CN103762346B - A kind of lithium ion conductor with nanoscale and preparation method thereof - Google Patents
A kind of lithium ion conductor with nanoscale and preparation method thereof Download PDFInfo
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- CN103762346B CN103762346B CN201410001335.5A CN201410001335A CN103762346B CN 103762346 B CN103762346 B CN 103762346B CN 201410001335 A CN201410001335 A CN 201410001335A CN 103762346 B CN103762346 B CN 103762346B
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- 239000010416 ion conductor Substances 0.000 title claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 43
- 239000006104 solid solution Substances 0.000 claims abstract description 40
- 239000002210 silicon-based material Substances 0.000 claims abstract description 21
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Inorganic materials [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 19
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Inorganic materials [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- -1 lithium halide Chemical class 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000012467 final product Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims 3
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims 2
- 150000002500 ions Chemical class 0.000 abstract description 9
- 230000007704 transition Effects 0.000 abstract description 5
- 239000012448 Lithium borohydride Substances 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 230000035755 proliferation Effects 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 4
- 239000002227 LISICON Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- ADTIQWBLDUXYKM-UHFFFAOYSA-N S(=O)(=O)(O)[Zn] Chemical compound S(=O)(=O)(O)[Zn] ADTIQWBLDUXYKM-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002226 superionic conductor Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
A kind of lithium ion conductor with nanoscale provided by the invention, comprise mesoporous silicon material and be dispersed in the solid solution phase particle in mesoporous silicon material, described solid solution phase particle is selected from LiBH
4solid solution phase particle, 4LiBH
4-LiF solid solution phase particle, 4LiBH
4-LiCl solid solution phase particle, 4LiBH
4-LiBr solid solution phase particle and 4LiBH
4one or more in-LiI solid solution phase particle, described mesoporous silicon material is SBA-15.This lithium ion conductor preparation method is simple, cost is lower, by lithium borohydride and lithium halide are dispersed in mesoporous silicon material, substantially reduce the diffusion path of ion, widen the proliferation network passage of ion, reduce the phase transition temperature of lithium ion conductor, thus substantially increase the conductivity of lithium ion conductor.
Description
Technical field
The invention belongs to battery material field, particularly a kind of lithium ion conductor with nanoscale and preparation method thereof.
Background technology
Lithium rechargeable battery is the power supply being widely used in the electronic equipments such as notebook computer, panel computer, mobile phone, digital vedio recording, camera at present, and future also very likely obtains large-scale application on plug-in or hybrid-electric car.But the electrolyte of existing lithium rechargeable battery adopts inflammable liquid state organics at present usually, when the size of battery amplify further, charge-discharge electric power improve further time, such electrolyte bring the potential safety hazard being much difficult to expect will to the use of battery.
In recent years, people propose to adopt inorganic matter solid-phase electrolyte to substitute organic liquid phase electrolyte, eliminate the potential safety hazard in lithium ion battery large-scale application process with this approach.Up to now, the solid phase material system that people have developed many oxide and sulfide can be used as the electrolyte of lithium rechargeable battery, as perovskite (ABO
3) the lanthanium titanate lithium (LLT) of type, there is NaA
2(PO
4)
3the sodium superionic conductors (NASICON) of structure, zinc germanate lithium (LISICON) and sulfo-zinc germanate lithium (Thio-LISICON) etc., these all belong to fast-ionic conductor.Such as, the fast-ionic conductor Li reported at present
10g
ep
2s
12, its room-temperature conductivity is 10
-2scm
-1, be a magnitude with the electrolytical conductivity of liquid phase organic substance.In addition increasing novel solid phase inorganic materials series is also had constantly to release, to realizing the target of full solid phase lithium ion battery.Recently that comparatively noticeable is the lithium borohydride (LiBH that northeastern Japan university proposes
4) as the new approaches of solid-phase electrolyte; Researcher finds near 113 DEG C, LiBH
4to high-temperature-phase (HT), phase in version occurs by low-temperature phase (LT), in the process, the conductivity of this material rises to 10 rapidly
-3scm
-1; The halide such as LiI, LiCl are added LiBH again by researcher
4form the solid solution phase that phase transition temperature is lower, its low temperature conductance property is more remarkable, and conductivity also promotes to some extent.This series of studies shows, LiBH
4and solid solution phase has the application potential quality becoming fast-ionic conductor.
