Effect of graphene nanosheets on electrochemical performance of Li4Ti5O12 in lithium-ion capacitors

In order to improve the electrochemical performance of lithium titanium oxide, Li₄Ti₅O₁₂ (LTO), for the use in the lithium-ion capacitors (LICs) application, LTO/graphene composites were synthesized through a solid state reaction. The composite exhibited an interwoven structure with LTO particles dispersed into graphene nanosheets network rather than an agglomerated state pristine LTO particles. It was found that there is an optimum percentage of graphene additives for the formation of pure LTO phase during the solid state synthesis of LTO/graphene composite. The effect of graphene nanosheets addition on electrochemical performance of LTO was investigated by a systemic characterization of galvanostatic cycling in lithium and lithium-ion cell configuration. The optimized composite exhibited a decreased polarization upon cycling and delivered a specific capacity of 173 mA h g⁻¹ at 0.1 C and a well maintained capacity of 65 mA h g⁻¹ even at 20 C. The energy density of 14 Wh kg⁻¹ at a power density of 2700 W kg⁻¹ was exhibited by a LIC full cell with a balanced mass ratio of anode to cathode along with a superior capacitance retention of 97% after 3000 cycles at a current density of 0.4 A g⁻¹. This boost in reversible capacity, rate capability and cycling performance was attributed to a synergistic effect of graphene nanosheets, which provided a short lithium ion diffusion path as well as facile electron conduction channels.     

Construction of pseudocapacitive Li2-xLaxZnTi3O8 anode for fast and super-stable lithium storage

Lithium-ion capacitors (LICs) composed of battery-type anodes with large energy densities and capacitor-type cathodes with high power densities are considered as appealing energy-storage devices. Here, a LIC with good performance is constructed using active carbon (AC) as the cathode and Li_1.95La_0.05ZnTi₃O₈ (LL5ZTO) as the anode. LL5ZTO doped with La is synthesized via a one-step solid-state route. The kinetics and structural stability of LZTO are enhanced by La-doping. Thus, LL5ZTO exhibits good Li-storage performance. The discharge specific capacity reaches 182.6 mAh g^?1 at 3 A g^?1 (120th cycle) for LL5ZTO. The LIC based on the LL5ZTO anode and the AC cathode delivers an energy density of 59.72 Wh kg^?1 at 846.4 W kg^?1, and a high power density of 8771 W kg^?1 at 19.49 Wh kg^?1. Furthermore, the capacity retention is over 90% after 3000 cycles for the LIC at 2 A g^?1. The good electrochemical performance indicates that the constructed LIC is expected to use in advanced energy storage devices.     

Synthesis and electrochemical performance of Li4Ti5O12 submicrospheres coated with TiN as anode materials for lithium-ion battery

The TiN coated Li₄Ti₅O₁₂ (LTO) submicrospheres with high electrochemical performance as anode materials for lithium-ion battery were synthesized successfully by solvothermal method and subsequent nitridation process in the presence of ammonia. The XRD results revealed that the crystal structure of LTO did not change after thermal nitridation process. The submicrospheres morphology of LTO and TiN film on the surface of LTO submicrospheres were characterized by FESEM and HRTEM, respectively. XPS result confirmed that a small amount of Ti changed from Ti⁴⁺ to Ti³⁺ after nitridation process, which will increase the electronic conductivity of LTO. Electrochemical results showed that electrochemical performance of TiN coated LTO anode materials compared favorably with that of pure LTO. Also its rate capability and cycling performance were apparently superior to those of pure LTO. The reversible capacity of TiN-LTO is 105.2 mA h g⁻¹ at a current density of 10 C after 100 cycles and maintain 92.9% of its initial discharge capacity, while that of pure LTO is only 83.6 mA h g⁻¹ with a capacity retention of 90.3%. Even at 20 C, the discharge capacity of TiN coated LTO sample is 101.3 mA h g⁻¹, compared with 77.3 mA h g⁻¹ for pristine LTO in the potential range 1.0–2.5 V (vs. Li/Li⁺).     

Li4Ti5O12 hollow microspheres assembled by nanosheets as an anode material for high-rate lithium ion batteries

In this paper, Li₄Ti₅O₁₂ (LTO) hollow microspheres with the shell consisting of nanosheets have been synthesized via a hydrothermal route and following calcination. Because of the favorable transport properties of this hollow structure, it is the rate performance at high current densities which is exceptional. When the LTO hollow microspheres were used as the anode material in lithium ion battery, they exhibited superior rate performance and high capacity even at a very high rate (131 mAh g⁻¹ at 50 C).     

