Sustainable Energy & Fuels
·
2023
·Vol. 7
·期 7
·1645-1655
·
IF 5.6
Wen He,Hui Ding,Chuandong Li,Xu Chen,Wensheng Yang
The Li7La3Zr2O12 (LLZO) electrolyte is typically introduced as an inorganic filler into poly(ethylene oxide) (PEO) to enhance the performance of batteries. However, LLZO particles inevitably come into contact with air and produce a Li2CO3 layer. The low ionic conductivity of Li2CO3 is not conducive to the conduction of Li+. Herein, LLZO particles were treated with salicylic acid (SA) to achieve dual functions. First, SA is used to effectively remove the Li2CO3 layer of the LLZO particles, which improves Li+ mobility at the interface of LLZO and the PEO matrix. Furthermore, SA treatment favors the uniform dispersion of LLZO and the positively charged SA-treated LLZO facilitates the immobilization of anions in LiTFSI, both of which promote the fast transport of Li+ in the PEO matrix. Therefore, the modified composite electrolyte exhibits an improved ionic transference number (0.63) and ionic conductivity (1.21 × 10−4 S cm−1 at 30 °C). The Li/Li symmetric battery can operate over 1300 h. Furthermore, the Li/LiFePO4 battery exhibits an impressive discharge capacity of 142.8 mA h g−1 after 150 cycles at 0.2C. These results indicate that SA treatment is a useful method for enhancing the electrochemical properties of the LLZO/PEO solid electrolyte.
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高影响因子
JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS
·
2025
·Vol. 36
·期 12
·1-14
·
IF 2.8
Mei Rui,Yan Feng,Hu Sizheng,Gong Zonggui,Guo Haoxuan,Wang Qijing,Zheng Xinghua
With the increasingly urgent safety requirement of lithium-ion batteries, more and more attention has been paid to Li 7 La 3 Zr 2 O 12 (LLZO)-based solid electrolytes with high ion conductivity and excellent electrochemical performance. Unfortunately, owing to the serious “Li-loss” and the abnormal grain growth (AGG) during the long-time high-temperature sintering process, it is difficult to achieve the high-quality LLZO electrolyte with uniform and fine grains, high density and excellent electrochemical performance. In this work, Ga/Mo co-doped LLZO solid-state electrolytes have been prepared by traditional sintering (TS) and two-step sintering (TSS). And the sintering mechanism, phase stability, microstructure evolution, and electrochemical performance have been systematically investigated. A small amount of Ga/Mo doping not only promotes the formation of the cubic garnet LLZO phase, but also enhances the stability of cubic phase. High density of 92.3% and uniform microstructure without AGG have been achieved via a small amount of Ga doping and TSS. Li 6.3 Ga 0.1 La 3 Zr 1.8 Mo 0.2 O 12 electrolytes, prepared by TSS of 1200 °C/15 min-1100 °C/8 h, exhibits high ion conductivity of 2.59 × 10 –4 S·cm −1 and critical current density (CCD) value of 0.5 mA·cm −2 , low electric conductivities of 4.77 × 10 –9 S·cm −1 , which suggests it is a potential electrolyte to apply in all-solid-state batteries.
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Jingtao Wang,Shiyuan Guo,Zhenghua Li,Weijie Kou,Jiachen Zhu,Jingchuan Dang,Yafang Zhang,Wenjia Wu
To achieve high energy density of all-solid-state lithium batteries, solid-state electrolytes (SSEs) are required to be thin and highly conductive. Although constructing efficient inorganic Li-ion transfer network can provide excellent conductivity for SSEs, it is still challenging for these SSEs to simultaneously realize thin thickness and mechanical stability. Herein, well-ordered vertical Li 7 La 3 Zr 2 O 12 sheet arrays (VLSA) were prepared, followed by introducing triple-layer ion-conducting polymers to fabricate 8 μm-thick VLSA composite solid electrolyte (CSE). We demonstrate that vertical and short VLSA (major path, accounting for 71.4% of Li-ion transfer) and VLSA/polymer interface (minor path, 27.8%) contribute to the high ionic conductivity of 2.60 × 10 −4 S cm −1 and ionic conductance of 0.5 S at 30 °C, ranking one of the highest values among reported SSEs. The stiff VLSA enhances the mechanical strength of CSE, while the polymer existing in VLSA channels serves as a deformable buffer, endowing CSE with bendable property. Besides, the trilayer polymer structure permits this electrolyte to be compatible with lithium anode and high-voltage cathode. Therefore, the high-loading LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM523) cell can be cycled with limited lithium anode (N/P ratio = 1.18) over 158 cycles with capacity retention upon 80%, realizing a high energy density of 458.4 Wh kg −1 .
