CN109585913A - Lithium borohydride and molybdenum disulfide compound system solid electrolyte material and its preparation method and application - Google Patents
Lithium borohydride and molybdenum disulfide compound system solid electrolyte material and its preparation method and application Download PDFInfo
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- 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
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- 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 kind of lithium borohydrides and molybdenum disulfide compound system solid electrolyte material and its preparation method and application.Compound system solid electrolyte material is xLiBH4‑yMoS2Ball-milling object or its high-temperature dehydrogenation reaction product, it is 1~10 that wherein x, which is 1~10, y,.The preparation method is that: under inert gas atmosphere, by LiBH4And MoS2According to ball milling is carried out after the mixing of above-mentioned molar ratio, alternatively, further ball milling product is fitted into Sievert type gas-solid reaction obturator, temperature programming dehydrogenation reaction is carried out, for desorption temperature from room temperature to 500 degrees Celsius, heating rate is 1~10 degrees celsius/minute.Material of the invention is a kind of lithium ion conductor of room temperature (T < 100 DEG C) superior performance, about compares LiBH at room temperature4High 3~4 orders of magnitude, can be used for preparing the solid electrolyte of all-solid lithium-ion battery.
Description
Technical field
The invention belongs to novel solid electrolyte materials, and in particular to a kind of xLiBH4-yMoS2Composite solid electrolyte
Material and its preparation method and application.
Background technique
Liquid electrolyte is all absorbed in the current research of lithium ion battery.Although liquid electrolyte has high ionic conductance
Rate and excellent electrode surface wetability, but the electrochemistry and thermal stability of difference, low ion selectivity, poor safety limitation
It is further to apply.In recent years, it has been proposed that substituting organic liquid electrolytes using solid electrolyte, on the one hand overcomes
On the other hand the above problem also provides possibility to develop new chemical cell.Up to now, the mainstream of researchers' exploitation
Solid electrolyte mainly have solid polyelectrolyte and inorganic solid electrolyte.Solid polyelectrolyte is with polyoxyethylene
Alkenyl solid polymer be representative, inorganic solid electrolyte it has been reported that type have Ca-Ti ore type, NASICON type, garnet
Type, sulfide type.
LiBH4It as a kind of composite metal hydride, is widely used in organic synthesis as reducing agent, until recent
It is just applied to energy storage and conversion art, including the application in hydrogen storage material and solid electrolyte.With most metallic hydrogens
Compound is the same, under different temperature and pressures, LiBH4Different crystal forms can be presented.The study found that near 113 degrees Celsius,
LiBH4Phase transition occurs from low-temperature phase (LT) to high-temperature-phase (HT), and in the process, the conductivity of the substance is rapidly increased to 10-3S cm-1.Further study show that by mixing halide ion (I-,Br-,Cl-) replace the BH of part4 -Its phase can be reduced
Transition temperature, to reach higher ionic conductivity at room temperature.This series of studies shows LiBH4Having becomes lithium ion
The potential quality of battery solid electrolyte.There has been no lithium borohydrides and molybdenum disulfide Application of composite in the report of solid electrolyte at present.
Summary of the invention
Goal of the invention: the purpose of the present invention is to provide a kind of lithium borohydrides and molybdenum disulfide compound system solid electrolyte
Material can promote lithium ion conduction performance, and it is a further object of the present invention to provide preparation methods and application.
A kind of technical solution: preparation method of lithium borohydride and molybdenum disulfide compound system solid electrolyte material, comprising:
By lithium borohydride and molybdenum disulfide mixing and ball milling, xLiBH is prepared4-yMoS2Compound, it is 1~10 that wherein x, which is 1~10, y,
X:y is molar ratio.
Further, it is 1~7 that x, which is 1~5, y, such as x:y=7:1,5:1,3:1,1:1,1:3,1:5 or 1:7.
The time of the mixing and ball milling is 3~5h, is further 3h.
It is further 20h first by the independent ball milling of lithium borohydride 20~30 hours before the mixing and ball milling.To increase boron hydrogen
The unformed property for changing lithium, provides more activation energy lower channel for the transmission of lithium ion.
The ratio of grinding media to material of the independent ball milling and mixing and ball milling is (40~45): 1, it is further 40:1, revolution speed is
400~500 turns per minute, be further 450 turns.The independent ball milling and mixing and ball milling under inert gas protection into
Row.
Further, in the preparation method of the lithium borohydride and molybdenum disulfide compound system solid electrolyte material,
xLiBH4-yMoS2Compound also carries out dehydrogenation reaction.
