CN109585913B - Lithium borohydride and molybdenum disulfide composite system solid electrolyte material and preparation method and application thereof - Google Patents
Lithium borohydride and molybdenum disulfide composite system solid electrolyte material and preparation method and application thereof Download PDFInfo
- Publication number
- CN109585913B CN109585913B CN201811445051.XA CN201811445051A CN109585913B CN 109585913 B CN109585913 B CN 109585913B CN 201811445051 A CN201811445051 A CN 201811445051A CN 109585913 B CN109585913 B CN 109585913B
- Authority
- CN
- China
- Prior art keywords
- solid electrolyte
- lithium borohydride
- molybdenum disulfide
- libh
- electrolyte 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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 lithium borohydride and molybdenum disulfide composite system solid electrolyte material and a preparation method and application thereof. The composite system solid electrolyte material is xLiBH4‑yMoS2The ball-milling compound or a high-temperature dehydrogenation reaction product thereof is disclosed, wherein x is 1-10, and y is 1-10. The preparation method comprises the following steps: under the inert gas atmosphere, LiBH4And MoS2And mixing according to the molar ratio, and then carrying out ball milling, or further loading the ball-milled product into a Sievert type gas-solid reaction closed device, and carrying out temperature programmed dehydrogenation reaction, wherein the dehydrogenation temperature is from room temperature to 500 ℃, and the temperature rise rate is 1-10 ℃ per minute. The material of the invention is a room temperature (T)<100 ℃) of lithium ion conductor with excellent performance, which is about equal to LiBH at room temperature43-4 orders of magnitude higher, and can be used for preparing solid electrolyte of all-solid-state lithium ion batteries.
Description
Technical Field
The invention belongs to a novel solid electrolyte material, and particularly relates to xLiBH4-yMoS2A composite solid electrolyte material, a preparation method and application thereof.
Background
Current research on lithium ion batteries has focused on liquid electrolytes. Although liquid electrolytes have high ionic conductivity and excellent electrode surface wettability, poor electrochemical and thermal stability, low ionic selectivity, poor safety limits their further applications. In recent years, solid electrolytes have been proposed to replace organic liquid electrolytes, which on the one hand overcomes the above-mentioned problems and on the other hand offers the possibility of developing new chemical batteries. The mainstream solid electrolytes developed by researchers to date are mainly polymer solid electrolytes and inorganic solid electrolytes. The polymer solid electrolyte is represented by a polyoxyethylene-based solid polymer, and the types of inorganic solid electrolytes that have been reported are perovskite type, NASICON type, garnet type, sulfide type.
LiBH4As a complex metal hydride, it has been widely used as a reducing agent in organic synthesis, and has not been applied until recently in the field of energy storage and conversion, including in hydrogen storage materialsMaterials and solid electrolytes. Like most metal hydrides, LiBH at different temperatures and pressures4Different crystal forms are present. The study found that around 113 degrees centigrade, LiBH4A phase transition from the low-temperature phase (LT) to the high-temperature phase (HT) takes place, and in the process, the conductivity of the substance rapidly increases to 10-3S cm-1. Further investigation revealed that by incorporating the halogen ion (I)-,Br-,Cl-) To replace a portion of a BH4 -The phase transition temperature thereof can be lowered to achieve higher ionic conductivity at room temperature. This series of studies indicates that LiBH4There is a potential to become a solid electrolyte for lithium ion batteries. At present, no report of the application of lithium borohydride and molybdenum disulfide in solid electrolyte in a compounding way is available.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a lithium borohydride and molybdenum disulfide composite system solid electrolyte material which can improve the lithium ion conduction performance, and the invention also aims to provide a preparation method and application thereof.
The technical scheme is as follows: a preparation method of a lithium borohydride and molybdenum disulfide composite system solid electrolyte material comprises the following steps: mixing lithium borohydride and molybdenum disulfide and ball-milling to prepare xLiBH4-yMoS2The compound, wherein x is 1-10, y is 1-10, x: and y is a molar ratio.
Further, x is 1 to 5, y is 1 to 7, for example, x: y is 7:1, 5:1, 3:1, 1:3,1: 5 or 1: 7.
