CN101786611B - Method for preparing boron nitride nanotube by Fe3BO6 ammoniation - Google Patents

Method for preparing boron nitride nanotube by Fe3BO6 ammoniation Download PDF

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CN101786611B
CN101786611B CN2010101120534A CN201010112053A CN101786611B CN 101786611 B CN101786611 B CN 101786611B CN 2010101120534 A CN2010101120534 A CN 2010101120534A CN 201010112053 A CN201010112053 A CN 201010112053A CN 101786611 B CN101786611 B CN 101786611B
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boron nitride
boron
fe3bo6
tube
nitride nanotube
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CN101786611A (en
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谷云乐
吴林君
王吉林
张来平
钱琼丽
李婕
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Wuhan Institute of Technology
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Abstract

The invention relates to a method for preparing a boron nitride nanotube by Fe3BO6 ammoniation, comprising the following steps of: mixing raw materials of an iron-contained compound and a boron-contained compound by adopting a dry mixing process or a liquid phase compound process to obtain a raw material mixture; pressing and shaping the raw material mixture; then preserving heat and reacting to prepare Fe3BO6; directly ammoniating Fe3BO6; soaking obtained products by using concentrated hydrochloric acid; then carrying out centrifugal separation, washing and drying to obtain the boron nitride nanotube. The invention has the advantages that the preparation process of Fe3BO6 is simple, has low cost and is suitable for industrial production; prepared Fe3BO6 can be directly used for preparing high-purity boron nitride nanotube materials at low cost in bulk without a separation and purification process and; Fe3BO6 not only contains the boron element but also contains the iron element, and as a catalyst, a boron nitride nanotube powder the purity of which is higher than 90 percent is prepared, and the yield of the boron nitride nanotube is higher than 85 percent, thereby solving the problems of low yield and low purity of the boron nitride nanotube.

