CN106673651B - A kind of lithium lanthanum zirconium oxygen ion conductor ceramic fibre and preparation method thereof - Google Patents
A kind of lithium lanthanum zirconium oxygen ion conductor ceramic fibre and preparation method thereof Download PDFInfo
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- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
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Abstract
The invention discloses a kind of lithium lanthanum zirconium oxygen ion conductor ceramic fibre, the chemical composition of the material is Li7La3Zr2O12, the ion conductor ceramic fibre length is 1~2.5 μm, and diameter is 80~120nm, and lithium ion conductivity is 1.5 × 10‑4S/cm~6 × 10‑ 3S/cm.The present invention also provides a kind of methods for preparing the ion conductor ceramic fibre, lithium carbonate, lanthana, zirconyl nitrate, nitric acid solution are mixed with after dehydrated alcohol Hybrid Heating with citric acid and ethylene glycol, constant temperature stirs to get precursor sol；Water-soluble polymer is mixed to obtain spinning colloidal sols with obtained precursor sol, spinning, calcining is successively carried out, obtains the stable ion conductor ceramic fibre of morphology and size；The method can significantly improve its lithium ion conductivity, and simple process and low cost, not high to equipment and environmental requirement, be suitble to 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 systems
Preparation Method.
Background technique
At this stage, lithium ion battery is directly connected there are positive and negative anodes there is short circuit phenomenon, and security performance cannot be guaranteed.Its
Reason is that most of electrolyte are liquid, in the electrolyte between be equipped with diaphragm, the positive and negative anodes of battery are separated, do not allow it straight
Lead in succession, so now commercial organic barrier film is usually non-conductive son, but simultaneously again in order to guarantee the positive normal open of lithium ion
It crosses, needing diaphragm, there are certain porositys, and battery-heating will cause the contraction of organic barrier film, and positive and negative anodes is caused directly to be connected
Form short circuit；Solid electrolyte is not volatile, general non-combustible, therefore selects solid electrolyte that can have excellent safety.
Ion conductor ceramics ionic conductivity with higher can quickly conduct the specific function pottery of ion as one kind
Porcelain has been to be concerned by more and more people, especially can conducting lithium ions ion conductor ceramic fibre；Ceramic fibre is as a kind of
Application has been obtained in many fields in ceramics with special appearance, and it is desirable to prepare solid electrolyte with it to replace
Original liquid electrolyte thoroughly solves the safety high of lithium ion battery.At present prepare ceramic fibre method be mainly
Method of electrostatic spinning and other templates.Cation ceramic fiber is relatively complicated using these techniques progress preparation process, at
This is higher, and chemical structure, appearance and size and the electric conductivity of the ion conductor ceramic fibre obtained using above-mentioned technique
There is difference, stability is poor.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of ion conductor ceramic fibre and preparation method thereof, the present invention
The ion conductor ceramic fibre appearance structure and size of offer are stablized.Technique can be simplified using the method for the invention, dropped
Low production cost improves the lithium ion conductivity of material.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A kind of lithium lanthanum zirconium oxygen ion conductor ceramic fibre, which is characterized in that chemical composition Li7La3Zr2O12, fibre length
It is 1~2.5 μm, diameter is 80~120nm, and lithium ion conductivity is 1.5 × 10-4S/cm~6 × 10-3S/cm。
The present invention also provides a kind of preparation methods of lithium lanthanum zirconium oxygen ion conductor ceramic fibre, comprising the following steps:
1) by lithium carbonate, lanthana, zirconyl nitrate, nitric acid solution and dehydrated alcohol Hybrid Heating, mixed liquor is obtained；
2) citric acid and ethylene glycol are mixed with the mixed liquor that the step 1) obtains, obtain lithium lanthanum zirconium oxygen presoma,
Middle lithium carbonate, lanthana, zirconyl nitrate, ethylene glycol and citric acid molar ratio be 7:3:4:28:14, before the lithium lanthanum zirconium oxygen
It drives body constant temperature and stirs to get precursor sol；
3) precursor sol for obtaining water-soluble polymer and the step 2) is mixed, and obtains spinning colloidal sols；
4) it is calcined after the spinning colloidal sols that step 3) obtains being carried out spinning, obtains ion conductor ceramic fibre.
Preferably, the mixing in the step 1) specifically: lithium carbonate and lanthana are dissolved in dust technology, obtain lithium-lanthanum
Nitric acid solution；Zirconyl nitrate is dissolved in dehydrated alcohol, zirconium solution is obtained；The lithium-lanthanum nitric acid solution is mixed with zirconium solution.