The desorption temperature is 450~550 degrees Celsius, and heating rate is 1~10 degrees celsius/minute, soaking time 0.5
~1 hour, it is preferred that the desorption temperature is 550 degrees Celsius, and heating rate is 5 degrees celsius/minutes, and soaking time is 0.5 small
When.In this temperature and the carry out dehydrogenation reaction that under heating rate, lithium borohydride can be stable.
The lithium borohydride and molybdenum disulfide compound system solid-state being prepared the present invention also provides the preparation method
Electrolyte.
The present invention also provides the lithium borohydrides and molybdenum disulfide compound system solid electrolyte material in preparation electricity
Application in the electrolyte of pond.Material of the invention is a kind of lithium ion conductor of room temperature (T < 100 DEG C) superior performance, at room temperature about
Compare LiBH4High 3~4 orders of magnitude, can be used for preparing the solid electrolyte of all-solid lithium-ion battery.
The present invention also provides a kind of cell electrolytes, include the lithium borohydride and molybdenum disulfide compound system solid-state
Electrolyte.
Compared with prior art, the invention has the benefit that
LiBH4With MoS2The compound of formation, the ionic conductivity LiBH simple in entire measuring temperature range internal ratio4
4 orders of magnitude are higher by, especially can achieve 10 in low-temperature region (25 degrees Celsius -30 degrees Celsius)-4S cm-1More than.Wherein
LiBH4-5MoS2In low-temperature space its ionic conductivity 10-4S cm-1More than；LiBH4-3MoS2、LiBH4-7MoS2In low-temperature space
Its ionic conductivity is 10-5S cm-1More than；LiBH4-MoS2In low-temperature space its ionic conductivity 10-6S cm-1More than.
LiBH4-5MoS2、LiBH4-3MoS2And LiBH4-MoS2High-temperature dehydrogenation product is in low-temperature space its ionic conductivity 10-4S cm-1
More than；3LiBH4-MoS2And 5LiBH4-MoS2High-temperature dehydrogenation product is in low-temperature space its ionic conductivity 10-3S cm-1More than.
Detailed description of the invention
Fig. 1 is material LiBH made from ball milling4-yMoS2(y=1,3,5) X ray diffracting spectrum；
Fig. 2 is material LiBH made from ball milling4-5MoS2Fourier transform infrared spectroscopy figure；
Fig. 3 is material LiBH made from ball milling4-5MoS2Raman spectrogram；
Fig. 4 is material xLiBH made from ball milling and high-temperature dehydrogenation4-MoS2(x=1,3,5) X-ray diffractogram；
Fig. 5 is material LiBH made from ball milling4-5MoS2HRTEM figure and selective electron diffraction map；
Fig. 6 is material xLiBH made from ball milling4-yMoS2(x:y=1:3,1:1,3:1,5:1) Hydrogen desorption isotherms；
Fig. 7 is material LiBH made from ball milling4-yMoS2(y=1,3,5,7) conductivity varies with temperature curve and activation
Energy；
Fig. 8 is material xLiBH made from ball milling and high-temperature dehydrogenation4-MoS2(x=1,3,5), LiBH4-yMoS2(y=3,5)
Conductivity vary with temperature curve and activation energy；
Fig. 9 is sandwich structure schematic diagram when testing AC impedance.
Specific embodiment
Combined with specific embodiments below, the present invention is furture elucidated, it should be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention, after the present invention has been read, those skilled in the art are to various equivalences of the invention
The modification of form falls within the application range as defined in the appended claims.
The invention proposes a kind of lithium borohydrides and molybdenum disulfide compound system solid electrolyte material, by xLiBH4-
yMoS2Composition, it is 1~10 that wherein x, which is 1~10, y,.By LiBH4-MoS2It is put into after being mixed according to stoichiometric ratio equipped with stainless steel
In the spherical tank of abrading-ball.Using planet gear type ball mill mechanical ball mill mode, in high-purity (99.9999%) inert gas shielding
Under, ball milling obtains xLiBH4-yMoS2Mixture.Then it is loaded into Sievert type gas-solid reaction obturator sample cell, into
The reaction of row high-temperature dehydrogenation.Since sample is easy to react with oxygen and water, all sample operations are filled with high-purity argon gas
Glove box in carry out, the oxygen and water content of glove box are below 1ppm concentration.
Below by the specific embodiment technical solution that the present invention will be described in detail.