Electrochemical performance of Li4Ti5O12 anode materials synthesized using a spray-drying method

In this study, spinel lithium titanate (Li₄Ti₅O₁₂, LTO) anode materials were synthesized from two titanium sources (P25 TiO₂, 100% anatase TiO₂) using a spray-drying method and subsequent calcination at various temperatures. The electrochemical performance of both a Li/LTO half cell and a LiNi_0.5Mn_1.5O₄/LTO (LNMO/LTO) full cell were investigated. The electrochemical performance of the LTO material prepared from P25 TiO₂ was superior to that of the LTO prepared from 100% anatase TiO₂. After modification of LTO material with AlPO₄, the LTO coated with 2 wt% of AlPO₄ (denoted “2%AlPO₄-LTO”) provided the best performances. The specific (delithiation) capacities of the 2%AlPO₄-LTO anode material was 189.7 mA h g⁻¹ at 0.1C/0.1C, 184.5 mA h g⁻¹ at 1C/1C, 178.8 mA h g⁻¹ at 5C/5C, and 173.1 mA h g⁻¹ at 10C/10C. From long-term cycling stability tests, the specific capacity at the first cycle and the capacity retention after cycling were 185.5 mA h g⁻¹ and 98.06%, respectively, after 200 cycles at 1C/1C and 182.1 mA h g⁻¹ and 99.18%, respectively, after 100 cycles at 1C/10C. For the LNMO/2%AlPO₄-LTO full cell, the average specific capacity (delithiation) and coulombic efficiency after the first five cycles were 164.8 mA h g⁻¹ and 93.30%, respectively, at 0.1C/0.1C. The specific capacities at higher C-rates were 156.1 mA h g⁻¹ at 0.2C/0.2C, 135.7 mA h g⁻¹ at 1C/1C, 97.5 mA h g⁻¹ at 3C/3C, and 46.5 mA h g⁻¹ at 5C/5C. After twenty-five cycles, the C-rate returned to 1C/1C and the specific capacity, coulombic efficiency, and capacity retention were maintained at 134.1 mA h g⁻¹, 99.17%, and 98.82%, respectively.     

Preparation and electrochemical performance of SnO2@carbon nanotube core–shell structure composites as anode material for lithium-ion batteries

Carbon nanotube-encapsulated SnO₂ (SnO₂@CNT) core–shell composite anode materials are prepared by chemical activation of carbon nanotubes (CNTs) and wet chemical filling. The results of X-ray diffraction and transmission electron microscopy measurements indicate that SnO₂ is filled into the interior hollow core of CNTs and exists as small nanoparticles with diameter of about 6 nm. The SnO₂@CNT composites exhibit enhanced electrochemical performance at various current densities when used as the anode material for lithium-ion batteries. At 0.2 mA cm^?2 (0.1C), the sample containing wt. 65% of SnO₂ displays a reversible specific capacity of 829.5 mAh g^?1 and maintains 627.8 mAh g^?1 after 50 cycles. When the current density is 1.0, 2.0, and 4.0 mA cm^?2 (about 0.5, 1.0, and 2.0C), the composite electrode still exhibits capacity retention of 563, 507 and 380 mAh g^?1, respectively. The capacity retention of our SnO₂@CNT composites is much higher than previously reported values for a SnO₂/CNT composite with the same filling yield. The excellent lithium storage and rate capacity performance of SnO₂@CNT core–shell composites make it a promising anode material for lithium-ion batteries.     

Hierarchical Li4Ti5O12 nanosheet arrays anchoring on carbon fiber cloth as ultra-stable free-standing anode of Li-ion battery

A flexible, free-standing composite anode with Li₄Ti₅O₁₂ nanosheet arrays anchoring on plain-weaved carbon fiber cloth (LTO@CC) is prepared by a hydrothermal and post-annealing process assisted by a TiO₂ seed layer. The LTO@CC anode free from polymeric binder and conducting agent exhibited much higher lithium storage capacity and cycling stability than the conventional slurry-processed electrode using the dandelion-like Li₄Ti₅O₁₂ microspheres prepared by the same hydrothermal process. A high specific capacity of 128.8 mA h g^?1 was obtained at a current rate of 30 C (1 C = 175 mA g^?1), and almost negligible capacity loses was observed when the cell was cycled at 10, 20 and 30 C each for 100 cycles. The carbon fiber matrix contributed to Li storage at low current rate, but the LTO nanosheet arrays have played the dominant role on the excellent rate capability. The improved electrochemical performance can be attributed to the synergetic effect between the hierarchical Li₄Ti₅O₁₂ nanosheet arrays and the carbon fiber matrix, which integrated short Li⁺ diffusion length, three-dimensional conductive architecture and well preserved structural integrity during the high rate and repeated charge-discharge measurements.     

