CN109896511A - A kind of Li1.3Al0.3Ti1.7(PO4)3Powder and its preparation method and application - Google Patents
A kind of Li1.3Al0.3Ti1.7(PO4)3Powder and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of Li1.3Al0.3Ti1.7(PO4)3Powder and its preparation method and application.The present invention is in order to solve the problems, such as that existing NASICON type solid electrolyte lithium ion conductivity is low and low density.One, the source Ti, the source Li, the source Al and the source P are weighed according to stoichiometric ratio；Two, the source Ti is dissolved in dust technology, adds the source Li and the source Al, complexing agent is added after being completely dissolved, until completely dissolved, pH value is adjusted, the source P is added, it is completely dissolved, dispersing agent is added, is stirred evenly, evaporation water is until obtain sticky wet gel, it is calcined after vacuum drying, cool to room temperature with the furnace, ball milling obtains Li1.3Al0.3Ti1.7(PO4)3Powder.Powder is ground, and the electrolytic thin-membrane being sintered after tabletting may be used as the solid electrolyte of all-solid lithium-ion battery and lithium-air battery.
Description
Technical field
The invention belongs to field of lithium；More particularly to a kind of Li1.3Al0.3Ti1.7(PO4)3Powder and preparation method thereof, and
Li1.3 Al0.3Ti1.7(PO4)3Powder is used to prepare all-solid lithium-ion battery NASICON type solid electrolyte.
Background technique
It uses solid compound as electrolyte in solid lithium battery, has effectively evaded caused by organic electrolyte
Safety risks.Compared to the organic electrolyte that conventional lithium ion battery uses, solid electrolyte not only stablize by property, avoids
Organic electrolyte is inflammable with the safety issues such as perishable；Meanwhile high mechanical strength, effectively Li dendrite can be prevented to make
At short circuit problem, to improve lithium battery capacity and energy density using lithium metal as battery cathode；And
And solid electrolyte has good machining property, so that solid lithium battery is easy to be fabricated to various forms, meets
Requirement of the part special dimension to battery appearance, has widened the application range of lithium ion battery.Limitation solid lithium battery at present
The factor of development be solid electrolyte ionic conduction performance is lower and the contact resistance of solid electrolyte and electrode material is big,
Whether which point, requires based on the ionic conduction performance for improving solid electrolyte.Therefore, solid electricity how is improved
The ionic conductivity of solution material becomes the hot spot of current research.
At this stage by the solid electrolyte of researchers institute extensive concern, it can be mainly divided into two major classes, polymer (has
Machine) electrolyte and inorganic solid electrolyte.Polymer dielectric crystallinity with higher at room temperature, under room temperature environment
Ionic conductivity it is relatively low, it usually needs be higher than its melt temperature more than at a temperature of can have comparatively ideal work
Make performance.Sulfide systems solid electrolyte has outstanding ionic conducting property, but when oxide electrode and sulfide are electrolysed
When matter is in contact, high resistance space charge layer can be formed in its interface.And in contrast, sulfide systems electrolyte electricity
Chemical window narrows, poor chemical stability, these deficiency all greatly limit sulfide solid electrolyte development and
Using.The oxide system electrolyte of high conductance includes Garnet type structure, LISICON type structure, NASICON type knot
Structure, Perovskite type structure and Anti-perovskite type structure etc..But since the preparation process of electrolyte powder is more multiple
It is miscellaneous, it consumes energy larger, increases preparation cost, be not easy to large-scale commercial production.
Summary of the invention
The present invention is low in order to solve the problems, such as existing solid electrolyte lithium ion conductivity, proposes a kind of oxide
NASICON type Li1.3Al0.3Ti1.7(PO4)3Solid electrolyte and preparation method thereof.
The Li of present invention selection NASICON type structure1.3Al0.3Ti1.7(PO4)3, for Li1.3Al0.3Ti1.7(PO4)3Material
Material, crystal grain and grain boundary resistance constitute its all-in resistance.Grain resistance is the intrinsic attribute of material, is difficult to change, so grain boundary resistance
It is the major influence factors of the ionic conductivity of electrolyte.Optimization grain boundary effect, which becomes, promotes Li1.3Al0.3Ti1.7(PO4)3Material
Expect the main means of conductivity.Lesser crystallite dimension helps to obtain finer and close electrolytic thin-membrane, improves crystal boundary conduction
Performance and promotion conductivity.Change will be probed into for how to reduce the research experience of grain boundary resistance, present invention selection based on people
Process conditions prepare the lesser Li of crystallite dimension1.3Al0.3Ti1.7(PO4)3Powder.