The mixing and ball milling time is 3-5 h, and further 3 h.
Before the mixing and ball milling, the lithium borohydride is separately ball milled for 20-30 hours, and the time is further 20 hours. So as to increase the amorphous performance of the lithium borohydride and provide more channels with lower activation energy for the transmission of lithium ions.
The ball material ratio of the single ball milling and the mixed ball milling is (40-45): 1, further 40:1, the revolution speed is 400-500 revolutions per minute, and further 450 revolutions. And the independent ball milling and the mixed ball milling are carried out under the protection of inert gas.
Further, in the preparation method of the lithium borohydride and molybdenum disulfide composite system solid electrolyte material, xLiBH4-yMoS2The complex also undergoes a dehydrogenation reaction.
The dehydrogenation temperature is 450-550 ℃, the heating rate is 1-10 ℃ per minute, the heat preservation time is 0.5-1 hour, preferably, the dehydrogenation temperature is 550 ℃, the heating rate is 5 ℃ per minute, and the heat preservation time is 0.5 hour. At the temperature and the heating rate, the lithium borohydride can stably perform dehydrogenation reaction.
The invention also provides the lithium borohydride and molybdenum disulfide composite system solid electrolyte material prepared by the preparation method.
The invention also provides the application of the lithium borohydride and molybdenum disulfide composite system solid electrolyte material in the preparation of battery electrolytes. The material of the invention is a room temperature (T)<100 ℃) of lithium ion conductor with excellent performance, which is about equal to LiBH at room temperature43-4 orders of magnitude higher, and can be used for preparing solid electrolyte of all-solid-state lithium ion batteries.
The invention also provides a battery electrolyte which comprises the lithium borohydride and molybdenum disulfide composite system solid electrolyte material.
Compared with the prior art, the invention has the beneficial effects that:
LiBH4and MoS2The resulting complex has an ionic conductivity that is comparable to LiBH alone over the entire temperature range of the assay4Higher than 4 orders of magnitude, especially can reach 10 degrees in a low-temperature region (25-30 degrees centigrade)-4S cm-1The above. Wherein LiBH4-5MoS2The ionic conductivity in the low temperature region is 10-4S cm-1The above; LiBH4-3MoS2、LiBH4-7MoS2The ionic conductivity in the low temperature region is 10-5S cm-1The above; LiBH4-MoS2The ionic conductivity in the low temperature region is 10-6S cm-1The above. LiBH4-5MoS2、LiBH4-3MoS2And LiBH4-MoS2High temperatureThe dehydrogenation product has an ionic conductivity of 10 in a low temperature region-4S cm-1The above; 3LiBH4-MoS2And 5LiBH4-MoS2The high-temperature dehydrogenation product has an ionic conductivity of 10 in the low-temperature region-3S cm-1The above.
Drawings
FIG. 1 shows LiBH of a ball-milled material4-yMoS2(y-1, 3,5) X-ray diffraction pattern;
FIG. 2 shows LiBH of a ball-milled material4-5MoS2Fourier transform infrared spectrogram of (1);
FIG. 3 shows LiBH of a ball-milled material4-5MoS2(ii) a Raman spectrogram;
FIG. 4 shows a material xLiBH prepared by ball milling and high-temperature dehydrogenation4-MoS2An X-ray diffraction pattern of (X ═ 1,3, 5);
FIG. 5 shows LiBH as a ball milled material4-5MoS2The HRTEM image and the selected area electron diffraction pattern of the image;
FIG. 6 is a diagram of a material xLiBH produced by ball milling4-yMoS2(x: y ═ 1:3,1:1,3:1,5:1) dehydrogenation curves;
FIG. 7 shows LiBH as a ball milled material4-yMoS2(y ═ 1,3,5,7) conductivity vs. temperature curve and activation energy;
FIG. 8 shows a material xLiBH prepared by ball milling and high-temperature dehydrogenation4-MoS2(x＝1,3,5),LiBH4-yMoS2(y-3, 5) temperature-dependent conductivity profile and activation energy;
FIG. 9 is a schematic diagram of a sandwich structure for testing AC impedance.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary and are not intended to limit the scope of the invention, as various equivalent modifications of the invention will occur to those skilled in the art upon reading the present disclosure and fall within the scope of the appended claims.
