A kind of Na3+2xZr2-xMxSi2PO12The preparation method of solid electrolyte powder body material
Technical field
The invention belongs to solid electrolyte material technical field, particularly to the system of a kind of Fast ion conductor powder body material
Preparation Method.
Background technology
, easily there is the problem such as leakage and electrode corrosion, at height in the most traditional secondary cell many employings liquid electrolyte
Blast it is also possible under temperature.By contrast, solid electrolyte have the highest heat stability, reliability, long cycle life and
Various geometric configuration.Na+With Li+Having similar embedding and electrical conduction mechanism, and Na element is widely distributed in the earth's crust, it is rich
Degree reaches 2.64%, easily obtains, cheap, can be used in fixed sources of energy field of storage.This means sodium ion electrolyte
There is good application prospect.Therefore, sodion solid electrolytes is of great interest.
Fast ion conductor, referred to as NASICON, be a kind of typical sodion solid electrolytes.Fast ion conductor
Be a kind of electrical conductivity height, stable performance, safe and reliable, prepare simple, cheap and Na+Can isotropism conduction material,
Also have do not react with Na, decomposition voltage is higher, sintering temperature is relatively low, to the advantage such as steam is insensitive.Its chemical formula is
Na1+xZr2SixP3–xO12, as x=2, i.e. Na3Zr2Si2PO12Ionic conductivity the highest, at room temperature up to 10–4S/cm number
Magnitude.
But this material there is problems in that traditional preparation method is mainly high temperature solid-state method, reaction temperature is
1100 DEG C so that the Na element in material and P element volatilization, destroy crystal structure, introduce SiO2And ZrO2Dephasign, reduces material
Electrical conductivity.And generally there is more serious reunion in the powder body using existing sol gel process to obtain.Current doping changes
Journal of Sex Research is concentrated mainly on the quadrivalent cation doping (Ge of Zr position4+、Sn4+And Ti4+Deng) and trivalent rare earth cation doping (Dy3 +、Yb3+And Er3+Deng).It is true that Ni2+And Zn2+Deng bivalent cation and Zr4+Ionic radius very close to, and equally with
Oxygen atom forms octahedral structure, and lower valence state can introduce more gap Na+And reduce Na+Migration resistance.Institute
With the M that adulterates in Zr position in theory2+(M=Co, Ni, Zn, Mg) can effectively promote the electrical conductivity of material.
Summary of the invention
The present invention seeks to solve that existing high temperature solid-state method reaction temperature is high, electrical conductivity is low and existing collosol and gel work
The problem that powder reuniting that skill obtains is serious, and a kind of Na is provided3+2xZr2–xMxSi2PO12The preparation of solid electrolyte powder body material
Method.
A kind of Na of the present invention3+2xZr2–xMxSi2PO12The preparation method of solid electrolyte powder body material is entered according to the following steps
OK:
One, by NaNO3、ZrO(NO3)2·2H2O、M(NO3)2·nH2O and (NH4)2HPO4Respectively with deionized water dissolving,
Obtain the NaNO that concentration is 1.5mol/L~6mol/L3Solution, concentration are the ZrO (NO of 0.25mol/L~1mol/L3)2Solution,
Concentration is the M (NO of 0.1mol/L~1mol/L3)2Solution and the (NH that concentration is 0.25mol/L~1mol/L4)2HPO4Solution;Institute
M (the NO stated3)2·nH2M=Co in O2+、Ni2+、Zn2+Or Mg2+;
Two, adding deionized water and dispersant in dehydrated alcohol, stirring is completely dissolved to dispersant, obtains dispersant molten
Liquid, then adds TEOS in dispersant solution, uses magnetic stirring apparatus under conditions of rotating speed is 15r/min~25r/min
Stirring is to mix homogeneously, then drips catalyst regulation pH to 0.5~3.5, then hydrolyzes under conditions of temperature is 40~60 DEG C
