CN114335758A - Garnet solid electrolyte based high-temperature molten lithium iodine battery - Google Patents
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Abstract
The invention discloses a garnet solid electrolyte-based high-temperature melting lithium iodine battery, and aims to solve the technical problems that iodine elements are easy to sublimate, iodides are easy to dissolve in liquid electrolyte, and lithium cathodes are corroded. It comprises a U-shaped garnet LLZTO (
The ceramic electrolyte tube is used as solid electrolyte, eutectic iodide is filled in the U-shaped tube to serve as a positive electrode, lithium metal is filled between the outer side of the U-shaped tube and the stainless steel shell to serve as a negative electrode, and a graphite rod is used as a current collector to conduct electricity, so that the basic structure of the garnet solid electrolyte high-temperature melting lithium iodine battery is formed. The garnet solid electrolyte high-temperature battery works at the temperature of 260 ℃, the voltage platform can be stabilized at 2.7V under the charge-discharge multiplying power of 0.2-5C, the specific capacity attenuation of the battery can be almost ignored after more than 2000 charge-discharge cycles under the high charge-discharge multiplying power of 3C, and the garnet solid electrolyte high-temperature battery is stabilized at 175 DEG C
。
Description
Technical Field
The invention relates to the technical field of electrochemical cells, in particular to a garnet solid electrolyte-based high-temperature molten lithium iodine cell.
Background
The electrochemical energy storage system is widely applied to the fields of electric automobiles, portable electronic equipment, power grid energy storage and the like.
With the innovation of technology, there is a great gap between the requirements for safety, high energy density and long cycle life and the currently dominant lithium ion (Li-ion) energy storage technology.
At present, the lithium metal in the lithium metal battery has the lowest potential (-3.04V) and the highest specific capacity (-2800)
) And is expected to meet the requirements. The lithium-iodine battery has high average working voltage (-2.9V) and high theoretical capacity (211) due to the unique advantages of the lithium-iodine battery
) Good rate capability and broad iodine content are receiving more and more attention.
Up to now, a large number of reports on lithium-iodine batteries have been liquid electrolyte lithium-iodine batteries.
Iodine element is easy to sublimate, iodide is easy to dissolve in liquid electrolyte, lithium negative electrode is corroded, and the like, so that the practical use of the rechargeable lithium-iodine battery is hindered.
Disclosure of Invention
The invention aims to solve the technical problems of easy sublimation of iodine elements, easy dissolution of iodide in liquid electrolyte and corrosion of a lithium cathode by providing a garnet-based solid electrolyte high-temperature melting lithium iodine battery.
In order to solve the technical problems, the invention adopts the following technical scheme:
designing a high-temperature melting lithium iodine battery based on a garnet solid electrolyte, which comprises the garnet solid electrolyte, a positive electrode material and a negative electrode material; the garnet solid electrolyte is LLZTO (
) Ceramic, the positive electrode material comprisesCsI/LiIAnd (3) co-melting the salt, wherein the negative electrode material is molten metal lithium.
Preferably, the garnet solid electrolyte is a U-shaped ceramic tube, and the positive electrode material is sealed in the U-shaped ceramic tube; and a stainless steel shell is arranged on the outer side of the U-shaped ceramic tube, and the negative electrode material is sealed in a space formed between the U-shaped ceramic tube and the stainless steel shell.
Preferably, the molar ratio of LiI to CsI in the positive electrode material is 9:1, the weight ratio of the positive electrode material is 95:5CsI/LiIA mixture of eutectic salts and carbon nanotubes.
Further, the current collector is a graphite rod.
Preferably, the garnet solid electrolyte is formed by high-temperature sintering, and can transmit lithium ions and block the positive electrode material and the negative electrode material.
Preferably, the working temperature of the battery is 260-460 ℃. At the working temperature of 260 ℃, the positive electrode eutectic salt CsI/LiI and the negative electrode lithium metal are in a molten state and are in stable contact with the interface of the U-shaped garnet solid electrolyte.