The invention provides a lithium borohydride and molybdenum disulfide complex systemA state electrolyte material consisting of xLiBH4-yMoS2The composition, wherein x is 1-10, and y is 1-10. Reacting LiBH4-MoS2Mixing according to the stoichiometric ratio, and putting into a spherical tank filled with stainless steel grinding balls. Adopting a mechanical ball milling mode of a planetary wheel ball mill to obtain xLiBH by ball milling under the protection of high-purity (99.9999%) inert gas4-yMoS2And (3) mixing. Then the obtained product is put into a sample pool of a Sievert type gas-solid reaction closed device for high-temperature dehydrogenation reaction. All sample manipulations were performed in a glove box filled with high purity argon gas, with oxygen and water levels below 1ppm, since the samples were readily reactive with oxygen and water.
The technical solution of the present invention will be described in detail by specific examples.
Example 1
In the absence of air (H)2O<1ppm，O2<1ppm) of LiBH, first of all4Ball milling, and mixing MoS2And ball milled LiBH4According to the set molar ratio (xLiBH)4-yMoS2) Calculating the mass, and putting the mass into a stainless steel ball tank filled with stainless steel grinding balls; adopting a mechanical ball milling mode of a planetary wheel ball mill to obtain xLiBH under the protection of high-purity (99.9999%) inert gas (argon)4-yMoS2Composite particles. The total mass of the sample in the ball tank is 1 g, the volume of the ball milling tank is 100 ml, the weight ratio of the grinding balls to the sample is 40:1, and the revolution speed is set to 450 revolutions per minute. LiBH4The time of the single ball milling is 20 hours, xLiBH4-yMoS2The ball milling time of the mixture was 3 hours. Taking out and ball milling to obtain xLiBH4-yMoS2And (3) placing the mixture into a sample pool of a Sievert type gas-solid reaction closed device, and carrying out high-temperature dehydrogenation reaction at 550 ℃, at the heating rate of 5 ℃ per minute and for 0.5 hour.
In this embodiment, x: y is 1:1, 1:3,1: 5, 1:7, 3:1 or 5: 1.
Example 2
Part of the xLiBH samples of example 1 with different raw material ratios was taken4-yMoS2Composite particles andthe material obtained after dehydrogenation is subjected to an X-ray diffraction (XRD) experiment, a sample cell is covered by a specific polymer film and is sealed with a glass slide by vacuum grease so as to prevent the action of water and oxygen in the air on the sample. The target material of the X-ray source is a Cu target, the tube voltage is 40kV, and the tube current is 40 mA. The obtained XRD patterns are shown in figures 1 and 4.
Ball milled xllibh4-yMoS2Only pure 2H-MoS is present in the complex (x: y ═ 1:1, 1:3,1: 5, 1:7, 3:1,5:1)2Phase, LiBH4Has become an amorphous phase and thus has no peak in XRD (fig. 1). xLiBH4-yMoS2After high temperature dehydrogenation of the complex (x: y ═ 1:1, 1:3,1: 5, 3:1,5:1), a new phase was generated and from the XRD pattern (fig. 4) it can be seen that LiMoS was present2、Li2S、MoB2、MoS2Four phases of which LiBH4-3MoS2With LiBH4-5MoS2Only MoS was visible after high temperature dehydrogenation2Phase (1); LiBH4-MoS2LiMoS can be seen after high-temperature dehydrogenation2And MoS2Phase (c); 3LiBH4-MoS2And 5LiBH4-MoS2LiMoS can be seen after high-temperature dehydrogenation2、Li2S and MoB2Three phases. Other amorphous phases are not excluded. The following reactions which may occur during high-temperature dehydrogenation are hereby deduced:
LiBH4-MoS2：
0.5LiBH4+MoS2→0.5LiMoS2+0.5B+H2+0.5MoS2(LiBH4surplus)
3LiBH4-MoS2：
3LiBH4+MoS2→0.5LiMoS2+Li2S+0.5MoB2+2B+0.5Li+6H2
Or
3LiBH4+MoS2→0.5LiMoS2+Li2S+0.5MoB2+2B+0.5LiH+5.75H2
Or
3LiBH4+MoS2→0.5LiMoS2+Li2S+0.5MoB2+1.5B+0.5LiBH4+5H2
5LiBH4-MoS2：
5LiBH4+MoS2→0.5LiMoS2+Li2S+0.5MoB2+4B+2.5Li+10H2
Or
5LiBH4+MoS2→0.5LiMoS2+Li2S+0.5MoB2+4B+2.5LiH+8.75H2
Or
5LiBH4+MoS2→0.5LiMoS2+Li2S+0.5MoB2+1.5B+2.5LiBH4+5H2。
Example 3