Description

Fe 3BO 6Ammonification prepares the method for boron nitride nano-tube
Technical field
The present invention relates to electrode material, nano material and field of ceramic material preparation, the concrete Fe that relates to 3BO 6Ammonification prepares the method for boron nitride nano-tube.
Background technology
In recent years, along with the proposition of social energy-conserving and environment-protective notion, the material of iron content has been caused especially various countries researchers' very big interest as the cathode material of second generation lithium ion battery.Wherein, Fe 3BO 6Be exactly one of desirable cathode material, this is because Fe 3BO 6In contain the Fe of excellent electro-chemical activity + 3With low weight B element.Discover Fe 3BO 6Lithium ion battery as the cathode material preparation has lower current potential (1.6V vs.Li/Li +), but have high capacitance (greater than 300mAh/kg).Owing to have unusual magneto-optic effect, the borate of iron always is the focus that people pay close attention in practical application and theoretical research field.In addition, Fe 3BO 6In the magnetoacoustics field relevant application prospect is arranged also.
Fe 3BO 6The preparation method mainly contain solid phase consolute method, rheological phase reaction method, chemical meteorological condensation method, chemical synthesis etc.Though in recent years at Fe 3BO 6Synthetic field has obtained certain success and progress, but complicated process of preparation, energy consumption height or productive rate are low usually.
Summary of the invention
Problem to be solved by this invention is to the deficiency of above-mentioned prior art a kind of Fe to be provided 3BO 6Ammonification prepares the method for boron nitride nano-tube, and wherein the preparation method is simple, and is with low cost, is fit to industrial mass manufacture.
The present invention is adopted solution to be by the problem of the above-mentioned proposition of solution: Fe 3BO 6Ammonification prepares the method for boron nitride nano-tube; It is characterized in that taking dry mixing process or liquid phase combination process to mix raw material iron containing compounds and boron-containing compound; Obtain mixed material, be pressed, prepared Fe in 5～90 minutes 700～900 ℃ of following insulation reaction then 3BO 6, directly with Fe 3BO 6800～1200 ℃ of following ammonifications 5～50 hours, products therefrom soaked through the concentrated hydrochloric acid of 35～38wt.% again, centrifugation then, and washing and dry can obtain boron nitride nano-tube.
Press such scheme, described iron containing compounds is any one in ferric nitrate, iron hydroxide and the iron chloride.
Press such scheme, described boron-containing compound is boric acid or boron oxide.
Press such scheme, the mol ratio of Fe in described iron containing compounds and the boron-containing compound: B is 3: 1.
Press such scheme, described boron oxide is an industrial goods diboron trioxide powder, and granularity is 100～300 orders.
Press such scheme, described dry mixing process is that load weighted raw material is added high speed mixer, mixes 3～30 minutes, and it is mixed.
Press such scheme, described liquid phase combination process is with the concentrated ammonia liquor that adds 25～28wt.% in the load weighted raw material, mixes and stirs 1～5 hour; The gained mixed liquor is poured in the cucurbit, utilized rotary evaporator, in 60～90 ℃ of water-baths; Distilled 4～12 hours, and took out pulverizing and get final product.
Press such scheme, described compression moulding technology is that mixed material is poured in the steel die, utilizes the pressurize 10～90 minutes of colding pressing of 500 tons of pressure of forcing press.
The present invention synthesizes Fe 3BO 6Chemical equation following:
H 3BO 3+3Fe(OH) 3＝Fe 3BO6+6H 2O
2H 3BO 3+6Fe(NO 3) 3·9H 2O+18NH 3·H 2O＝2Fe 3BO 6+9N 2+9O 2+102H 2O
H 3BO 3+3FeCl 3·7H 2O+9NH 3·H 2O＝Fe 3BO 6+13H 2O+9HCl+9NH 3
B 2O 3+6Fe(OH) 3＝2Fe 3BO 6+9H 2O
B 2O 3+6Fe(NO 3) 3·9H 2O+18NH 3·H 2O＝2Fe 3BO 6+9N 2+9O 2+99H 2O
B 2O 3+6FeCl 3·7H 2O+18NH 3·H 2O＝2Fe 3BO 6+51H 2O+18HCl+18NH 3
The reaction equation that the encapsulation steps of liquid phase combination process of the present invention relates to is exemplified below:
H 3BO 3+Fe 3++OH -→H 3BO 3Fe(OH) 3↓ (1)
Formula (1) is that boric acid and ferric nitrate and ammoniacal liquor are feedstock production Fe 3BO 6Reaction equation.At first boric acid and ferric nitrate are added in the distilled water, fully mix, add ammoniacal liquor then.Fe 3+With OH -In conjunction with generating Fe (OH) 3In the process of deposition, parcel suspended state boric acid, i.e. Fe 3+With OH -Reaction forms Fe (OH) 3, parcel H 3BO 3Particle and form deposition.
Synthetic Fe 3BO 6Reaction be exemplified below:
2H 3BO 3+6Fe(NO 3) 3·9H 2O+18NH 3·H 2O＝2Fe 3BO 6+9N 2+9O 2+102H 2O (2)
H 3BO 3+3Fe(OH) 3＝Fe 3BO 6+6H 2O (3)
Shown in (2)-(3), H 3BO 3Fe (OH) 3Coating is through the drying that dewaters, 700～900 ℃ of reactions, makes boric acid and Fe (OH) behind the briquetting 3React and form Fe 3BO 6Owing in the course of reaction N is arranged 2, O 2, H 2Gases such as O generate, and make Fe 3BO 6Product is sintered to the porous honeycomb solid.
Fe 3BO 6+4NH 3→BN+3Fe+6H 2O+3/2N 2 (4)
Ammonification generates the reaction of boron nitride nano-tube suc as formula shown in (4).Fe 3BO 6By the ammonia reduction, form boron nitride nano-tube, Fe, N 2, H 2O.
According to nanotube VLS catalytic growth mechanism, the catalyst Fe that in the aminating reaction system, is evenly distributed is or/and constitute the dynamic equilibrium system between the particle of multicomponent system [Fe-B-N], gas phase B* and N* atom and the solid phase boron nitride three.NH 3Reaction constantly produces B*, N* atomic time, and under iron particle or the effect of polynary particle as catalyst and shape template, balance moves to the boron nitride direction.The formation of boron nitride; Originally become the shell structurre of the multilayer type that is similar to fullerene in the catalyst granules superficial growth; Because the shape of catalyst particle can not be constant fully; Cause the solid phase boron nitride of catalyst pellets sub-surface to be grown and extension, thereby formed boron nitride nano-tube towards certain direction.
