CN106673651A - Li7La3Zr2O12 ion conductor ceramic fiber and preparation method thereof - Google Patents
Li7La3Zr2O12 ion conductor ceramic fiber and preparation method thereof Download PDFInfo
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
- C04B2235/3203—Lithium oxide or oxide-forming salts thereof
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
Abstract
The invention discloses Li7La3Zr2O12 ion conductor ceramic fiber. The material has the chemical composition of Li7La3Zr2O12, has the ion conductor ceramic fiber length of 1-2.5 mu m, the diameter of 80-120 nm and the lithium ion conductivity of 1.5*10<-4> S/cm-6*10<-3> S/cm. The invention further provides a method for preparing the ion conductor ceramic fiber. Lithium carbonate, lanthanum oxide, zirconyl nitrate, a nitric acid solution and absolute ethyl alcohol are mixed, heated and then mixed with citric acid and ethylene glycol, and the mixture is stirred at the constant temperature, and precursor sol is obtained; spinning sol is obtained by mixing a water-soluble polymer and the obtained precursor sol, spinning and calcination are performed sequentially, and ion conductor ceramic fiber with stable morphology and size is obtained. The method can improve the lithium ion conductivity significantly, adopts a simple process, is low in cost, has low requirements for equipment and environment and is suitable for industrial application.
Description
Technical field
The present invention relates to technical field of inorganic material, more particularly to a kind of lithium lanthanum zirconium oxygen ion conductor ceramic fibre and its system
Preparation Method.
Background technology
At this stage, there is the direct conducting of both positive and negative polarity and short circuit phenomenon occur in lithium ion battery, and security performance cannot be guaranteed.Its
Reason is that most of electrolyte are liquid, in the electrolyte between be provided with barrier film, the both positive and negative polarity of battery is separated, do not allow its straight
Lead in succession, so now commercial organic barrier film is usually non-conductive son, but while and in order to ensure the positive normal open of lithium ion
Cross, need barrier film to there is certain porosity, and battery-heating will cause the contraction of organic barrier film, cause both positive and negative polarity directly to turn on
Form short circuit；Solid electrolyte is not volatile, general non-combustible, therefore can have excellent safety from solid electrolyte.
Ion conductor ceramics have higher ionic conductivity, used as a kind of specific function pottery that can quickly conduct ion
Porcelain, is increasingly paid close attention to by people, particularly can conducting lithium ions ion conductor ceramic fibre；Ceramic fibre is used as one kind
Ceramics with special appearance, in many fields application is had been obtained for, it is desirable to prepare solid electrolyte with it replace
Original liquid electrolyte, thoroughly solves the safety high of lithium ion battery.The method for preparing ceramic fibre at present is mainly
Method of electrostatic spinning and other templates.It is relatively complicated that cation ceramic fiber is prepared technique using these techniques, into
This is higher, and the chemical constitution of the ion conductor ceramic fibre obtained using above-mentioned technique, appearance and size and electric conductivity
There is difference, less stable.
The content of the invention
In view of this, it is an object of the invention to provide a kind of ion conductor ceramic fibre and preparation method thereof, the present invention
The ion conductor ceramic fibre appearance structure of offer is stablized with size.Using the method for the invention can Simplified flowsheet, drop
Low production cost, improves the lithium ion conductivity of material.