Synthesis and electrochemical performance of Li4Ti5O12/Ag composite prepared by electroless plating

To improve the electrochemical and anti flatulence performance of Li₄Ti₅O₁₂, Ag modified Li₄Ti₅O₁₂ (LTO) with high electrochemical performance as anode materials for lithium-ion battery was synthesized successfully by two-step solid phase sintering and subsequent electroless plating process in the presence of silver. The effect of Ag modification on the physical and electrochemical properties were investigated by the extensive material characterization of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM). The results showed that the samples possessed single spinel structure, it could be observed that the LTO/Ag composite and the pure LTO shared the same vibration frequencies, which indicated that the crystal structure of LTO didn’t change after electroless plating process, and the particles were uniformly and regularly shaped within 0.5–1.0 µm. Electrochemical performance of the samples were evaluated by the charging and discharging, cyclic voltammetry, electrochemical impedance spectroscopy, cycling and rate tests. It's obvious that the LTO/Ag composite prepared at the 10 min of electroless plating showed the highest performance with capacitance of 182.3 mA h/g at 0.2 C current rates. What's more, the LTO/Ag composites still maintained 92% of its initial capacity even after 50 charge/discharge cycles. Modification of appropriate Ag not only benefits the reversible intercalation and deintercalation of Li⁺, but also improves the diffusion coefficient of lithium ion. Besides, modification of appropriate Ag lower electrochemical polarization leads to higher conductivity and cycle performance of LTO, which is consistent with the results of the best reversible capacities.     

NiSe2 encapsulated in N-doped TiN/carbon nanoparticles intertwined with CNTs for enhanced Na-ion storage by pseudocapacitance

Transitional metal selenides are considered as potential anode candidates for sodium-ion batteries (SIBs) because of their relatively high theoretical capacity and environmental benign. However, the large volume change derived from the conversion reaction and the sluggish kinetics due to the inherent low electrochemical conductivity hinder their practical application. Herein, composite materials of NiSe₂ encapsulated in nitrogen-doped TiN/carbon nanoparticles with carbon nanotubes (CNTs) on the surface (NiSe₂@N-TCP/CNTs) are fabricated via pyrolysis and selenization processes. In this composite, TiN inside the carbon matrix can enhance the conductivity and structural stability. CNTs that are in-situ grown on the surface not only further enhance the conductivity of the composites, but also offer sufficient space to buffer the volume expansion and alleviate serious aggregation of NiSe₂ nanoparticles. Benefit from these merits, the NiSe₂@N-TCP/CNTs showed a lower charge transfer resistance and a faster Na⁺ diffusion rate than materials without growing CNTs. When used as the anode of SIBs, the NiSe₂@N-TCP/CNTs electrode delivered a reversible capacity of 344.0 mAh g^?1 after 1000 cycles at 0.2 A g^?1, and still maintained at 272.7 mAh g^?1 even at a high current density of 2 A g^?1. The remarkable electrochemical performance is mainly attributed to the special designed hierarchical structures and pseudocapacitance sodium storage behavior.     

Chemically driven synthesis of Ti3+ self-doped Li4Ti5O12 spinel in molten salt

Surface doping of Li₄Ti₅O₁₂ (LTO) with Ti³⁺ ions is an effective way to enhance its electrochemical properties for lithium ion batteries (LIBs). Herein, a molten salt approach was reported to synthesize Ti³⁺ self-doped LTO powder. The reaction mechanism and the role of molten salt for the synthesis have been systemically discussed. Finally, electrochemical performance of the LTO powder was preliminarily evaluated as anode material of LIBs. The molten salt accelerated the mass transportation for the formation of LTO by transferring a solid diffusion to the diffusion of ions in a liquid media. Self-doping of Ti³⁺ ions on the surface of LTO particles was achieved by controlling equilibriums of chemical reactions in the reactor. Electrochemical performance of the LTO powders was effectively promoted by doping Ti³⁺ ions on the surface. The discharge capacity of the Ti³⁺ self-doped LTO powder prepared at 850°C was 171 mAhg⁻¹, and the capacity dacayed 9.9% after 200 cycles at a rate of 0.5 C.     