Part of the xLiBH samples of example 1 with different raw material ratios was taken4-yMoS2The composite particles were tested by fourier infrared spectroscopy (FTIR), and since the test sample had to be isolated from air, the preparation was carried out all the way in a glove box. Sample powder by mass ratio: KBr powder was mixed at a ratio of 1:200, and the mixture was ground to homogeneity. The prepared powder was stored in a brown glass bottle. Before FTIR test, the powder sample is taken out of the glass bottle, an appropriate amount of powder is taken and put into a tabletting mold, and the pressure is reduced for 1 minute under the pressure of 12MPa, then the pressure is relieved for 30 seconds, and the pressure is reduced for 1 minute again, so that the flaky test sample is obtained. The test results are shown in fig. 2.
As can be seen from the figure, pure LiBH4Two characteristic peaks of B-H in the prepared LiBH4-5MoS2The LiBH still exists in the complex, which can be proved4The presence of a phase. Due to LiBH4In the preparation of LiBH4-MoS2The content of the compound is less, so the compound is compared with pure LiBH4The intensity of the peak is weaker. In other proportions of the ball milled product, two characteristic B-H peaks were also observed.
Example 4
Part of the LiBH from example 1 was removed4-5MoS2The composite particles were subjected to Raman spectroscopy (Raman) using a laser Raman spectrometer at 532nmWave number range of 2500cm-1To 200cm-1. The test results are shown in fig. 3.
From the figure, MoS can be seen2Two characteristic vibration peaks of (A) and LiBH4Middle BH4 -The vibration peak of (a), which exists both at room temperature and after high temperature testing, can further prove that LiBH4The presence of a phase. Due to LiBH being prepared4-MoS2MoS in composite2High content of LiBH4Less content, so LiBH4Middle BH4 -The peak of vibration of (a) is weak. Corresponding MoS can be seen in the ball-milled products with other proportions2Two characteristic vibration peaks of (A) and LiBH4Middle BH4 -The peak of vibration of (1).
Example 5
A trace of LiBH from example 1 was removed4-MoS2And (3) analyzing the microscopic morphology and the phase structure of the composite particles by using a high-resolution transmission electron microscope, mixing trace composite particles with alcohol, ultrasonically dispersing for two minutes until the mixture is uniform, and then sucking trace mixed liquid to be dropped on a copper net for testing. The test results are shown in fig. 5.
As can be seen from the figure, LiBH4Is an amorphous phase and is dispersed in MoS2Peripheral, MoS2Still maintain the lamellar structure, have good crystallinity, and can see MoS from the selected area electron diffraction pattern2Three crystal planes of (110), (101), and (200).
Example 6
Dehydrogenation performance testing of the samples was obtained by temperature programmed dehydrogenation in a PCT apparatus. The xLiBH obtained by ball milling in example 14-yMoS2The compound is put into a sample pool of a Sievert type gas-solid reaction closed device, the temperature is raised to 550 ℃ from room temperature, the temperature raising rate is 5 ℃ per minute, and the heat preservation time is 0.5 hour. The dehydrogenation curve obtained is shown in FIG. 6.
As can be seen from the figure, with LiBH4The initial dehydrogenation temperature of the compound is obviously reduced from 270 ℃ to 200 ℃; the amount of dehydrogenation also increases significantly from1.2% increased to 5.5%. Wherein, LiBH4-3MoS2The initial dehydrogenation temperature of the catalyst is about 270 ℃, and the dehydrogenation amount is 1.2 percent; LiBH4-MoS2The initial dehydrogenation temperature of the catalyst is about 200 ℃, and the dehydrogenation amount is 1.5 percent; 3LiBH4-MoS2The initial dehydrogenation temperature of the catalyst is about 200 ℃, and the dehydrogenation amount is 3.7 percent; 5LiBH4-MoS2The initial dehydrogenation temperature of (2) was about 200 degrees celsius and the amount of dehydrogenation was 5.5%.