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高影响因子
Journal of Energy Storage
·
2023
·
IF 9.4
Yanan Teng,Huan Liu,Qi Wang,Yan He,YongChang Hua,Chunping Li,Jie Bai
Garnet type Li 7 La 3 Zr 2 O 12 solid electrolyte exhibits excellent thermal stability and high ionic conductivity, which is an ideal solid electrolyte. However, it is found that the cubic phase is a high conductivity phase and the synthesis condition is harsh. Therefore, low temperature synthesis and partial element substitution are expected to prepare cubic phase LLZO. In this paper, the LLZO cubic phase structure is stabilized by electrospinning technology and high-priced cation substitution strategy, and the transportation efficiency of lithium ions is improved. The experimental results show that LLZO NFs inorganic filler with stable cubic phase structure is obtained when the molar amount of In 3+ is 0.2. The In 3+ with large ion radius replaces the Li + inside the crystal, effectively increases the lithium vacancy concentration, and increases the Li + transport path inside the crystal, and successfully doubles the ionic conductivity of the composite solid electrolyte at 60 °C (9.39 × 10 −4 S/cm). The lithium ions migration number and electrochemical window were increased to 0.19 and 5.2 V respectively. With excellent cycle performance (60 °C), it can cycle 2000 cycles at a high rate of 0.5 C charge and discharge, and the Coulomb efficiency has been close to 100 %. Li|PL-LILZO NFs (0.2)|LFP all-solid-state lithium batteries can light small bulbs at room temperature and have practical application prospects. Therefore, in the composite electrolyte, the increase of the lithium ions pathway inside the active inorganic filler crystal will also improve the comprehensive performance of the composite electrolyte for preparation.
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高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Xiao Huang,Jiawen Tang,Yongjian Zhou,Kun Rui,Xin Ao,Yan Yang,Bingbing Tian
Li7La3Zr2O12 (LLZO) is one of the most promising candidate solid electrolytes for high-safety solid-state batteries. However, similar to other solid electrolytes containing volatile components during high-temperature sintering, the preparation of densified LLZO with high conductivity is challenging involving the complicated gas–liquid–solid sintering mechanism. Further attention on establishing low-cost laborastory-scale preparation craft platform of LLZO ceramic is also required. This work demonstrates a “pellet on gravel” sintering strategy, which is performed in a MgO crucible and box furnace under ambient air without any special equipment or expensive consumables. In addition, the competition between lithium loss from the sintering system and internal grain densification is critically studied, whereas the influences of particle surface energy, Li-loss amount, and initial excess Li2O amount are uncovered. Based on the sintering behavior and mechanism, optimized craft platform for preparing dense LLZO solid electrolytes including mixing, calcination, particle tailoring and sintering is provided. Finally, exemplary Ta-doped LLZO pellets with 2 wt % La2Zr2O7 additives sintered at 1260–1320 °C for 20 min deliver Li+ conductivities of ∼9 × 10–4 S cm–1 at 25 °C, relative densities of >96%, and a dense cross-sectional microstructure. As a practical demonstration, LLZO solid electrolyte with optimized performance is applied in both Li–Li symmetric cells and Li–S batteries. This work sheds light on the practical production of high-quality LLZO ceramics and provides inspiration for sintering ceramics containing volatile compounds.