The present invention is based on above understanding, by LiBH
4and halide solid solution phase particle carries out nano-dispersed, obtain and be of a size of ~ the LiBH of about 5nm
4and halide solid solution phase particle.Along with the refinement of particle, not only shorten the diffusion path of ion, more widened the proliferation network passage of ion, also reduced the phase transition temperature of this material simultaneously, thus the low-temperature conductivity of such material is significantly increased.
Summary of the invention
Goal of the invention: the object of the present invention is to provide lithium ion conductor with nanoscale that a kind of phase transition temperature is low, conductivity is high and preparation method thereof.
Technical scheme: a kind of lithium ion conductor with nanoscale provided by the invention, comprise mesoporous silicon material and be dispersed in the solid solution phase particle in mesoporous silicon material, described solid solution phase particle is selected from LiBH
4solid solution phase particle, 4LiBH
4-LiF solid solution phase particle, 4LiBH
4-LiCl solid solution phase particle, 4LiBH
4-LiBr solid solution phase particle and 4LiBH
4one or more in-LiI solid solution phase particle, described mesoporous silicon material is SBA-15.
As preferably, described solid solution phase particle is nano-scale particle, and more preferably, the particle diameter of described solid solution phase particle is below 10nm.
Preferred as another kind, the mass ratio of described mesoporous silicon material and solid solution phase particle is 2:(1-4).
Present invention also offers the above-mentioned preparation method with the lithium ion conductor of nanoscale, comprise the following steps: under inert gas shielding, solid solution phase particle and mesoporous silicon material are mixed, ball milling, to obtain final product.
As preferably, Ball-milling Time is 4-6h, and ratio of grinding media to material is (20-60): 1, and ball mill revolution speed is 200-600rpm.
Wherein, the preparation method of described solid solution phase particle is: by mol ratio be 4:1 lithium halide respectively with LiBH
4mixing, ball milling, to obtain final product.
As preferably, Ball-milling Time is 1-3h, and ratio of grinding media to material is (20-60): 1, and ball mill revolution speed is 200-600rpm.
Beneficial effect: the lithium ion conductor preparation method with nanoscale provided by the invention is simple, cost is lower, by lithium borohydride and lithium halide are dispersed in mesoporous silicon material, substantially reduce the diffusion path of ion, widen the proliferation network passage of ion, reduce the phase transition temperature of lithium ion conductor, thus substantially increase the conductivity of lithium ion conductor.
Prior art shows, LiBH
4and halide is when temperature is more than 110 DEG C, it is the fast-ionic conductor that a kind of conductivity is very high.And in the present invention, to LiBH
4/ SBA-15,4LiBH
4-LiF/SBA-15,4LiBH
4-LiCl/SBA-15,4LiBH
4-LiBr/SBA-15 and 4LiBH
4-LiI/SBA-15, its nano-dispersed form ionic conduction characteristic all has than body phase morphology (bulk) sample and improves (see figure 3) further, particularly 60 ~ 110
othe nano-dispersed that the several temperature spots of C obtain /SBA-15, its ionic conductivity is than the LiBH of pure phase
4ion conductivity value exceeds more than 10 times.The 4LiBH of nano-dispersed
4-LiI/SBA-15 is compared to body phase 4LiBH
4-LiI also exceeds more than 10 times (as Fig. 4).4LiBH
4-LiF/SBA-15,4LiBH
4-LiCl/SBA-15,4LiBH
4-LiBr/SBA-15 is at lower temperature (60
oc) ionic conductivity time and body phase 4LiBH
4-LiF, 4LiBH
4-LiCl, 4LiBH
4-LiBr compares also has several times amplitude to improve, and shows ideal low-temperature ion conductive characteristic.
Accompanying drawing explanation
Fig. 1 is LiBH
4with the X-ray diffraction spectrogram after SBA-15 material ball milling;
Fig. 2 is LiBH
4with the transmission electron microscope photo after SBA-15 material ball milling;
Fig. 3 is LiBH
4with LiBH
4the conductivity of/SBA-15 varies with temperature curve comparison;
Fig. 4 is 4LiBH
4-LiI and 4LiBH
4the conductivity of-LiI/SBA-15 varies with temperature curve comparison.