Example 7
The ionic conductivity performance test of the sample is obtained by an alternating current impedance test method on an electrochemical workstation. The sample obtained in the example 1 is pressed into a wafer with the diameter of 12.5 mm and the thickness of about 1 mm under the pressure of 10-15 MPa. Two lithium foil sheets were placed on both sides of the sample wafer as electrodes in a sandwich configuration (lithium sheet/solid electrolyte sheet/lithium sheet), as a schematic figure 9. Then at 1 ton/cm2The pressure of (3) presses the lithium foil sheet against the sample sheet. All preparations were carried out under high purity argon (99.9999%). The frequency range of the ac impedance test is from 1MHz to 1 Hz. The sample is heated at a rate of 2 degrees centigrade per minute, and impedance spectra are collected at intervals of 5 degrees centigrade. The temperature was raised from room temperature to 120 ℃. And fitting the obtained alternating current impedance Nyquist spectrogram and Zview to obtain the ionic conductivity, and drawing a change curve of the conductivity along with the temperature. And the ionic conductivity and the temperature have an Arrhenius relation:
σ＝σ0exp(-Ea/kT)
σ is the ionic conductivity, Ea is the activation energy, k is the boltzmann constant, and T is the temperature.
According to the equation, the activation energy Ea can be obtained by fitting the obtained change curve of the conductivity along with the temperature. The results are shown in FIGS. 7 and 8.
Ball milled xllibh4-yMoS2The ionic conductivity of the composite samples was substantially higher than pure LiBH over the entire temperature range measured4And MoS2And following MoS2The amount of (A) increases, and the ionic conductivity also increases, reaching a maximum at a molar ratio of 1:5 and reaching 10 at room temperature (25 ℃ C.)-4S cm-1Above, but further increase in MoS2In the above amount, the ionic conductivity may decrease. As can be seen from the inset, with MoS2The amount of the complex is increased, the activation energy of the complex is obviously reduced, and pure LiBH is used4Near 1eV to xLiBH4-yMoS2About 0.2-0.6 eV of the complex. The ionic conductivity and activation energy of each sample are shown in table 1 below.
TABLE 1
| Ionic conductivity at room temperature (S cm)-1) | Activation energy (eV) | |
| LiBH4-MoS2 | 3.476*10-6 | 0.57 |
| LiBH4-3MoS2 | 6.7*10-5 | 0.28 |
| LiBH4-5MoS2 | 1.2*10-4 | 0.39 |
| LiBH4-7MoS2 | 2.5*10-5 | 0.26 |
LiBH after ball milling and high-temperature dehydrogenation4-MoS2The ionic conductivity of the composite samples was substantially higher than pure LiBH over the entire temperature range measured4And MoS2And with LiBH4The amount of (A) increases, and the ionic conductivity also increases, reaching a maximum at a molar ratio of 5:1 and reaching 10 at room temperature (25 ℃ C.)-3S cm-1The above. As can be seen from the inset, the activation energy of the dehydrogenated product is low, about 0.1-0.3 eV. The ionic conductivity and activation energy of each sample are shown in the following table (table 2).
TABLE 2
Claims (9)
1. A preparation method of a lithium borohydride and molybdenum disulfide composite system solid electrolyte material is characterized by comprising the following steps: mixing lithium borohydride and molybdenum disulfide and ball-milling to prepare xLiBH4-yMoS2A complex, wherein x: y is 1:5, 1:7, 3:1 or 5:1, x: and y is a molar ratio.
2. The method for preparing the solid electrolyte material of the lithium borohydride and molybdenum disulfide composite system according to claim 1, wherein the method comprises the following steps: the mixing and ball milling time is 3-5 h.
