CN109888375A - A kind of doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte and its preparation method and application - Google Patents
A kind of doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte and its preparation method and application Download PDFInfo
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- CN109888375A CN109888375A CN201910173953.0A CN201910173953A CN109888375A CN 109888375 A CN109888375 A CN 109888375A CN 201910173953 A CN201910173953 A CN 201910173953A CN 109888375 A CN109888375 A CN 109888375A
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Abstract
The present invention discloses a kind of doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte and its preparation method and application, which is the titanium phosphate sodium nano material of metallic aluminium, lanthanum or Fe2O3 doping, general formula Na1+xMxTi2‑x(PO4)3, wherein M is metallic aluminium, lanthanum or iron, and the value of x is 0.1~0.4.Preparation method includes the following steps: (1) synthesis mother liquid: sodium salt and concentrated phosphoric acid, titanium material and lanthanum raw material, iron material or aluminum feedstock are dissolved in organic solvent respectively, obtain mixed solution A, B, C, mixed solution A and C are successively added drop-wise in mixed solution B, it is stirred after being added dropwise to complete, obtains porous nano crystalline substance immiscible material mother liquor；(2) crystallization handle: mother liquor is added in reaction kettle, 130~160 DEG C at a temperature of react 2~4h；Washing removal organic solvent, is dried to obtain solid electrolyte material.The doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte is used as the electrolyte of solid-state sodium-ion battery, can realize high ionic conductivity at room temperature.
Description
Technical field
The present invention relates to sodium-ion battery electrolyte, in particular to a kind of doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte and
Preparation method and application belong to sodium-ion battery technical field.
Background technique
All-solid sodium ion battery is concerned in recent years, wherein sodium-sulphur battery is the representative for comparing successful application, so
And sodium-sulphur battery operating temperature is higher, needs higher operation cost, simultaneously results in potential safety problem.
Therefore, the all-solid sodium ion battery that develop to work at ambient temperature has very important significance.Quan Gu
State sodium ion electrolyte is the important component of all-solid-state battery, it determines safety and chemical property, cycle life
With the energy density of battery.Solid electrolyte is concentrated mainly on solid polymer electrolyte (SPE), inoganic solids combined electrolysis
On matter, glass ceramic electrolyte and amorphous solid electrolyte.
Currently, NASICON type ceramic material NaTi2(PO4)3It (NTP) is considered as most attractive sodium-ion battery
(SIB) electrode, theoretical capacity are up to 132.8mAhg-1, thermal stability is good.Applicant carries out the electrolyte of the titanium sode cell
It improves, forms the technology of the present invention.
Summary of the invention
Goal of the invention: for the high problem of existing sodium-ion battery operating temperature, the present invention provides a kind of doping phosphoric acid
Titanium sodium porous nano crystalline substance electrolyte, and the nanocrystalline electrolyte preparation method is provided, and the nanocrystalline electrolyte is used
In the application of solid-state sodium-ion battery.
Technical solution: doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte of the present invention, the nanocrystalline electrolyte are gold
Belong to the titanium phosphate sodium nano material of aluminium, lanthanum or Fe2O3 doping, general formula Na1+xMxTi2-x(PO4)3, wherein M be metallic aluminium, lanthanum or
Iron, the value of x are 0.1~0.4.
Doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte preparation method of the present invention, includes the following steps:
Step 1, synthesis mother liquid: sodium salt and concentrated phosphoric acid, titanium material and lanthanum raw material, iron material or aluminum feedstock are dissolved in respectively
Organic solvent obtains mixed solution A, mixed solution B and mixed solution C, mixed solution A and mixed solution C is successively added drop-wise to
It in mixed solution B, is stirred evenly after being added dropwise to complete, obtains porous nano crystalline substance immiscible material mother liquor；
Step 2, crystallization is handled: step 1 gained immiscible material mother liquor being added in reaction kettle, in 130~160 DEG C of temperature
Spend lower 2~4h of hydro-thermal reaction；It is washed out removal organic solvent, is dried to obtain solid electrolyte material.
In above-mentioned steps 1, the molar ratio of lanthanum raw material, iron material or aluminum feedstock and titanium material, sodium salt and phosphate radical is 1~
10:10~30:10~35:10~50.