Preferably, the mode heated in the step 1) is heating water bath, and 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 temperature that constant temperature stirs in the step 2) is 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, spinning is carried out in the step 4) by the way of gas spinning, the air velocity that gas is spun is 10~80m/s.
Preferably, stating the temperature calcined in step 4) is 900~1500 DEG C, and the time of calcining is 0.5~12h.
A kind of ion conductor ceramic fibre provided by the invention, the chemical composition of the material are Li7La3Zr2O12, it is described from
The size of sub- conductive ceramic fiber is stablized, and length is 1~2.5 μm, and diameter is 80~120nm, and appearance structure is cubic phase,
It completes by the transformation of amorphous state to crystalline state, lithium ion conductivity is 1.5 × 10-4S/cm~6 × 10-3S/cm is significantly mentioned
It is high；The mechanical performances such as the heat resistanceheat resistant shrinkage of diaphragm can be enhanced using ion conductor ceramic fibre painting cloth diaphragm, reduce
Plugging rate makes up diaphragm because being coated with reduced lithium ion conductivity, enhances its high rate performance.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the X-ray diffraction spectrum of lithium lanthanum zirconium oxygen ceramic fibre prepared by the embodiment of the present invention 1；
Fig. 2 is the SEM figure of the precursor fibre before the embodiment of the present invention 1 is calcined；
Fig. 3 is the lithium lanthanum zirconium oxygen ion conductor ceramic fibre SEM figure that the embodiment of the present invention 1 obtains.
Specific embodiment
The present invention provides a kind of lithium lanthanum zirconium oxygen ion conductor ceramic fibre, the chemical groups of the ion conductor ceramic fibre
As Li7La3Zr2O12, crystal form form is cubic phase.
In the present invention, the length of the ion conductor ceramic fibre is 1~2.5 μm, and diameter is 80~120nm, preferably
Fibre length be 1.5~2.2 μm, diameter be 90~110nm, preferred fibre length be 2 μm, diameter 100nm.
In the present invention, the 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。
The present invention also provides a kind of preparation methods of lithium lanthanum zirconium oxygen ion conductor ceramic fibre, comprising the following steps:
1) by lithium carbonate, lanthana, zirconyl nitrate, nitric acid solution and dehydrated alcohol Hybrid Heating, mixed liquor is obtained；
2) citric acid and ethylene glycol are mixed with the mixed liquor that the step 1) obtains, obtain lithium lanthanum zirconium oxygen presoma,
Middle lithium carbonate, lanthana, zirconyl nitrate, ethylene glycol and citric acid molar ratio be 7:3:4:28:14, before the lithium lanthanum zirconium oxygen
It drives body constant temperature and stirs to get precursor sol；
3) precursor sol for obtaining water-soluble polymer and the step 2) is mixed, and obtains spinning colloidal sols；
4) it is calcined after the spinning colloidal sols that step 3) obtains being carried out spinning, obtains ion conductor ceramic fibre.
The present invention do not have to the source of raw material and reagent it is any specifically limited, using raw material well known to those skilled in the art
Source or commercial goods.
Lithium carbonate, lanthana, zirconyl nitrate, nitric acid solution and dehydrated alcohol Hybrid Heating are obtained mixed liquor by the present invention.
Preferably, the mixing specifically: lithium carbonate and lanthana are dissolved in nitric acid solution, obtain lithium-lanthanum nitric acid solution；By Nitric Acid Oxidation
Zirconium is dissolved in dehydrated alcohol, obtains zirconium solution；The lithium-lanthanum nitric acid solution is mixed with zirconium solution.In the present invention, the carbonic acid
The theoretical molar of lithium and lanthana is than being preferably 7:3；In the present invention, the mass concentration of the nitric acid solution be preferably 10~
20%, more preferably 15%；The Theoretical Mass score of the lanthana and lithium carbonate in lithium-lanthanum nitric acid 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.
Zirconyl nitrate is dissolved in dehydrated alcohol by the present invention, 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 is for dissolving no particular/special requirement, using this field
Conventional method.
After mixing in the step 1), water bath with thermostatic control ring of the present invention preferably by obtained mixed system at 50~80 DEG C
Heating stirring is carried out under border, obtains mixed liquor.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 lithium carbonate, lanthana, zirconyl nitrate, ethylene glycol and citric acid molar ratio be 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, is used for dissolving step 1) obtained mixed liquor, citric acid is organic complex
Agent, with metallic compound reacting forming complex prevent precipitating generate, row at stable dispersed phase, while in subsequent step
Water-soluble polymer generates synergistic effect, prevents from causing subsequent mixing uneven because dispersed phase is unstable, prevents each element not
It can be uniformly dispersed in colloidal sol.