Embodiment 1
In isolation air (H2O < 1ppm, O2< 1ppm) under the conditions of, first by LiBH4Ball milling, then by MoS2After ball milling
LiBH4According to the molar ratio (xLiBH of setting4-yMoS2) quality is calculated, it is put into the stainless steel spherical tank equipped with stainless steel abrading-ball；
It is obtained under high-purity (99.9999%) inert gas (argon gas) protection using planet gear type ball mill mechanical ball mill mode
xLiBH4-yMoS2Composite particles.Sample gross mass is 1 gram in spherical tank, and ball milling tank volume is 100 milliliters, abrading-ball and sample
Weight ratio is 40:1, and revolution revolving speed is set as 450 turns per minute.LiBH4The time of independent ball milling is 20 hours, xLiBH4-
yMoS2Mixture Ball-milling Time is 3 hours.It takes out ball milling and obtains xLiBH4-yMoS2Then mixture is loaded into Sievert
In type gas-solid reaction obturator sample cell, high-temperature dehydrogenation reaction is carried out, desorption temperature is 550 degrees Celsius, and heating rate is taken the photograph for 5
Family name degree/min, soaking time are 0.5 hour.
In the present embodiment, x:y=1:1,1:3,1:5,1:7,3:1 or 5:1.
Embodiment 2
Take out the part xLiBH of 1 different ratios of raw materials sample of embodiment4-yMoS2Gained after composite particles and its dehydrogenation
Material carries out X-ray diffraction (XRD) experiment, and sample cell is covered by specific polymeric membrane, and with vacuum grease that it is close with glass slide
Envelope, to prevent the effect of water and oxygen to sample in air.The target of x-ray source used is Cu target, tube voltage 40kV, pipe electricity
Stream is 40mA.Resulting XRD spectra such as Fig. 1, shown in 4.
XLiBH after ball milling4-yMoS2There was only pure 2H- in compound (x:y=1:1,1:3,1:5,1:7,3:1,5:1)
MoS2Phase, LiBH4Unformed phase has been had changed into, therefore has not had peak (Fig. 1) in XRD.xLiBH4-yMoS2Compound (x:y=1:
1,1:3,1:5,3:1,5:1) after high-temperature dehydrogenation, has and generate new phase, from XRD diagram (Fig. 4), it can be seen that LiMoS2、Li2S、
MoB2、MoS2Four phases, wherein LiBH4-3MoS2With LiBH4-5MoS2It can only see MoS after high-temperature dehydrogenation2Phase；LiBH4-MoS2
LiMoS can be seen after high-temperature dehydrogenation2And MoS2Phase；3LiBH4-MoS2And 5LiBH4-MoS2It can see after high-temperature dehydrogenation
LiMoS2、Li2S and MoB2Three kinds of phases.It is not excluded for also some other unformed phase.It releases accordingly as follows in high-temperature dehydrogenation process
The middle possible reaction occurred:
LiBH4-MoS2:
0.5LiBH4+MoS2→0.5LiMoS2+0.5B+H2+0.5MoS2(LiBH4It is superfluous)
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。
Embodiment 3
Take out the part xLiBH of 1 different ratios of raw materials sample of embodiment4-yMoS2It is infrared that composite particles carry out Fourier
Spectrum (FTIR) test, because laboratory sample is necessary and air exclusion, so preparation whole process carries out in glove box.In mass ratio,
Sample powder: KBr powder=1:200 ratio mixes two kinds of powder, and grinding is uniform.The powder prepared is packed into the small of brown
It is saved in vial.Before FTIR test, powder sample is taken out from vial, appropriate powder is taken to be put into compression mold,
Under 12MPa pressure, presses 1 minute, then release 30 seconds, then press 1 minute, obtain sheet test sample.Test result such as Fig. 2 institute
Show.
It can be seen from the figure that pure LiBH4Two B-H characteristic peaks preparation LiBH4-5MoS2It is still deposited in compound
It can prove LiBH4The presence of phase.Due to LiBH4In the LiBH of preparation4-MoS2Content is less in compound, therefore compared to
Pure LiBH4, the intensity at peak is weaker.In the ball milling product of other ratios, also it can be seen that two B-H characteristic peaks.
Embodiment 4
Take out the LiBH of section Example 14-5MoS2Composite particles carry out Raman spectrum (Raman) test, laser used
The wavelength of Raman spectrometer is 532nm, wave-number range 2500cm-1To 200cm-1.Test results are shown in figure 3.