In order to realize foregoing invention purpose, the present invention provides technical scheme below：
A kind of lithium lanthanum zirconium oxygen ion conductor ceramic fibre, it is characterised in that chemical composition is Li7La3Zr2O12, fibre length
For 1~2.5 μm, a diameter of 80~120nm, lithium ion conductivity is 1.5 × 10-4S/cm~6 × 10-3S/cm。
Present invention also offers a kind of preparation method of lithium lanthanum zirconium oxygen ion conductor ceramic fibre, comprises the following steps：
1) by lithium carbonate, lanthana, zirconyl nitrate, salpeter solution and dehydrated alcohol Hybrid Heating, mixed liquor is obtained；
2) by citric acid and ethylene glycol and the step 1) mixed liquor that obtains mixes, and obtains lithium lanthanum zirconium oxygen presoma, its
The mol ratio of middle lithium carbonate, lanthana, zirconyl nitrate, ethylene glycol and citric acid is 7:3:4:28:14, before the lithium lanthanum zirconium oxygen
Drive the stirring of body constant temperature and obtain precursor sol；
3) by water-soluble polymer and the step 2) precursor sol that obtains mixes, and obtains spinning colloidal sols；
4) by step 3) spinning colloidal sols that obtain carry out being calcined after spinning, obtain ion conductor ceramic fibre.
Preferably, the step 1) in mixing be specially：Lithium carbonate and lanthana are dissolved in into dust technology, lithium-lanthanum is obtained
Salpeter solution；Zirconyl nitrate is dissolved in dehydrated alcohol, zirconium solution is obtained；The lithium-lanthanum salpeter solution is mixed with zirconium solution.
Preferably, the step 1) in the mode of heating be heating in water bath, the temperature of heating is 50~80 DEG C.
Preferably, the concentration of lithium lanthanum zirconium oxygen is 0.1~0.4mol/L in the lithium lanthanum zirconium oxygen presoma.
Preferably, the step 2) in constant temperature stirring temperature be 50~80 DEG C.
Preferably, the water-soluble polymer is PVP and/or PVA.
Preferably, the water-soluble polymer is mixed in the form of water-soluble polymer aqueous solution with precursor sol, institute
The mass concentration for stating water-soluble polymer aqueous solution is 10~20%, the water-soluble polymer aqueous solution and precursor sol
Volume ratio is 2~5:1.
Preferably, the step 4) in carry out spinning by the way of gas spins, the air velocity that gas spins is 10~80m/s.
Preferably, state step 4) in the temperature of calcining be 900~1500 DEG C, time of calcining is 0.5~12h.
A kind of ion conductor ceramic fibre that the present invention is provided, the chemical composition of the material is Li7La3Zr2O12, it is described from
The size of sub- conductive ceramic fiber is stablized, and length is 1~2.5 μm, and a diameter of 80~120nm, appearance structure is Emission in Cubic,
Complete by the transformation of amorphous state to crystalline state, lithium ion conductivity is 1.5 × 10-4S/cm~6 × 10-3S/cm, is significantly carried
It is high；Applying cloth diaphragm using the ion conductor ceramic fibre can strengthen the mechanical performances such as the heat resistanceheat resistant shrinkage of barrier film, reduce
Plugging rate, makes up the lithium ion conductivity that barrier film is reduced because of coating, strengthens its high rate performance.
Description of the drawings
With reference to the accompanying drawings and detailed description the present invention is further detailed explanation.
Fig. 1 is the X-ray diffraction spectrum of the lithium lanthanum zirconium oxygen ceramic fibre prepared by the embodiment of the present invention 1；
Fig. 2 is the SEM figures of the precursor fibre before the calcining of the embodiment of the present invention 1；
Fig. 3 is the lithium lanthanum zirconium oxygen ion conductor ceramic fibre SEM figures that the embodiment of the present invention 1 is obtained.
Specific embodiment
The invention provides a kind of lithium lanthanum zirconium oxygen ion conductor ceramic fibre, the chemical group of the ion conductor ceramic fibre
Become Li7La3Zr2O12, crystal formation form is Emission in Cubic.
In the present invention, the length of the ion conductor ceramic fibre is 1~2.5 μm, a diameter of 80~120nm, preferably
Fibre length be 1.5~2.2 μm, a diameter of 90~110nm, preferred fibre length be 2 μm, a diameter of 100nm.