Effect of heat treatment on electrochemical characteristics of spinel lithium titanium oxide

Spinel structured LTO (lithium titanium oxide), Li₄Ti₅O₁₂, materials have gained renewed interest in electrodes for lithium-ion batteries. Powder precursors were mixed by HEBM (high energy-ball mill) and Li₄Ti₅O₁₂ was formed by calcinations at high temperature. The influence of excess Li on the structural characteristics of lithium titanium oxide was investigated. According to the XRD and SEM analysis, uniformly distributed Li₄Ti₅O₁₂ particles were synthesized. Li₄Ti₅O₁₂ had different characteristics due to the precursor sizes and the heat treatment temperatures. LTO from micro TiO₂ showed the highest discharge capacity at 750 °C for 12 h. LTO from nano TiO₂ showed the highest discharge capacity at 700 °C for 12 h. Lithium-ion battery with Li₄Ti₅O₁₂ anode and lithium metal cathode showed the capacity of 170 mAh/g at 1.0–3.0 V.     

NiFe-NiFe2O4/rGO composites: Controlled preparation and superior lithium storage properties

Binary transition-metal oxides with spinel structure have great potential as advanced anode materials for lithium-ion batteries (LIBs). Herein, NiFe-NiFe₂O₄/ reduced graphene oxide (rGO) composites are obtained via a facile cyanometallic framework precursor strategy to improve the lithium storage performance of NiFe₂O₄. In the composites, NiFe-NiFe₂O₄ nanoparticles with adjustable mass ratios of NiFe₂O₄ to NiFe alloy are homogeneously deposited on rGO sheets. As anode material for LIBs, the optimized NiFe-NiFe₂O₄/rGO composite displays remarkably enhanced lithium storage performance with an initial specific capacity as high as 1362 mAh g⁻¹ at 0.1 A g⁻¹ and a decent capacity retention of ca. 80% after 130 cycles. Besides, the composite delivers a reversible capacity of 550 mAh g⁻¹ at 1 A g⁻¹ after 300 cycles. During the charge–discharge cycles, the aggregation of the NiFe-NiFe₂O₄ nanoparticles and the structural collapse of the electrode can be well alleviated by rGO sheets. Moreover, the conductivity of the electrode can be significantly improved by the well-conductive NiFe alloy and rGO sheets. All these contribute to the improved lithium storage performance of NiFe-NiFe₂O₄/rGO composites.     

Preparation and electrochemical performance of SiCN–CNTs composite anode material for lithium ion batteries

The composite of silicon carbonitride (SiCN) and carbon nanotubes (CNTs) was synthesized by sintering the mixture of polysilylethylenediamine-derived amorphous SiCN and multi-walled CNTs at a temperature of 1,000 °C for 1 h in argon. The as-prepared SiCN–CNTs material, which was used as anode active substance in a lithium ion battery, showed excellent electrochemical performance. Charge–discharge tests showed the SiCN–CNTs anode provided a high initial specific discharge capacity of 1176.6 mA h g⁻¹ and a steady specific discharge capacity of 450–400 mA h g⁻¹ after 30 charge–discharge cycles at 0.2 mA cm⁻². Both of the abovementioned values are higher than that of pure polymer-derived SiCN, CNTs, and commercial graphite at the same charge–discharge condition. It was deduced that the CNTs in the composite not only improved the electronic conductivity and offered channels and sites for the immigrating and intercalating of Li⁺ but also stabilized the structure of the composite.     

Investigation the sodium storage kinetics of H1.07Ti1.73O4@rGO composites for high rate and long cycle performance

Insertion type material has been attracted plenty of attentions as the anode of sodium ion batteries (SIBs) due to the low volume change induced long cycle stability. H_1.07Ti_1.73O₄ (HTO), a two-dimensional layered material, is a new insertion type anode material for SIBs reported in this study. Layered HTO composites were decorated with rGO nanosheets via an electrostatic assembly method followed by hydrothermal treatment. When adapted as the anode material of SIBs, HTO@rGO composite exhibits an enhanced sodium ion storage behavior, including high rate capability and long cycle stability. It can deliver high capacities of 142.8 and 66.7 mA h g⁻¹ at 100 and 10 000 mA g⁻¹, respectively. Moreover, it can keep a capacity of 75.1 mA h g⁻¹ at 5 A g⁻¹ after even 5000 cycles, corresponding to a high capacity retention of 70.8% (0.0058% capacity decay per cycle). HTO exhibits a small volume expansion of 19.6% by in-situ transmission electron microscopy (in-situ TEM). The diffusion coefficient of sodium ions is increased from 1.77 × 10⁻¹⁴ cm² s⁻¹ in HTO composites to 4.80 × 10⁻¹⁴ cm² s⁻¹ in HTO@rGO composites. Our designed and synthesized HTO@rGO provides a new route for high rate and long cycle stable SIBs anode materials.     