MoS as we can see from the figure2Two eigen vibration peaks and LiBH4Middle BH4 -Vibration peak, and in room temperature and process
Exist after high temperature test, can further prove LiBH4The presence of phase.Due to the LiBH in preparation4-MoS2In compound
MoS2Content is more, LiBH4Content is less, therefore LiBH4Middle BH4 -Vibration peak it is weaker.In the ball milling product of other ratios, also
Corresponding MoS can be seen2Two eigen vibration peaks and LiBH4Middle BH4 -Vibration peak.
Embodiment 5
Take out the LiBH of micro embodiment 14-MoS2Composite particles utilize high-resolution transmission electron microscope pair
Its analysis for carrying out microscopic appearance and phase structure, micro composite particles is mixed with alcohol, ultrasonic disperse two minutes, until its
Uniformly, then drawing on minipool drop to copper mesh can be tested.Test results are shown in figure 5.
It can be seen from the figure that LiBH4For unformed phase, disperse is distributed in MoS2Around, MoS2Still keep lamella knot
Structure, and crystallinity is good, it can be seen that MoS from selective electron diffraction map2(110), (101), (200) three crystal faces.
Embodiment 6
The dehydrogenation test of sample is the progress temperature programming dehydrogenation acquisition in PCT equipment.1 ball milling of embodiment is obtained
The xLiBH arrived4-yMoS2Compound is fitted into Sievert type gas-solid reaction obturator sample cell, and it is Celsius to be raised to 550 from room temperature
Degree, heating rate are 5 degrees celsius/minutes, and soaking time is 0.5 hour.Obtained Hydrogen desorption isotherms are as shown in Figure 6.
It can be seen from the figure that with LiBH4Amount increase, the starting desorption temperature of compound is remarkably decreased, by 270
Degree Celsius fall below 200 degrees Celsius；Amount of dehydrogenation also significantly rises, and has been raised to 5.5% by 1.2%.Wherein, LiBH4-3MoS2Rise
Beginning desorption temperature is about 270 degrees Celsius, amount of dehydrogenation 1.2%；LiBH4-MoS2Starting desorption temperature be about 200 degrees Celsius, take off
Hydrogen amount is 1.5%；3LiBH4-MoS2Starting desorption temperature be about 200 degrees Celsius, amount of dehydrogenation 3.7%；5LiBH4-MoS2's
Originating desorption temperature is about 200 degrees Celsius, amount of dehydrogenation 5.5%.
Embodiment 7
The ionic conductance performance test of sample is to obtain on electrochemical workstation in ac impedance measurement method.It will be real
It applies the sample obtained of example 1 and 12.5 millimeters of one diameter, the disk that about 1 millimeter of thickness is pressed into the pressure of 10~15 megapascal.
According to sandwich structure (lithium piece/solid electrolyte piece/lithium piece), two pieces of lithium paillons are placed on the two sides of sample disk as electricity
Pole, schematic diagram are shown in Fig. 9.Again with 1 ton/cm2Pressure lithium paillon and sample strip compressed cause.All preparations are all in high-purity argon gas
(99.9999%) it is carried out under.The frequency range of ac impedance measurement is from 1MHz to 1Hz.Sample is with the speed of 2 degrees celsius/minutes
Degree heating, at interval of impedance spectrum of 5 degrees Celsius of acquisitions.Temperature rises to 120 degrees Celsius by room temperature.Pass through the AC impedance of acquisition
Nyquist spectrogram and Zview are fitted to obtain ionic conductivity, and can make conductivity variation with temperature curve.And from
There is Arrhenius relationship between electron conductivity and temperature:
σ=σ0exp(-Ea/kT)
σ is ionic conductivity, and Ea is activation energy, and k is Boltzmann constant, and T is temperature.
According to this equation, being fitted to obtained conductivity variation with temperature curve can be obtained activation energy.
As a result such as Fig. 7, shown in 8.
XLiBH after ball milling4-yMoS2The ionic conductivity of composite sample is substantially all high within the scope of entire measuring temperature
In pure LiBH4And MoS2, and with MoS2Amount increase, ionic conductivity is also rising, and reaches when molar ratio reaches 1:5
Highest reaches 10 under room temperature (25 degrees Celsius)-4S cm-1More than, but further increase MoS2Amount when, ionic conductivity can under
Drop.It can be seen that by illustration, with MoS2Amount increase, the activation of compound can significantly reduce, by pure LiBH4Nearly 1eV drop to
xLiBH4-yMoS2About 0.2~0.6eV of compound.The ionic conductivity and activation energy of each sample see the table below (table 1).