Preferably, the charge-discharge positive-negative electrode reaction of the battery follows the equation:
。
preferably, the specific capacity of the battery is kept at 175 after more than 2000 cycles under the voltage range of 2.3V-3.5V and the charge-discharge rate of 3C
。
Compared with the prior art, the invention has the beneficial technical effects that:
1. the invention adopts a U-shaped garnet ceramic electrolyte tube as a solid electrolyte, eutectic iodide is filled in the U-shaped tube as a positive electrode, lithium metal is filled between the outer side of the U-shaped tube and a stainless steel shell as a negative electrode, and a graphite rod is used as a current collector. A Molten Lithium Ion Battery (MLIB) consisting of a molten lithium negative electrode and a molten CsI/LiI eutectic salt positive electrode at a medium operating temperature of 260 ℃. The lithium anode and the iodide cathode and the LLZTO solid electrolyte both present liquid-solid interfaces, present low interface impedance and good interface contact, the eutectic salt anode is packaged in a U-shaped garnet ceramic tube, and iodine substances and multi-iodide formed in the circulation process can be better limited in the anode, so that self-discharge is blocked, and good reversibility is maintained. Molten metal lithium is arranged between the stainless steel shell and the ceramic tube, the battery is charged firstly and then discharged, and specific electrode reactions are as follows:
a large amount of iodine is generated in the charging process, and the iodine is prevented from sublimating due to the good closed environment of the ceramic tube, so that the iodine is stored in a eutectic salt form in the discharging process. So as to achieve the effect of high cycle number and hardly losing the activity of the anode material. The lithium ion battery has the advantages that the lithium ion battery does not corrode a lithium cathode or consume an iodide anode, so that the overall cycle life of the battery is prolonged.
2. The high temperature resistance of the U-shaped garnet solid electrolyte ceramic tube and the melting point of the stainless steel shell are far higher than that of lithium metal, the lithium metal cathode is in a sealed area between the ceramic tube and the stainless steel shell, is not lost in a molten state, is not polluted by the external environment, does not have side reaction of the solid electrolyte and the lithium cathode, and is in a safe working temperature range between 260 ℃ and 460 ℃, so that the solid lithium battery has a high safety coefficient.
3. The solid-state molten lithium-iodine battery also overcomes the problem of poor conductivity of a solid electrolyte, and under the condition that the state of charge (SOC) is changed from 0% to 100%, the internal resistance of the solid-state molten lithium-iodine battery is changed from 4 omega to 4.7 omega, which indicates that the internal part of the battery still maintains electrochemical stability in the charging and discharging processes.
4. The CsI/LiI eutectic salt positive electrode has excellent multiplying power performance in the garnet solid electrolyte high-temperature molten lithium iodine battery, so that the garnet solid electrolyte high-temperature battery works at the temperature of 260 ℃, the voltage platform can be stabilized at 2.7V under the charge and discharge multiplying power of 0.2-5C, the specific capacity attenuation of the battery can be almost ignored after more than 2000 charge and discharge cycles under the high charge and discharge multiplying power of 3C, and the battery is stabilized at 175 DEG C
。
Drawings
Fig. 1 is a schematic design diagram of a garnet solid electrolyte high-temperature melting lithium iodine battery of the present invention, in which (a) is a schematic cross-sectional view of an example of the configuration, (b) is a view of a change in the composition of a eutectic salt positive electrode during (charge) discharge, (c) is an optical image of a U-shaped garnet electrolyte and an iodide positive electrode sealed inside after cycling, and (d) is an optical photograph of a cycled and artificially broken iodide positive electrode.