Effect of calcination temperature on morphology and electrochemical performance of PbLi2Ti6O14

As a promising anode material, PbLi₂Ti₆O₁₄ has attracted the attention of many researchers. In this work, a series of PbLi₂Ti₆O₁₄ are prepared by solid state method at five different calcination temperatures and used as anode materials in lithium ion batteries. Through a series of tests, the results show that the phase purity, morphology and electrochemical performance of PbLi₂Ti₆O₁₄ can be seriously influenced by calcination temperature. When the calcination temperature is 900?°C, the phase-pure PbLi₂Ti₆O₁₄ can be obtained with relatively small particle size, excellent cycle performance and outstanding lithium ion diffusion behavior. It provides an initial charge capacity of 151.3?mA?h?g^?1 at 100?mA?g^?1. After 100 cycles, it shows a reversible capacity of 142.0?mA?h?g^?1 with superior capacity retention of 93.85%. In contrast, PbLi₂Ti₆O₁₄ formed at 800?°C displays an unsatisfactory performance due to the presence of impurity, even though it has the smallest particle size and the largest lithium ion diffusion coefficient among the five samples. The reversible capacity is only 82.6?mA?h?g^?1 after 100 cycles with capacity retention of 53.9%. In order to further study the lithium ion diffusion behavior of PbLi₂Ti₆O₁₄, the in-situ X-ray diffraction technique is also implemented. It is found that during the lithiation/delithiation process, the stable framework can effectively inhibit the volume change and ensures the excellent electrochemical performance of PbLi₂Ti₆O₁₄.     

Ti2Nb10O29@C hollow submicron ribbons for superior lithium storage

Titanium niobate prepared by traditional techniques has the shortcomings of low ion diffusion coefficient as well as poor electrical conductivity, which drastically reduce its applicability. In this work, we prepare carbon coated Ti₂Nb₁₀O₂₉ hollow submicron ribbons (Ti₂Nb₁₀O₂₉@C HSR) using a simple electrospinning procedure. As anode material for lithium-ion batteries (LIBs), it delivers a high charge capacity of 259.7 mAh g^?1 at 1 C with low capacity loss of 0.013% in long-term cycles. Increased the current density to 5 C, Ti₂Nb₁₀O₂₉@C HSR can maintain a reversible capacity of 189.9 mAh g^?1, indicating its good rate performance. Additionally, this work uses in-situ X-ray diffraction (XRD) to provide an explanation for the lithium storage process in Ti₂Nb₁₀O₂₉@C HSR, demonstrating the high reversibility during charge/discharge cycles. Therefore, Ti₂Nb₁₀O₂₉@C HSR has outstanding cycle adaptability and structural reversibility to be a promising anode for LIBs.     

Synthesis of 1D-MoS2/graphene nanotubes aided with sodium chloride for reversible lithium storage

A novel negative material consisting of graphene nanotubes and ultrathin MoS₂ is synthesized by a simple one-step hydrothermal method assisted with Sodium chloride. The MoS₂/Graphene electrodes deliver a specific capacity of 1350 mAh g^?1 under 0.1 A g^?1 and high rate capability (retaining 85.5% capacity from 0.1 A g^?1 to 0.8 A g^?1). A high remarkable capacity of 820 mAh g^?1 can still be recovered at 0.5 A g^?1 after 500 cycles, and the average coulombic efficiency was as high as 99.98% during the additional 500 cycles. The excellent Li-ion storage performance of MoS₂/Graphene nanotubes may be attributed to the ultra-thin MoS₂ flakes and curled graphene nanotubes. This structural feature has a strong adsorption capacity for lithium ions, which can provide a broad space for ion storage. A large number of active sites dispersed in the layered molybdenum disulfide promote the kinetics of the electrochemical reaction, empowering the ultra-thin layered molybdenum disulfide to get a higher theoretical capacity. In addition, the existence of the tubular structure alleviates volume expansion and provides a way for the rapid movement of electrons and diffusion of Li⁺ during repeated cycles.     