1h~5h obtains Sol A;Described deionized water is 1:(300~500 with the volume ratio of dehydrated alcohol);Described dispersant with
The mol ratio of TEOS is 1:(1.8~2.2);The amount of the material of described dispersant and the volume ratio of dehydrated alcohol be (0.8~
1.2)mol:100L;
Three, in the Sol A that step 2 obtains, the most dropwise dropping concentration is the NaNO of 1.5mol/L~6mol/L3Molten
Liquid, concentration are the ZrO (NO of 0.25mol/L~1mol/L3)2Solution, concentration are the M (NO of 0.1mol/L~1mol/L3)2Solution
With (the NH that concentration is 0.25mol/L~1mol/L4)2HPO4Solution, obtains sol B, and being then heated to temperature is 70~90 DEG C,
The volume stirred under conditions of temperature is 70~90 DEG C to sol B becomes the 1/3 of sol B initial volume, obtains colloidal sol C;
The described dispersant in Sol A and concentration are the (NH of 0.25mol/L~1mol/L4)2HPO4NH in solution4 +'s
Mol ratio is (0.8~1.2): 2;Described concentration is the NaNO of 1.5mol/L~6mol/L3NaNO in solution3: concentration is
ZrO (the NO of 0.25mol/L~1mol/L3)2ZrO (NO in solution3)2: concentration is the M (NO of 0.1mol/L~1mol/L3)2Solution
In M (NO3)2: concentration is the (NH of 0.25mol/L~1mol/L4)2HPO4(NH in solution4)2HPO4Mol ratio be 3:(2
x):x:1;Wherein 0 < x≤0.3;
Four, colloidal sol C step 3 obtained is sealing and is obtaining gel D, by gel after still aging 24h under the conditions of lucifuge
D puts in baking oven dries 24h under conditions of temperature is 70~90 DEG C and obtains presoma;
Five, presoma step 4 obtained loads in alumina crucible after grinding, and then alumina crucible is put into sky
In steam stove, it is warmed up to 850~950 DEG C with the heating rate of 4 DEG C/min~6 DEG C/min, is then 850~950 DEG C in temperature
Under the conditions of calcine 6h~12h, be ground to particle diameter in 0.4 μm~0.6 μm, obtain finely disseminated Na3+2xZr2–xMxSi2PO12Solid
Electrolyte powder body material.
Beneficial effects of the present invention:
Present invention sol-gal process, by control catalyst type, calcining heat, calcination time, dispersant with
And NaNO3(NH4)2HPO4Consumption, the Na that prepared composition is uniformly, good dispersion, reactivity are high3+2xZr2–xMxSi2PO12(M
=Co2+,Ni2+,Zn2+,Mg2+) pure phase powder body, diameter of particle is 0.4 μm~0.6 μm, and the method for the present invention reduces block materials
Sintering temperature, the beneficially lifting of electrical conductivity, and operational approach is simple, reproducible, can realize producing in enormous quantities.The present invention
Concrete advantage as follows:
(1) use sol-gal process to make raw material reach the other uniform mixing of molecular level, be particularly advantageous in doped chemical and melt
Entering in crystal structure, the product component finally obtained is uniform.
(2) sol-gal process can reduce reaction temperature, not only energy-and time-economizing, it is also possible to reduces because of Na element and P element
The SiO that volatilization produces2And ZrO2Dephasign.
(3) by controlling catalyst type, calcining heat, calcination time, dispersant and NaNO3(NH4)2HPO4Consumption, effectively reduce diameter of particle and also promote its dispersibility, efficiently avoid the powder body that sol-gal process often occurs
Agglomeration, is conducive to promoting the consistency of ceramic block.
(4) dehydrated alcohol has simultaneously worked as effect the most molten, that dilute and inhibit.
(5) acid catalyzed reaction condition accelerates the hydrolytic process of TEOS and suppresses the polycondensation process of product, in dropping electrolysis
Being difficult to coagulation during matter solution, controllability is good.
(6) operation is simple for the present invention, with short production cycle, can apply in large-scale commercial production.