Fig. 2 is a schematic diagram of the electrochemical reaction mechanism of a molten lithium ion battery, wherein (a) is a binary phase diagram of CsI and LiI (the dashed line indicates an operating temperature of 260 ℃), (b) is the effect of the remaining LiI on the molar mass ratio of eutectic salts CsI/LiI and SOC, (C) is the variation of the molar mass ratio of eutectic salts CsI/LiI with the state of charge (SOC), (d) is the XRD test of the eutectic salt positive electrode, (e) is the ICP-OES test of element I, Cs and Li in the state of charge, and (f) is a typical (charge) discharge voltage curve of the molten lithium iodine battery at 0.2 ℃.
Fig. 3 is SEM electron micrographs of high (a) and low (b) for the eutectic salt composition morphology, mortar treated initial eutectic salt, and high (C) and low (d) for the positive electrode in the fully charged state, and (e) is a schematic representation of the electrochemical reaction of the electrode during charging and discharging at a working temperature of 260 ℃.
Fig. 4 is an electrochemical performance test graph in which (a) is a CV curve of a first cycle having a voltage range of 2.0 to 3.5V, (b) a constant current voltage curve of the first five cycles having a voltage window of 2.3 to 3.2V at 1C, (C) a constant current cycle performance of the molten lithium-iodine battery at 1C, (d) a nyquist curve of the molten lithium-iodine battery after 100 charge and discharge cycles, (e) a GITT test of pulse charge and discharge at a current density of 0.2C with an interval rest time of 10 min, and (f) a lithium ion diffusion coefficient based on the result of (e).
Fig. 5 is a test chart of rate and cycle life performance, wherein (a) is rate performance characteristics and cycle discharge capacities at 0.2, 1, 3 and 5C, respectively, (b) corresponding voltage-capacity curves at different rates, (C) is measured data of a garnet solid electrolyte high temperature melting lithium iodine battery in an operating state (260 ℃) cycled at a 3C charge-discharge rate, wherein the lithium iodide loading is 593g, and (d) is calculated power and energy density compared with representative LTO and LFP.
Fig. 6 is a schematic diagram of battery safety at different operating temperatures.
FIG. 7 is a diagram illustrating a cold start cycle performance test.
Detailed Description
The following examples are intended to illustrate the present invention in detail and should not be construed as limiting the scope of the present invention in any way.
Example 1: a garnet-based solid electrolyte high-temperature melting lithium iodine battery comprises a solid electrolyte, a positive electrode material and a negative electrode material.
(1) Preparation of solid electrolyte
The U-shaped LLZTO garnet ceramic electrolyte is prepared by a high-temperature solid-phase reaction method. Mixing Li according to stoichiometric ratio of chemical formula2CO3(chemical reagent of Chinese national drug group, 20% excess, 99.99%) La2O3(chemical reagent of Chinese national drug group, Inc., purity 99.99%), ZrO 22(Chinese Aladdin, purity 99.99%) and Ta2O5(Europeanization, China, purity 99.99%) powder was sufficiently ground, and then heated at 900 ℃ for 6 hours to prepare a pre-sintered powder. Then 1.2 wt.% of Al2O3(Chinese Aladdin, 99.99%) was added to the above powder. Subsequently, a green body was produced in a U-shaped tube and cold isostatic pressed at 330 MPa for 2 min. After high-temperature sintering at 1140 ℃ for 16h, a cubic garnet ceramic electrolyte tube was obtained. The inside diameter, outside diameter and depth of the electrolyte tube were about 4, 7 and 30 mm, respectively.
(2) Preparation of cathode material
The positive electrode material was a eutectic salt composed of lithium iodide (99%, Shanghai lithium industries, Ltd.) and cesium iodide (99%, Shanghai lithium industries, Ltd.). Lithium iodide and cesium iodide were mixed well at a molar ratio of 9:1 and heated in a quartz cell at 350 ℃ for 10 h. Subsequently, it was cooled to room temperature and ambient temperature, and the obtained eutectic salt was ground with a mortar for use.