Zn–Mn-ptcda derived two-dimensional leaf-like Zn0·697Mn0·303Se/C composites as anode materials for high-capacity Li-ion batteries

As the most widely used energy storage device today, lithium-ion batteries (LIBs) will determine the convenience and durability of people's future energy life to a certain extent. At present, there are many and mature researches on cathode materials for LIBs, so it is crucial to seek a high-performance anode material. In recent years, due to considerable theoretical capacity, abundant raw material reserves and unique physicochemical properties, Zn and Mn selenium compounds have become research hotspots for LIBs anode materials. In this work, a new MOF material Zn–Mn-ptcda was synthesized by a simple hydrothermal reaction. Using Zn–Mn-ptcda as the precursor, two-dimensional (2D) elliptical leaf-shaped Zn_0·697Mn_0·303Se/C composites were synthesized by direct selenization. Zn_0.697Mn_0.303Se/C has a large specific surface area of 213.9 m² g^?1, belongs to the mesoporous structure, and possesses excellent lithium storage performance, especially the rate performance. It has a reversible capacity of 1005.14 mAh g^?1 after 110 cycles at a current density of 100 mA g^?1. After 1000 cycles at a high current density of 1 A g^?1, it still maintains a good capacity of 653.79 mAh g^?1.     

Investigation of Li5Cr7Ti6O25 as novel anode material for high-power lithium-ion batteries

In this work, Li₅Cr₇Ti₆O₂₅ as a new anode material for rechargeable batteries is fabricated through a simple sol-gel method at different calcination temperatures. The X-ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy, charge/discharge curve and cyclic voltammograms are utilized to study the crystal structures, morphologies and electrochemical properties of as-obtained Li₅Cr₇Ti₆O₂₅ samples. The impact of calcination temperatures on morphologies and electrochemical properties of Li₅Cr₇Ti₆O₂₅ is discussed in detail. The test result shows that the 800 °C is a proper calcination temperature for Li₅Cr₇Ti₆O₂₅ with excellent electrochemical properties. Cycled at 200 mA g⁻¹, it displays a high initial reversible capacity of 146.6 mA h g⁻¹ and retains a considerable capacity of 130.8 mA h g⁻¹ after 300 cycles. Even cycled at large current density of 500 mA g⁻¹, the initial reversible capacity of 129.6 mA h g⁻¹ with the capacity retention of 88% after 300 cycles is achieved, which is obviously higher than that of Li₅Cr₇Ti₆O₂₅ prepared at 700 °C (80.5 mA h g⁻¹ and 68%) and 900 °C (98.4 mA h g⁻¹ and 80%). In addition, in-situ XRD analysis reveals that Li₅Cr₇Ti₆O₂₅ exhibits a reversible structural change during lithiation and delithiation processes. The above prominent electrochemical performance indicates the great potential of the Li₅Cr₇Ti₆O₂₅ obtained at 800 °C as anode material for rechargeable batteries.     

Rapid preparation and performances of garnet electrolyte with sintering aids for solid-state Li–S battery

Lithium-sulfur (Li–S) batteries are attractive due to their high theoretical energy density. However, conventional Li–S batteries with liquid electrolytes undergo polysulfide shuttle-effect and lithium dendrite formation during charge/discharge process, leading to poor electrochemical performance and safety issues. Garnet type Li₇La₃Zr₂O₁₂ (LLZO) solid-state electrolyte (SSE) restricts the penetration of polysulfides and exhibits high ionic conductivity at room temperature (RT). Herein, Li_6.5La₃Zr_1.5Nb_0.5O₁₂ (LLZNO) ceramic electrolyte using Li₃PO₄ (LPO) as sintering aids (LLZNO-LPO) is prepared by the rapid sintering method and is applied to construct a shuttle-effect free solid-state Li–S battery. The SSE displays high conductive pure cubic-LLZO phase; during the rapid sintering, LPO melts and junctions the voids between the grains, thus improves Li⁺ conductivity. As a result, the LLZNO-LPO ceramic electrolyte with Li⁺ conductivity of 4.3 × 10^?4 S cm^?1 and high critical current density (CCD) of 1.2 mA cm^?2 is obtained at RT. The Li–S solid-state battery which utilizes LLZNO-LPO ceramic electrolyte can deliver an initial discharge capacity of 943 mA h·g^?1 and 602 mA h·g^?1 retention after 60 cycles. In the same time, the initial coulombic efficiency is as high as 99.5%, indicating that the SSE can effectively block the polysulfide shuttle towards the Li anode and fulfill a shuttle-free Li–S battery.