Accompanying drawing explanation
Fig. 1 is test Na prepared by3.4Zr1.8Zn0.2Si2PO12Powder body and Na3Zr2Si2PO12The XRD comparison diagram of powder body
Spectrum;Wherein 1 Na prepared by test one3.4Zr1.8Zn0.2Si2PO12Powder body, 2 is Na3Zr2Si2PO12Powder body;
Fig. 2 is test Na prepared by3.4Zr1.8Zn0.2Si2PO12The SEM photograph of powder body;
Fig. 3 is test Na prepared by two3.2Zr1.9Ni0.1Si2PO12Powder body and Na3Zr2Si2PO12The XRD comparison diagram of powder body
Spectrum;Wherein 1 Na prepared by test two3.2Zr1.9Ni0.1Si2PO12Powder body, 2 is Na3Zr2Si2PO12Powder body;
Fig. 4 is test Na prepared by two3.2Zr1.9Ni0.1Si2PO12The SEM photograph of powder body.
Detailed description of the invention
Detailed description of the invention one: a kind of Na of present embodiment3+2xZr2–xMxSi2PO12The system of solid electrolyte powder body material
Preparation Method sequentially includes the following steps:
One, by NaNO3、ZrO(NO3)2·2H2O、M(NO3)2·nH2O and (NH4)2HPO4Respectively with deionized water dissolving,
Obtain the NaNO that concentration is 1.5mol/L~6mol/L3Solution, concentration are the ZrO (NO of 0.25mol/L~1mol/L3)2Solution,
Concentration is the M (NO of 0.1mol/L~1mol/L3)2Solution and the (NH that concentration is 0.25mol/L~1mol/L4)2HPO4Solution;Institute
M (the NO stated3)2·nH2M=Co in O2+、Ni2+、Zn2+Or Mg2+;
Two, adding deionized water and dispersant in dehydrated alcohol, stirring is completely dissolved to dispersant, obtains dispersant molten
Liquid, then adds TEOS in dispersant solution, uses magnetic stirring apparatus under conditions of rotating speed is 15r/min~25r/min
Stirring is to mix homogeneously, then drips catalyst regulation pH to 0.5~3.5, then hydrolyzes under conditions of temperature is 40~60 DEG C
1h~5h obtains Sol A;Described deionized water is 1:(300~500 with the volume ratio of dehydrated alcohol);Described dispersant with
The mol ratio of TEOS is 1:(1.8~2.2);The amount of the material of described dispersant and the volume ratio of dehydrated alcohol be (0.8~
1.2)mol:100L;
Three, in the Sol A that step 2 obtains, the most dropwise dropping concentration is the NaNO of 1.5mol/L~6mol/L3Molten
Liquid, concentration are the ZrO (NO of 0.25mol/L~1mol/L3)2Solution, concentration are the M (NO of 0.1mol/L~1mol/L3)2Solution
With (the NH that concentration is 0.25mol/L~1mol/L4)2HPO4Solution, obtains sol B, and being then heated to temperature is 70~90 DEG C,
The volume stirred under conditions of temperature is 70~90 DEG C to sol B becomes the 1/3 of sol B initial volume, obtains colloidal sol C;
The described dispersant in Sol A and concentration are the (NH of 0.25mol/L~1mol/L4)2HPO4NH in solution4 +'s
Mol ratio is (0.8~1.2): 2;Described concentration is the NaNO of 1.5mol/L~6mol/L3NaNO in solution3: concentration is
ZrO (the NO of 0.25mol/L~1mol/L3)2ZrO (NO in solution3)2: concentration is the M (NO of 0.1mol/L~1mol/L3)2Solution
In M (NO3)2: concentration is the (NH of 0.25mol/L~1mol/L4)2HPO4(NH in solution4)2HPO4Mol ratio be 3:(2
x):x:1;Wherein 0 < x≤0.3;
Four, colloidal sol C step 3 obtained is sealing and is obtaining gel D, by gel after still aging 24h under the conditions of lucifuge
D puts in baking oven dries 24h under conditions of temperature is 70~90 DEG C and obtains presoma;
Five, presoma step 4 obtained loads in alumina crucible after grinding, and then alumina crucible is put into sky
In steam stove, it is warmed up to 850~950 DEG C with the heating rate of 4 DEG C/min~6 DEG C/min, is then 850~950 DEG C in temperature
Under the conditions of calcine 6h~12h, be ground to particle diameter in 0.4 μm~0.6 μm, obtain finely disseminated Na3+2xZr2–xMxSi2PO12Solid
Electrolyte powder body material.