In the present invention, described ion conductor ceramic fibre lithium ion conductivity is 1.5 × 10-4S/cm~6 × 10-3S/
Cm, preferably 3.6 × 10-4S/cm~1.2 × 10-3S/cm, more preferably 7 × 10-4S/cm~9.3 × 10-4S/cm。
Present invention also offers a kind of preparation method of lithium lanthanum zirconium oxygen ion conductor ceramic fibre, comprises the following steps：
1) by lithium carbonate, lanthana, zirconyl nitrate, salpeter solution and dehydrated alcohol Hybrid Heating, mixed liquor is obtained；
2) by citric acid and ethylene glycol and the step 1) mixed liquor that obtains mixes, and obtains lithium lanthanum zirconium oxygen presoma, its
The mol ratio of middle lithium carbonate, lanthana, zirconyl nitrate, ethylene glycol and citric acid is 7:3:4:28:14, before the lithium lanthanum zirconium oxygen
Drive the stirring of body constant temperature and obtain precursor sol；
3) by water-soluble polymer and the step 2) precursor sol that obtains mixes, and obtains spinning colloidal sols；
4) by step 3) spinning colloidal sols that obtain carry out being calcined after spinning, obtain ion conductor ceramic fibre.
The present invention does not have any particular restriction to the source of raw material and reagent, using raw material well known to those skilled in the art
Source or commercial goods.
Lithium carbonate, lanthana, zirconyl nitrate, salpeter solution and dehydrated alcohol Hybrid Heating are obtained mixed liquor by the present invention.
Preferably, the mixing is specially：Lithium carbonate and lanthana are dissolved in into salpeter solution, lithium-lanthanum salpeter solution is obtained；By Nitric Acid Oxidation
Zirconium is dissolved in dehydrated alcohol, obtains zirconium solution；The lithium-lanthanum salpeter solution is mixed with zirconium solution.In the present invention, the carbonic acid
The theoretical molar ratio preferably 7 of lithium and lanthana:3；In the present invention, the mass concentration of the salpeter solution be preferably 10~
20%, more preferably 15%；The Theoretical Mass fraction of the lanthana and lithium carbonate in lithium-lanthanum salpeter solution is preferably 6%
~10% and 10.2%~16.3%；In the present invention, the actual mass of lithium carbonate will have more 8~12%, preferably 10%, to mend
Repay the volatilization of lithium under high temperature.
The present invention is dissolved in zirconyl nitrate in dehydrated alcohol, obtains zirconium solution.In the present invention, the zirconyl nitrate is in nothing
Mass fraction in water-ethanol is preferably 18.8%~31.6%；The present invention does not have particular/special requirement for dissolving, using this area
Conventional method.
The step 1) in mixing after, water bath with thermostatic control ring of the present invention preferably by the mixed system for obtaining at 50~80 DEG C
Heated and stirred is carried out under border, mixed liquor is obtained.In the present invention, the temperature of the water bath with thermostatic control is more preferably 60~70 DEG C；
After obtaining mixed liquor, the present invention mixes the mixed liquor with citric acid and ethylene glycol, obtains lithium lanthanum zirconium oxygen forerunner
Body.In the present invention, the mol ratio of the lithium carbonate, lanthana, zirconyl nitrate, ethylene glycol and citric acid is 7:3:4:28:14；Institute
The concentration for stating lithium lanthanum zirconium oxygen in lithium lanthanum zirconium oxygen presoma is 0.1~0.4mol/L, and preferred concentration is 0.2~0.3mol/L, more
Preferably 0.25mol/L.
In the present invention, ethylene glycol is organic solvent, for dissolving step 1) mixed liquor that obtains, citric acid is organic complex
Agent, with metallic compound reacting forming complex prevent precipitation produce, go into stable dispersion phase, at the same with subsequent step in
Water-soluble polymer produces synergism, prevents from causing follow-up batch mixing uneven because dispersion phase is unstable, prevents each element not
In can be uniformly dispersed in colloidal sol.