3. The method for preparing the solid electrolyte material of the lithium borohydride and molybdenum disulfide composite system according to claim 1, wherein the method comprises the following steps: before mixing and ball milling, the lithium borohydride is separately ball milled for 20-30 hours.
4. The method for preparing a lithium borohydride and molybdenum disulfide composite system solid electrolyte material according to claim 2 or 3, characterized in that: the ball material ratio of the single ball milling and the mixed ball milling is (40-45): 1, the revolution speed is 400-500 revolutions per minute.
5. The method for preparing the solid electrolyte material of the lithium borohydride and molybdenum disulfide composite system according to claim 1, wherein the method comprises the following steps: xLiBH4-yMoS2The complex also undergoes a dehydrogenation reaction.
6. The method for preparing the solid electrolyte material of the lithium borohydride and molybdenum disulfide composite system according to claim 5, wherein the method comprises the following steps: the dehydrogenation temperature is 450-550 ℃, and the heating rate is 1-10 ℃ per minute.
7. The lithium borohydride and molybdenum disulfide composite solid electrolyte material prepared by the preparation method according to any one of claims 1 to 3 and 5 to 6.
8. The use of the lithium borohydride and molybdenum disulfide composite system solid state electrolyte material of claim 7 in the preparation of a battery electrolyte.
9. A battery electrolyte, characterized by: the solid electrolyte material comprising the lithium borohydride-molybdenum disulfide composite system according to claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811445051.XA CN109585913B (en) | 2018-11-29 | 2018-11-29 | Lithium borohydride and molybdenum disulfide composite system solid electrolyte material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811445051.XA CN109585913B (en) | 2018-11-29 | 2018-11-29 | Lithium borohydride and molybdenum disulfide composite system solid electrolyte material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109585913A CN109585913A (en) | 2019-04-05 |
| CN109585913B true CN109585913B (en) | 2021-08-24 |
Family
ID=65925673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811445051.XA Active CN109585913B (en) | 2018-11-29 | 2018-11-29 | Lithium borohydride and molybdenum disulfide composite system solid electrolyte material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109585913B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372367A (en) * | 2019-07-12 | 2019-10-25 | 成都新柯力化工科技有限公司 | A kind of lithium battery high-ductility ceramic solid electrolyte material and preparation method |
| CN110247109B (en) * | 2019-07-16 | 2021-06-01 | 广州天赐高新材料股份有限公司 | Sulfide solid electrolyte and preparation method and application thereof |
| CN110828904B (en) * | 2019-11-07 | 2022-06-14 | 东南大学 | Lithium halide and two-dimensional material composite solid electrolyte material, and preparation method and application thereof |
| CN111584931A (en) * | 2020-05-13 | 2020-08-25 | 无锡新锂辰能源科技有限公司 | Lithium borohydride and sulfide composite system solid electrolyte and preparation method and application thereof |
| CN114602511B (en) * | 2020-12-04 | 2023-02-24 | 中国科学院大连化学物理研究所 | Reduced transition metal sulfide catalyst for catalytic hydrogenation of polycyclic aromatic hydrocarbon compounds and preparation method thereof |
| CN114464877B (en) * | 2022-01-05 | 2023-09-29 | 东南大学 | Composite solid electrolyte material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103606712A (en) * | 2008-05-13 | 2014-02-26 | 国立大学法人东北大学 | Solid electrolyte, method for producing the same, and secondary battery comprising solid electrolyte |
| CN103746141A (en) * | 2014-01-02 | 2014-04-23 | 东南大学 | Li-B-N-H compound fast-ion conductor and preparation method thereof |
| JP2014160572A (en) * | 2013-02-20 | 2014-09-04 | Nagase Chemtex Corp | Positive electrode mixture and all-solid-state lithium sulfur battery |
| CN106384842A (en) * | 2016-11-15 | 2017-02-08 | 复旦大学 | Nano LiBH4-SiO2 solid electrolyte and preparation method thereof |