Present embodiment sol-gal process, by controlling catalyst type, calcining heat, calcination time, dispersant kind
Class and NaNO3(NH4)2HPO4Consumption, the Na that prepared composition is uniformly, good dispersion, reactivity are high3+2xZr2– xMxSi2PO12(M=Co2+,Ni2+,Zn2+,Mg2+) pure phase powder body, diameter of particle is 0.4 μm~0.6 μm, the side of present embodiment
Method reduces the lifting of the sintering temperature of block materials, beneficially electrical conductivity, and operational approach is simple, reproducible, can realize
Produce in enormous quantities.Particularly advantage of the invention is as follows:
(1) use sol-gal process to make raw material reach the other uniform mixing of molecular level, be particularly advantageous in doped chemical and melt
Entering in crystal structure, the product component finally obtained is uniform.
(2) sol-gal process can reduce reaction temperature, not only energy-and time-economizing, it is also possible to reduces because of Na element and P element
The SiO that volatilization produces2And ZrO2Dephasign.
(3) by controlling catalyst type, calcining heat, calcination time, dispersant and NaNO3(NH4)2HPO4Consumption, effectively reduce diameter of particle and also promote its dispersibility, effectively evaded the powder body that sol-gal process often occurs
Agglomeration, is conducive to promoting the consistency of ceramic block.
(4) dehydrated alcohol has simultaneously worked as effect the most molten, that dilute and inhibit.
(5) acid catalyzed reaction condition accelerates the hydrolytic process of TEOS and suppresses the polycondensation process of product, in dropping electrolysis
Being difficult to coagulation during matter solution, controllability is good.
(6) operation is simple for present embodiment, with short production cycle, can apply in large-scale commercial production.
Detailed description of the invention two: present embodiment is unlike detailed description of the invention one: the dispersion described in step 2
Agent is citric acid, PEG1000 or CTAB.Other steps and parameter are identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment is unlike detailed description of the invention one or two: described in step 2
Catalyst is concentrated nitric acid, oxalic acid or acetic acid.Other steps and parameter are identical with detailed description of the invention one or two.
Detailed description of the invention four: present embodiment is unlike one of detailed description of the invention one to three: institute in step 2
The deionized water stated is 1:400 with the volume ratio of dehydrated alcohol.Other steps and one of parameter and detailed description of the invention one to three
Identical.
Detailed description of the invention five: present embodiment is unlike one of detailed description of the invention one to four: institute in step 2
The dispersant stated is 1:2 with the mol ratio of TEOS.Other steps and parameter are identical with one of detailed description of the invention one to four.
Detailed description of the invention six: present embodiment is unlike one of detailed description of the invention one to five: institute in step 2
The amount of the material of the dispersant stated and the volume ratio of dehydrated alcohol are 1mol:100L.Other steps and parameter and specific embodiment party
One of formula one to five is identical.
Detailed description of the invention seven: present embodiment is unlike one of detailed description of the invention one to six: in step 2 to
Adding deionized water and dispersant in dehydrated alcohol, stirring is completely dissolved to dispersant, obtains dispersant solution, then to dispersion
Agent solution adds TEOS, stirs to mix homogeneously under conditions of rotating speed is 20r/min, then drip catalyst regulation pH to 2,
Then under conditions of temperature is 50 DEG C, hydrolyzes 1h obtains Sol A.Other steps and parameter and detailed description of the invention one to six it
One is identical.
Detailed description of the invention eight: present embodiment is unlike one of detailed description of the invention one to seven: institute in step 3
Dispersant in the Sol A stated and concentration are the (NH of 0.25mol/L~1mol/L4)2HPO4NH in solution4 +Mol ratio be 1:
2.Other steps and parameter are identical with one of detailed description of the invention one to seven.