Li of the present invention1.3Al0.3Ti1.7(PO4)3Powder is to replace LiTi using Al element doping2(PO4)3Ti member in material
What element obtained, TiO6Octahedra and PO4Tetrahedron is connected to form rigid backbone [A by total apex angle oxygen atom2(BO4)3]-
([Ti2(PO4)3]-), Li+It is migrated in three-dimensional tunnel structure；Li1.3Al0.3Ti1.7(PO4)3Raw powder's production technology is by following
What step carried out:
Step 1: weighing the source Ti, the source Li, the source Al and the source P according to stoichiometric ratio；
Step 2: the weighed source Ti of step 1 is added in dust technology, magnetic agitation adds step 1 to being completely dissolved
Then complexing agent is added to being completely dissolved in the weighed source Li and the source Al, magnetic agitation, until completely dissolved, add ammonium hydroxide tune
PH value is saved to 5, the weighed source P of step 1 then is being added, magnetic agitation adds dispersing agent, magnetic agitation to being completely dissolved
To uniform, then evaporation water is calcined after vacuum drying until obtain sticky wet gel, cools to room temperature with the furnace, ball milling,
Obtain Li1.3Al0.3Ti1.7(PO4)3Powder.
It further limits, the source Li described in step 1 is one of lithium nitrate, lithium acetate, lithium carbonate.
It further limits, the source Al described in step 1 is aluminum nitrate or aluminum sulfate.
It further limits, the source Ti described in step 1 is butyl titanate.
It further limits, the source P described in step 1 is one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid.
Further limit, in step 2 the mass percent concentration of dust technology be the source 20%~30%, Ti quality with
The volume ratio of dust technology is (10g~12g): (90mL~110mL).
It further limits, complexing agent described in step 2 is citric acid, the complexing agent and Ti2+、Li+And Al3+Always rub
Your ratio is (1~2): 1.
It further limits, dispersing agent described in step 2 is hydroxyl acid derivative, polyhydroxy-alcohol, cationic are living
Property agent, acetamide, one of acetone, the molar ratio of the dispersing agent and complexing agent is (0.5~2): 1；The carboxylic acid
Analog derivative is lactic acid, tartaric acid or glycolic；Polyhydroxy-alcohol is glycerine；The cationic surface active agent is 16
Alkyl trimethyl ammonium bromide.
It further limits, is dried in vacuo at 180 DEG C~220 DEG C in step 2, time 3h-4h.
It further limits, calcination temperature is 800 DEG C -900 DEG C, calcination time 5h-6h in step 2, and heating rate is
2℃/min-5℃/min。
It further limits, step 2 milling parameters: revolving speed 400rpm-450rpm, Ball-milling Time 8h-12h,
Ratio of grinding media to material is 5:1, and ball-milling medium is dehydrated alcohol.
I in the present invention1.3Al0.3Ti1.7(PO4)3Powder is used to prepare all-solid lithium-ion battery NASICON type solid state electrolysis
Matter film is by Li1.3Al0.3Ti1.7(PO4)3Powder grinding, made of being sintered after tabletting.
It further limits, is 20Mpa-25Mpa condition lower sheeting, pressure maintaining 20min in pressure；.
It further limits, the sintering temperature is 900 DEG C -950 DEG C, sintering time 3h-5h, heating rate 2
℃/min-5℃/min。
The size of microcrystal of all-solid lithium-ion battery NASICON type solid electrolyte film of the present invention is 6-10 μm, fine and close
Degree is up to 94%~97.6%, and room temperature grain boundary conductivities are up to 4.67 × 10-4S/cm~8.2 × 10-4S/cm, room temperature total conductivity
Up to 4.04 × 10-4S/cm~6.7 × 10-4S/cm。
Li in the present invention1.3Al0.3Ti1.7(PO4)3In the preparation process of electrolyte powder: complexing agent complexation of metal ions shape
At spatial mesh structure, the addition of dispersing agent increases the steric hindrance between metel complex ion, mitigates gel in drying process
In reunion.Gel forms loose porous xerogel after drying out, pyrolytic generates gas to xerogel in air atmosphere
Body generates the oxide powder for meeting stoichiometric ratio.Electrolyte powder obtained obtains partial size after high-energy mechanical ball milling
Smaller powder is pressed into electrolyte element embryo under high pressure, and fine and close electrolytic thin-membrane is obtained after high temperature sintering.Lesser crystal grain
Size and good consistency ensure the higher lithium ion conductivity of electrolytic thin-membrane.