Table 1
| 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 composite sample is within the scope of entire measuring temperature
Substantially all it is higher than pure LiBH4And MoS2, and with LiBH4Amount increase, ionic conductivity is also rising, and reaches in molar ratio
Reach highest when 5:1, reaches 10 under room temperature (25 degrees Celsius)-3S cm-1More than.It can be seen that by illustration, the work of product after dehydrogenation
Change can be lower, about 0.1~0.3eV.The ionic conductivity and activation energy of each sample see the table below (table 2).
Table 2
Claims (10)
1. the preparation method of a kind of lithium borohydride and molybdenum disulfide compound system solid electrolyte material, it is characterised in that: by boron
Lithium hydride and molybdenum disulfide mixing and ball milling, are prepared xLiBH4-yMoS2Compound, it is 1~10, x:y that wherein x, which is 1~10, y,
For molar ratio.
2. the preparation method of lithium borohydride according to claim 1 and molybdenum disulfide compound system solid electrolyte material,
It is characterized by: it is 1~7 that x, which is 1~5, y,.
3. the preparation method of lithium borohydride according to claim 1 and molybdenum disulfide compound system solid electrolyte material,
It is characterized by: the time of mixing and ball milling is 3~5h.
4. the preparation method of lithium borohydride according to claim 1 and molybdenum disulfide compound system solid electrolyte material,
It is characterized by: before mixing and ball milling, first by the independent ball milling of lithium borohydride 20~30 hours.
5. the preparation side of lithium borohydride according to claim 3 or 4 and molybdenum disulfide compound system solid electrolyte material
Method, it is characterised in that: the ratio of grinding media to material of independent ball milling and mixing and ball milling is (40~45): 1, revolution speed is per minute 400~
500 turns.
6. the preparation method of lithium borohydride according to claim 1 and molybdenum disulfide compound system solid electrolyte material,
It is characterized by: xLiBH4-yMoS2Compound also carries out dehydrogenation reaction.
7. the preparation method of lithium borohydride according to claim 6 and molybdenum disulfide compound system solid electrolyte material,
It is characterized by: desorption temperature is 450~550 degrees Celsius, heating rate is 1~10 degrees celsius/minute.
8. the lithium borohydride that described in any item preparation methods are prepared according to claim 1~7 and molybdenum disulfide complex
It is solid electrolyte material.
9. lithium borohydride according to claim 8 and molybdenum disulfide compound system solid electrolyte material are preparing battery electricity
The application of Xie Zhizhong.
10. a kind of cell electrolyte, it is characterised in that: include lithium borohydride according to any one of claims 8 and molybdenum disulfide complex
It is solid electrolyte material.
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|---|---|---|---|---|
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Citations (7)
| 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 |
| CN105556731A (en) * | 2013-09-02 | 2016-05-04 | 三菱瓦斯化学株式会社 | Solid-state battery |
| CN105580185A (en) * | 2013-09-02 | 2016-05-11 | 三菱瓦斯化学株式会社 | Solid-state battery and method for manufacturing electrode active material |
| CN106384842A (en) * | 2016-11-15 | 2017-02-08 | 复旦大学 | Nano LiBH4-SiO2 solid electrolyte and preparation method thereof |
| 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 (8)
| 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 |
| CN105556731A (en) * | 2013-09-02 | 2016-05-04 | 三菱瓦斯化学株式会社 | Solid-state battery |
| CN105580185A (en) * | 2013-09-02 | 2016-05-11 | 三菱瓦斯化学株式会社 | Solid-state battery and method for manufacturing electrode active material |
| 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 |
| 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 |
| 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 |
|---|
| ZHAO, YAN等: "Improved dehydrogenation performance of LiBH4 by 3D hierarchical flower-like MoS2 spheres additives", 《JOURNAL OF POWER SOURCES》 * |
| 杨晓婵: "日本开发出锂离子在室温可高速移动的锂硼氢化物", 《现代材料动态》 * |
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| 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 |
| CN110247109A (en) * | 2019-07-16 | 2019-09-17 | 广州天赐高新材料股份有限公司 | A kind of sulfide solid electrolyte and its preparation method and application |
| CN110828904A (en) * | 2019-11-07 | 2020-02-21 | 东南大学 | Lithium halide and two-dimensional material composite solid electrolyte material, 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 |
| CN114602511A (en) * | 2020-12-04 | 2022-06-10 | 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 |
| WO2023130671A1 (en) * | 2022-01-05 | 2023-07-13 | 东南大学 | Composite solid electrolyte material, and preparation method therefor and use thereof |
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