Detailed description of the invention nine: present embodiment is unlike one of detailed description of the invention one to eight: institute in step 3
The concentration stated is the NaNO of 1.5mol/L~6mol/L3NaNO in solution3: concentration is the ZrO of 0.25mol/L~1mol/L
(NO3)2ZrO (NO in solution3)2: concentration is the M (NO of 0.1mol/L~1mol/L3)2M (NO in solution3)2: concentration is
(the NH of 0.25mol/L~1mol/L4)2HPO4(NH in solution4)2HPO4Mol ratio be 3:1.8:0.2:1:2.Other steps
And parameter is identical with one of detailed description of the invention one to eight.
Detailed description of the invention ten: present embodiment is unlike one of detailed description of the invention one to nine: institute in step 3
The concentration stated is the NaNO of 1.5mol/L~6mol/L3NaNO in solution3: concentration is the ZrO of 0.25mol/L~1mol/L
(NO3)2ZrO (NO in solution3)2: concentration is the M (NO of 0.1mol/L~1mol/L3)2M (NO in solution3)2: concentration is
(the NH of 0.25mol/L~1mol/L4)2HPO4(NH in solution4)2HPO4Mol ratio be 3:1.9:0.1:1:2.Other steps
And parameter is identical with one of detailed description of the invention one to nine.
Detailed description of the invention 11: present embodiment is unlike one of detailed description of the invention one to ten: in step 3
Being heated to temperature is 80 DEG C, and the volume stirred under conditions of temperature is 80 DEG C to sol B becomes the 1/3 of sol B initial volume,
Obtain colloidal sol C.Other steps and parameter are identical with one of detailed description of the invention one to ten.
Detailed description of the invention 12: present embodiment is unlike one of detailed description of the invention one to ten one: step 4
Middle colloidal sol C step 3 obtained is sealing and is obtaining gel D after still aging 24h under the conditions of lucifuge, and gel D is put into baking oven
In under conditions of temperature is 80 DEG C dry 24h obtain presoma.Other steps and parameter and detailed description of the invention one to ten one
One of identical.
Detailed description of the invention 13: present embodiment is unlike one of detailed description of the invention one to ten two: step 5
In be warmed up to 900 DEG C with the heating rate of 5 DEG C/min, then under conditions of temperature is 900 DEG C calcine 9h, being ground to particle diameter is
0.5 μm, obtains finely disseminated Na3+2xZr2–xMxSi2PO12Solid electrolyte powder body material.Other steps and parameter are real with concrete
Execute one of mode one to ten two identical.
By following verification experimental verification beneficial effects of the present invention:
Test one: a kind of Na of this test3+2xZr2–xMxSi2PO12The preparation method of solid electrolyte powder body material is by following
Step is carried out:
One, by the NaNO of 2.89g3, the ZrO (NO of 5.08g3)2·2H2Zn (the NO of O, 0.60g3)2·2H2O's and 1.32g
(NH4)2HPO4Respectively with deionized water dissolving, obtain the NaNO that concentration is 1.7mol/L3Solution, concentration are 0.45mol/L's
ZrO(NO3)2Solution, concentration are the Zn (NO of 0.2mol/L3)2Solution and concentration are the (NH of 0.25mol/L4)2HPO4Solution;
The concentration obtained is the NaNO of 1.7mol/L3The volume of solution is 20mL;Concentration is the ZrO (NO of 0.45mol/L3)2