Fig. 5 is 4LiBH
4-LiF/SBA-15,4LiBH
4-LiCl/SBA-15,4LiBH
4-LiBr/SBA-15 and 4LiBH
4the conductivity of-LiI/SBA-15 varies with temperature curve comparison.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, concrete material proportion, process conditions and result thereof described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
Embodiment 14LiBH
4-LiF, 4LiBH
4-LiCl, 4LiBH
4-LiBr, 4LiBH
4the preparation of-LiBr
4LiBH
4the preparation of the solid solution phases such as-LiF: be the LiBH of 95% by purity
4the LiF being 99% with purity is that the ratio of 4:1 mixes with mol ratio, and adopt planet gear type ball mill machinery ball milling, ratio of grinding media to material is 40:1, and Ball-milling Time is 2 hours, and revolution speed is 400rpm, obtained nano-scale particle.
4LiBH
4the preparation of-LiCl solid solution phase: be the LiBH of 95% by purity
4the LiCl being 99% with purity is that the ratio of 4:1 mixes with mol ratio, and adopt planet gear type ball mill machinery ball milling, ratio of grinding media to material is 40:1, and Ball-milling Time is 2 hours, and revolution speed is 400rpm, obtained nano-scale particle.
4LiBH
4the preparation of-LiBr solid solution phase: be the LiBH of 95% by purity
4the LiBr being 99% with purity is that the ratio of 4:1 mixes with mol ratio, and adopt planet gear type ball mill machinery ball milling, ratio of grinding media to material is 60:1, and Ball-milling Time is 1 hour, and revolution speed is 200rpm, obtained nano-scale particle.
LiBH
4the preparation of-LiI solid solution phase: be the LiBH of 95% by purity
4the LiI being 99% with purity is that the ratio of 4:1 mixes with mol ratio, and adopt planet gear type ball mill machinery ball milling, ratio of grinding media to material is 20:1, and Ball-milling Time is 3 hours, and revolution speed is 600rpm, obtained nano-scale particle.
Embodiment 2LiBH
4the preparation of/SBA-15
At isolated air (H
2o<1ppm, O
2<1ppm), under condition, be the LiBH of 1:1 by mass ratio
4particle and the mixture of mesoporous silicon material SBA-15 be placed in the steel ball tank that stainless steel abrading-ball is housed; the weight ratio of abrading-ball and sample is 40:1; under high-purity (99.9999%) inert gas shielding; adopt planet gear type ball mill machinery ball milling 5h; revolution rotating speed is 400rpm, the obtained lithium ion conductor LiBH with nanoscale
4/ SBA-15.Due to sample easily and oxygen and water react, all sample operation are all carried out in the glove box being filled with high-purity argon gas, and the oxygen of glove box and water content are all lower than 1ppm concentration.
Utilize X-ray diffraction (XRD) to test and detect LiBH
4/ SBA-15.Sample cell is covered by specific polymeric membrane, and itself and slide is sealed with vacuum grease, and to stop water in air and oxygen to the effect of sample, the target of x-ray source used is Cu target, and tube voltage is 40kV, and tube current is 40mA; The XRD spectra of gained as shown in Figure 1.
Utilize transmission electron microscope observing LiBH
4/ SBA-15, with high-purity tetrahydrofuran solution ultrasonic disperse, fishes for partial particulate with carbon film copper mesh, installing rear sample for use in transmitted electron microscope room of putting into rapidly vacuumizes to be seen, Fig. 2 is the sample topography that transmission electron microscope observing arrives, and particle is nano-scale particle as seen from the figure, and its particle diameter is below 10nm.
Measure LiBH
4the conductivity of/SBA-15 varies with temperature relation.By LiBH
4/ SBA-15 is pressed into a diameter 10mm with the pressure of 40MPa, and thickness is about former of 2mm, and two pieces of lithium paillon foils are placed on the two sides of sample disk as electrode, then with 1 ton/cm
2pressure lithium paillon foil and sample strip compressed cause.All preparations and test are all carried out under high-purity argon gas (99.9999%).The frequency range of ac impedance measurement is from 1MHz to 100mHz.Sample heats up with the speed of 2 DEG C/min, gathers an impedance spectrum at interval of 10 DEG C.Before each image data, temperature all will balance at least 40 minutes.Temperature from ambient rises to 140 DEG C, and cooling gets back to 30 DEG C more afterwards.Ion transfer impedance and admittance is obtained by the AC impedance Nyquist spectrogram obtained.Conductivity variation with temperature curve is shown in Fig. 3, as seen from the figure: LiBH
4/ SBA-15 conductive characteristic is than body phase morphology sample LiBH
4greatly improve, LiBH
4/ SBA-15 in the ionic conductivity of low temperature part than the LiBH of pure phase
4have and more obviously promote, 60 ~ 110
othe ion conductivity value that several temperature spots of C obtain all exceeds more than 10 times than the latter.