The present invention is prepared for little crystallite size Li using sol-gal process1.3Al0.3Ti1.7(PO4)3Solid electrolyte powder,
It is a kind of simple and effective preparation method.In collosol and gel precursor liquid configuration process, complexing agent citric acid complex metal from
Son keeps metel complex ion evenly dispersed.Before gel-forming, point that lipoid substance can be formed with metel complex ion is added
Powder, the burning that wet gel passes through lipoid substance in the drying process obtain loose porous xerogel.The lipid of long-chain
It closes object and increases the steric hindrance between metel complex ion, alleviate the reunion of wet gel in the drying process and shrink, obtain small
The Li of little crystallite size can be obtained by high-temperature calcination for the xerogel of particle1.3Al0.3Ti1.7(PO4)3Solid electrolyte powder
Body.
The present invention joined the lactic acid dispersing agent with esterification, peptizaiton in collosol and gel precursor liquid, both protect
Metel complex ion in the solution evenly dispersed has been demonstrate,proved, and has increased the steric hindrance between metel complex ion, it is therefore prevented that gel
Particle agglomeration in the drying process finally obtains the Li that crystallite dimension is 6-10 μm1.3Al0.3Ti1.7(PO4)3Solid electrolyte
Film.
Current existing dispersing agent majority is alcohols, can only utilize the free carboxy phase of hydroxyl and metel complex ion in alcohol
Even, it does not ensure that and forms enough steric hindrances between metel complex ion, there are still biggish particles for the gel after drying.
Hydroxyl acids dispersing agent lactic acid that the present invention uses while there is hydroxyl and carboxyl, can not only on metel complex ion
Free carboxyl is connected, and can also be connected with the hydroxyl to dissociate on metel complex ion, greatly increase metel complex ion
Between steric hindrance, form the lipid structures of long-chain, the low-temperature burning of lipoid substance in the drying process can more sufficiently
Progress, the gas and heat for release of burning can preferably prevent the particle agglomeration of gel in the drying process.
Detailed description of the invention:
Fig. 1 is the Li that embodiment 1 obtains1.3Al0.3Ti1.7(PO4)3The SEM of solid electrolyte film section schemes；
Fig. 2 is the Li that embodiment 2 obtains1.3Al0.3Ti1.7(PO4)3The SEM of solid electrolyte film section schemes；
Fig. 3 is the Li that embodiment 1 obtains1.3Al0.3Ti1.7(PO4)3The XRD diagram of solid electrolyte powder；
Fig. 4 is the Li that embodiment 1 obtains1.3Al0.3Ti1.7(PO4)3Solid electrolyte film AC impedance spectroscopy；
Fig. 5 is the Li that embodiment 2 obtains1.3Al0.3Ti1.7(PO4)3Solid electrolyte film AC impedance spectroscopy.
Specific embodiment:
Embodiment 1: Li in the present embodiment1.3Al0.3Ti1.7(PO4)3Raw powder's production technology carries out in the steps below:
Step 1: weighing butyl titanate, lithium nitrate, aluminum nitrate and ammonium dihydrogen phosphate according to stoichiometric ratio；
Step 2: the weighed butyl titanate of step 1 is added in the dust technology that mass percent concentration is 20%, with
200r/min rate carries out magnetic agitation to (being completely dissolved) is clarified, and adds the weighed lithium nitrate of step 1 and aluminum nitrate,
Then citric acid is added to being completely dissolved in magnetic agitation, until completely dissolved, add ammonium hydroxide and adjust pH value to 5, then exist
The weighed ammonium dihydrogen phosphate of step 1 is added, magnetic agitation adds lactic acid to being completely dissolved, and magnetic agitation is to uniform, then
The evaporation water at 80 DEG C is until obtain sticky transparent wet gel, then be placed in vacuum oven, the vacuum at 180 DEG C
It is dry, the xerogel of black is formed, is subsequently placed in Muffle furnace and is calcined, 800 DEG C is warming up to the speed of 3 DEG C/min, protects
Temperature 5 hours, cools to room temperature with the furnace, then be placed in ball grinder, and dehydrated alcohol is added zirconia ball and makees as dispersion solvent
For grinding bead, the mass ratio of ball material is 5:1, and mechanical ball mill 8 hours under 400rpm revolving speed, drying with water bath is collected at 80 DEG C
Get up, obtains the Li of white1.3Al0.3Ti1.7(PO4)3Powder.