The volume of solution is 40mL;Concentration is the Zn (NO of 0.2mol/L3)2The volume of solution is 5mL;Concentration is 0.25mol/L's
(NH4)2HPO4The volume of solution is 40mL;
Two, add 2.5mL deionized water and 4.20g citric acid to 1L dehydrated alcohol, stir and be completely dissolved to dispersant, obtain
To dispersant solution, then adding 4.5mLTEOS in dispersant solution, using magnetic stirring apparatus is 20r/min's at rotating speed
Under the conditions of stir to mix homogeneously, then drip concentrated nitric acid regulation pH to 2, then under conditions of temperature is 50 DEG C hydrolyze 1h obtain
Sol A;
Described dispersant is 1:2 with the mol ratio of TEOS;The amount of the material of described dispersant and the body of dehydrated alcohol
Long-pending ratio is 1mol:100L;
Three, in the Sol A that step 2 obtains, the most dropwise dropping concentration is the NaNO of 1.7mol/L3Solution, concentration are
ZrO (the NO of 0.45mol/L3)2Solution, concentration are the Zn (NO of 0.2mol/L3)2Solution and concentration are the (NH of 0.25mol/L4)2HPO4Solution, obtains sol B, and being then heated to temperature is 80 DEG C, stirs the volume to sol B under conditions of temperature is 80 DEG C
Become the 1/3 of sol B initial volume, obtain colloidal sol C;
The described dispersant in Sol A and concentration are the (NH of 0.25mol/L4)2HPO4NH in solution4 +Mol ratio be
1:2;Described concentration is the NaNO of 1.7mol/L3NaNO in solution3: concentration is the ZrO (NO of 0.45mol/L3)2In solution
ZrO(NO3)2: concentration is the Zn (NO of 0.2mol/L3)2Zn (NO in solution3)2: concentration is the (NH of 0.25mol/L4)2HPO4Molten
(NH in liquid4)2HPO4Mol ratio be 3:1.8:0.2:1:2;
Four, colloidal sol C step 3 obtained is sealing and is obtaining gel D, by gel after still aging 24h under the conditions of lucifuge
D puts in baking oven dries 24h under conditions of temperature is 80 DEG C and obtains presoma;
Five, presoma step 4 obtained loads in alumina crucible after grinding, and then alumina crucible is put into sky
In steam stove, it is warmed up to 900 DEG C with the heating rate of 5 DEG C/min, under conditions of temperature is 900 DEG C, then calcines 9h, is ground to
Particle diameter is 0.5 μm, obtains finely disseminated Na3.4Zr1.8Zn0.2Si2PO12Solid electrolyte powder body material.
(1) X-ray diffractometer analysis test Na obtained by is utilized3.4Zr1.8Zn0.2Si2PO12Powder body and
Na3Zr2Si2PO12The thing phase composition of powder body, obtains the Na obtained by test one as shown in Figure 13.4Zr1.8Zn0.2Si2PO12Powder body
And Na3Zr2Si2PO12The XRD figure spectrum of powder body.
Contrast Na3Zr2Si2PO12And Na3.4Zr1.8Zn0.2Si2PO12XRD figure spectrum understand, Na3.4Zr1.8Zn0.2Si2PO12's
Diffraction maximum entirety offsets to the right, does not has miscellaneous peak to occur, illustrates that thing is correct mutually, Zn2+Successfully replace Zr4+Enter in lattice.
(2) utilize scanning electron microscope to Na3.4Zr1.8Zn0.2Si2PO12The tissue topography of powder body characterizes, and obtains
The Na obtained by test one as shown in Figure 23.4Zr1.8Zn0.2Si2PO12The SEM photograph of powder body.
Result shows, the Na prepared by the inventive method3.4Zr1.8Zn0.2Si2PO12Powder body hard aggregation-free, good dispersion, removes
Individual particles particle diameter is about 1 μm, and the particle diameter of most granules is between 0.2 μm~0.5 μm.
