CN103762346A - Lithium ion conductor with nanoscale and preparation method thereof - Google Patents
Lithium ion conductor with nanoscale and preparation method thereof Download PDFInfo
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- CN103762346A CN103762346A CN201410001335.5A CN201410001335A CN103762346A CN 103762346 A CN103762346 A CN 103762346A CN 201410001335 A CN201410001335 A CN 201410001335A CN 103762346 A CN103762346 A CN 103762346A
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- 239000010416 ion conductor Substances 0.000 title claims abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 42
- 239000006104 solid solution Substances 0.000 claims abstract description 38
- 239000002210 silicon-based material Substances 0.000 claims abstract description 20
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Inorganic materials [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 17
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Inorganic materials [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- -1 lithium halide Chemical class 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 abstract description 9
- 239000012448 Lithium borohydride Substances 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 36
- 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
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 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
- 230000007704 transition Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 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
- 230000035755 proliferation Effects 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
- 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
- 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
- 238000002474 experimental method Methods 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 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
- KUJOABUXCGVGIY-UHFFFAOYSA-N lithium zinc Chemical compound [Li].[Zn] KUJOABUXCGVGIY-UHFFFAOYSA-N 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
- 238000012360 testing method Methods 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
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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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
- 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
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- 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
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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
- 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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Abstract
The invention provides a lithium ion conductor with a nanoscale. The lithium ion conductor comprises a mesoporous silicon material and solid solution phase particles dispersed in the mesoporous silicon material, wherein the solid solution phase particles are selected from one or more of LiBH4 solid solution phase particles, 4LiBH4-LiF solid solution phase particles, 4LiBH4-LiCl solid solution phase particles, 4LiBH4-LiBr solid solution phase particles and 4LiBH4-LiI solid solution phase particles; the mesoporous silicon material is SBA-15. The lithium ion conductor has the beneficial effects that a preparation method of the lithium ion conductor is simple and is relatively low in cost; by dispersing lithium borohydride and lithium halide in the mesoporous silicon material, the diffusion path of the ions is greatly shortened, the diffusion network channel of the ions is widened, and the phase inversion temperature of the lithium ion conductor is reduced, thus greatly improving the electrical conductivity of the 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 that is widely used at present the electronic equipments such as notebook computer, panel computer, mobile phone, digital vedio recording, camera, and also very likely obtain large-scale application future on plug-in or hybrid-electric car.But the electrolyte of existing lithium rechargeable battery adopts inflammable liquid state organics at present conventionally, when the size of battery is further amplified, discharged and recharged power and further improves, such electrolyte bring to the use of battery to be much difficult to the potential safety hazard of expecting.
In recent years, people propose to adopt inorganic matter solid-phase electrolyte to substitute organic liquid phase electrolyte, with this approach, eliminate the potential safety hazard in lithium ion battery large-scale application process.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, germanic acid zinc lithium (LISICON) and sulfo-germanic acid zinc lithium (Thio-LISICON) etc., these all belong to fast-ionic conductor.For example, the fast-ionic conductor Li reporting at present
10g
ep
2s
12, its room-temperature conductivity is 10
-2s cm
-1, with the electrolytical conductivity of liquid phase organic substance be a magnitude.In addition also have increasing novel solid phase inorganic materials series constantly to release, to realizing the target of full solid phase lithium ion battery.That recently 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 ℃, LiBH
4by low-temperature phase (LT), to high-temperature-phase (HT), occurred to change mutually, in this process, the conductivity of this material rises to rapidly 10
-3s cm
-1; Researcher adds LiBH by halide such as LiI, LiCl again
4form the lower solid solution phase of phase transition temperature, 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 and becomes the application of fast-ionic conductor potential quality.
The present invention is based on above understanding, by LiBH
4and halide solid solution phase particle carries out nano-dispersed, the LiBH of be of a size of～5nm of acquisition left and right
4and halide solid solution phase particle.Along with the refinement of particle, not only shortened the diffusion path of ion, more widened the proliferation network passage of ion, also reduced the phase transition temperature of this material, thereby the low-temperature conductivity of such material is significantly increased simultaneously.
Summary of the invention
Goal of the invention: what the object of the present invention is to provide that a kind of phase transition temperature is low, conductivity is high has lithium ion conductor of nanoscale 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).
The present invention also provides the preparation method of the above-mentioned lithium ion conductor with nanoscale, comprises the following steps: under inert gas shielding, by solid solution phase particle and mesoporous silicon material mix, ball milling, obtain.
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: the lithium halide that is 4:1 by mol ratio respectively with LiBH
4mix, ball milling, obtain.
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, greatly shortened the diffusion path of ion, widened the proliferation network passage of ion, reduce the phase transition temperature of lithium ion conductor, thereby greatly improved the conductivity of lithium ion conductor.
Prior art shows, LiBH
4and halide is when more than 110 ℃ in temperature, 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 further raising (see figure 3) than body phase morphology (bulk) sample, particularly 60～110
othe nano-dispersed that 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 than body phase 4LiBH
4-LiI also exceeds 10 times above (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 comparatively desirable 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, the described concrete material proportion of embodiment, process conditions and result thereof be only for the present invention is described, and should also can not limit the present invention described in detail in claims.
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: the LiBH that is 95% by purity
4the ratio of the LiF that is 99% with purity take mol ratio as 4:1 mixed, and adopts planet gear type ball mill machinery ball milling, and ratio of grinding media to material is 40:1, and Ball-milling Time is 2 hours, and revolution speed is 400rpm, makes nano-scale particle.