Wherein, the quality of butyl titanate and the volume ratio of dust technology are 12g:100mL in step 2；The citric acid with
Ti2+、Li+And Al3+Total moles ratio be 1:1；(mole) of the lactic acid and citric acid is than being 1:1.
The Li of the present embodiment1.3Al0.3Ti1.7(PO4)3Powder is to replace LiTi using Al element doping2(PO4)3In material
Ti element obtains, TiO6Octahedra and PO4Tetrahedron is connected to form rigid backbone [A by total apex angle oxygen atom2(BO4)3]-
([Ti2(PO4)3]-), Li+It is migrated in three-dimensional tunnel structure.
Using Li1.3Al0.3Ti1.7(PO4)3Powder prepares all-solid lithium-ion battery NASICON type solid electrolyte film,
It is completed particular by following step:
By Li1.3Al0.3Ti1.7(PO4)3Powder grinding is put into the stainless steel compression mold that diameter is 25mm, is in gauge pressure
Pressure maintaining 20min, obtains biscuit under the tabletting conditions of 20MPa；Plain embryo is placed on ceramic wafer, is placed in Muffle furnace and is sintered
Process is warming up to 900 DEG C with the speed of 3 DEG C/min, and heat preservation has just obtained the Li of white after 3 hours1.3Al0.3Ti1.7 (PO4)3Electricity
Solve matter film.
The present embodiment joined the lactic acid dispersing agent with esterification, peptizaiton in collosol and gel precursor liquid, both
It ensure that metel complex ion in the solution evenly dispersed, and increase the steric hindrance between metel complex ion, it is therefore prevented that is solidifying
The particle agglomeration of glue in the drying process finally obtains the Li that crystallite dimension is 6-8 μm1.3Al0.3Ti1.7(PO4)3Solid electrolytic
Matter film.
The dispersing agent lactic acid of the present embodiment is carboxylic acid, while having hydroxyl and carboxyl, can not only on metel complex ion
Free carboxyl is connected, and can also be connected with the hydroxyl to dissociate on metel complex ion, greatly increase metel complex ion
Between steric hindrance, form the lipid structures of long-chain, the low-temperature burning of lipoid substance in the drying process can more sufficiently
Progress, the gas and heat for release of burning can preferably prevent the particle agglomeration of gel in the drying process.
The Li that the present embodiment obtains1.3Al0.3Ti1.7(PO4)3Solid electrolyte film consistency is up to 94%.
The Li that the present embodiment obtains1.3Al0.3Ti1.7(PO4)3The SEM figure of solid electrolyte section is as shown in Figure 1；From Fig. 1
It can be seen that Li1.3Al0.3Ti1.7(PO4)3Even grain size is tightly combined between crystal grain, and porosity is lower, and crystal boundary obviously subtracts
It is few, with 6-8 μm of crystallite dimension；The Li that the present embodiment obtains1.3Al0.3Ti1.7(PO4)3The XRD diagram of solid electrolyte powder
As shown in Figure 3；The Li that the present embodiment obtains1.3Al0.3Ti1.7(PO4)3The AC impedance figure of solid electrolyte is intended as shown in Fig. 4
Closing impedance data can be calculated its room temperature grain boundary conductivities up to 8.2 × 10-4S/cm, room temperature total conductivity is up to 6.7 × 10- 4S/cm。
The Li that the present embodiment obtains1.3Al0.3Ti1.7(PO4)3Solid electrolyte film may be used as all-solid lithium-ion battery
Solid electrolyte.