Test two: a kind of Na of this test3+2xZr2–xMxSi2PO12The preparation method of solid electrolyte powder body material is by following
Step is carried out:
One, by the NaNO of 5.43g3, the ZrO (NO of 10.16g3)2·2H2Ni (the NO of O, 0.58g3)2·2H2O and 2.64g
(NH4)2HPO4Respectively with deionized water dissolving, obtain the NaNO that concentration is 1.6mol/L3Solution, concentration are 0.475mol/L
ZrO (NO3)2Solution, concentration are the Ni (NO of 0.2mol/L3)2Solution and concentration are the (NH of 0.25mol/L4)2HPO4Solution;
The concentration obtained is the NaNO of 1.6mol/L3The volume of solution is 40mL;Concentration is the ZrO of 0.475mol/L
(NO3)2The volume of solution is 80mL;Concentration is the Ni (NO of 0.2mol/L3)2The volume of solution is 10mL;Concentration is 0.25mol/
(the NH of L4)2HPO4The volume of solution is 80mL;
Two, adding 5mL deionized water and 8.40g citric acid to 2L dehydrated alcohol, stirring is completely dissolved to dispersant, obtains
Dispersant solution, then adds 9mLTEOS in dispersant solution, and using magnetic stirring apparatus is the condition of 20r/min at rotating speed
Lower stirring is to mix homogeneously, then drips concentrated nitric acid regulation pH to 2, then hydrolyzes 1h under conditions of temperature is 50 DEG C and obtains colloidal sol
A;
Described dispersant is 1:2 with the mol ratio of TEOS;The amount of the material of described dispersant and the body of dehydrated alcohol
Long-pending ratio is 1mol:100L;
Three, in the Sol A that step 2 obtains, the most dropwise dropping concentration is the NaNO of 1.6mol/L3Solution, concentration are
ZrO (the NO of 0.475mol/L3)2Solution, concentration are the Ni (NO of 0.2mol/L3)2Solution and concentration are the (NH of 0.25mol/L4)2HPO4Solution, obtains sol B, and being then heated to temperature is 80 DEG C, stirs the volume to sol B under conditions of temperature is 80 DEG C
Become the 1/3 of sol B initial volume, obtain colloidal sol C;
The described dispersant in Sol A and concentration are the (NH of 0.25mol/L4)2HPO4NH in solution4 +Mol ratio be
1:2;Described concentration is the NaNO of 1.6mol/L3NaNO in solution3: concentration is the ZrO (NO of 0.475mol/L3)2In solution
ZrO(NO3)2: concentration is the Ni (NO of 0.2mol/L3)2Ni (NO in solution3)2: concentration is the (NH of 0.25mol/L4)2HPO4Molten
(NH in liquid4)2HPO4Mol ratio be 3:1.9:0.1:1:2;
Four, colloidal sol C step 3 obtained is sealing and is obtaining gel D, by gel after still aging 24h under the conditions of lucifuge
D puts in baking oven dries 24h under conditions of temperature is 80 DEG C and obtains presoma;
Five, presoma step 4 obtained loads in alumina crucible after grinding, and then alumina crucible is put into sky
In steam stove, it is warmed up to 900 DEG C with the heating rate of 5 DEG C/min, under conditions of temperature is 900 DEG C, then calcines 9h, is ground to
Particle diameter is 0.5 μm, obtains finely disseminated Na3.2Zr1.9Ni0.1Si2PO12Solid electrolyte powder body material.
(3) Na obtained by X-ray diffractometer analysis test two is utilized3.2Zr1.9Ni0.1Si2PO12Powder body and
Na3Zr2Si2PO12The thing phase composition of powder body, obtains Na obtained by test two as shown in Figure 33.2Zr1.9Ni0.1Si2PO12Powder body and
Na3Zr2Si2PO12The XRD figure spectrum of powder body.
Contrast Na3Zr2Si2PO12And Na3.2Zr1.9Ni0.1Si2PO12XRD figure spectrum understand Na3.2Zr1.9Ni0.1Si2PO12's
Diffraction maximum entirety offsets to the right, does not has miscellaneous peak to occur, illustrates that thing is correct mutually, Ni2+Successfully replace Zr4+Enter in lattice.
(4) utilize scanning electron microscope to Na3.2Zr1.9Ni0.1Si2PO12The tissue topography of powder body characterizes, and obtains
Na obtained by test two as shown in Figure 43.2Zr1.9Ni0.1Si2PO12The SEM photograph of powder body.
Result shows, Na prepared by the inventive method3.2Zr1.9Ni0.1Si2PO12Powder body is without substantially reunion, good dispersion, grain
Footpath is substantially between 0.2 μm~0.5 μm, and only individual particles particle diameter is about 1 μm.