After obtaining lithium lanthanum zirconium oxygen presoma, it is molten that lithium lanthanum zirconium oxygen presoma constant temperature stirring is obtained presoma by the present invention
Glue.In the present invention, the temperature of the constant temperature stirring is preferably 50~80 DEG C, more preferably 60~70 DEG C；The constant temperature stirring
Time preferably 12~24h, more preferably 15~20h.
The present invention mixes the precursor sol for obtaining and water-soluble polymer, obtains spinning colloidal sols.In the present invention
The water-soluble polymer is mixed in the form of water-soluble polymer aqueous solution with precursor sol；It is described water-soluble in the present invention
Property polymer is preferably PVP and/or PVA.The mass concentration of the water-soluble polymer aqueous solution is preferably 10~20%, more excellent
Elect 15% as；The water-soluble polymer aqueous solution is preferably 2~5 with the volume ratio of precursor sol:1, more preferably 3:1
~4:1；Stir or stir using this area conventional magnetic.
After obtaining spinning colloidal sols, the spinning colloidal sols are carried out spinning by the present invention, the spinning fibre calcining for obtaining, and are obtained
To ion conductor ceramic fibre.In the present invention, the mode that the preferred gas of the spinning spins, concrete grammar is：Extract spinning colloidal sols
In syringe, by topping-up pump, spinning colloidal sols are outpoured with 3ml/h speed from coaxial syringe needle interior axle, air-flow is with 10~80m/s
Speed pass through from outer shaft, spinning colloidal sols are drawn in the air fiber, the solvent in colloidal sol also volatilizees rapidly during this time,
Eventually form nano level fiber, collect in the porous cage modle catcher of liquid outlet 20cm, and mutually winding group
Into the nanofiber presoma of three dimensional structure.
In the present invention, the calcining is that gas is spun the nanofiber presoma for obtaining to forge under 900~1500 DEG C of high temperature
Burn 0.5~12h；The temperature of the calcining is more preferably 1000~1400 DEG C, most preferably 1200~1300 DEG C；The calcining
Time is more preferably 1~8h, most preferably 2~5h.
In the present invention, the calcining can vapor away solvent and organic polymer in fiber, additionally it is possible to make ceramic fibre
Dimension crystallization, in calcination process with crystal grain grow up and crystalline phase change.Calcining can be generated between 900 DEG C~1500 DEG C
The lithium lanthanum zirconium oxygen of Emission in Cubic, calcination time can guarantee that the sufficient growth of crystal grain between 0.5~12h, if calcining heat mistake
Low, the time is too short, and the crystal grain of formation is too little will to cause crystal boundary excessive, affect the conduction of lithium ion, if calcining heat is too high, when
Between it is long, the crystal grain too senior general of formation is broken can fiber morphology；So calcining heat and time are to need strictly to be controlled ability
The electric conductivity of its lithium ion is improved while obtaining and stablizing the ion conductor ceramic fibre of pattern and size.
The preparation method of the lithium lanthanum zirconium oxygen ion conductor ceramic fibre that the present invention is provided, with lithium carbonate, lanthana, Nitric Acid Oxidation
Zirconium, salpeter solution and dehydrated alcohol are carried out after Hybrid Heating for raw material, add citric acid and ethylene glycol mixing, obtain lithium lanthanum zirconium oxygen
Presoma, the mol ratio of lithium carbonate, lanthana, zirconyl nitrate, ethylene glycol and citric acid is 7 in the presoma:3:4:28:
14, the blended stirring of precursor sol obtains spinning colloidal sols, spinning is carried out successively and calcining obtains a kind of appearance structure and size
The stable ion conductor ceramic fibre of size, the chemical composition of the material is Li7La3Zr2O12, fibre length is 1~2.5 μm, directly
Footpath is 80~120nm, and appearance structure is completed by the transformation of amorphous state to crystalline state for Emission in Cubic, and lithium ion conductivity is obtained significantly
Rise to 1.5 × 10-4S/cm~6 × 10-3S/cm, and the method for the invention process is simple, low cost, entirely prepared
Journey is not high to equipment and environmental requirement, is adapted to commercial Application.