Embodiment 2: Li in the present embodiment1.3Al0.3Ti1.7(PO4)3Raw powder's production technology carries out in the steps below:
Step 1: weighing butyl titanate, lithium acetate, aluminum sulfate and diammonium hydrogen phosphate according to stoichiometric ratio；
Step 2: the weighed butyl titanate of step 1 is added in the dust technology that mass percent concentration is 20%, with
200r/min rate carries out magnetic agitation to (being completely dissolved) is clarified, and adds the weighed lithium acetate of step 1 and aluminum sulfate,
Then citric acid is added to being completely dissolved in magnetic agitation, until completely dissolved, add ammonium hydroxide and adjust pH value to 5, then exist
The weighed diammonium hydrogen phosphate of step 1 is added, magnetic agitation adds glycerine to being completely dissolved, and magnetic agitation is to uniform, so
Evaporation water then is placed in vacuum oven until obtain sticky transparent wet gel at 80 DEG C afterwards, true at 200 DEG C
Sky is dry, forms the xerogel of black, is subsequently placed in Muffle furnace and is calcined, is warming up to 900 DEG C with the speed of 5 DEG C/min,
Heat preservation 6 hours, cools to room temperature with the furnace, then be placed in ball grinder, and zirconia ball is added as dispersion solvent in dehydrated alcohol
As grinding bead, the mass ratio of ball material is 5:1, mechanical ball mill 10 hours under 450rpm revolving speed, and drying with water bath is extremely at 80 DEG C
Constant weight collects, and obtains the Li of white1.3Al0.3Ti1.7(PO4)3Powder.
Wherein, the quality of butyl titanate and the volume ratio of dust technology are 12g:100mL in step 2；The citric acid with
Ti2+、Li+And Al3+Total moles ratio be 2:1；The molar ratio of the glycerine and citric acid is 0.5:1.
The Li of the present embodiment1.3Al0.3Ti1.7(PO4)3Powder is to replace LiTi using Al element doping2(PO4)3In material
Ti element obtains, TiO6Octahedra and PO4Tetrahedron is connected to form rigid backbone [A by total apex angle oxygen atom2(BO4)3]-
([Ti2(PO4)3]-), Li+It is migrated in three-dimensional tunnel structure.
Using Li1.3Al0.3Ti1.7(PO4)3Powder prepares all-solid lithium-ion battery NASICON type solid electrolyte film,
It is completed particular by following step:
By Li1.3Al0.3Ti1.7(PO4)3Powder grinding is put into the stainless steel compression mold that diameter is 25mm, is in gauge pressure
Pressure maintaining 20min, obtains biscuit under the tabletting conditions of 22MPa；Plain embryo is placed on ceramic wafer, is placed in Muffle furnace and is sintered
Process is warming up to 950 DEG C with the speed of 5 DEG C/min, and heat preservation has just obtained the Li of white after 4 hours1.3Al0.3Ti1.7 (PO4)3Electricity
Solve matter film.
The present embodiment joined the glycerol dispersion agent with esterification, peptizaiton in collosol and gel precursor liquid,
Not only it ensure that metel complex ion in the solution evenly dispersed, but also increased the steric hindrance between metel complex ion, it is therefore prevented that
The particle agglomeration of gel in the drying process finally obtains the Li that crystallite dimension is 8-10 μm1.3Al0.3Ti1.7(PO4)3Solid electricity
Solve matter film.
The dispersing agent glycerine of the present embodiment is polyhydroxy-alcohol, can be connected with the carboxyl to dissociate on metel complex ion, increase
Steric hindrance between metel complex ion, forms lipid structures, and the low-temperature burning of lipoid substance in the drying process can be with
It more fully carries out, the gas and heat for release of burning can prevent the particle agglomeration of gel in the drying process.
The Li that the present embodiment obtains1.3Al0.3Ti1.7(PO4)3Solid electrolyte film consistency is up to 97.6%.