Embodiment 34LiBH
4the preparation of-LiI/SBA-15
At isolated air (H
2o<1ppm, O
2<1ppm), under condition, be the 4LiBH of 2:1 by mass ratio
4the particle of-LiI and the mixture of mesoporous silicon material SBA-15 are placed in the steel ball tank that stainless steel abrading-ball is housed; the weight ratio of abrading-ball and sample is 20:1; under high-purity (99.9999%) inert gas shielding; adopt planet gear type ball mill machinery ball milling 6h; revolution rotating speed is 600rpm, the obtained lithium ion conductor 4LiBH with nanoscale
4-LiI/SBA-15.Due to sample easily and oxygen and water react, all sample operation are all carried out in the glove box being filled with high-purity argon gas, and the oxygen of glove box and water content are all lower than 1ppm concentration.
XRD is consistent with embodiment 2 with transmission electron microscope picture.
Conductivity variation with temperature curve is shown in Fig. 4, as seen from the figure: the 4LiBH of nano-dispersed
4-LiI/SBA-15 is at lower temperature (60
oc) ionic conductivity time is compared to body phase 4LiBH
4-LiI exceeds 10 times.
Embodiment 44LiBH
4the preparation of-LiCl/SBA-15
At isolated air (H
2o<1ppm, O
2<1ppm), under condition, be the 4LiBH of 1:2 by mass ratio
4the particle of-LiCl and the mixture of mesoporous silicon material SBA-15 are placed in the steel ball tank that stainless steel abrading-ball is housed; the weight ratio of abrading-ball and sample is 40:1; under high-purity (99.9999%) inert gas shielding; adopt planet gear type ball mill machinery ball milling 5h; revolution rotating speed is 400rpm, the obtained lithium ion conductor 4LiBH with nanoscale
4-LiCl/SBA-15.Due to sample easily and oxygen and water react, all sample operation are all carried out in the glove box being filled with high-purity argon gas, and the oxygen of glove box and water content are all lower than 1ppm concentration.
XRD is consistent with embodiment 2 with transmission electron microscope picture.
Conductivity variation with temperature curve is consistent with embodiment 3,4LiBH
4-LiCl/SBA-15 conductive characteristic is than body phase morphology sample LiBH
4greatly improve, see Fig. 5.
Embodiment 54LiBH
4the preparation of-LiBr/SBA-15
At isolated air (H
2o<1ppm, O
2<1ppm), under condition, be the 4LiBH of 1:1 by mass ratio
4the particle of-LiBr and the mixture of mesoporous silicon material SBA-15 are placed in the steel ball tank that stainless steel abrading-ball is housed; the weight ratio of abrading-ball and sample is 60:1; under high-purity (99.9999%) inert gas shielding; adopt planet gear type ball mill machinery ball milling 4h; revolution rotating speed is 200rpm, the obtained lithium ion conductor 4LiBH with nanoscale
4-LiBr/SBA-15.Due to sample easily and oxygen and water react, all sample operation are all carried out in the glove box being filled with high-purity argon gas, and the oxygen of glove box and water content are all lower than 1ppm concentration.
XRD is consistent with embodiment 2 with transmission electron microscope picture.
Conductivity variation with temperature curve is consistent with embodiment 3,4LiBH
4-LiBr/SBA-15 conductive characteristic is than body phase morphology sample LiBH
4greatly improve, see Fig. 5.
