CN114335758B - Garnet solid electrolyte based high-temperature molten lithium iodine battery - Google Patents
Garnet solid electrolyte based high-temperature molten lithium iodine battery Download PDFInfo
- Publication number
- CN114335758B CN114335758B CN202210022945.8A CN202210022945A CN114335758B CN 114335758 B CN114335758 B CN 114335758B CN 202210022945 A CN202210022945 A CN 202210022945A CN 114335758 B CN114335758 B CN 114335758B
- Authority
- CN
- China
- Prior art keywords
- solid electrolyte
- battery
- garnet
- lithium
- electrode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a garnet solid electrolyte-based high-temperature melting lithium iodine battery, and aims to solve the problems that iodine elements are easy to sublimate, iodides are easy to dissolve in liquid electrolyte and lithium cathodes are corrodedAnd (5) problems are solved. 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, metal lithium 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 unique advantages
) Good rate capability and a wide 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 that a garnet solid electrolyte-based high-temperature melting lithium iodine battery is provided, so that iodine elements are easy to sublimate, iodides are easy to dissolve in a liquid electrolyte, and lithium cathodes are corroded.
In order to solve the technical problem, 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 95CsI/LiIA molten salt of a compound of formula (I) anda mixture of 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 operating 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 both 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. Molten Lithium Ion Battery (MLIB) consisting of a molten lithium negative electrode and a molten CsI/LiI eutectic salt positive electrode at a moderate working 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 the U-shaped garnet ceramic tube, iodine substances and multi-iodide formed in the circulation process can be better limited in the anode, self-discharge is blocked, and good reversibility is kept. Molten metal lithium is arranged between the stainless steel shell and the ceramic tube, the battery is charged firstly, and then is discharged, and the 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 but 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 positioned 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, is positioned in a safe working temperature range between 260 ℃ and 460 ℃, and is a solid lithium battery with extremely 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 a 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 the iodide positive electrode after cycling and artificial crushing.
Fig. 2 is a schematic diagram of the electrochemical reaction mechanism of a molten lithium ion battery, in which (a) is a binary phase diagram of CsI and LiI (the dotted line indicates the operating temperature of 260 ℃), (b) is the effect of the remaining LiI on the molar mass ratio of eutectic salt CsI/LiI and SOC, (C) is the change of the molar mass ratio of eutectic salt 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 elements I, cs and Li in the state of charge, and (f) is a typical (charge) discharge voltage curve of a 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 high-temperature melting lithium iodine battery based on garnet solid electrolyte comprises the 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 the stoichiometric ratio of chemical formula 2 CO 3 (chemical reagent of Chinese national drug group, 20% excess, 99.99%) and La 2 O 3 (chemical reagent of Chinese national drug group, inc., purity 99.99%), zrO 2 2 (Chinese Aladdin, purity 99.99%) and Ta 2 O 5 (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 Al 2 O 3 (Chinese Aladdin, 99.99%) was added to the 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 tubes 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.). When the molar ratio was 9. Subsequently, it was cooled to room temperature and ambient temperature, and the obtained eutectic salt was ground with a mortar for use.
Further, preparationCsI/LiIThe eutectic salt and a mixture of carbon nanotubes (south beijing XFNANO technologies ltd, china) (weight ratio 95.
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 a MiniFlex 600 at room temperature with a scan rate of 10 · min. The element content was determined by inductively coupled plasma optical emission spectroscopy (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 lithium metal used had a capacity 2 times that of the positive electrode. The assembled cells were tested in an argon filled glove box (Etelux, lab 2000). The muffle furnace (Keying, 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, interference amplitude of 5 mV, frequency of 100 mHz-1000 kHz. Constant current intermittent titration (GITT) technique adopts current pulse interval with current density of 10.6 mA-cm -2 The 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 iodide 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 ℃. For clarity of illustration of (charge) and (discharge) linesThe dotted line box is enlarged in fig. 1 (b) for the redox reaction of the electrode. 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 temperature, 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 I 2 Will 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 charging 2 Has 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. Furthermore, we also destroyed the LLZTO electrolyte tube after cycling fig. 1 (d), and it is evident that the complex iodonium salt cathode was 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 ℃, in order to increase the LiI ratio as much as possible, the molar ratio of lithium iodide to cesium iodide is 9. After the battery pack is assembled, liI in the liquid molten salt undergoes an oxidation-reduction reaction, and the rock salt is spontaneously converted into liquid salt through a dynamic equilibrium process. When the SOC was increased from 0% to 50%, the LiI molar ratio was changed from 0.9 to 0.81, and the composition was slightly changed, indicating that the structural change was 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, which isThe value was 0.15. The correlation between the change in the LiI molar ratio and 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 fast first and slow later 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 Cs 2 Li 3 I 5 (ii) strong eutectic phase signal (PDF # 37-0950). After the charging operation, we can find the resulting I 2 Shows the main diffraction peak (PDF # 43-0304) and better chemical transformation reaction. In particular, in order to unambiguously calculate the LiI content remaining after charging, the ICP-OES test after cathode cycling is provided in fig. 2 (e) with molar ratios of I, cs and Li of 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. In addition, reversibility was investigated in terms of the element molar ratio of I, cs and Li after complete discharge (fig. S2 in ESM). Typical (charge) discharge curves as shown in fig. 2 (f), almost the same SOC completed during (charge) discharge indicates high cycle reversibility. It is noted that the (charge) discharge process 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.