The Li that the present embodiment obtains1.3Al0.3Ti1.7(PO4)3The SEM figure of solid electrolyte section is as shown in Figure 2；From Fig. 2
It can be seen that Li1.3Al0.3Ti1.7(PO4)3Even grain size is tightly combined between crystal grain, and porosity is lower, and crystal boundary is less,
With 8-10 μm of crystallite dimension；The Li that the present embodiment obtains1.3Al0.3Ti1.7(PO4)3The AC impedance figure of solid electrolyte is such as
Shown in Fig. 5, fitting impedance data can be calculated its room temperature grain boundary conductivities up to 4.67 × 10-4S/cm, room temperature total conductivity can
Up to 4.04 × 10-4S/cm。
Embodiment 3: Li in the present embodiment1.3Al0.3Ti1.7(PO4)3Raw powder's production technology carries out in the steps below:
Step 1: weighing butyl titanate, lithium acetate, aluminum sulfate and diammonium hydrogen phosphate according to stoichiometric ratio；
Step 2: the weighed butyl titanate of step 1 is added in the dust technology that mass percent concentration is 20%, with
200r/min rate carries out magnetic agitation to (being completely dissolved) is clarified, and adds the weighed lithium acetate of step 1 and aluminum sulfate,
Then citric acid is added to being completely dissolved in magnetic agitation, until completely dissolved, add ammonium hydroxide and adjust pH value to 5, then exist
The weighed diammonium hydrogen phosphate of step 1 is added, magnetic agitation adds tartaric acid to being completely dissolved, and magnetic agitation is to uniform, so
Evaporation water then is placed in vacuum oven until obtain sticky transparent wet gel at 80 DEG C afterwards, true at 200 DEG C
Sky is dry, forms the xerogel of black, is subsequently placed in Muffle furnace and is calcined, is warming up to 900 DEG C with the speed of 5 DEG C/min,
Heat preservation 6 hours, cools to room temperature with the furnace, then be placed in ball grinder, and zirconia ball is added as dispersion solvent in dehydrated alcohol
As grinding bead, the mass ratio of ball material is 5:1, mechanical ball mill 10 hours under 450rpm revolving speed, and drying with water bath is extremely at 80 DEG C
Constant weight collects, and obtains the Li of white1.3Al0.3Ti1.7(PO4)3Powder.
Wherein, the quality of butyl titanate and the volume ratio of dust technology are 12g:100mL in step 2；The citric acid with
Ti2+、Li+And Al3+Total moles ratio be 1.5:1；The molar ratio of the tartaric acid and citric acid is 2:1.
The Li of the present embodiment1.3Al0.3Ti1.7(PO4)3Powder is to replace LiTi using Al element doping2(PO4)3In material
Ti element obtains, TiO6Octahedra and PO4Tetrahedron is connected to form rigid backbone [A by total apex angle oxygen atom2(BO4)3]-
([Ti2(PO4)3]-), Li+It is migrated in three-dimensional tunnel structure.
Using Li1.3Al0.3Ti1.7(PO4)3Powder prepares all-solid lithium-ion battery NASICON type solid electrolyte film,
It is completed particular by following step:
By Li1.3Al0.3Ti1.7(PO4)3Powder grinding is put into the stainless steel compression mold that diameter is 25mm, is in gauge pressure
Pressure maintaining 20min, obtains biscuit under the tabletting conditions of 25MPa；Plain embryo is placed on ceramic wafer, is placed in Muffle furnace and is sintered
Process is warming up to 950 DEG C with the speed of 4 DEG C/min, and heat preservation has just obtained the Li of white after 5 hours1.3Al0.3Ti1.7 (PO4)3Electricity
Solve matter film.
Embodiment 4: Li in the present embodiment1.3Al0.3Ti1.7(PO4)3Raw powder's production technology carries out in the steps below:
Step 1: weighing butyl titanate, lithium nitrate, aluminum nitrate and ammonium dihydrogen phosphate according to stoichiometric ratio；
Step 2: the weighed butyl titanate of step 1 is added in the dust technology that mass percent concentration is 20%, with
200r/min rate carries out magnetic agitation to (being completely dissolved) is clarified, and adds the weighed lithium nitrate of step 1 and aluminum nitrate,
Then citric acid is added to being completely dissolved in magnetic agitation, until completely dissolved, add ammonium hydroxide and adjust pH value to 5, then exist
The weighed ammonium dihydrogen phosphate of step 1 is added, magnetic agitation adds glycolic to being completely dissolved, and magnetic agitation is to uniform, so
Evaporation water then is placed in vacuum oven until obtain sticky transparent wet gel at 80 DEG C afterwards, true at 180 DEG C
Sky is dry, forms the xerogel of black, is subsequently placed in Muffle furnace and is calcined, is warming up to 800 DEG C with the speed of 3 DEG C/min,
Heat preservation 5 hours, cools to room temperature with the furnace, then be placed in ball grinder, and zirconia ball is added as dispersion solvent in dehydrated alcohol
As grinding bead, the mass ratio of ball material is 5:1, mechanical ball mill 8 hours under 400rpm revolving speed, and drying with water bath is extremely at 80 DEG C
Constant weight collects, and obtains the Li of white1.3Al0.3Ti1.7(PO4)3Powder.