Lithium lanthanum zirconium oxygen ion conductor ceramic fibre provided the present invention with reference to embodiment and preparation method thereof is carried out
Detailed description, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
Stoichiometrically weigh lithium carbonate (Li2CO3) 5.69g, lanthana (La2O3) 9.77g, zirconyl nitrate (ZrO
(NO3)2) 9.25g, by lithium carbonate (Li2CO3), lanthana (La2O3) it is dissolved in the dilute nitric acid solution that 80g concentration is 15%, by nitre
Sour oxygen zirconium (ZrO (NO3)2) 20g dehydrated alcohol is dissolved in, the volatilization of lithium under 10% is weighed wherein lithium carbonate to compensate high temperature more.
The above-mentioned salpeter solution dissolved with lithium carbonate and lanthana is mixed with the dehydrated alcohol dissolved with zirconyl nitrate, and 50
DEG C water bath with thermostatic control environment under be stirred, add 53.80g citric acids and 8.69g ethylene glycol, constant temperature stirring 12h obtains molten
Glue.
Weigh the PVP solution that 50g mass concentrations are 10% to mix with the colloidal sol for obtaining, be sufficiently stirred for 24h.Using what is obtained
Colloidal sol enters circulation of qi promoting spinning, and gas is spun gained fiber and calcined at 1000 DEG C by its gas flow rate in 10m/s, and calcination time is 1h, is obtained
To ion conductor ceramic fibre.Test result indicate that the length of gained ion conductor ceramic fibre is 2 μm, and a diameter of 100nm, lithium
Ionic conductivity is 7 × 10-4S/cm。
The transformation having occurred that after sintering from amorphous state to crystalline state is can be seen that by Fig. 1 XRD spectrums, is generated vertical
The Li of square phase7La3Zr2O12。
Analyzed from Fig. 2 and Fig. 3, embodiment 1 is in sintering process, and Organic substance and polymer are vapored away, unsintered
Fiber there occurs fracture, and at 2 μm or so, diameter maintains good threadiness to the fibre length after sintering in 100nm or so
Structure.
Embodiment 2
Stoichiometrically weigh lithium carbonate (Li2CO3) 5.69g, lanthana (La2O3) 9.77g, zirconyl nitrate (ZrO
(NO3)2) 9.25g, by lithium carbonate (Li2CO3), lanthana (La2O3) it is dissolved in the dilute nitric acid solution that 50g concentration is 20%, by nitre
Sour oxygen zirconium (ZrO (NO3)2) 40g dehydrated alcohol is dissolved in, the volatilization of lithium under 10% is weighed wherein lithium carbonate to compensate high temperature more.
The above-mentioned salpeter solution dissolved with lithium carbonate and lanthana is mixed with the dehydrated alcohol dissolved with zirconyl nitrate, and 80
DEG C water bath with thermostatic control environment under be stirred, add 53.80g citric acids and 8.69g ethylene glycol, constant temperature stirring 24h obtains molten
Glue.
Weigh the PVP solution that 45g mass concentrations are 10% to mix with the colloidal sol for obtaining, be sufficiently stirred for 48h.Using what is obtained
Colloidal sol enters circulation of qi promoting spinning, and gas is spun gained fiber and calcined at 900 DEG C by its gas flow rate in 80m/s, and calcination time is 12h, is obtained
To ion conductor ceramic fibre.Test result indicate that the length of gained ion conductor ceramic fibre is 2.5 μm, a diameter of 120nm,
Lithium ion conductivity is 3.6 × 10-4S/cm。
Embodiment 3
Stoichiometrically weigh lithium carbonate (Li2CO3) 11.17g, lanthana (La2O3) 19.54g, zirconyl nitrate (ZrO
(NO3)2) 18.5g, by lithium carbonate (Li2CO3), lanthana (La2O3) it is dissolved in the dilute nitric acid solution that 150g concentration is 10%, will
Zirconyl nitrate (ZrO (NO3)2) 40g dehydrated alcohol is dissolved in, the volatilization of lithium under 8% is weighed wherein lithium carbonate to compensate high temperature more.