研究领域:
材料科学
·
固体离子学
·
陶瓷工艺
·
储能技术
·
电池技术
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高影响因子
Membranes
·
2023
·Vol. 13
·期 2
·216
·
IF 4.2
Shishuo Liang,Dong Yang,Jianhua Hu,Shusen Kang,Xue Zhang,Yanchen Fan
With the rapid development of energy storage and electric vehicles, thiophosphate-based all-solid-state batteries (ASSBs) are considered the most promising power source. In order to commercialize ASSBs, the interfacial problem between high-voltage cathode active materials and thiophosphate-based solid-state electrolytes needs to be solved in a simple, effective way. Surface coatings are considered the most promising approach to solving the interfacial problem because surface coatings could prevent direct physical contact between cathode active materials and thiophosphate-based solid-state electrolytes. In this work, Li7La3Zr2O12(LLZO) and LiNbO3(LNO) coatings for LiCoO2(LCO) were fabricated by in-situ interfacial growth of two high-Li+conductive oxide electrolytes on the LCO surface and tested for thiophosphate-based ASSBs. The coatings were obtained from a two-step traditional sol–gel coatings process, the inner coatings were LNO, and the surface coatings were LLZO. Electrochemical evaluations confirmed that the two-layer coatings are beneficial for ASSBs. ASSBs containing LLZO-co-LNO coatings LiCoO2(LLZO&LNO@LCO) significantly improved long-term cycling performance and discharge capacity compared with those assembled from uncoated LCO. LLZO&LNO@LCO||Li6PS5Cl (LPSC)||Li-In delivered discharge capacities of 138.8 mAh/g, 101.8 mAh/g, 60.2 mAh/g, and 40.2 mAh/g at 0.05 C, 0.1 C, 0.2 C, and 0.5 C under room temperature, respectively, and better capacity retentions of 98% after 300 cycles at 0.05 C. The results highlighted promising low-cost and scalable cathode material coatings for ASSBs.Keywords:solid-state batteries;LiCoO2;sulfide solid-state electrolyte;LiNbO3-coating;LLZO-coating
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PubMed
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2023
·
IF 6.2
Yanhua Zhang,Yuhang Mei,Xinglong Gao,Yumei Xiao,Zijun Tang,Xing Xiang,Jiadong Deng
The lithium dendrite problem of Li 7 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) solid electrolyte restricts the practical application and development of all-solid-state lithium batteries (ASSLBs). Herein, a LiPON interlayer with Li + conductive and electron non-conductive dynamic properties is constructed at the Li/LLZTO interface. Results show that the electronic conductivity of solid electrolyte after LiPON modification decreased by nearly three orders of magnitude, indicating that it has good ability to hinder electron conduction . The interlayer enhances the wettability between the Li metal anode and LLZTO, resulting in a decrease of battery resistance from 3400 Ω to 700 Ω. The critical current density of the ASSLBs increase from 0.1 mA cm −2 to 1.2 mA cm −2 at room temperature, and the battery cycle number increase from 31 h to over 1000 h. XPS deep etching results show that the LiPON/LLZTO interface has good electrochemical stability. The Kelvin probe force microscope displays a sharp increase in potential within the LiPON interlayer, indicating its successful hindrance of electron conduction to the solid electrolyte. The effective inhibition of lithium dendrites growth is due to LiPON can promote the Li + transmission from LLZTO solid electrolyte to Li anode, and also hinder the electron conduction to LLZTO to form lithium dendrites.
研究领域:
材料科学
·
电化学
·
能源存储
·
固态电池
·
界面工程
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DOI
高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Zhiqiang Fang,Ming Zhao,Yan Peng,Shiyou Guan
Solid-state electrolytes can guarantee the safe operation of high-energy density lithium metal batteries (LMBs). However, major challenges still persist with LMBs due to the use of solid electrolytes, that is, poor ionic conductivity and poor compatibility at the electrolyte/electrode interface, which reduces the operational stability of solid-state LMBs. Herein, a novel fiber-network-reinforced composite polymer electrolyte (CPE) was designed by combining an organic plastic salt (OPS) with a bicontinuous electrospun polyvinylidene fluoride-co-hexafluoropropylene (PVDF–HFP)/Li7La3Zr2O12 (LLZO) membrane. The presence of LLZO in the composite helps to promote the dissociation of FSI– from OPSs. Subsequently, the dissociated FSI– is then involved in the formation of a LiF-rich solid electrolyte interphase (SEI) layer on the lithium anode via a reductive decomposition reaction, which was affirmed by theoretical calculations and experimental results. Due to the LiF-rich SEI layer, the Li/Li symmetric cell was able to demonstrate a long cyclic life of over 2600 h at a current density of 0.1 mA cm–2. More importantly, the as-prepared CPE achieved a high ionic conductivity of 2.8 × 10–4 S cm–1 at 25 °C, and the Li/LiFePO4 cell based on the CPE exhibited a high discharge capacity and 83.3% capacity retention after 500 cycles at 1.0 C. Thus, the strategy proposed in this work can inspire the future development of highly conductive solid electrolytes and compatible interface designs toward high-energy density solid-state LMBs.