After obtaining lithium lanthanum zirconium oxygen presoma, it is molten that the lithium lanthanum zirconium oxygen presoma constant temperature is stirred to get presoma by the present invention
Glue.In the present invention, the temperature of the constant temperature stirring is preferably 50~80 DEG C, and more preferably 60~70 DEG C；The constant temperature stirring
Time preferably 12~for 24 hours, more preferably 15~20h.
Obtained precursor sol and water-soluble polymer are mixed the present invention, obtain 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
It is selected as 15%；The volume ratio of the water-soluble polymer aqueous solution and precursor sol is 2~5:1, more preferably 3:1
~4:1；It stirs or stirs evenly using this field conventional magnetic.
After obtaining spinning colloidal sols, the spinning colloidal sols are carried out spinning by the present invention, and obtained spinning fibre calcining obtains
To ion conductor ceramic fibre.In the present invention, the mode that the preferred gas of the spinning is spun, method particularly includes: extract spinning colloidal sols
In syringe, by topping-up pump, spinning colloidal sols are outpoured with 3ml/h speed from coaxial syringe needle inner shaft, air-flow is with 10~80m/s
Speed pass through from outer shaft, spinning colloidal sols are drawn into fiber in the sky, the solvent in colloidal sol also during this time rapidly volatilization,
Nanoscale fiber is eventually formed, is collected in the porous cage modle collector apart from liquid outlet 20cm, and mutually winding group
At the nanofiber presoma of three-dimensional structure.
In the present invention, the calcining is that the nanofiber presoma for spinning gas is forged 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
Tie up crystallization, in calcination process with crystal grain grow up and the variation of crystal phase.Calcining can generate between 900 DEG C~1500 DEG C
The lithium lanthanum zirconium oxygen of cubic phase, calcination time can guarantee the sufficient growth of crystal grain between 0.5~12h, if calcination temperature mistake
Low, the time is too short, and the crystal grain of formation is too small to will lead to that crystal boundary is excessive, influences the conduction of lithium ion, if calcination temperature is excessively high, when
Between it is too long, the crystal grain of formation it is too big by it is broken can fiber morphology；So calcination temperature and time are to need to carry out strict control ability
The electric conductivity of its lithium ion is improved while obtaining stablizing the ion conductor ceramic fibre of morphology and size size.
The preparation method of lithium lanthanum zirconium oxygen ion conductor ceramic fibre provided by the invention, with lithium carbonate, lanthana, Nitric Acid Oxidation
Zirconium, nitric acid solution and dehydrated alcohol are that citric acid and ethylene glycol mixing is added, obtains lithium lanthanum zirconium oxygen after raw material carries out Hybrid Heating
Presoma, lithium carbonate in the presoma, lanthana, zirconyl nitrate, ethylene glycol and citric acid molar ratio be 7:3:4:28:
14, precursor sol is mixed, and obtains spinning colloidal sols, is successively carried out spinning and calcining and is obtained a kind of appearance structure and size
The stable ion conductor ceramic fibre of size, the chemical composition of the material are Li7La3Zr2O12, fibre length is 1~2.5 μm, directly
Diameter is 80~120nm, and appearance structure is that cubic phase is completed by the transformation of amorphous state to crystalline state, and lithium ion conductivity obtains significantly
Rise to 1.5 × 10-4S/cm~6 × 10-3S/cm, and the method for the invention simple process and low cost, entirely prepared
Journey is not high to equipment and environmental requirement, is suitble to industrial application.
Lithium lanthanum zirconium oxygen ion conductor ceramic fibre provided by the invention and preparation method thereof is carried out below with reference to embodiment
Detailed description, but they cannot 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) be dissolved in the dilute nitric acid solution that 80g concentration is 15%, by nitre
Sour oxygen zirconium (ZrO (NO3)2) be dissolved in 20g dehydrated alcohol, wherein lithium carbonate weighs 10% to compensate the volatilization of lithium under high temperature more.
It is mixed above-mentioned dissolved with the nitric acid solution of lithium carbonate and lanthana 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 acid and 8.69g ethylene glycol, constant temperature stirring 12h obtains molten
Glue.