The above-mentioned salpeter solution dissolved with lithium carbonate and lanthana is mixed with the dehydrated alcohol dissolved with zirconyl nitrate, and 60
DEG C water bath with thermostatic control environment under be stirred, add 107.60g citric acids and 17.38g ethylene glycol, constant temperature stirring 15h is obtained
Colloidal sol.
Weigh the PVP solution that 80g mass concentrations are 15% to mix with the colloidal sol for obtaining, be sufficiently stirred for h.It is molten using what is obtained
Glue enters circulation of qi promoting spinning, and gas is spun gained fiber and calcined at 1500 DEG C by its gas flow rate in 80m/s, and calcination time is 1h, is obtained
Ion conductor ceramic fibre.Test result indicate that the length of gained ion conductor ceramic fibre is 1.5 μm, and a diameter of 80nm, lithium
Ionic conductivity is 1.2 × 10-3S/cm。
Embodiment 4
Stoichiometrically weigh lithium carbonate (Li2CO3) 11.59g, lanthana (La2O3) 19.54g, zirconyl nitrate (ZrO
(NO3)2) 18.5g, by lithium carbonate (Li2CO3), lanthana (La2O3) it is dissolved in the dilute nitric acid solution that 125g concentration is 13%, will
Zirconyl nitrate (ZrO (NO3)2) 40g dehydrated alcohol is dissolved in, the volatilization of lithium under 12% is weighed wherein lithium carbonate to compensate high temperature more.
The above-mentioned salpeter solution dissolved with lithium carbonate and lanthana is mixed with the dehydrated alcohol dissolved with zirconyl nitrate, and 70
DEG C water bath with thermostatic control environment under be stirred, add 107.60g citric acids and 17.38g ethylene glycol, constant temperature stirring 20h is obtained
Colloidal sol.
Weigh the PVP solution that 120g mass concentrations are 10% to mix with the colloidal sol for obtaining, be sufficiently stirred for h.Using what is obtained
Colloidal sol enters circulation of qi promoting spinning, and gas is spun gained fiber and calcined at 1200 DEG C by its gas flow rate in 80m/s, and calcination time is 5h, is obtained
To ion conductor ceramic fibre.Test result indicate that the length of gained ion conductor ceramic fibre is 2 μm, and a diameter of 120nm, lithium
Ionic conductivity is 9.3 × 10-4S/cm。
Embodiment 5
Weigh the gained Li of embodiment 17La3Zr2O12Ceramic fibre 20.0g, bonding agent carboxymethyl cellulose 0.3g, bonding agent
Styrene-butadiene latex 2.0g, dispersant sodium carboxymethyl cellulose 0.04g, in being dissolved in 25.0g water, are mixed using the method for high-speed stirred
Close, be to accelerate rate of dispersion, rapid dispersion is carried out using ultrasonic assistant.Obtained solution is applied to into thickness using coating method
For 20 μm, by PP, (aperture is 0.05 μm, and porosity is the polymer organic layer for 40%) constituting (film layer is commercialization PP films)
On, and be fully dried in 55 DEG C, a kind of ion conductor ceramic fibre composite diaphragm is obtained, performance test is as shown in table 1, sharp
The ion conductor ceramic fibre provided with application can improve the punctured resistance and tensile strength of barrier film, charge-discharge magnification performance
Raising, the reduction of the internal resistance of cell all show that its lithium ion conductivity is improved.