Wherein, the mass percent of concentrated phosphoric acid is preferably >=85wt%.In each raw material, sodium salt can for sodium acetate, sodium phosphate,
At least one of disodium hydrogen phosphate or sodium carbonate.Titanium material can in butyl titanate, titanium tetrachloride or barium titanate at least
It is a kind of.Lanthanum raw material can be at least one of lanthana, lanthanum acetate or lanthanum nitrate, and iron material can be di-iron trioxide, tri-chlorination
At least one of iron or ferric nitrate, aluminum feedstock can be at least one of aluminum nitrate, aluminium oxide or aluminum sulfate.Organic solvent is excellent
It is selected as ethylene glycol or polyethylene glycol.
In step 1, mixed solution A and mixed solution C are successively added drop-wise in mixed solution B, generally stirred after being added dropwise to complete
5~8min is mixed, porous nano crystalline substance immiscible material mother liquor is obtained.
In step 2, hydrothermal reaction condition is best are as follows: the hydro-thermal reaction 3h at 140 DEG C.Reaction time is too long or temperature is excessively high
The electric conductivity of product can be influenced to a certain extent.
Doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte of the present invention be used for solid-state sodium-ion battery application, be by
The doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte is used as the electrolyte of solid-state sodium-ion battery.
The utility model has the advantages that compared with the prior art, the advantages of the present invention are as follows: (1) doping phosphoric acid titanium sodium micropore of the invention
Nanocrystalline electrolyte granular is of uniform size, consistency is high, is used for solid-state sodium-ion battery, has operating temperature low, stable
The characteristics of property height and electrochemical window mouth width, it can realize high conductance at room temperature, room-temperature conductivity reaches as high as 5.2 ×
10-4S·cm-1；(2) doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte preparation process of the invention is simple, and reaction temperature is lower,
Reaction time is shorter, and raw material resources are abundant, is suitble to large-scale production.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) figure that aluminium titanium phosphate sodium porous nano crystalline substance is mixed made from embodiment 1；
Fig. 2 is transmission electron microscope (TEM) figure that aluminium titanium phosphate sodium porous nano crystalline substance is mixed made from embodiment 1；
Fig. 3 is the ac impedance spectroscopy that aluminium titanium phosphate sodium porous nano crystalline substance is mixed made from embodiment 1；
Fig. 4 is the ac impedance spectroscopy of undoped titanium phosphate sodium porous nano crystalline substance.
Fig. 5 is respectively with Na1.4Fe0.4Ti1.6(PO4)3Material and NaTi2(PO4)3Material is the electricity of button made of electrode slice
Specific capacity variation diagram after the multiple charge and discharge cycles in pond.
Specific embodiment
Technical solution of the present invention is described further with reference to the accompanying drawing.
Doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte of the invention is the titanium phosphate sodium nanometer of metallic aluminium, lanthanum or Fe2O3 doping
Material, general formula Na1+xMxTi2-x(PO4)3, wherein M is metallic aluminium, lanthanum or iron, and the value of x is 0.1~0.4.Three kinds of metals
In, the electric conductivity of the titanium phosphate sodium nano material of La doped at room temperature is optimal.
Embodiment 1
The modulation of porous nano crystalline substance mother liquor: it is added in small beaker first, adds step 1: weighing sodium acetate trihydrate 1.1mmol
Concentrated phosphoric acid 8ml and ethylene glycol 24ml, ultrasound is to being completely dissolved.Step 2: 10ml ethylene glycol is first added into large beaker second, then drip
Add weighed 2.0mmol titanium tetrachloride, with magnetic stirring apparatus uniform stirring and ethylene glycol is added dropwise dropwise and is settled to 60ml.Third
Step: it weighs aluminum nitrate 0.1mmol and small beaker third is added and ethylene glycol 25ml is added；Step 4: the mixed liquor in beaker first is stirred
It mixes uniformly, is added drop-wise in beaker second, the mixed solution in beaker third is added drop-wise to dropwise in beaker second dropwise finally, process is added dropwise
Middle foundation solution colour is by being continuously improved mixing speed when limpid change milkiness, after lighter, then appropriate reduction mixing speed
Continue to stir.5min is stirred after being added dropwise to complete, and doping phosphoric acid titanium sodium porous nano crystalline substance mother liquor modulating liquid can be obtained.