Embodiment 64LiBH
4the preparation of-LiF/SBA-15
At isolated air (H
2o<1ppm, O
2<1ppm) under condition, by 4LiBH
4the particle of-LiF and the mixture of mesoporous silicon material SBA-15 are placed in the steel ball tank that stainless steel abrading-ball is housed; the weight ratio of abrading-ball and sample is 40:1; under high-purity (99.9999%) inert gas shielding; adopt planet gear type ball mill machinery ball milling 5h; revolution rotating speed is 400rpm, the obtained lithium ion conductor 4LiBH with nanoscale
4-LiF/SBA-15.Due to sample easily and oxygen and water react, all sample operation are all carried out in the glove box being filled with high-purity argon gas, and the oxygen of glove box and water content are all lower than 1ppm concentration.
XRD is consistent with embodiment 2 with transmission electron microscope picture.
Conductivity variation with temperature curve is consistent with embodiment 3,4LiBH
4-LiF/SBA-15 conductive characteristic is than body phase morphology sample LiBH
4greatly improve, see Fig. 5.
Claims (2)
1. there is a lithium ion conductor for nanoscale, it is characterized in that: comprise mesoporous silicon material and be dispersed in the solid solution phase particle in mesoporous silicon material, described solid solution phase particle is selected from LiBH
4solid solution phase particle, 4LiBH
4-LiF solid solution phase particle, 4LiBH
4-LiCl solid solution phase particle, 4LiBH
4-LiBr solid solution phase particle and 4LiBH
4one or more in-LiI solid solution phase particle, described mesoporous silicon material is SBA-15, wherein, described solid solution phase particle is scattered in described mesoporous silicon material by the following method: under inert gas shielding, solid solution phase particle and mesoporous silicon material are mixed, ball milling, obtaining final product, Ball-milling Time is 4-6h, ratio of grinding media to material is (20-60): 1, and ball mill revolution speed is 200-600rpm; Wherein, described LiBH
4the preparation method of solid solution phase particle is by LiBH
4mixing, ball milling, the preparation method of other solid solution phase particles be by mol ratio be 4: 1 lithium halide respectively with LiBH
4mixing, ball milling, to obtain final product, described lithium halide be selected from LiF, LiCl, LiBr and LiI any one, wherein, ball milling condition is Ball-milling Time is 1-3h, and ratio of grinding media to material is (20-60): 1, and ball mill revolution speed is 200-600rpm; Described solid solution phase particle is nano-scale particle, and particle diameter is 5nm ~ 10nm.
2. the lithium ion conductor with nanoscale according to claim 1, is characterized in that: the mass ratio of described mesoporous silicon material and solid solution phase particle is 2: (1 ~ 4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410001335.5A CN103762346B (en) | 2014-01-02 | 2014-01-02 | A kind of lithium ion conductor with nanoscale and preparation method thereof |
Applications Claiming Priority (1)
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| CN104393338A (en) * | 2014-11-21 | 2015-03-04 | 东南大学 | LiBH4-silver/silver halide compound fast-ion conductor and preparation method thereof |
| CN109937506A (en) * | 2016-11-15 | 2019-06-25 | 株式会社村田制作所 | Lithium ion conduction body, all-solid-state battery, electronic equipment, electronic card, wearable device and electric vehicle |
| CN106384842B (en) * | 2016-11-15 | 2019-07-05 | 复旦大学 | A kind of nanometer of LiBH4-SiO2Solid electrolyte and preparation method thereof |
| CN108736064B (en) * | 2018-07-11 | 2020-12-04 | 桑德新能源技术开发有限公司 | Composite lithium borohydride solid electrolyte and preparation method and equipment thereof |
| CN109244535B (en) * | 2018-11-01 | 2021-01-19 | 上海理工大学 | Preparation method of lithium borohydride based solid electrolyte material |
| CN112331909A (en) * | 2020-10-12 | 2021-02-05 | 南京航空航天大学 | Lithium ion conductor of ammonia-doped lithium borohydride composite material system and preparation method thereof |
| CN118173790B (en) * | 2024-05-16 | 2024-09-06 | 四川新能源汽车创新中心有限公司 | Solid-state battery anode material and preparation method and application thereof |
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| CN103101880A (en) * | 2013-01-29 | 2013-05-15 | 广州有色金属研究院 | Lithium borohydride/rare earth magnesium base alloy composite hydrogen storage material and preparation method thereof |
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| Nanoconfined LiBH4 and Enhanced Mobility of Li+ and BH- Studied by Solid-State NMR;Margriet H.W.Verkuijlen et al;《The Journal of Physical Chemistry C》;20121231;22169-22178 * |
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