It weighs the PVP solution that 50g mass concentration is 10% to mix with obtained colloidal sol, be sufficiently stirred for 24 hours.Utilize what is obtained
Colloidal sol carries out gas spinning, and gas is spun gained fiber and calcined at 1000 DEG C, calcination time 1h is obtained by gas flow rate in 10m/s
To ion conductor ceramic fibre.The experimental results showed that the length of gained ion conductor ceramic fibre is 2 μm, diameter 100nm, lithium
Ionic conductivity is 7 × 10-4S/cm。
The transformation from amorphous state to crystalline state is had occurred that after sintering it can be seen from Fig. 1 XRD spectrum, is generated vertical
The Li of square phase7La3Zr2O12。
By Fig. 2 and Fig. 3 analysis it is found that embodiment 1 during the sintering process, organic matter and polymer vapor away, unsintered
Fiber is broken, and for the fibre length after being sintered at 2 μm or so, diameter maintains good threadiness 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) be dissolved in the dilute nitric acid solution that 50g concentration is 20%, by nitre
Sour oxygen zirconium (ZrO (NO3)2) be dissolved in 40g dehydrated alcohol, wherein lithium carbonate weighs 10% to compensate the volatilization of lithium under high temperature more.
It is mixed above-mentioned dissolved with the nitric acid solution of lithium carbonate and lanthana 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 acid and 8.69g ethylene glycol, constant temperature stirring obtains molten for 24 hours
Glue.
It weighs the PVP solution that 45g mass concentration is 10% to mix with obtained colloidal sol, 48h is sufficiently stirred.Utilize what is obtained
Colloidal sol carries out gas spinning, and gas is spun gained fiber and calcined at 900 DEG C, calcination time 12h is obtained by gas flow rate in 80m/s
To ion conductor ceramic fibre.The experimental results showed that the length of gained ion conductor ceramic fibre is 2.5 μm, diameter 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) be dissolved in the dilute nitric acid solution that 150g concentration is 10%, it will
Zirconyl nitrate (ZrO (NO3)2) be dissolved in 40g dehydrated alcohol, wherein lithium carbonate weighs 8% to compensate the volatilization of lithium under high temperature more.
It is mixed above-mentioned dissolved with the nitric acid solution of lithium carbonate and lanthana 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 acid and 17.38g ethylene glycol, constant temperature stirring 15h is obtained
Colloidal sol.
It weighs the PVP solution that 80g mass concentration is 15% to mix with obtained colloidal sol, h is sufficiently stirred.It is molten using what is obtained
Glue carries out gas spinning, and gas is spun gained fiber and calcined at 1500 DEG C, calcination time 1h is obtained by gas flow rate in 80m/s
Ion conductor ceramic fibre.The experimental results showed that the length of gained ion conductor ceramic fibre is 1.5 μm, diameter 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) be dissolved in the dilute nitric acid solution that 125g concentration is 13%, it will
Zirconyl nitrate (ZrO (NO3)2) be dissolved in 40g dehydrated alcohol, wherein lithium carbonate weighs 12% to compensate the volatilization of lithium under high temperature more.
It is mixed above-mentioned dissolved with the nitric acid solution of lithium carbonate and lanthana 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 acid and 17.38g ethylene glycol, constant temperature stirring 20h is obtained
Colloidal sol.
It weighs the PVP solution that 120g mass concentration is 10% to mix with obtained colloidal sol, h is sufficiently stirred.Utilize what is obtained
Colloidal sol carries out gas spinning, and gas is spun gained fiber and calcined at 1200 DEG C, calcination time 5h is obtained by gas flow rate in 80m/s
To ion conductor ceramic fibre.The experimental results showed that the length of gained ion conductor ceramic fibre is 2 μm, diameter 120nm, lithium
Ionic conductivity is 9.3 × 10-4S/cm。
Embodiment 5
Weigh 1 gained Li of embodiment7La3Zr2O12Ceramic fibre 20.0g, bonding agent carboxymethyl cellulose 0.3g, bonding agent
Styrene-butadiene latex 2.0g, dispersing agent sodium carboxymethylcellulose 0.04g, is dissolved in 25.0g water, is mixed using the method for high-speed stirred
It closes, to accelerate rate of dispersion, assists carrying out rapid dispersion using ultrasonic wave.Obtained solution is applied to thickness using coating method
For 20 μm of the polymer organic layer being made of PP (aperture is 0.05 μm, porosity 40%) (film layer is commercialization PP film)
On, and carry out sufficiently drying in 55 DEG C, a kind of ion conductor ceramic fibre composite diaphragm is obtained, performance test is as shown in table 1, benefit
It can be improved the punctured resistance and tensile strength of diaphragm, charge-discharge magnification performance with the ion conductor ceramic fibre that application provides
Raising, the internal resistance of cell reduction all show that its lithium ion conductivity is improved.