Further, preparationCsI/LiIA mixture (weight ratio 95: 5) of eutectic salt and carbon nanotubes (nanjing XFNANO technologies ltd, china) was made into a eutectic positive electrode material and thoroughly mixed with a mortar before use.
The above experimental preparation was done in a glove box.
(3) Testing and characterization
Morphological and structural characterization was performed by Scanning Electron Microscopy (SEM) (zeiss, Auriga Bu). X-ray diffraction (XRD) measurements were performed using MiniFlex 600 at room temperature with a scan rate of 10 ℃/min. The element content was determined by inductively coupled plasma emission spectrometry (ICP-OES).
(4) Battery assembly and electrochemical performance testing
The eutectic salt anode material is placed in a U-shaped ceramic electrolyte tube, and a conductive graphite rod is used as a current collector. Heat resistant silicone rubber was selected as the sealant to ensure that the positive electrode material was in the solid electrolyte tube. The lithium metal negative electrode was placed outside the solid state electrolyte, i.e., in a stainless steel housing. The negative electrode used had a capacity of 2 times the capacity of the positive electrode. The assembled cell was placed in an argon-filled glove box (Etelux, Lab 2000). Muffle (KSL-1100X) provides the cell operating temperature. The LiI electrode specific capacity is calculated according to the theoretical capacity (200 mAh g)-1). Cyclic Voltammetry (CV) curves (scan rate of 0.1 mV · s) were obtained from an electrochemical station (shanghai, CHI 760E). The constant current cycling test was performed in a LAND 2001A battery system (LANDH, Wuhan, Landhe) with a voltage setting range of 2.3-3.2V. Electrochemical Impedance Spectroscopy (EIS) was measured by CHI760E with a disturbance amplitude of 5 mV and a frequency of 100 mHz-1000 kHz. Constant current intermittent titration technique (GITT) adopts current pulse interval with current density of 10.6 mA cm-2The standing time is 10 min until complete discharge.
Example 2: the MLIB (molten lithium iodine cell) structure is shown in fig. 1 (a) where CLE (eutectic iodine salt) is placed inside a U-shaped LLZTO electrolyte tube and molten lithium is placed in a stainless steel housing with an operating temperature of 260 ℃. To clearly illustrate the electrode redox reaction in the (charge) discharge behavior, the dashed box is enlarged in fig. 1 (b). It is evident that both the assembled lithium anode and the molten cathode exhibit liquid-solid interface contact with the garnet LLZTO electrolyte at operating temperatures, thus ensuring unimpeded transfer of lithium ions at low interface resistance. Here, first of all, a charging process is carried out, with decomposition of LiI, liquid I2Will be formed at the positive electrode, where a 98% state of charge capacity (SOC) relative to theoretical (based on the capacity of lithium iodide added to the battery) is achieved at 0.2C. During the discharging process, i.e., the process of converting iodine into lithium iodide, the depth of discharge (DOD) of 100% based on the charge capacity can be completed and returned to the initial state. Fig. 1 (c) is an optical photograph of the structure of the positive electrode after the test, showing a relatively intact structure without any breakage. Despite the occurrence of I during charging2Has strong volatility, but the iodine salt composite material can still be well sealed in the ceramic LLZTO electrolyte tube. Furthermore, lithium metal attached to the outside of the electrolyte shows excellent wetting between the garnet ceramic electrolyte and the lithium anode during cycling. In addition, we also destroyed the LLZTO electrolyte tube after circulation, FIG. 1 (d), and it is evident that the iodine complex is visibleThe salt cathode is perfectly filled in the U-shaped electrolyte.