研究领域:
材料科学
·
储能
·
电化学
·
电池技术
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高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2018
·
IF 3.779
Xiaolan Chen,Tian Wang,Wanzheng Lu,Tianxiang Cao,Mingzhe Xue,Bing Li,Cunman Zhang
A modified solution method was applied to synthesize cubic garnet solid-state electrolyte Li 7 La 3 Zr 2 O 12 (LLZO) and Li 6.45 Ca 0.05 La 2.95 Ta 0.6 Zr 1.4 O 12 (LCLTZO). The synergetic doping of Ca and Ta is found to induce the formation of cubic LCLZTO with high ionic conductivity of 4.03 × 10 −4 S cm −1 while LLZO without substitution exhibits tetragonal phase with low conductivity. A Li-S cell with sulfur cathode and as-prepared LCLTZO solid electrolyte “separator” was conducted to deliver large initial discharge capacity of 1090 mAh g −1 with high initial Coulombic efficiency up to 92%. Cell with LCLTZO also exhibited better cycling performance at 0.2 C and extremely high Coulombic efficiency (close to 100%) than the cell without solid electrolyte. Better rate performance was also achieved at lower rate (0.2 C, 0.5 C and 1 C) by cell with LCLTZO although it lost advantages at higher rate of 2 C and 5 C due to the limitation of ionic conductivity of LCLTZO. Energy dispersive X-ray spectroscopy (EDS) provided direct evidence that LCLTZO solid electrolyte greatly suppressed the shuttle effect generated by polysulfides . The electrochemical impedance spectroscopy was applied to discuss the difference between cells with and without LCLTZO during the discharge process. Charge transfer reaction referred to soluble polysulfides was found to be slower in cell with LCLTZO than that in cell without solid electrolyte.
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高影响因子
JOURNAL OF POWER SOURCES
·
2021
·
IF 9.127
Xuewen Zheng,Ting Yang,Jianghai Wei,Chengyang Wang,Mingming Chen
Solid electrolytes have been actively researched for rechargeable lithium batteries , but low ion conductivity ( σ ) and the growth of lithium dendrites hinder their practical applications. This study synthesizes a composite solid electrolyte combining polyethylene oxide (PEO) with Li 7 La 3 Zr 2 O 12 nanofibers (LLZO NFs) and quenching in liquid nitrogen . The LLZO NFs efficiently increase the σ and mechanical strength of composite polymer electrolytes (CPEs), thereby promoting the uniform deposition of lithium metal and inhibiting the growth of lithium dendrites. More importantly, the quenching markedly reduces the crystallinity of the electrolyte, which further enhances the ionic conductivity even at 30 °C. The CPEs exhibit high σ (1.09 × 10 −4 S cm −1 at 30 °C) and enlarged electrochemical window (up to 5 V vs . Li/Li + ). An integrated all-solid-state lithium metal battery (ASSLMBs) (labeled as LiFePO 4 |PEO/LLZO NFs/LiTFSI- q |Li) delivers high initial discharge capacity (138.8 mAh g −1 ) and excellent cycling stability (74.8% at 0.5C after 300 cycles) with remarkable capacity retention (84.0% at 1C after 200 cycles) at 45 °C. This strategy enables the promotion and application of ASSLMBs at room temperature.
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高影响因子
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