Table 1
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of lithium lanthanum zirconium oxygen ion conductor ceramic fibre, it is characterised in that chemical composition is Li7La3Zr2O12, fibre length is
1~2.5 μm, a diameter of 80~120nm, lithium ion conductivity is 1.5 × 10-4S/cm~6 × 10-3S/cm。
2. the preparation method of lithium lanthanum zirconium oxygen ion conductor ceramic fibre described in claim 1, comprises the following steps：
1) by lithium carbonate, lanthana, zirconyl nitrate, salpeter solution and dehydrated alcohol Hybrid Heating, mixed liquor is obtained；
2) by citric acid and ethylene glycol and the step 1) mixed liquor that obtains mixes, and obtains lithium lanthanum zirconium oxygen presoma, the carbon
The mol ratio of sour lithium, lanthana, zirconyl nitrate, ethylene glycol and citric acid is 7:3:4:28:14, by the lithium lanthanum zirconium oxygen presoma
Constant temperature stirring obtains precursor sol；
3) by water-soluble polymer and the step 2) precursor sol that obtains mixes, and obtains spinning colloidal sols；
4) by step 3) spinning colloidal sols that obtain carry out being calcined after spinning, obtain ion conductor ceramic fibre.
3. preparation method according to claim 2, it is characterised in that the step 1) in mixing be specially：By carbonic acid
Lithium and lanthana are dissolved in dust technology, obtain lithium-lanthanum salpeter solution；Zirconyl nitrate is dissolved in dehydrated alcohol, zirconium solution is obtained；Will
The lithium-lanthanum salpeter solution mixes with zirconium solution.
4. preparation method according to claim 2, it is characterised in that the step 1) in the mode of heating add for water-bath
Heat, the temperature of heating is 50~80 DEG C.
5. preparation method according to claim 2, it is characterised in that lithium lanthanum zirconium oxygen is dense in the lithium lanthanum zirconium oxygen presoma
Spend for 0.1~0.4mol/L.
6. preparation method according to claim 2, it is characterised in that the step 2) in constant temperature stirring temperature be 50~
80℃。
7. preparation method according to claim 2, it is characterised in that the water-soluble polymer is PVP and/or PVA.
8. the preparation method according to claim 2 or 7, it is characterised in that the water-soluble polymer is with water-soluble polymeric
The form of thing aqueous solution mixes with precursor sol, and the mass concentration of the water-soluble polymer aqueous solution is 10~20%, institute
It is 2~5 that water-soluble polymer aqueous solution is stated with the volume ratio of precursor sol:1.
9. preparation method according to claim 2, it is characterised in that the step 4) in spinning by the way of gas spinning,
The air velocity that gas spins is 10~80m/s.
10. preparation method according to claim 2, it is characterised in that the step 4) in calcining temperature be 900~
1500 DEG C, the time of calcining is 0.5~12h.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107162049A (en) * | 2017-06-05 | 2017-09-15 | 清华大学 | Lithium lanthanum zirconium epoxide oxide-based nanomaterial and preparation method thereof |
| CN107316965A (en) * | 2017-06-09 | 2017-11-03 | 北京科技大学 | Lithium lanthanum zirconium oxygen nanofiber, preparation method of composite film and solid state battery application |
| CN107342435A (en) * | 2017-08-30 | 2017-11-10 | 清陶（昆山）能源发展有限公司 | A kind of method for preparing lithium ion battery solid electrolyte |
| CN107681196A (en) * | 2017-09-22 | 2018-02-09 | 山东森鑫环保科技有限公司 | Without synthetic polymer flexible solid dielectric film and its preparation method and its application |