Fig. 3 is a view of structural morphology of the eutectic salt positive electrode before and after the redox reaction 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 the solid CsI is gradually separated from the molten iodine during charging. 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. Fig. 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% -1 High 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 (~ 4.7 Ω) is slightly larger than that in the discharged stateValue (-4 omega) which is attributable to the formation of molten salt in the discharged state and crystalline cesium iodide in the state different from the charged state. 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. 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, m A 、V M And m A Represents the actual mass (g) and molar volume (cm) of the active material A 3 ·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 test. The result shows that the diffusion coefficient of the lithium ions obtained by calculation in the charging and discharging processes of the eutectic iodide cathode has remarkable stability. Notably, the lithium ion diffusion coefficient showed 10 -7 To 10 -6 cm 2 ·s -1 Even 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) 2 Battery 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 liquid electrolyte systems using very low active material loadings. At 5C (current density of about 266 mA cm, calculated from the inner surface of the electrolyte tube) -2 ) Capacity over 160.1mAh g -1 This is superior to batteries based on organic electrolytes in performance. Further, as shown in FIG. 5 (b), a typical case at different current densitiesType voltage-capacity curve. 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 -1 Long-term cycling performance was tested at 3C. Even after 2000 cycles, the cycle performance is stable and the capacity fading is negligible, which is close to 100% of 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 LiTi 2 O 4 (LTO) and LiFePO 4 Two 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-I 2 Rate 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. Experiment ofThe results show that lithium anodes and eutectic salt cathodes in the molten state exhibit high rate performance and stability. The capacity is 197.6mAh g at 0.2C and 5C current density, respectively -1 And 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 (7)
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 ceramic, and the positive electrode material comprisesCsI/LiIThe molten salt is fused, and the negative electrode material is molten metal lithium;
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.
2. The garnet-based solid electrolyte high temperature molten lithium iodine battery of claim 1, wherein a molar ratio of LiI to CsI in the positive electrode material is 9:1, the weight ratio of the cathode material is 95CsI/LiIEutectic salt and carbon nanotube eutectic mixture.
3. 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.
4. 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.
5. The garnet solid electrolyte-based high temperature molten lithium iodine battery of claim 1, wherein the operating temperature of the battery is 260-460 ℃.
6. The garnet-based solid electrolyte high temperature molten lithium iodine battery according to claim 1, wherein the charge and discharge positive and negative reactions of the battery follow the equation:
7. 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
。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2021116554996 | 2021-12-31 | ||
| CN202111655499 | 2021-12-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114335758A CN114335758A (en) | 2022-04-12 |
| CN114335758B true CN114335758B (en) | 2023-03-17 |
Family
ID=81027618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210022945.8A Active CN114335758B (en) | 2021-12-31 | 2022-01-10 | Garnet solid electrolyte based high-temperature molten lithium iodine battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114335758B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4315975A (en) * | 1979-08-15 | 1982-02-16 | Matsushita Electric Industrial Co., Ltd. | Solid-state lithium-iodine primary battery |
| CN106159318A (en) * | 2015-04-07 | 2016-11-23 | 中国科学院上海硅酸盐研究所 | Novel slice type solid-state serondary lithium battery that garnet-type solid electrolyte supports and preparation method thereof |
| CN106207255A (en) * | 2015-05-06 | 2016-12-07 | 南开大学 | Organic electrolyte system lithium iodine secondary cell and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2343337A1 (en) * | 1976-03-04 | 1977-09-30 | Gen Electric | Sealed lithium iodine cell - having lithium sodium aluminate solid electrolyte sepg. anode and cathode |