Wherein, the quality of butyl titanate and the volume ratio of dust technology are 12g:100mL in step 2；The citric acid with
Ti2+、Li+And Al3+Total moles ratio be 1:1；The molar ratio of the glycolic and citric acid is 1:1.
The Li of the present embodiment1.3Al0.3Ti1.7(PO4)3Powder is to replace LiTi using Al element doping2(PO4)3In material
Ti element obtains, TiO6Octahedra and PO4Tetrahedron is connected to form rigid backbone [A by total apex angle oxygen atom2(BO4)3]-
([Ti2(PO4)3]-), Li+It is migrated in three-dimensional tunnel structure.
Using Li1.3Al0.3Ti1.7(PO4)3Powder prepares all-solid lithium-ion battery NASICON type solid electrolyte film,
It is completed particular by following step:
By Li1.3Al0.3Ti1.7(PO4)3Powder grinding is put into the stainless steel compression mold that diameter is 25mm, is in gauge pressure
Pressure maintaining 20min, obtains biscuit under the tabletting conditions of 20MPa；Plain embryo is placed on ceramic wafer, is placed in Muffle furnace and is sintered
Process is warming up to 900 DEG C with the speed of 3 DEG C/min, and heat preservation has just obtained the Li of white after 3 hours1.3Al0.3Ti1.7 (PO4)3Electricity
Solve matter film.
Claims (11)
1. a kind of Li1.3Al0.3Ti1.7(PO4)3Powder, it is characterised in that Li1.3Al0.3Ti1.7(PO4)3Powder is mixed using Al element
Miscellaneous substitution LiTi2(PO4)3What the Ti element in material obtained, TiO6Octahedra and PO4Tetrahedron is connected by total apex angle oxygen atom
Form rigid backbone [A2(BO4)3]-([Ti2(PO4)3]-), Li+It is migrated in three-dimensional tunnel structure.
2. Li as described in claim 11.3Al0.3Ti1.7(PO4)3Raw powder's production technology, it is characterised in that the preparation method
It carries out in the steps below:
Step 1: weighing the source Ti, the source Li, the source Al and the source P according to stoichiometric ratio；
Step 2: the weighed source Ti of step 1 is added in dust technology, magnetic agitation adds step 1 and weighs to being completely dissolved
The source Li and the source Al, then complexing agent is added to being completely dissolved in magnetic agitation, until completely dissolved, add ammonium hydroxide and adjust pH
Then to 4~6 the weighed source P of step 1 is being added, magnetic agitation adds dispersing agent, magnetic agitation is extremely to being completely dissolved in value
Uniformly, then evaporation water calcines after vacuum drying up to obtaining sticky wet gel, cools to room temperature with the furnace, ball milling obtains
Li1.3Al0.3Ti1.7(PO4)3Powder.
3. preparation method according to claim 2, it is characterised in that the source Li described in step 1 is lithium nitrate, lithium acetate, carbon
One of sour lithium；The source Al is aluminum nitrate or aluminum sulfate；The source Ti is butyl titanate；The source P is biphosphate
One of ammonium, diammonium hydrogen phosphate, phosphoric acid.
4. preparation method according to claim 2, it is characterised in that the mass percent concentration of dust technology is in step 2
The quality in the source 20%~30%, Ti and the volume ratio of dust technology are (10g~12g): (90mL~110mL).
5. preparation method according to claim 2, it is characterised in that complexing agent described in step 2 is citric acid, the complexing
Agent and Ti2+、Li+And Al3+Total moles ratio be (1~2): 1.