The crystallization of porous nano crystal sodium ion electrolyte is handled: step 1: mother liquor modulating liquid is assigned to two
It in the reaction kettle of 100ml and seals, reaction kettle is placed in baking oven, be arranged to 140 DEG C of reaction 3h.Naturally cold after the reaction was completed
But.Step 2: product is removed liquid solvent by the way that centrifuge washing for several times is dry, it is finally placed in drying in 70 DEG C of baking oven,
The product obtained after drying is finally ground into 20min, aluminium doping phosphoric acid titanium natrium nanocrystalline powder, SEM figure and TEM can be obtained
Figure such as Fig. 1~2, it can be seen that porous nano crystal sodium ion electrolyte even particle distribution, crystallite dimension are 200nm left
It is right；Its ac impedance spectroscopy such as Fig. 3, porous nano crystalline substance charge transfer resistance are about 140 Ω.
After tested, aluminium doped micropore nanocrystalline solids electrolyte Na made from the present embodiment1.1Al0.1Ti1.9(PO4)3Room temperature
Lower conductivity is up to 2.499 × 10-4S·cm-1。
Embodiment 2
The modulation of porous nano crystalline substance mother liquor: it is added in small beaker first, adds step 1: weighing sodium acetate trihydrate 1.1mmol
Concentrated phosphoric acid 8ml and ethylene glycol 24ml, ultrasound is to being completely dissolved.Step 2: 10ml ethylene glycol is first added into large beaker second, then drip
Add weighed 2.0mmol titanium tetrachloride, with magnetic stirring apparatus uniform stirring and ethylene glycol is added dropwise dropwise and is settled to 60ml.Third
Step: it weighs aluminum nitrate 0.1mmol and small beaker third is added and ethylene glycol 25ml is added；Step 4: the mixed liquor in beaker first is stirred
It mixes uniformly, is added drop-wise in beaker second, the mixed solution in beaker third is added drop-wise to dropwise in beaker second dropwise finally, process is added dropwise
Middle foundation solution colour is by being continuously improved mixing speed when limpid change milkiness, after lighter, then appropriate reduction mixing speed
Continue to stir.5min is stirred after being added dropwise to complete, and doping phosphoric acid titanium sodium porous nano crystalline substance mother liquor modulating liquid can be obtained.
The crystallization of porous nano crystal sodium ion electrolyte is handled: step 1: mother liquor modulating liquid is assigned to two
It in the reaction kettle of 100ml and seals, reaction kettle is placed in baking oven, be arranged to 130 DEG C of reaction 3h.Naturally cold after the reaction was completed
But.Step 2: product is removed liquid solvent by the way that centrifuge washing for several times is dry, it is finally placed in drying in 70 DEG C of baking oven,
The product obtained after drying is finally ground into 20min, aluminium doping phosphoric acid titanium natrium nanocrystalline powder, SEM figure and TEM can be obtained
Close in embodiment 1, crystallite dimension is 500~600nm or so.
After tested, aluminium doped micropore nanocrystalline solids electrolyte Na made from the present embodiment1.1Al0.1Ti1.9(PO4)3Room temperature
Lower conductivity is up to 1.579 × 10-4S·cm-1。
Embodiment 3
The modulation of porous nano crystalline substance mother liquor: it is added in small beaker first, adds step 1: weighing sodium acetate trihydrate 1.1mmol
Concentrated phosphoric acid 8ml and ethylene glycol 24ml, ultrasound is to being completely dissolved.Step 2: 10ml ethylene glycol is first added into large beaker second, then drip
Add weighed 2.0mmol titanium tetrachloride, with magnetic stirring apparatus uniform stirring and ethylene glycol is added dropwise dropwise and is settled to 60ml.Third
Step: it weighs aluminum nitrate 0.1mmol and small beaker third is added and ethylene glycol 25ml is added；Step 4: the mixed liquor in beaker first is stirred
It mixes uniformly, is added drop-wise in beaker second, the mixed solution in beaker third is added drop-wise to dropwise in beaker second dropwise finally, process is added dropwise
Middle foundation solution colour is by being continuously improved mixing speed when limpid change milkiness, after lighter, then appropriate reduction mixing speed
Continue to stir.5min is stirred after being added dropwise to complete, and doping phosphoric acid titanium sodium porous nano crystalline substance mother liquor modulating liquid can be obtained.
The crystallization of porous nano crystal sodium ion electrolyte is handled: step 1: mother liquor modulating liquid is assigned to two
It in the reaction kettle of 100ml and seals, reaction kettle is placed in baking oven, be arranged to 160 DEG C of reaction 3h.Naturally cold after the reaction was completed
But.Step 2: product is removed liquid solvent by the way that centrifuge washing for several times is dry, it is finally placed in drying in 70 DEG C of baking oven,
The product obtained after drying is finally ground into 20min, aluminium doping phosphoric acid titanium natrium nanocrystalline powder, SEM figure and TEM can be obtained
Close in embodiment 1, crystallite dimension is 400nm or so.
After tested, aluminium doped micropore nanocrystalline solids electrolyte Na made from the present embodiment1.1Al0.1Ti1.9(PO4)3Room temperature
Lower conductivity is up to 4.566 × 10-5S·cm-1。
Embodiment 4
The modulation of porous nano crystalline substance mother liquor: it is added in small beaker first, adds step 1: weighing sodium acetate trihydrate 1.1mmol
Concentrated phosphoric acid 8ml and ethylene glycol 24ml, ultrasound is to being completely dissolved.Step 2: 10ml ethylene glycol is first added into large beaker second, then drip
Add weighed 1.9mmol titanium tetrachloride, with magnetic stirring apparatus uniform stirring and ethylene glycol is added dropwise dropwise and is settled to 60ml.Third
Step: it weighs aluminum nitrate 0.1mmol and small beaker third is added and ethylene glycol 25ml is added；Step 4: the mixed liquor in beaker first is stirred
It mixes uniformly, is added drop-wise in beaker second, the mixed solution in beaker third is added drop-wise to dropwise in beaker second dropwise finally, process is added dropwise
Middle foundation solution colour is by being continuously improved mixing speed when limpid change milkiness, after lighter, then appropriate reduction mixing speed
Continue to stir.5min is stirred after being added dropwise to complete, and doping phosphoric acid titanium sodium porous nano crystalline substance mother liquor modulating liquid can be obtained.
The crystallization of porous nano crystal sodium ion electrolyte is handled: step 1: mother liquor modulating liquid is assigned to two
It in the reaction kettle of 100ml and seals, reaction kettle is placed in baking oven, be arranged to 140 DEG C of reaction 4h.Naturally cold after the reaction was completed
But.Step 2: product is removed liquid solvent by the way that centrifuge washing for several times is dry, it is finally placed in drying in 70 DEG C of baking oven,
The product obtained after drying is finally ground into 20min, aluminium doping phosphoric acid titanium natrium nanocrystalline powder, SEM figure and TEM can be obtained
Close in embodiment 1, crystallite dimension is 300nm or so.
After tested, aluminium doped micropore nanocrystalline solids electrolyte Na made from the present embodiment1.1Al0.1Ti1.9(PO4)3Room temperature
Lower conductivity is up to 1.423 × 10-4S·cm-1。
Embodiment 5
The modulation of porous nano crystalline substance mother liquor: it is added in small beaker first, adds step 1: weighing sodium acetate trihydrate 1.2mmol
Concentrated phosphoric acid 8ml and ethylene glycol 24ml, ultrasound is to being completely dissolved.Step 2: 10ml ethylene glycol is first added into large beaker second, then drip
Add weighed 1.8mmol titanium tetrachloride, with magnetic stirring apparatus uniform stirring and ethylene glycol is added dropwise dropwise and is settled to 60ml.Third
Step: it weighs aluminum nitrate 0.2mmol and small beaker third is added and ethylene glycol 25ml is added；Step 4: the mixed liquor in beaker first is stirred
It mixes uniformly, is added drop-wise in beaker second, the mixed solution in beaker third is added drop-wise to dropwise in beaker second dropwise finally, process is added dropwise
Middle foundation solution colour is by being continuously improved mixing speed when limpid change milkiness, after lighter, then appropriate reduction mixing speed
Continue to stir.5min is stirred after being added dropwise to complete, and doping phosphoric acid titanium sodium porous nano crystalline substance mother liquor modulating liquid can be obtained.
The crystallization of porous nano crystal sodium ion electrolyte is handled: step 1: mother liquor modulating liquid is assigned to two
It in the reaction kettle of 100ml and seals, reaction kettle is placed in baking oven, be arranged to 140 DEG C of reaction 3h.Naturally cold after the reaction was completed
But.Step 2: product is removed liquid solvent by the way that centrifuge washing for several times is dry, it is finally placed in drying in 70 DEG C of baking oven,
The product obtained after drying is finally ground into 20min, aluminium doping phosphoric acid titanium natrium nanocrystalline powder, SEM figure and TEM can be obtained
Close in embodiment 1, crystallite dimension is 300nm or so.
After tested, aluminium doped micropore nanocrystalline solids electrolyte Na made from the present embodiment1.2Al0.2Ti1.8(PO4)3Room temperature
Lower conductivity is up to 1.843 × 10-4S·cm-1。
Embodiment 6
The modulation of porous nano crystalline substance mother liquor: it is added in small beaker first, adds step 1: weighing sodium acetate trihydrate 1.4mmol
Concentrated phosphoric acid 8ml and ethylene glycol 24ml, ultrasound is to being completely dissolved.Step 2: 15ml ethylene glycol is first added into large beaker second, then drip
Add weighed 1.6mmol titanium tetrachloride, with magnetic stirring apparatus uniform stirring and ethylene glycol is added dropwise dropwise and is settled to 60ml.Third
Step: it weighs aluminum nitrate 0.4mmol and small beaker third is added and ethylene glycol 25ml is added；Step 4: the mixed liquor in beaker first is stirred
It mixes uniformly, is added drop-wise in beaker second, the mixed solution in beaker third is added drop-wise to dropwise in beaker second dropwise finally, process is added dropwise
Middle foundation solution colour is by being continuously improved mixing speed when limpid change milkiness, after lighter, then appropriate reduction mixing speed
Continue to stir.5min is stirred after being added dropwise to complete, and doping phosphoric acid titanium sodium porous nano crystalline substance mother liquor modulating liquid can be obtained.
The crystallization of porous nano crystal sodium ion electrolyte is handled: step 1: mother liquor modulating liquid is assigned to two
It in the reaction kettle of 100ml and seals, reaction kettle is placed in baking oven, be arranged to 140 DEG C of reaction 3h.Naturally cold after the reaction was completed
But.Step 2: product is removed liquid solvent by the way that centrifuge washing for several times is dry, it is finally placed in drying in 70 DEG C of baking oven,
The product obtained after drying is finally ground into 20min, aluminium doping phosphoric acid titanium natrium nanocrystalline powder, SEM figure and TEM can be obtained
Figure is close with embodiment 1, and crystallite dimension is 200~300nm.
After tested, aluminium doped micropore nanocrystalline solids electrolyte Na made from the present embodiment1.4Al0.4Ti1.6(PO4)3Room temperature
Lower conductivity is up to 2.356 × 10-4S·cm-1。
Embodiment 7
The modulation of porous nano crystalline substance mother liquor: it is added in small beaker first, adds step 1: weighing sodium acetate trihydrate 1.1mmol
Concentrated phosphoric acid 8ml and ethylene glycol 24ml, ultrasound is to being completely dissolved.Step 2: 11ml ethylene glycol is first added into large beaker second, then drip
Add weighed 2.0mmol titanium tetrachloride, with magnetic stirring apparatus uniform stirring and ethylene glycol is added dropwise dropwise and is settled to 60ml.Third
Step: it weighs lanthanum nitrate 0.1mmol and small beaker third is added and ethylene glycol 25ml is added；Step 4: the mixed liquor in beaker first is stirred
It mixes uniformly, is added drop-wise in beaker second, the mixed solution in beaker third is added drop-wise to dropwise in beaker second dropwise finally, process is added dropwise
Middle foundation solution colour is by being continuously improved mixing speed when limpid change milkiness, after lighter, then appropriate reduction mixing speed
Continue to stir.5min is stirred after being added dropwise to complete, and doping phosphoric acid titanium sodium porous nano crystalline substance mother liquor modulating liquid can be obtained.
The crystallization of porous nano crystal sodium ion electrolyte is handled: step 1: mother liquor modulating liquid is assigned to two
It in the reaction kettle of 100ml and seals, reaction kettle is placed in baking oven, be arranged to 140 DEG C of reaction 3h.Naturally cold after the reaction was completed
But.Step 2: product is removed liquid solvent by the way that centrifuge washing for several times is dry, it is finally placed in drying in 70 DEG C of baking oven,
The product obtained after drying is finally ground into 20min, La doped titanium phosphate natrium nanocrystalline powder, SEM figure and TEM can be obtained
Scheme, crystallite dimension 300nm close with embodiment 1.
After tested, La doped porous nano crystalline substance solid electrolyte Na made from the present embodiment1.1La0.1Ti1.9(PO4)3Room temperature
Lower conductivity is up to 5.201 × 10-4S·cm-1。
Embodiment 8
The modulation of porous nano crystalline substance mother liquor: it is added in small beaker first, adds step 1: weighing sodium acetate trihydrate 1.4mmol
Concentrated phosphoric acid 8ml and ethylene glycol 24ml, ultrasound is to being completely dissolved.Step 2: 12ml ethylene glycol is first added into large beaker second, then drip
Add weighed 1.6mmol titanium tetrachloride, with magnetic stirring apparatus uniform stirring and ethylene glycol is added dropwise dropwise and is settled to 60ml.Third
Step: it weighs lanthanum nitrate 0.4mmol and small beaker third is added and ethylene glycol 25ml is added；Step 4: the mixed liquor in beaker first is stirred
It mixes uniformly, is added drop-wise in beaker second, the mixed solution in beaker third is added drop-wise to dropwise in beaker second dropwise finally, process is added dropwise
Middle foundation solution colour is by being continuously improved mixing speed when limpid change milkiness, after lighter, then appropriate reduction mixing speed
Continue to stir.5min is stirred after being added dropwise to complete, and doping phosphoric acid titanium sodium porous nano crystalline substance mother liquor modulating liquid can be obtained.
The crystallization of porous nano crystal sodium ion electrolyte is handled: step 1: mother liquor modulating liquid is assigned to two
It in the reaction kettle of 100ml and seals, reaction kettle is placed in baking oven, be arranged to 140 DEG C of reaction 3h.Naturally cold after the reaction was completed
But.Step 2: product is removed liquid solvent by the way that centrifuge washing for several times is dry, it is finally placed in drying in 70 DEG C of baking oven,
The product obtained after drying is finally ground into 20min, La doped titanium phosphate natrium nanocrystalline powder, SEM figure and TEM can be obtained
Scheme, crystallite dimension 300nm close with embodiment 1.
After tested, La doped porous nano crystalline substance solid electrolyte Na made from the present embodiment1.4La0.4Ti1.6(PO4)3Room temperature
Lower conductivity is up to 3.274 × 10-4S·cm-1。
Embodiment 9
The modulation of porous nano crystalline substance mother liquor: it is added in small beaker first, adds step 1: weighing sodium acetate trihydrate 1.1mmol
Concentrated phosphoric acid 8ml and ethylene glycol 24ml, ultrasound is to being completely dissolved.Step 2: 13ml ethylene glycol is first added into large beaker second, then drip
Add weighed 2.0mmol titanium tetrachloride, with magnetic stirring apparatus uniform stirring and ethylene glycol is added dropwise dropwise and is settled to 60ml.Third
Step: it weighs di-iron trioxide 0.05mmol and small beaker third is added and ethylene glycol 25ml is added；Step 4: by the mixing in beaker first
Liquid stirs evenly, and is added drop-wise in beaker second dropwise, and finally the mixed solution in beaker third is added drop-wise to dropwise in beaker second, is added dropwise
In the process according to solution colour by mixing speed is continuously improved when limpid change milkiness, after lighter, then appropriate reduce is stirred
Speed continues to stir.5min is stirred after being added dropwise to complete, and doping phosphoric acid titanium sodium porous nano crystalline substance mother liquor modulating liquid can be obtained.
The crystallization of porous nano crystal sodium ion electrolyte is handled: step 1: mother liquor modulating liquid is assigned to two
It in the reaction kettle of 100ml and seals, reaction kettle is placed in baking oven, be arranged to 140 DEG C of reaction 3h.Naturally cold after the reaction was completed
But.Step 2: product is removed liquid solvent by the way that centrifuge washing for several times is dry, it is finally placed in drying in 70 DEG C of baking oven,
The product obtained after drying is finally ground into 30min, Fe2O3 doping titanium phosphate natrium nanocrystalline powder, SEM figure and TEM can be obtained
Figure is close with embodiment 1, and crystallite dimension is 100~160nm.
After tested, Fe2O3 doping porous nano crystalline substance solid electrolyte Na made from the present embodiment1.1Fe0.1Ti1.9(PO4)3Room temperature
Lower conductivity is up to 2.076 × 10-4S·cm-1。
Embodiment 10
The modulation of porous nano crystalline substance mother liquor: it is added in small beaker first, adds step 1: weighing sodium acetate trihydrate 1.4mmol
Concentrated phosphoric acid 8ml and ethylene glycol 24ml, ultrasound is to being completely dissolved.Step 2: 14ml ethylene glycol is first added into large beaker second, then drip
Add weighed 1.6mmol titanium tetrachloride, with magnetic stirring apparatus uniform stirring and ethylene glycol is added dropwise dropwise and is settled to 60ml.Third
Step: it weighs di-iron trioxide 0.2mmol and small beaker third is added and ethylene glycol 25ml is added；Step 4: by the mixing in beaker first
Liquid stirs evenly, and is added drop-wise in beaker second dropwise, and finally the mixed solution in beaker third is added drop-wise to dropwise in beaker second, is added dropwise
In the process according to solution colour by mixing speed is continuously improved when limpid change milkiness, after lighter, then appropriate reduce is stirred
Speed continues to stir.5min is stirred after being added dropwise to complete, and doping phosphoric acid titanium sodium porous nano crystalline substance mother liquor modulating liquid can be obtained.
The crystallization of porous nano crystal sodium ion electrolyte is handled: step 1: mother liquor modulating liquid is assigned to two
It in the reaction kettle of 100ml and seals, reaction kettle is placed in baking oven, be arranged to 140 DEG C of reaction 3h.Naturally cold after the reaction was completed
But.Step 2: product is removed liquid solvent by the way that centrifuge washing for several times is dry, it is finally placed in drying in 70 DEG C of baking oven,
The product obtained after drying is finally ground into 20min, Fe2O3 doping titanium phosphate natrium nanocrystalline powder, SEM figure and TEM can be obtained
Scheme, crystallite dimension 200nm close with embodiment 1.
After tested, Fe2O3 doping porous nano crystalline substance solid electrolyte Na made from the present embodiment1.4Fe0.4Ti1.6(PO4)3Room temperature
Lower conductivity is up to 1.372 × 10-4S·cm-1。
Comparative example
The modulation of porous nano crystalline substance mother liquor: it is added in small beaker first, adds dense step 1: weighing sodium acetate trihydrate 2mmol
Phosphoric acid 8ml and ethylene glycol 24ml, ultrasound is to being completely dissolved.Step 2: 15ml ethylene glycol is first added into large beaker second, then it is added dropwise
4mmol titanium tetrachloride is weighed, with magnetic stirring apparatus uniform stirring and ethylene glycol is added dropwise dropwise and is settled to 60ml.Step 3: will burn
Mixed liquor in cup first stirs evenly, and is added drop-wise in beaker second dropwise, according to solution colour by limpid change milkiness during dropwise addition
When mixing speed is continuously improved, after lighter, then the appropriate mixing speed that reduces continues to stir.It is stirred after being added dropwise to complete
5min can be obtained undoped with titanium phosphate sodium porous nano crystalline substance mother liquor modulating liquid.
The crystallization of porous nano crystal sodium ion electrolyte is handled: step 1: mother liquor modulating liquid is assigned to two
It in the reaction kettle of 100ml and seals, reaction kettle is placed in baking oven, be arranged to 140 DEG C of reaction 3h.Naturally cold after the reaction was completed
But.Step 2: product is removed liquid solvent by the way that centrifuge washing for several times is dry, it is finally placed in drying in 70 DEG C of baking oven,
The product obtained after drying is finally ground into 20min, can be obtained undoped with titanium phosphate natrium nanocrystalline powder, ac impedance spectroscopy
As shown in Figure 4.
After tested, undoped with porous nano crystalline substance solid electrolyte NaTi made from the present embodiment2(PO4)3Conductivity at room temperature
Up to 1.556 × 10-4S·cm-1。
By Na made from embodiment 101.4Fe0.4Ti1.6(PO4)3NaTi made from material and comparative example2(PO4)3Material difference
Be made electrode slice be assembled into button cell test, test result such as Fig. 5, button cell after 200 charge and discharge cycles,
Na1.4Fe0.4Ti1.6(PO4)3Material specific capacity maintains 100mAh/g or so, in contrast, NaTi2(PO4)3Material specific capacity is only
There is 75mAh/g or so, it is seen then that Na1.4Fe0.4Ti1.6(PO4)3The specific capacity of material has obvious rising, illustrates to receive with undoped with micropore
The brilliant electrolyte of rice is compared, and doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte is in sodium-ion battery, stability to be more
It is good.
Claims (9)
1. a kind of doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte, which is characterized in that the nanocrystalline electrolyte be metallic aluminium, lanthanum or
The titanium phosphate sodium nano material of Fe2O3 doping, general formula Na1+xMxTi2-x(PO4)3, wherein M is metallic aluminium, lanthanum or iron, the value of x
It is 0.1~0.4.
2. a kind of doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte preparation method described in claim 1, which is characterized in that packet
Include following steps:
Step 1, synthesis mother liquid: sodium salt and concentrated phosphoric acid, titanium material and lanthanum raw material, iron material or aluminum feedstock are dissolved in respectively to be had
Solvent obtains mixed solution A, mixed solution B and mixed solution C, mixed solution A and mixed solution C is successively added drop-wise to mixed
It closes in solution B, completes dropwise addition process under magnetic stirring apparatus uniform stirring to get immiscible material mother liquor is arrived；
Step 2, crystallization is handled: step 1 gained immiscible material mother liquor being added in reaction kettle, at a temperature of 130~160 DEG C
2~4h of hydro-thermal reaction, washing removal organic solvent, is dried to obtain solid electrolyte material after natural cooling.
3. doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte preparation method according to claim 2, which is characterized in that step
In rapid 1, the molar ratio of the lanthanum raw material, iron material or aluminum feedstock and titanium material, sodium salt and phosphate radical is 1~10:10~30:10
~35:10~50.
4. doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte preparation method according to claim 2, which is characterized in that step
In rapid 1, mass percent >=85wt% of the concentrated phosphoric acid.
5. doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte preparation method according to claim 2, which is characterized in that step
In rapid 1, the sodium salt is at least one of sodium acetate, sodium phosphate, disodium hydrogen phosphate or sodium carbonate.
6. doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte preparation method according to claim 2, which is characterized in that step
In rapid 1, the titanium material is at least one of butyl titanate, titanium tetrachloride or barium titanate.
7. doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte preparation method according to claim 2, which is characterized in that step
In rapid 1, the lanthanum raw material is at least one of lanthana, lanthanum acetate or lanthanum nitrate, and iron material is di-iron trioxide, tri-chlorination
At least one of iron or ferric nitrate, aluminum feedstock are at least one of aluminum nitrate, aluminium oxide or aluminum sulfate.
8. doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte preparation method according to claim 2, which is characterized in that step
In rapid 1, the organic solvent is ethylene glycol or polyethylene glycol.
9. the application that doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte described in claim 1 is used for solid-state sodium-ion battery.
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