To clearly illustrate the phase change of the active material during (charge) discharge, fig. 2 (a) shows a phase diagram of CsI/LiI, which presents a typical binary phase diagram with a solid-liquid transition temperature of only 208 ℃. At an operating temperature of 260 ℃, the molar ratio of lithium iodide to cesium iodide was 9:1 in order to increase the LiI ratio as much as possible. After the battery pack is assembled, LiI in the liquid molten salt undergoes an oxidation-reduction reaction, and rock salt is spontaneously converted into liquid salt through a dynamic equilibrium process. When the SOC increases from 0% to 50%, the LiI molar ratio changes from 0.9 to 0.81, and the composition changes slightly, indicating that the structural change is gentle. Thereafter, the molten salt can be completely converted into a liquid salt, in which case the molar ratio of LiI is about 0.66. After that, all LiI becomes a liquid phase in a molten state, and then solid CsI precipitates and dissolves during charging to become eutectic iodide again. More importantly, when the SOC reaches 98%, the molar ratio of LiI is still high, with a value of 0.15. The correlation between the change in the LiI molar ratio and the SOC was further investigated in fig. 2 (b) and 2 (c). As the remaining LiI gradually decreases, the degree of change in the LiI/(CsI + LiI) value shows a decreasing trend while the SOC continues to increase. The rate of increase of SOC in fig. 2 (c) is first fast and then slow as the LiI ratio decreases. XRD phase testing performed at room temperature also helps to determine the phase composition diagram 2 (d) during (charge) discharge. Wherein the PI tape corresponds to a smooth curve for isolating oxygen and moisture in the air. It is evident that in the initial state, the prepared complex iodide cathode showed Cs2Li3I5(ii) strong eutectic phase signal (PDF # 37-0950). After the charging operation, we can find the resulting I2Shows the main diffraction peak (PDF # 43-0304) and better chemical conversion reaction. In particular, in order to unequivocally calculate the LiI content remaining after charging, the ICP-OES test after cathodic cycling is provided in fig. 2 (e), where the molar ratios of I, Cs and Li were 1.855, 1.572 and 0.282, respectively. Based on the total iodide mass (CsI/LiI of 726 mg in a single cell, molar ratio 1: 9), a high utilization of 98% could be verified. After complete discharge, according to I,Reversibility was investigated for the element molar ratio of Cs and Li (fig. S2 in ESM). Typical (charge) discharge curves as shown in fig. 2 (f), almost the same SOC achieved during (charge) discharge indicates high cycle reversibility. It is noted that the (charge) discharge shows an almost constant voltage plateau, which is more level with respect to organic liquid systems. In the molten lithium iodine cell, a stable discharge voltage of about 2.75V was exhibited, and the polarization potential was very low, only 30 mV.
In fig. 3, the structural morphology of the eutectic salt positive electrode before and after the redox reaction was investigated by SEM. Before charging, low and high power SEM images are shown in fig. 3. 3 (a) and 3 (b) represent the homogeneous phase of the eutectic salt after mortar treatment, even though it consists of non-uniform particles. However, the charged cathode may find a completely different structure. The low power SEM image in fig. 3 (c) shows that the molten LiI decomposes to produce a large amount of ultrafine CsI cubic particles and elemental iodine. From their binary phase diagrams, it is readily understood that during charging, the solid CsI gradually separates from the molten iodine. In the magnified SEM image of fig. 3 (d), cubic CsI particles with good uniformity were observed. In addition, the small size of the CsI particles around 500 nm ensures that eutectic salts are more easily formed in combination with LiI generated during discharge, which contributes to improvement of reversibility and ion kinetics in electrochemistry. The (charge) discharge process diagram in fig. 3 (e) can directly illustrate the chemical reaction of the eutectic salt cathode. I.e. first a charging process is performed in which the ionized LiI active material in the conductive carbon network decomposes to form iodine and lithium metal and exhibits good reactivity. In the reverse reaction, when the liquid iodine active substance is combined with the nano-sized CsI, good reversibility is again exhibited by the generation of a molten CsI/LiI eutectic salt.