| CN107732102A (en) * | 2017-09-19 | 2018-02-23 | 常州市丰瑞电子有限公司 | A kind of preparation method of composite lithium ion cell barrier film |
| CN108511797A (en) * | 2018-05-09 | 2018-09-07 | 哈尔滨工业大学（威海） | A kind of Li7La3Zr2O12Solid electrolyte preparation method |
| CN108511793A (en) * | 2018-02-06 | 2018-09-07 | 东华大学 | Solid-state lithium lanthanum zirconium oxygen ceramic nanofibers electrolytic thin-membrane and its preparation |
| CN109167094A (en) * | 2018-08-28 | 2019-01-08 | 长沙矿冶研究院有限责任公司 | A kind of organic/inorganic composite solid electrolyte film and preparation method thereof based on fibrous fast-ionic conductor |
| CN110828754A (en) * | 2019-11-20 | 2020-02-21 | 江苏塔菲尔新能源科技股份有限公司 | Inorganic fast ion conductor nano fiber and preparation method and application thereof |
| CN111393163A (en) * | 2020-03-23 | 2020-07-10 | 景德镇陶瓷大学 | Perovskite anode material and preparation method and application thereof |
| CN114394632A (en) * | 2022-02-23 | 2022-04-26 | 浙江格派钴业新材料有限公司 | Preparation method of nanoscale LLZO coated high-nickel positive electrode material |
| CN115650722A (en) * | 2022-05-09 | 2023-01-31 | 西南科技大学 | Gel and application thereof in circulator composite substrate |
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| TING YANG.ETC: "Nanostructured Garnet-Type Solid Electrolytes for Lithium Batteries：Electrospinning Syntheis of Li7La3Zr2O12 Nanowires and Particle Size-Dependent Phase Transformation", 《THE JOURNAL OF PHASICAL CHEMISTRY C》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107162049A (en) * | 2017-06-05 | 2017-09-15 | 清华大学 | Lithium lanthanum zirconium epoxide oxide-based nanomaterial and preparation method thereof |
| CN107316965A (en) * | 2017-06-09 | 2017-11-03 | 北京科技大学 | Lithium lanthanum zirconium oxygen nanofiber, preparation method of composite film and solid state battery application |
| CN107342435A (en) * | 2017-08-30 | 2017-11-10 | 清陶（昆山）能源发展有限公司 | A kind of method for preparing lithium ion battery solid electrolyte |
| CN107732102A (en) * | 2017-09-19 | 2018-02-23 | 常州市丰瑞电子有限公司 | A kind of preparation method of composite lithium ion cell barrier film |
| CN107681196A (en) * | 2017-09-22 | 2018-02-09 | 山东森鑫环保科技有限公司 | Without synthetic polymer flexible solid dielectric film and its preparation method and its application |
| CN108511793A (en) * | 2018-02-06 | 2018-09-07 | 东华大学 | Solid-state lithium lanthanum zirconium oxygen ceramic nanofibers electrolytic thin-membrane and its preparation |
| CN108511797A (en) * | 2018-05-09 | 2018-09-07 | 哈尔滨工业大学（威海） | A kind of Li7La3Zr2O12Solid electrolyte preparation method |
| CN109167094A (en) * | 2018-08-28 | 2019-01-08 | 长沙矿冶研究院有限责任公司 | A kind of organic/inorganic composite solid electrolyte film and preparation method thereof based on fibrous fast-ionic conductor |
| CN110828754A (en) * | 2019-11-20 | 2020-02-21 | 江苏塔菲尔新能源科技股份有限公司 | Inorganic fast ion conductor nano fiber and preparation method and application thereof |
| CN110828754B (en) * | 2019-11-20 | 2022-02-08 | 江苏正力新能电池技术有限公司 | Inorganic fast ion conductor nano fiber and preparation method and application thereof |
| CN111393163A (en) * | 2020-03-23 | 2020-07-10 | 景德镇陶瓷大学 | Perovskite anode material and preparation method and application thereof |
| CN114394632A (en) * | 2022-02-23 | 2022-04-26 | 浙江格派钴业新材料有限公司 | Preparation method of nanoscale LLZO coated high-nickel positive electrode material |
| CN115650722A (en) * | 2022-05-09 | 2023-01-31 | 西南科技大学 | Gel and application thereof in circulator composite substrate |
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