4LiBH
4the preparation of-LiCl solid solution phase: the LiBH that is 95% by purity
4the ratio of the LiCl that is 99% with purity take mol ratio as 4:1 mixed, and adopts planet gear type ball mill machinery ball milling, and ratio of grinding media to material is 40:1, and Ball-milling Time is 2 hours, and revolution speed is 400rpm, makes nano-scale particle.
4LiBH
4the preparation of-LiBr solid solution phase: the LiBH that is 95% by purity
4the ratio of the LiBr that is 99% with purity take mol ratio as 4:1 mixed, and adopts planet gear type ball mill machinery ball milling, and ratio of grinding media to material is 60:1, and Ball-milling Time is 1 hour, and revolution speed is 200rpm, makes nano-scale particle.
LiBH
4the preparation of-LiI solid solution phase: the LiBH that is 95% by purity
4the ratio of the LiI that is 99% with purity take mol ratio as 4:1 mixed, and adopts planet gear type ball mill machinery ball milling, and ratio of grinding media to material is 20:1, and Ball-milling Time is 3 hours, and revolution speed is 600rpm, makes nano-scale particle.
Embodiment 2LiBH
4the preparation of/SBA-15
At isolated air (H
2o<1ppm, O
2<1ppm) under condition, the LiBH that is 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, makes the lithium ion conductor LiBH with nanoscale
4/ SBA-15.Because sample is easy and oxygen G&W reacts, all sample operation are all carried out in the glove box that is 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) experiment to detect LiBH
4/ SBA-15.Sample cell is covered by specific polymeric membrane, and with vacuum grease, itself and slide is sealed, and to stop the effect to sample of water in air and oxygen, 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 the ultrasonic dispersion of high-purity tetrahydrofuran solution, fishes for part particle with carbon film copper mesh, installing the rear sample for use in transmitted electron microscope chamber 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, the former of about 2mm of thickness, and the two sides that two lithium paillon foils are placed on to sample disk is as electrode, then with 1 ton/cm
2pressure lithium paillon foil and sample strip are compressed and are caused.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 ℃/min, at interval of 10 ℃, gathers an impedance spectrum.Before each image data, temperature is all wanted balance at least 40 minutes.Temperature rises to 140 ℃ by room temperature, and cooling is got back to 30 ℃ more afterwards.By the AC impedance Nyquist spectrogram obtaining, obtain ion transfer impedance and admittance.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 more obviously and 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, the 4LiBH that is 2:1 by mass ratio
4the mixture of the particle of-LiI and mesoporous silicon material SBA-15 is 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, makes the lithium ion conductor 4LiBH with nanoscale
4-LiI/SBA-15.Because sample is easy and oxygen G&W reacts, all sample operation are all carried out in the glove box that is 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, the 4LiBH that is 1:2 by mass ratio
4the mixture of the particle of-LiCl and mesoporous silicon material SBA-15 is 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, makes the lithium ion conductor 4LiBH with nanoscale
4-LiCl/SBA-15.Because sample is easy and oxygen G&W reacts, all sample operation are all carried out in the glove box that is 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, the 4LiBH that is 1:1 by mass ratio
4the mixture of the particle of-LiBr and mesoporous silicon material SBA-15 is 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, makes the lithium ion conductor 4LiBH with nanoscale
4-LiBr/SBA-15.Because sample is easy and oxygen G&W reacts, all sample operation are all carried out in the glove box that is 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 mixture of the particle of-LiF and mesoporous silicon material SBA-15 is 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, makes the lithium ion conductor 4LiBH with nanoscale
4-LiF/SBA-15.Because sample is easy and oxygen G&W reacts, all sample operation are all carried out in the glove box that is 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 (7)
1. a lithium ion conductor with nanoscale, 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.
2. a kind of lithium ion conductor with nanoscale claimed in claim 1, is characterized in that: described solid solution phase particle is nano-scale particle.
3. a kind of lithium ion conductor with nanoscale claimed in claim 1, is characterized in that: the mass ratio of described mesoporous silicon material and solid solution phase particle is 2:(1-4).
4. a preparation method for the lithium ion conductor with nanoscale claimed in claim 1, is characterized in that: under inert gas shielding, by solid solution phase particle and mesoporous silicon material mix, ball milling, obtain.
5. the preparation method of a kind of lithium ion conductor with nanoscale according to claim 4, is characterized in that: 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.
6. the preparation method of a kind of lithium ion conductor with nanoscale according to claim 4, is characterized in that: the preparation method of described solid solution phase particle is: the lithium halide that is 4:1 by mol ratio respectively with LiBH
4mix, ball milling, obtain.
7. the preparation method of a kind of lithium ion conductor with nanoscale according to claim 4, is characterized in that: 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.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN106384842A (en) * | 2016-11-15 | 2017-02-08 | 复旦大学 | Nano LiBH4-SiO2 solid electrolyte and preparation method thereof |
| CN108736064A (en) * | 2018-07-11 | 2018-11-02 | 桑德集团有限公司 | A kind of compound lithium borohydride solid electrolyte and preparation method thereof and equipment |
| CN109244535A (en) * | 2018-11-01 | 2019-01-18 | 上海理工大学 | The preparation method of lithium borohydride base solid electrolyte material |
| 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 |
| 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 |
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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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| 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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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104393338A (en) * | 2014-11-21 | 2015-03-04 | 东南大学 | LiBH4-silver/silver halide 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 |
| 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 |
| CN108736064A (en) * | 2018-07-11 | 2018-11-02 | 桑德集团有限公司 | A kind of compound lithium borohydride solid electrolyte and preparation method thereof and equipment |
| 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 |
| CN109244535A (en) * | 2018-11-01 | 2019-01-18 | 上海理工大学 | The preparation method of lithium borohydride base solid electrolyte material |
| 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 |
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