To further investigate the advanced electrochemical reaction mechanism, electrochemical performance tests of the full cell were performed as shown in fig. 4. It is clear that the CV curve studies show a wide voltage window of 2.0-3.5V, and only one pair of redox peaks appears in fig. 4 (a), indicating good safety when overcharging and overdischarging are encountered. In addition, the curve after the initial cycling approximately overlaps with the potential polarization thereafter, showing good reversibility. Figure 4 (b) shows a typical constant current voltage curve for the first five cycles at a current density of 1C over a voltage range of 2.3-3.2V. As with the CV plot, each cycle also shows a pair of redox. More importantly, all cycles showed significant consistency, indicating good cycling stability.
The cycle characteristics of 100 cycles are also obtained in fig. 4 (c). It is clear that the capacity fade is almost negligible, i.e. 190mA · g can be achieved with a Coulombic Efficiency (CE) close to 100%-1High specific capacity of (2). EIS testing helps to better understand cyclic variations. As shown in fig. 4 (d), nyquist plots were obtained in the charge and discharge states of 100 cycles, respectively. The x-axis intercept represents the ohmic impedance (Ro). The medium-high frequency semi-circular arcs and the low-frequency diagonal arcs represent the charge transfer resistance (Rct) and the weber impedance (Rw), respectively, of the electrolyte-electrode interface. In contrast, Ro in the charged state (. about.4.7. OMEGA.) is slightly greater than in the discharged state (. about.4. OMEGA.), which is attributable to the formation of molten salts in the discharged state, unlike the charged state, to the formation of crystalline cesium iodide. Similar Rct values for both figures may explain the stable interfacial contact between the electrode and the garnet electrode. A stable interface structure between the molten salt and the garnet electrolyte was also confirmed. In order to better examine the kinetics of the electrochemical reaction, a GITT test of the charge and discharge process was performed at a current density of 0.2C in fig. 4 (e). In FIG. 4 (f), the lithium ion diffusion coefficient is obtained by simplifying the formula (1) below
Wherein τ is the constant current pulse duration, mA、VMAnd mARepresents the actual mass (g) and molar volume (cm) of the active material A3·mol-1) And molar mass (g. mol)-1). S is the effective contact area between the electrode and the electrolyte. Δ Es and Δ E τ are the voltage change at steady state and the polarization of the current pulse in each single-step experiment. The results show that the calculated lithium ions are inThe diffusion coefficient of the eutectic iodide cathode in the charging and discharging process has obvious stability. Notably, the lithium ion diffusion coefficient showed 10-7To 10-6 cm2·s-1Even two orders of magnitude higher than typical layered oxide cathodes for room temperature systems.
To meet practical application, rate capability and long cycle life capability for molten Li-I of eutectic CsI/LiI positive electrode (LiI mass 539 mg)2Battery systems are also of critical importance. As shown in fig. 5 (a), at current densities of 0.2 to 5C, the cycling capacity may exhibit good retention, even better than using liquid electrolyte systems with very low active material loading. At 5C (current density of about 266 mA cm, calculated from the inner surface of the electrolyte tube)-2) Capacity over 160.1mAh g-1This is superior to batteries based on organic electrolytes in performance. In addition, a typical voltage-capacity curve at different current densities is shown in fig. 5 (b). Notably, at different current densities, a flat (charge) discharge potential plateau can be found in each cycle and no significant voltage polarization is present, indicating a significant rate capability. In addition, the capacity in FIG. 5 (C) is about 180.2 mAh g-1Long-term cycling performance was tested at 3C. Even after 2000 cycles, the cycle performance is stable and the capacity fading is negligible, which is shown to be close to 100% in the CE. More importantly, the power density and energy density based on the active material LiI were evaluated as shown in fig. 5 (d). It is known that based on LiTi2O4(LTO) and LiFePO4Two of the most advanced lithium ion battery systems for (LPO) cathodes have found widespread use with their excellent power and energy densities. However, based on this molten Li-I2Rate performance of the battery system (fig. 5 (a) and 5 (b)) the calculated power density and energy density showed more excellent values.