| EP3043412B1 (en) * | 2013-09-02 | 2020-04-29 | Mitsubishi Gas Chemical Company, Inc. | Solid-state battery and method for manufacturing electrode active material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2922382C (en) * | 2013-09-02 | 2022-04-05 | Mitsubishi Gas Chemical Company, Inc. | Solid-state battery in which lithium ions are responsible for electrical conduction |
| WO2017066810A1 (en) * | 2015-10-13 | 2017-04-20 | Arizona Board Of Regents On Behalf Of Arizona State University | Chelating ionic liquids for magnesium battery electrolytes and systems |
-
2018
- 2018-11-29 CN CN201811445051.XA patent/CN109585913B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103606712A (en) * | 2008-05-13 | 2014-02-26 | 国立大学法人东北大学 | Solid electrolyte, method for producing the same, and secondary battery comprising solid electrolyte |
| JP2014160572A (en) * | 2013-02-20 | 2014-09-04 | Nagase Chemtex Corp | Positive electrode mixture and all-solid-state lithium sulfur battery |
| EP3043412B1 (en) * | 2013-09-02 | 2020-04-29 | Mitsubishi Gas Chemical Company, Inc. | Solid-state battery and method for manufacturing electrode active material |
| CN103746141A (en) * | 2014-01-02 | 2014-04-23 | 东南大学 | Li-B-N-H compound fast-ion conductor and preparation method thereof |
| CN106384842A (en) * | 2016-11-15 | 2017-02-08 | 复旦大学 | Nano LiBH4-SiO2 solid electrolyte and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Improved dehydrogenation performance of LiBH4 by 3D hierarchical flower-like MoS2 spheres additives;Zhao, Yan等;《Journal of Power Sources》;20151230;第300卷;第358-364页 * |
| 日本开发出锂离子在室温可高速移动的锂硼氢化物;杨晓婵;《现代材料动态》;20091231(第5期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109585913A (en) | 2019-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109585913B (en) | Lithium borohydride and molybdenum disulfide composite system solid electrolyte material and preparation method and application thereof | |
| WO2017007030A1 (en) | Lithium solid electrolyte | |
| EP3407363B1 (en) | Method for manufacturing ion conductor | |
| CN110431703A (en) | The manufacturing method of LGPS system solid electrolyte | |
| CA3096602A1 (en) | Lgps-based solid electrolyte and production method | |
| CN108238616A (en) | A kind of cubic phase sulfide and preparation method thereof | |
| CN103746141B (en) | A kind of Li-B-N-H compound fast-ion conductor and preparation method thereof | |
| CN108155411A (en) | A kind of lithium borohydride compound fast-ionic conductor and preparation method thereof | |
| Dao et al. | Improvement of the ionic conductivity on new substituted borohydride argyrodites | |
| CN108736064A (en) | A kind of compound lithium borohydride solid electrolyte and preparation method thereof and equipment | |
| CN100362683C (en) | Full-solid-state minisize lithium cell electrolyte preparing method | |
| Skov et al. | Towards Solid‐State Magnesium Batteries: Ligand‐Assisted Superionic Conductivity | |
| JPWO2019156158A1 (en) | Solid electrolyte | |
| Zhang et al. | Electrochemical performance of sulfide solid electrolyte Li10GeP2S12 synthesized by a new method | |
| CN106785012A (en) | A kind of boron hydride compound system solid electrolyte material and its preparation method and application | |
| CN112467197B (en) | Lithium borohydride/decaborane solid electrolyte and preparation method thereof | |
| CN103762346A (en) | Lithium ion conductor with nanoscale and preparation method thereof | |
| CN109888376A (en) | A kind of sulfide sodion solid electrolytes and preparation method thereof | |
| Fu et al. | Halide Heterogeneous Structure Boosting Ionic Diffusion and High‐Voltage Stability of Sodium Superionic Conductors | |
| WO2023130671A1 (en) | Composite solid electrolyte material, and preparation method therefor and use thereof | |
| EP3505500A1 (en) | Sulfide solid electrolyte | |
| CN110828904B (en) | Lithium halide and two-dimensional material composite solid electrolyte material, and preparation method and application thereof | |
| CN104851473B (en) | A kind of LiCl material and preparation method thereof | |
| Liang et al. | Physical and electrochemical behavior of affordable Na3SbS4 solid electrolyte at different heat treatment temperatures | |
| CN109301336A (en) | Amorphous state sulfide solid electrolyte and preparation method thereof, lithium ion 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 |