cathode interface that keep unchanged and intact in structure during long-term cycling. Hence, it can be concluded that the performance degradation of the bulk-type Li|LLZTO|LCO-LLZTO ASSBs is primarily due to the continuous deterioration of the Li/LLZTO interface. Based on the previous electrochemical results (figures S8, 4(a)), generally, lowering the areal Li plating/stripping capacity could alleviate the deterioration of the Li/LLZTO interface, thus improving the cycling stability the ASSBs. To investigate the effects of cathode areal capacity on the electrochemical performance of Li|LLZTO|LCO-LLZTO ASSBs, we decreased the areal capacity to 0.49 mAh cm-2. As expected, the cycling stability is significantly enhanced. It shows that the capacity retention is high up to 92.3% after 50 cycles (figure S11(a)). And the Li metal anode still maintains intimate contact with LLZTO electrolyte (figure S11(b)). The difference in behavior of the Li/LLZTO interface demonstrates the effectiveness of the low cathode capacity in lessening the contact loss between Li anode and LLZTO electrolyte, which forcefully proves that the stability of the Li/LLZTO interface plays a vital role in the cycling stability of the bulk-type Li|LLZTO|LCO-LLZTO ASSBs with high areal capacities.
To date, various works have been reported to construct LLZO-based ASSBs, as shown in table 1. It is obvious that the Li|LLZTO|LCO-LLZTO full cell in this work demonstrates outstanding operating current density, areal capacity, and cycling stability. For pursuing better electrochemical performance, subsequent research endeavors can be made in improving the mechanical stability of a Li/LLZO interface during repeated high-capacity (>3 mAh cm-2) Li plating/stripping process, for example, combining 3D interface construction and multifunctional interlayers, and then adapting it to ASSB systems, thereby achieving high capacity and extended cycling.
| Reference | Cathode | Temp. (C) | Current density ( | Areal capacity (mAh cm-2) | Voltage range (V) | No. of cycles (Capacity retention) |
| [29] | LCO (Al2O3 interlayer) | NR | 3.85 (0.1 C) | 0.039 | 2.5-4.2 | 100 (85%) |
| [31] | LCO-LLZO- Li2.3C0.7B0.3O3 | 25 100 | 5.75 | 0.094 0.106 | 3.0-4.05 | 100 (94%) 40 (63.2%) |
| [32] | LCO-LLZO- Al2O3 | 100 | 38.4 | 0.116 | 2.8-4.2 | 16 (92%) |
| [33] | LCO-Li2BO2- In2O5Sn | 80 | 14 (0.1 C) | 0.14 | 3.0-4.5 | 25 (55%) |
| [36] | LCO-LBO- In2O5Sn | RT | 5 | 0.056 | 2.8-4.3 | 6 (87%) |
| [37] | LCO-LBO- In2(1-x)Sn2xO3 | 80 | 15 (0.08 C) | 0.188 | 2.8-4.3 | 20 (86%) |
| [38] | LCO-LLZO | 80 | 4.2 | 0.086 | 3.0-4.05 | 14 (97.5%) |
| [42] | LCO-LLZO- Li2.985B0.005OCl | 90 | 4.8 (0.05 C) | 0.096 | 3.0-4.1 | 50 (64%) |
| This work | LCO-LLZO- LBO | 100 | 100 100 100 | 1.40 0.73 0.49 | 3.0-4.05 | 50 (66.7%) 50 (81.7%) 50 (92.3%) |
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In summary, a solid and durable cathode/garnet interface is successfully constructed by low temperature densification strategy using the SPS method with LBO as sintering additive. The intimate LCO-LLZTO/LLZTO interface and the cross-linked structure of the composite cathode are efficiently constructed and provide unimpeded ionic/electronic conducting pathways, ensuring high electrochemical activity under high areal capacity. As a consequence, the initial LCO-LLZTO/LLZTO interfacial impedance RLCO-LLZTO/LLZTO is remarkably reduced to 3.9 cm2 (100 C), and the areal capacity is high up to 2.02 mAh cm-2. EIS and SEM analyses reveal that the capacity decay of the bulk-type Li|LLZTO|LCO-LLZTO ASSBs is mainly attributed to the degradation of the Li/LLZTO interface induced by the uneven Li plating/stripping, which results in interfacial contact loss and continuous increase in interfacial impedance, while the LCO/LLZTO interface possesses high stability, and maintains intimate contact and extremely low interfacial impedance even after long-term operation. The deterioration of the Li/LLZTO interface can be mitigated via decreasing the areal capacity of Li plating/stripping. The Li|LLZTO|LCO-LLZTO full cells with areal capacities of 0.73 mAh cm-2 and 0.49 mAh cm-2 exhibit superior cycling stability with capacity retention of 81.7% and 92.3% after 50 cycles, respectively. Overall, our investigation proposes a promising methodology to address the key challenge of a cathode/LLZTO interface and provides guidance for future development of high-capacity garnet-based ASSBs.
This work was supported by the National Key R&D Program of China (Grant No. 2021YFB2401800), the National Natural Science Foundation of China (Grants Nos. 21875196, 22279108, 21935009 and 22021001) and the Fundamental Research Funds for Xiamen University (No. 20720202019).
Conflict of interest
The authors declare no conflict of interest.
Authors to whom any correspondence should be addressed.
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Figures(5) / Tables(1)
Copyright © 2021 Materials Futures Editorial Office
Supported by: Beijing Renhe Information Technology Co., Ltd. 
| Reference | Cathode | Temp. (C) | Current density ( | Areal capacity (mAh cm-2) | Voltage range (V) | No. of cycles (Capacity retention) |
| [29] | LCO (Al2O3 interlayer) | NR | 3.85 (0.1 C) | 0.039 | 2.5-4.2 | 100 (85%) |
| [31] | LCO-LLZO- Li2.3C0.7B0.3O3 | 25 100 | 5.75 | 0.094 0.106 | 3.0-4.05 | 100 (94%) 40 (63.2%) |
| [32] | LCO-LLZO- Al2O3 | 100 | 38.4 | 0.116 | 2.8-4.2 | 16 (92%) |
| [33] | LCO-Li2BO2- In2O5Sn | 80 | 14 (0.1 C) | 0.14 | 3.0-4.5 | 25 (55%) |
| [36] | LCO-LBO- In2O5Sn | RT | 5 | 0.056 | 2.8-4.3 | 6 (87%) |
| [37] | LCO-LBO- In2(1-x)Sn2xO3 | 80 | 15 (0.08 C) | 0.188 | 2.8-4.3 | 20 (86%) |
| [38] | LCO-LLZO | 80 | 4.2 | 0.086 | 3.0-4.05 | 14 (97.5%) |
| [42] | LCO-LLZO- Li2.985B0.005OCl | 90 | 4.8 (0.05 C) | 0.096 | 3.0-4.1 | 50 (64%) |
| This work | LCO-LLZO- LBO | 100 | 100 100 100 | 1.40 0.73 0.49 | 3.0-4.05 | 50 (66.7%) 50 (81.7%) 50 (92.3%) |
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