In addition, to further verify safety, a higher operating temperature test was performed (fig. 6). Therefore, excellent electrochemical performance and safety can be obtained even at 460 ℃, which is attributable to the excellent chemical stability of the LLZTO electrolyte without the characteristic of thermal runaway. In order to meet the requirements of the cold start test, i.e. the process of cooling to room temperature and returning to 260 ℃, it is necessary to test its structural stability. The results show that the system still exhibits excellent cycling performance after the cold start process (fig. 7), showing that the system is better at eliminating structural changes and application reliability.
In conclusion, the invention successfully prepares an advanced garnet electrolyte-based solid-state lithium-iodine battery system by using the eutectic CsI/LiI salt as the cathode. Here, the use of a U-shaped garnet LLZTO electrolyte tube with high ionic conductivity can completely solve the two inherent problems of side reactions in the lithium anode and shuttling of polyiodides in the cathode in the liquid electrolyte system, which are also key factors affecting the long cycle life of the battery. In addition, the good reversibility of the system is illustrated in terms of a binary phase diagram and SOC at 260 ℃ operating temperature. The experimental results show that the lithium anode and the eutectic salt cathode in the molten state show high rate performance and stability. The capacity is 197.6mAh g at 0.2C and 5C current density, respectively-1And 160.1mAh · g-1. The overcharge and overdischarge protection tests and the high temperature operation tests also indicate the significant reliability of the system. Therefore, the high safety and the high energy density enable the solid-state lithium-iodine battery system to have better practical application potential.
The invention is explained in detail above with reference to the drawings and the embodiments; however, it will be understood by those skilled in the art that various changes in the specific parameters of the embodiments described above may be made or equivalents may be substituted for elements thereof without departing from the scope of the present invention, so as to form a plurality of specific embodiments, which are all common variations of the present invention and will not be described in detail.
Claims (8)
1. A high-temperature melting lithium iodine battery based on garnet solid electrolyte is characterized by comprising the garnet solid electrolyte, a positive electrode material and a negative electrode material; the garnet solid electrolyte is LLZTO ceramicThe pole material comprisesCsI/LiIAnd (3) co-melting the salt, wherein the negative electrode material is molten metal lithium.
2. The garnet solid electrolyte-based high temperature molten lithium iodine battery of claim 1, wherein the garnet solid electrolyte is a U-shaped ceramic tube, the positive electrode material being sealed within the U-shaped ceramic tube; and a stainless steel shell is arranged on the outer side of the U-shaped ceramic tube, and the negative electrode material is sealed in a space formed between the U-shaped ceramic tube and the stainless steel shell.
3. The garnet-based solid electrolyte high-temperature molten lithium iodine battery as claimed in claim 1, wherein the molar ratio of LiI to CsI in the positive electrode material is 9:1, the weight ratio of the positive electrode material is 95:5CsI/LiIEutectic salt and carbon nanotube eutectic mixture.
4. The garnet solid-state electrolyte high temperature molten lithium iodine battery of claim 1, further comprising a current collector, the current collector being a graphite rod.
5. The garnet solid electrolyte-based high-temperature molten lithium iodine battery as claimed in claim 1, wherein the garnet solid electrolyte is sintered at a high temperature, and can transmit lithium ions and block the positive electrode material and the negative electrode material.
6. The garnet solid-state electrolyte high-temperature molten lithium iodine battery as claimed in claim 1, wherein the operating temperature of the battery is 260-.
7. The garnet-based solid electrolyte high-temperature molten lithium iodine battery as claimed in claim 1, wherein the charge-discharge positive and negative reactions of the battery follow the equation:
。
8. the garnet solid electrolyte-based high temperature molten lithium iodine battery of claim 1, wherein the battery has a specific capacity maintained at 175 after more than 2000 cycles in a voltage range of 2.3V to 3.5V at a charge-discharge rate of 3C
。
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