| US6214061B1 (en) * | 1998-05-01 | 2001-04-10 | Polyplus Battery Company, Inc. | Method for forming encapsulated lithium electrodes having glass protective layers |
| JP5446401B2 (en) * | 2009-04-06 | 2014-03-19 | セイコーエプソン株式会社 | Lithium iodine battery and method for producing lithium iodine battery |
| CN104752758A (en) * | 2013-12-25 | 2015-07-01 | 北京有色金属研究总院 | Solid electrolyte material with low interface impedance and preparation method of solid electrolyte material |
| WO2020135111A1 (en) * | 2018-12-28 | 2020-07-02 | Yi Cui | High energy density molten lithium-sulfur and lithium-selenium batteries with solid electrolyte |
| US11552328B2 (en) * | 2019-01-18 | 2023-01-10 | Sila Nanotechnologies, Inc. | Lithium battery cell including cathode having metal fluoride core-shell particle |
| CN111276695A (en) * | 2020-02-17 | 2020-06-12 | 电子科技大学 | All-solid-state lithium fluorinated carbon secondary battery and preparation method thereof |
| CN112234185B (en) * | 2020-10-28 | 2022-08-30 | 珠海冠宇电池股份有限公司 | Positive pole piece and application thereof |
-
2022
- 2022-01-10 CN CN202210022945.8A patent/CN114335758B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4315975A (en) * | 1979-08-15 | 1982-02-16 | Matsushita Electric Industrial Co., Ltd. | Solid-state lithium-iodine primary battery |
| CN106159318A (en) * | 2015-04-07 | 2016-11-23 | 中国科学院上海硅酸盐研究所 | Novel slice type solid-state serondary lithium battery that garnet-type solid electrolyte supports and preparation method thereof |
| CN106207255A (en) * | 2015-05-06 | 2016-12-07 | 南开大学 | Organic electrolyte system lithium iodine secondary cell and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114335758A (en) | 2022-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Li-free cathode materials for high energy density lithium batteries | |
| TWI466370B (en) | Mixed metal olivine electrode materials for lithium ion batteries | |
| CN104428253B (en) | The nickelate compound of doping | |
| CN108899580A (en) | A kind of lithium ion solid conductor, preparation method and solid lithium battery | |
| CN111180692B (en) | Negative electrode active material for battery and preparation method thereof | |
| CN110459798A (en) | The sulfide solid electrolyte and preparation method and solid state battery of core-shell structure | |
| JP2008034368A (en) | Lithium ion storage battery containing contains tio2-b as anode active substance | |
| KR19990076829A (en) | Electrode material for electrochemical lithium insertion | |
| Lou et al. | Mg-doped Li1. 2Mn0. 54Ni0. 13Co0. 13O2 nano flakes with improved electrochemical performance for lithium-ion battery application | |
| CN104968606A (en) | Mixed oxide of titanium and niobium comprising a trivalent metal | |
| CN101752562B (en) | Compound doped modified lithium ion battery anode material and preparation method thereof | |
| US20120202115A1 (en) | Anode active material, anode, battery, and method of manufacturing anode | |
| CN110104677B (en) | Composite lithium titanate material and preparation method and application thereof | |
| CN103782423A (en) | Positive electrode active material for non-aqueous electrolyte secondary cell, and non-aqueous electrolyte secondary cell | |
| US6183912B1 (en) | High energy glass containing carbon electrode for lithium battery | |
| Liu et al. | Low-temperature and high-performance Si/graphite composite anodes enabled by sulfite additive | |
| CN112514136A (en) | Solid electrolyte based molten lithium electrochemical cell | |
| CN101439861A (en) | Rechargeable magnesium cell anode material and preparation thereof | |
| Li et al. | Ultra-long KFeS 2 nanowires grown on Fe foam as a high-performance anode for aqueous solid-state energy storage | |
| Hu et al. | Fabrication of phosphorus-doped carbon-decorated Li4Ti5O12 anode and its lithium storage performance for Li-ion batteries | |
| JP2003229126A (en) | Electrode active material for non-aqueous electrolyte secondary battery | |
| CN111162269B (en) | Negative electrode active material for battery and preparation method thereof | |
| Zhuang et al. | LiCoO 2 electrode/electrolyte interface of Li-ion batteries investigated by electrochemical impedance spectroscopy | |
| JP2002246025A (en) | Electrode active material for non-aqueous electrolyte secondary battery, and electrode and battery containing the same | |
| CN114335758B (en) | Garnet solid electrolyte based high-temperature molten lithium iodine battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |