CN105800685B - A kind of regular octahedron shape is fluorinated the preparation method of bismuth material - Google Patents
A kind of regular octahedron shape is fluorinated the preparation method of bismuth material Download PDFInfo
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Abstract
The present invention relates to the preparation method that a kind of regular octahedron shape is fluorinated bismuth material, comprise the following steps：1) bismuth nitrate is dissolved in deionized water, adds concentrated nitric acid, prepare the bismuth nitrate solution that molar concentration is 45~55mM；2) sodium fluoride is dissolved in deionized water, adds polyvinylpyrrolidone, prepare the Fluorinse that molar concentration is 37.5~125mM；3) bismuth nitrate solution is added in Fluorinse, reaction is stood at 20~30 DEG C, be precipitated thing；Described bismuth nitrate solution is with the volume ratio of Fluorinse:1:3.5~4.5；4) by step 3) in obtain sediment filtering, washing, dry, that is, obtain regular octahedron shape fluorination bismuth material.This preparation method single step reaction can just synthesize regular octahedron shape fluorination bismuth material, cost-effective and environmental protection；Not only purity is high for product, and the homogeneous rule of appearance and size, is conducive to large-scale mass production from now on.
Description
Technical field
Preparation method the present invention relates to be fluorinated bismuth, and in particular to a kind of regular octahedron shape is fluorinated the preparation side of bismuth material
Method.
Background technology
In recent years, Bi based compounds are because noticeable with special layer structure and appropriately sized energy gap.
As a kind of metal fluoride positive electrode, BiF3Reacted by reversible transformation, obtain storage volume high.Although BiF3Matter
Amount specific energy is only 905Wh/kg, but its energy density per unit volume is up to 7170Wh/l.BiF3As a kind of typical ionic compound,
The positive electrode of secondary cell can be made with the elements doped lithium such as carbon and silver, and all chemical valences of material can be made full use of, so made
Have the advantages that exchange electronics is more, cell voltage is high and energy density is big in electrode process, more deep ground with to it
Study carefully, BiF3Will be as promising lithium ion secondary battery anode material of new generation.
At present, BiF is prepared3Method be typically oxide/sulfide/hydroxide of bismuth (III) etc. in HF atmosphere
Gas-solid phase reaction is carried out, or at a certain temperature, F2There is gas-solid phase reaction by bismuth metal powder in gas.This kind of reaction consumption
When, power consumption and environmental pollution it is big, thus valuable product.Additionally, chelating the bismuth (III) in five water bismuth nitrates by mannitol
Ion separates out bismuth hydroxide in alkaline solution, and bismuth hydroxide stirs 12h in HF solution and solid-liquid reaction generation BiF occurs3's
It is feasible on theoretical method, but actual yield is very low, and impurity is more and product is unstable.
Chinese invention patent (CN 101212050A) discloses a kind of preparation side of bismuth trifluoride anode material of Li secondary battery
Method, specifically includes and for bismuth salt to be dissolved in acetum preparation bismuth salt acetum, adds surfactant；Soluble fluoride is prepared simultaneously
Salt or HF ethanol waters, obtain alcohol fluorine mixed solution；Mix two kinds of solution at 0~45 DEG C and obtain BiF3Sediment, then mistake
Filter washing is dried, and obtains BiF3Product, but the preparation method can not obtain the fluorination bismuth of specific morphology.Therefore at present,
Not yet it is related to prepare at room temperature the report of the synthetic technology that regular octahedron is fluorinated bismuth material.
The content of the invention
The purpose of the present invention is to solve the shortcomings of the prior art, there is provided one kind being capable of the positive octahedral of one-step synthesis at room temperature
Body shape is fluorinated the preparation method of bismuth material.
Technical scheme provided by the present invention is：
A kind of regular octahedron shape is fluorinated the preparation method of bismuth material, comprises the following steps：
1) bismuth nitrate is dissolved in deionized water, adds concentrated nitric acid, prepare the bismuth nitrate that molar concentration is 45~55mM molten
Liquid；
2) sodium fluoride is dissolved in deionized water, adds polyvinylpyrrolidone, preparation molar concentration is 37.5~125mM
Fluorinse；
3) bismuth nitrate solution is added in Fluorinse, reaction is stood at 20~30 DEG C, be precipitated thing；Described
Bismuth nitrate solution is with the volume ratio of Fluorinse:1:3.5~4.5；
4) by step 3) in obtain sediment filtering, washing, dry, that is, obtain regular octahedron shape fluorination bismuth material.
In above-mentioned technical proposal, reacted using water solution system at room temperature, using bismuth nitrate as bismuth source, sodium fluoride is made
It is Fluorine source, while concentrated nitric acid and polyvinylpyrrolidone are added, by controlling raw material type, concentration, reaction temperature and solution
Between volume ratio, can obtain pattern, size uniformity rule regular octahedron.The simplification of preparation method is realized, is not required to
To use any firing equipment, it is to avoid energy waste；The surfactant for not using strong toxicity, price high, it is cost-effective simultaneously
And environmental protection；Wherein bismuth nitrate is common bismuth salt, and sodium fluoride is common villiaumite, and both of which cost is relatively low, prepares gained
Regular octahedron shape fluorination bismuth material purity is high, is conducive to large-scale mass production from now on.
Preferably, described step 1) in the volume ratio of bismuth nitrate solution and concentrated nitric acid be 20:1.2~0.8.Add dense
Nitric acid is conducive to the dissolving in deionized water of bismuth nitrate crystal, at the same neutralize sodium fluoride it is soluble in water and produce alkalescence, make
Obtain solution and be in neutral state, be conducive to octahedral formation.
Preferably, described step 2) in polyvinylpyrrolidone mass concentration be 6.2~37.5g/L.Add
Polyvinylpyrrolidone is a kind of good dispersant, can effectively control being uniformly distributed for nucleus, it is to avoid reunited so that octahedra
Can equably grow.
Preferably, described step 1) in prepare bismuth nitrate solution concentration be 48~53mM.
Preferably, described step 2) in prepare Fluorinse concentration be 60~125mM.
Preferably, described step 4) in sediment by respectively washing 3~5 times of deionized water and absolute ethyl alcohol.
Preferably, described step 1) in prepare bismuth nitrate solution concentration be 48~52mM, bismuth nitrate solution with
The volume ratio of concentrated nitric acid is 20:1.1~0.9；Described step 2) in prepare Fluorinse concentration be 100~125mM,
The mass concentration of polyvinylpyrrolidone is 20~30g/L；Described bismuth nitrate solution is with the volume ratio of Fluorinse:1:
3.8~4.2.In above-mentioned technical proposal, the concentration of the bismuth nitrate solution for being used, the volume ratio of bismuth nitrate solution and concentrated nitric acid,
The technological parameter such as the concentration of Fluorinse and the mass concentration of polyvinylpyrrolidone mutually cooperates with, influences each other so that
The product regular octahedron shape of gained is fluorinated pattern, the more homogeneous rule of size of bismuth material, and purity is higher.
As further preferred, described step 3) in stir standing reaction 4~6 days.
Compared with the existing technology, beneficial effects of the present invention are embodied in：
(1) preparation method provided by the present invention only needs to single step reaction at ambient temperature can just synthesize regular octahedron shape
Fluorination bismuth material；
(2) preparation method provided by the present invention need not use any firing equipment, it is to avoid energy waste；Do not use
Strong toxicity, price surfactant high, cost-effective and environmental protection；
(3) not only purity is high to prepare gained regular octahedron shape fluorination bismuth material, and the homogeneous rule of appearance and size, is conducive to
Large-scale mass production from now on.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum that the regular octahedron shape that embodiment 1 is prepared is fluorinated bismuth material；
Fig. 2 is the scanning electron microscope (SEM) photograph of 12000 times of the regular octahedron shape fluorination bismuth material that embodiment 1 is prepared；
Fig. 3 is the scanning electron microscope (SEM) photograph of 50000 times of the regular octahedron shape fluorination bismuth material that embodiment 1 is prepared；
Fig. 4 is the transmission electron microscope picture that the regular octahedron shape that embodiment 1 is prepared is fluorinated bismuth material；
Fig. 5 is the scanning electron microscope (SEM) photograph of 12000 times of the regular octahedron shape fluorination bismuth material that embodiment 2 is prepared；
Fig. 6 is the scanning electron microscope (SEM) photograph of 24000 times of the regular octahedron shape fluorination bismuth material that embodiment 3 is prepared；
Fig. 7 is the scanning electron microscope (SEM) photograph of 24000 times of the regular octahedron shape fluorination bismuth material that embodiment 4 is prepared；
Fig. 8 is the scanning electron microscope (SEM) photograph of 24000 times of the material that comparative example 1 is prepared；
Fig. 9 is the scanning electron microscope (SEM) photograph of 8000 times of the material that comparative example 2 is prepared；
Figure 10 is the scanning electron microscope (SEM) photograph of 6000 times of the material that comparative example 3 is prepared；
Figure 11 is the scanning electron microscope (SEM) photograph of 15000 times of the material that comparative example 4 is prepared；
Figure 12 is the scanning electron microscope (SEM) photograph of 20000 times of the material that comparative example 5 is prepared.
Specific embodiment
With reference to embodiment, the present invention will be further described：
The present invention is using Normal Temperature Hydrolysis synthesis, and it is pure that agents useful for same is analysis.
The crystal phase structure of sample is analyzed using Rigaku D/max-rB rotary anodes x-ray diffractometer, X-ray is Cu
Target K α (λ=0.15406nm), voltage 45kV, electric current 40mA；Slit DS:1 °, SS:1 °, RS:1°；Step-length：0.02°；Scanning model
Enclose 10 ° -90 °；5 °/min of sweep speed.The pattern of sample is observed by the type SEM of FEI-Quanta FEG 650.
Embodiment 1
By 0.485g Bi (NO3)3·5H2O is dissolved in the deionized water of 19ml, adds 1ml HNO3, it is configured to concentration
It is the bismuth nitrate solution of 50mM；0.42g NaF are dissolved in the deionized water of 80ml, 2g PVP are added, being configured to concentration is
The Fluorinse of 0.125M；Bismuth nitrate solution is added in Fluorinse, reaction 5 days are stood after stirring；To obtain
Sediment respectively with respectively cleaning 3 times of deionized water and absolute ethyl alcohol, 60 DEG C dry 12h in air dry oven, that is, obtain positive eight
Face body shape fluorination bismuth material.
Align octahedral shape fluorination bismuth material carry out X-ray diffraction analysis, as a result as shown in figure 1, prepare fluorination bismuth into
It is part single, belong to centroid cubic crystal system (JCPDS 51-0944), Fm3m space groups, and with crystallinity very high.
Align octahedral shape fluorination bismuth material and be scanned electronic microscope photos, as shown in Figures 2 and 3, sample prepared by embodiment 1
It is made up of the micro nano structure of regular octahedron, regular octahedron structural style is single, uniform, rule.Shone from high power ESEM
Piece can be seen that every piece of octahedral length of side and be about~2 μm.Embodiment 1 is can be seen that from the transmission electron microscope photo of Fig. 4 samples
The sample of preparation is solid construction.
Embodiment 2
By 0.485g Bi (NO3)3·5H2O is dissolved in the deionized water of 19ml, adds 1ml HNO3, it is configured to concentration
It is the bismuth nitrate solution of 50mmol/L；0.42g NaF are dissolved in the deionized water of 80ml, 0.5g PVP are added, is configured to
Concentration is the NaF solution of 0.125mol/L；Bismuth nitrate solution is added in Fluorinse, is stood at 25 DEG C after stirring
Reaction 5 days；The sediment that will be obtained is respectively with respectively cleaning 3 times, 60 DEG C of dryings in air dry oven of deionized water and absolute ethyl alcohol
12h, that is, obtain regular octahedron shape fluorination bismuth material.Electronic microscope photos is scanned to products obtained therefrom, as shown in figure 5, by positive octahedral
The micro nano structure composition of body, regular octahedron structural style is single, uniform, rule.
Embodiment 3
By 0.485g Bi (NO3)3·5H2O is dissolved in the deionized water of 19ml, adds 1ml HNO3, it is configured to concentration
It is the bismuth nitrate solution of 50mmol/L；0.42g NaF are dissolved in the deionized water of 80ml, 3g PVP are added, is configured to dense
Spend the NaF solution for 0.125mol/L；Bismuth nitrate solution is added in Fluorinse, is stood instead at 25 DEG C after stirring
Answer 5 days；The sediment that will be obtained is respectively with respectively cleaning 3 times, 60 DEG C of dryings in air dry oven of deionized water and absolute ethyl alcohol
12h, that is, obtain regular octahedron shape fluorination bismuth material.Electronic microscope photos is scanned to products obtained therefrom, as shown in fig. 6, by positive octahedral
The micro nano structure composition of body, regular octahedron structural style is single, uniform, rule.
Embodiment 4
By 0.485g Bi (NO3)3·5H2O is dissolved in the deionized water of 19ml, adds 1ml HNO3, it is configured to concentration
It is the bismuth nitrate solution of 50mmol/L；0.126g NaF are dissolved in the deionized water of 80ml, 2g PVP are added, is configured to dense
Spend the NaF solution for 0.0375mol/L；Bismuth nitrate solution is added in Fluorinse, is stood at 25 DEG C after stirring
Reaction 5 days；The sediment that will be obtained is respectively with respectively cleaning 3 times, 60 DEG C of dryings in air dry oven of deionized water and absolute ethyl alcohol
12h, that is, obtain regular octahedron shape fluorination bismuth material.Electronic microscope photos is scanned to products obtained therefrom, as shown in fig. 7, by positive octahedral
The micro nano structure composition of body, regular octahedron structural style is single, uniform, rule.
Comparative example 1
By 0.485g Bi (NO3)3·5H2O is dissolved in the deionized water of 19ml, adds 1ml HNO3, it is configured to concentration
It is the bismuth nitrate solution of 50mmol/L；0.084g NaF are dissolved in the deionized water of 80ml, 2g PVP are added, is configured to dense
Spend the NaF solution for 0.025mol/L；Bismuth nitrate solution is added in Fluorinse, is stood instead at 25 DEG C after stirring
Answer 5 days；The sediment that will be obtained is respectively with respectively cleaning 3 times, 60 DEG C of dryings in air dry oven of deionized water and absolute ethyl alcohol
12h.Electronic microscope photos is scanned to products obtained therefrom, as shown in figure 8, pattern is essentially the micro nano structure composition of regular octahedron,
But there is cotton-shaped or membranaceous impurity, regular octahedron corner angle fuzzy, the no longer homogeneous rule of pattern, mainly due to fluorination in surface
The concentration of sodium solution reduces, bismuth nitrate solution excess.
Comparative example 2
By 0.485g Bi (NO3)3·5H2O is dissolved in the deionized water of 19ml, adds 1ml HNO3, it is configured to concentration
It is the bismuth nitrate solution of 50mmol/L；0.84g NaF are dissolved in the deionized water of 80ml, 2g PVP are added, is configured to dense
Spend the NaF solution for 0.25mol/L；Bismuth nitrate solution is added in Fluorinse, is stood instead at 25 DEG C after stirring
Answer 5 days；The sediment that will be obtained is respectively with respectively cleaning 3 times, 60 DEG C of dryings in air dry oven of deionized water and absolute ethyl alcohol
12h.Electronic microscope photos is scanned to products obtained therefrom, as shown in figure 9, the pattern of gained is no longer regular octahedron, main cause exists
It is excessive in the concentration of Fluorinse, influence the growth of regular octahedron pattern.
Comparative example 3
By 0.485g Bi (NO3)3·5H2O is dissolved in the deionized water of 19ml, adds 1ml HNO3, it is configured to concentration
It is the bismuth nitrate solution of 50mmol/L；By 0.37g NH4F is dissolved in the deionized water of 80ml, adds 2g PVP, is configured to dense
Spend the NH for 0.125mol/L4F solution；Bismuth nitrate solution is added in ammonium fluoride solution, is stood at 25 DEG C after stirring
Reaction 5 days；The sediment that will be obtained is respectively with respectively cleaning 3 times, 60 DEG C of dryings in air dry oven of deionized water and absolute ethyl alcohol
12h.Electronic microscope photos is scanned to products obtained therefrom, as shown in Figure 10, the pattern of gained is no longer regular octahedron, and main cause exists
Ammonium fluoride is selected in Fluorine source, and ammonium salt can influence octahedral formation with acidity.
Comparative example 4
By 0.485g Bi (NO3)3·5H2O is dissolved in the deionized water of 19ml, adds 1ml HNO3, it is configured to concentration
It is the bismuth nitrate solution of 50mmol/L；0.42g NaF are dissolved in the deionized water of 80ml, 2g PVP are added, is configured to dense
Spend the NaF solution for 0.125mol/L；Bismuth nitrate solution is added in Fluorinse, is stood instead at 35 DEG C after stirring
Answer 5 days；The sediment that will be obtained is respectively with respectively cleaning 3 times, 60 DEG C of dryings in air dry oven of deionized water and absolute ethyl alcohol
12h.Electronic microscope photos is scanned to products obtained therefrom, as shown in figure 11, pattern is essentially the micro nano structure composition of regular octahedron,
But depression, breach occurs in regular octahedron surface, main reason is that standing reaction temperature is too high, regular octahedron pattern is had influence on
Nucleation and slow growth.
Comparative example 5
By 0.485g Bi (NO3)3·5H2O is dissolved in the deionized water of 19ml, adds 0.6ml HNO3, it is configured to dense
Spend the bismuth nitrate solution for 50mmol/L；0.42g NaF are dissolved in the deionized water of 80ml, 2g PVP are added, is configured to
Concentration is the NaF solution of 0.125mol/L；Bismuth nitrate solution is added in Fluorinse, is stood at 25 DEG C after stirring
Reaction 5 days；The sediment that will be obtained is respectively with respectively cleaning 3 times, 60 DEG C of dryings in air dry oven of deionized water and absolute ethyl alcohol
12h.Electronic microscope photos is scanned to products obtained therefrom, as shown in figure 12, the pattern of gained is spherical, the HNO that main cause is added3
It is very few so that solution alkaline, influence octahedral growth.
Claims (7)
1. a kind of regular octahedron shape is fluorinated the preparation method of bismuth material, it is characterised in that comprise the following steps：
1) bismuth nitrate is dissolved in deionized water, adds concentrated nitric acid, prepare the bismuth nitrate solution that molar concentration is 45~55mM；
2) sodium fluoride is dissolved in deionized water, adds polyvinylpyrrolidone, prepare the fluorine that molar concentration is 37.5~125mM
Change sodium solution；The mass concentration of described polyvinylpyrrolidone is 6.2~37.5g/L；
3) bismuth nitrate solution is added in Fluorinse, reaction is stood at 20~30 DEG C, be precipitated thing；Described nitric acid
Bismuth solution is with the volume ratio of Fluorinse:1:3.5~4.5；
4) by step 3) in obtain sediment filtering, washing, dry, that is, obtain regular octahedron shape fluorination bismuth material.
2. regular octahedron shape according to claim 1 is fluorinated the preparation method of bismuth material, it is characterised in that described step
1) bismuth nitrate solution and the volume ratio of concentrated nitric acid are 20 in:1.2~0.8.
3. regular octahedron shape according to claim 1 is fluorinated the preparation method of bismuth material, it is characterised in that described step
1) concentration of the bismuth nitrate solution prepared in is 48~53mM.
4. regular octahedron shape according to claim 1 is fluorinated the preparation method of bismuth material, it is characterised in that described step
2) concentration of the Fluorinse prepared in is 60~125mM.
5. regular octahedron shape according to claim 1 is fluorinated the preparation method of bismuth material, it is characterised in that described step
4) sediment is by respectively washing 3~5 times of deionized water and absolute ethyl alcohol in.
6. regular octahedron shape according to claim 1 is fluorinated the preparation method of bismuth material, it is characterised in that described step
1) concentration of the bismuth nitrate solution prepared in is 48~52mM, and bismuth nitrate solution is 20 with the volume ratio of concentrated nitric acid:1.1~0.9；
Described step 2) in the concentration of Fluorinse prepared be 100~125mM, the mass concentration of polyvinylpyrrolidone is 20
~30g/L；Described bismuth nitrate solution is with the volume ratio of Fluorinse:1:3.8~4.2.
7. the regular octahedron shape according to claim 1 or 6 is fluorinated the preparation method of bismuth material, it is characterised in that described
Step 3) in stir standing reaction 4~6 days.
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