Table 1
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of lithium lanthanum zirconium oxygen ion conductor ceramic fibre, which is characterized in that chemical composition Li7La3Zr2O12, fibre length is
1~2.5 μm, diameter is 80~120nm, and lithium ion conductivity is 1.5 × 10-4S/cm~6 × 10-3S/cm；
The preparation method of the lithium lanthanum zirconium oxygen ion conductor ceramic fibre, comprises the steps of:
1) by lithium carbonate, lanthana, zirconyl nitrate, nitric acid solution and dehydrated alcohol Hybrid Heating, mixed liquor is obtained；
2) citric acid and ethylene glycol are mixed with the mixed liquor that the step 1) obtains, obtains lithium lanthanum zirconium oxygen presoma, the carbon
Sour lithium, lanthana, zirconyl nitrate, ethylene glycol and citric acid molar ratio be 7:3:4:28:14, by the lithium lanthanum zirconium oxygen presoma
Constant temperature stirs to get precursor sol；
3) precursor sol for obtaining water-soluble polymer and the step 2) is mixed, and obtains spinning colloidal sols；
4) it is calcined after the spinning colloidal sols that step 3) obtains being carried out spinning, obtains ion conductor ceramic fibre；
The temperature calcined in the step 4) is 900~1500 DEG C, and the time of calcining is 12h.
2. the preparation method of lithium lanthanum zirconium oxygen ion conductor ceramic fibre described in claim 1, comprises the steps of:
1) by lithium carbonate, lanthana, zirconyl nitrate, nitric acid solution and dehydrated alcohol Hybrid Heating, mixed liquor is obtained；
2) citric acid and ethylene glycol are mixed with the mixed liquor that the step 1) obtains, obtains lithium lanthanum zirconium oxygen presoma, the carbon
Sour lithium, lanthana, zirconyl nitrate, ethylene glycol and citric acid molar ratio be 7:3:4:28:14, by the lithium lanthanum zirconium oxygen presoma
Constant temperature stirs to get precursor sol；
3) precursor sol for obtaining water-soluble polymer and the step 2) is mixed, and obtains spinning colloidal sols；
4) it is calcined after the spinning colloidal sols that step 3) obtains being carried out spinning, obtains ion conductor ceramic fibre；
The temperature calcined in the step 4) is 900~1500 DEG C, and the time of calcining is 12h.
3. preparation method according to claim 2, which is characterized in that the mixing in the step 1) specifically: by carbonic acid
Lithium and lanthana are dissolved in dust technology, obtain lithium-lanthanum nitric acid solution；Zirconyl nitrate is dissolved in dehydrated alcohol, zirconium solution is obtained；It will
The lithium-lanthanum nitric acid solution is mixed with zirconium solution.
4. preparation method according to claim 2, which is characterized in that the mode heated in the step 1) adds for water-bath
Heat, the temperature of heating are 50~80 DEG C.
5. preparation method according to claim 2, which is characterized in that lithium lanthanum zirconium oxygen is dense in the lithium lanthanum zirconium oxygen presoma
Degree is 0.1~0.4mol/L.
6. preparation method according to claim 2, which is characterized in that in the step 2) constant temperature stir temperature be 50~
80℃。
7. preparation method according to claim 2, which is characterized in that the water-soluble polymer is PVP and/or PVA.
8. the preparation method according to claim 2 or 7, which is characterized in that the water-soluble polymer is with water-soluble polymeric
The form of object aqueous solution is mixed with precursor sol, and the mass concentration of the water-soluble polymer aqueous solution is 10~20%, institute
The volume ratio for stating water-soluble polymer aqueous solution and precursor sol is 2~5:1.
9. preparation method according to claim 2, which is characterized in that in the step 4) spinning using gas spinning by the way of,
The air velocity that gas is spun is 10~80m/s.
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| 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 |
| CN107342435B (en) * | 2017-08-30 | 2020-06-16 | 清陶（昆山）能源发展有限公司 | Method for preparing solid electrolyte for lithium ion battery |
| 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 |
| CN108511793B (en) * | 2018-02-06 | 2021-01-15 | 东华大学 | Solid lithium lanthanum zirconium oxygen ceramic nano fiber electrolyte film and preparation thereof |
| CN108511797B (en) * | 2018-05-09 | 2022-07-19 | 哈尔滨工业大学（威海） | Li7La3Zr2O12Solid electrolyte preparation method |
| CN109167094B (en) * | 2018-08-28 | 2021-04-13 | 长沙矿冶研究院有限责任公司 | Organic/inorganic composite solid electrolyte membrane based on fibrous fast ion conductor and preparation method 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 |
| CN111393163B (en) * | 2020-03-23 | 2023-06-30 | 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 |
| CN115650722B (en) * | 2022-05-09 | 2023-06-27 | 西南科技大学 | Gel and application thereof in circulator composite substrate |
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