6. preparation method according to claim 2, it is characterised in that dispersing agent described in step 2 be hydroxyl acid derivative,
The molar ratio of one of polyhydroxy-alcohol, cationic surface active agent, acetamide, acetone, the dispersing agent and complexing agent is
(0.5~2): 1；The hydroxyl acid derivative is lactic acid, tartaric acid or glycolic；Polyhydroxy-alcohol is glycerine；It is described sun from
Subtype surfactant is cetyl trimethylammonium bromide.
7. preparation method according to claim 2, it is characterised in that it is dried in vacuo at 180 DEG C~220 DEG C in step 2,
Time is 3h-4h.
8. preparation method according to claim 2, it is characterised in that calcination temperature is 800 DEG C -900 DEG C in step 2, is forged
The burning time is 5h-6h, and heating rate is 2 DEG C/min-5 DEG C/min.
9. according to the method described in claim 2, it is characterized in that step 2 milling parameters: revolving speed 400rpm-
450rpm, Ball-milling Time 8h-12h, ratio of grinding media to material 5:1, ball-milling medium are dehydrated alcohol.
10. a kind of Li as described in claim 11.3Al0.3Ti1.7(PO4)3The application of powder, it is characterised in that Li1.3Al0.3Ti1.7
(PO4)3Powder is used to prepare all-solid lithium-ion battery NASICON type solid electrolyte, is by Li1.3Al0.3Ti1.7(PO4)3Powder
Tabletting after body grinding, made of re-sintering.
11. application according to claim 10, it is characterised in that pressure be 20Mpa-25Mpa condition lower sheeting, pressure maintaining
20min；The sintering temperature is 900 DEG C -950 DEG C, sintering time 3h-5h, and heating rate is 2 DEG C/min-5 DEG C/min.
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| WO2021029229A1 (en) * | 2019-08-09 | 2021-02-18 | 出光興産株式会社 | Electrode composite material and method for manufacturing same |
| CN112768755A (en) * | 2021-01-04 | 2021-05-07 | 长沙矿冶研究院有限责任公司 | Preparation method of NASION type solid electrolyte aluminum-containing phosphate |
| CN112850682A (en) * | 2021-01-23 | 2021-05-28 | 河北科技大学 | Inorganic membrane material and preparation method and application thereof |
| CN114804055A (en) * | 2022-05-16 | 2022-07-29 | 广东凯金新能源科技股份有限公司 | Solid electrolyte with high density and small size and preparation method thereof |
| CN115744856A (en) * | 2022-10-20 | 2023-03-07 | 广州博粤新材料科技有限公司 | Phosphate solid electrolyte and batch preparation method thereof |
| CN115744856B (en) * | 2022-10-20 | 2024-05-28 | 广州博粤新材料科技有限公司 | Phosphate solid electrolyte and batch preparation method thereof |
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2019
- 2019-04-02 CN CN201910259147.5A patent/CN109896511A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 杨程响等: "改进型溶胶-凝胶法制备Li1.3Al0.3Ti1.7(PO4)3", 《电池》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021029229A1 (en) * | 2019-08-09 | 2021-02-18 | 出光興産株式会社 | Electrode composite material and method for manufacturing same |
| CN112768755A (en) * | 2021-01-04 | 2021-05-07 | 长沙矿冶研究院有限责任公司 | Preparation method of NASION type solid electrolyte aluminum-containing phosphate |
| CN112850682A (en) * | 2021-01-23 | 2021-05-28 | 河北科技大学 | Inorganic membrane material and preparation method and application thereof |
| CN112850682B (en) * | 2021-01-23 | 2022-09-09 | 河北科技大学 | Inorganic membrane material and preparation method and application thereof |
| CN114804055A (en) * | 2022-05-16 | 2022-07-29 | 广东凯金新能源科技股份有限公司 | Solid electrolyte with high density and small size and preparation method thereof |
| CN115744856A (en) * | 2022-10-20 | 2023-03-07 | 广州博粤新材料科技有限公司 | Phosphate solid electrolyte and batch preparation method thereof |
| CN115744856B (en) * | 2022-10-20 | 2024-05-28 | 广州博粤新材料科技有限公司 | Phosphate solid electrolyte and batch preparation method thereof |
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