The raw material that the present invention is used removes B 2O 3Be outside the raw material of industry, iron containing compounds, boric acid and other reagent all are that analysis is pure, also can be chemically pure reagents.
Beneficial effect of the present invention is: the present invention adopts and mixes later on sintering again, or the compound knot prepared of reburning later of liquid phase has gone out the borate Fe of iron 3BO 6, preparation technology is simple, and is with low cost, is fit to suitability for industrialized production, prepared Fe 3BO 6Need not process for separating and purifying, can directly be used for low-cost prepared in batches high-purity nitrogenize boron nano-tube material, Fe 3BO 6Not only boracic but also contain ferro element as catalyst is prepared purity greater than 90% boron nitride nano-tube powder, and the boron nitride nano-tube yield has solved the difficult problem that the boron nitride nano-tube productive rate is little, purity is low greater than 85%.
Description of drawings
Fig. 1 is the Fe of embodiment 1 preparation 3BO 6XRD spectra;
Fig. 2 is the Fe of embodiment 1 preparation 3BO 6FTIR figure;
Fig. 3 is the XRD spectra of the boron nitride nano-tube of embodiment 5 preparations;
Fig. 4 is the SEM photo of the boron nitride nano-tube of embodiment 5 preparations;
Fig. 5 is the FTIR figure of the boron nitride nano-tube of embodiment 5 preparations.
The specific embodiment
Further introduce the present invention through embodiment below, but embodiment can not be construed as limiting the invention.Each cited in the technical scheme of the present invention raw material can both be realized the present invention, and the bound value of each raw material, interval value can both realize the present invention; Do not enumerate embodiment one by one at this.Bound value, the interval value of technological parameter of the present invention (like temperature, time and rotating speed etc.) can both be realized the present invention, do not enumerate embodiment one by one at this.
Embodiment 1
Adopt dried multifuel combustion knot prepared Fe 3BO 6, be feedstock production Fe with iron hydroxide and boric acid 3BO 6Technology, its first step batching: Fe (OH) 3And H 3BO 3All be AR, take by weighing 23.40g Fe (OH) 3, 4.51g H 3BO 3The second step batch mixing: load weighted raw material is added high speed mixer (18000 rev/mins), mixed 6 minutes, it is mixed; The 3rd one-step forming: compound is poured in the steel die, utilized 500 tons of forcing presses, pressurize 30 minutes; The 4th step sintering: the molding massive thing is put into retort, insert in the heating furnace of argon shield, be incubated 90 minutes down, take out weighing, obtain Fe in 700 ℃ 3BO 6Quality is 19.71g.
The X-ray diffraction analysis (XRD) of the gained sample that the present invention relates to is with XD-5A type x-ray powder diffraction instrument (30kV; 20mA; ), 2 θ are 10-80 ° of scope.Be EDS with the SEM of JSM-5510LV model and analyze, method for making sample is directly to adopt the product powder distribution on the double faced adhesive tape and be bonded on the sample copper platform and observe behind the metal spraying.Infrared spectrum analysis (FTIR) is with the sample preparation of KBr pressed disc method, adopts Impact 420 class infrared spectrometer to carry out the mapping of infrared spectrum.
Fig. 1 has provided Fe 3BO 6The XRD spectra of sample.With JCPDS standard card number (NO.73-1385) quadrature Fe mutually 3BO 6
The XRD diffraction maximum of crystal meets finely.By each crystal face d value of XRD, calculating the product lattice constant is a=1.0685nm, b=0.8594nm, and c=0.4481nm and standard card a=1.050nm, b=0.8550nm, c=0.4470nm conforms to basically, shows that product is quadrature phase Fe 3BO 6Crystal structure.
Table 1 is Fe 3BO 6The constituent content analysis of sample, its atomic ratio are Fe: B: O=3.06: 1: 6.20, and with Fe 3BO 6Theoretical atomic ratio (3: 1: 6) is approaching, shows that prepared sample is quadrature phase Fe 3BO 6
Table 1Fe 3BO 6The composition analysis of sample
Element (Element) Content (At%)
Fe 29.84
B 9.74
O 60.42
Fig. 2 is Fe 3BO 6The FTIR spectrogram of sample.Fe 3BO 6Structure and mineral Mg 3SiO 4(OH) 2Structural similarity contains [BO simultaneously 3] group and [BO 4] group, therefore, its infrared spectrum shows the characteristic absorption peak of the two simultaneously.Can know 649cm by spectrogram -1And 548cm -1The absworption peak of position is [BO 3] symmetrical stretching vibration of group.649cm -1The absworption peak at place is [BO 4] in-plane bending vibration of group.799cm -1The absworption peak at place is [BO 4] symmetrical stretching vibration of group.1025cm -1The absworption peak at place is [BO 4] asymmetric stretching vibration and the [BO of group 3] the coefficient result of symmetrical stretching vibration of group.1197cm -1The absworption peak of position is [BO 3] in-plane bending vibration of group.1459cm -1The absworption peak at place is [BO 3] the asymmetric stretching vibration of group.3215cm -1With the absworption peak of 2262 positions is because the hydrone due to the sample surfaces generation hydrolysis or the stretching vibration of OH key.
Embodiment 2
Adopt the complex sintered prepared Fe of liquid phase 3BO 6, with ferric nitrate (Fe (NO 3) 39H 2O) and boric acid (H 3BO 3) introduce Fe for raw material 3BO 6Preparation technology.First step batching: Fe (NO 3) 39H 2O and H 3BO 3All be AR, take by weighing 88.40gFe (NO 3) 39H 2O, 4.52g H 3BO 3The reaction of second step coats: load weighted material is poured in the 1000ml beaker, and adding the 50g mass fraction is 25～28% concentrated ammonia liquors, stirs 2 hours.The 3rd goes on foot the crushing process that dewaters: mixed liquor is poured in the cucurbit, utilized rotary evaporator, in 90 ℃ of water-baths, distilled 6 hours, take out and pulverize; The 4th one-step forming: compound is poured in the steel die, utilized 500 tons of forcing presses, pressurize 25 minutes; The 5th step sintering: the molding massive thing is put into retort, insert in the heating furnace of argon shield, be incubated 60 minutes down, take out weighing, obtain Fe in 800 ℃ 3BO 6Quality is 19.64g.
Embodiment 3
Adopt dried multifuel combustion knot prepared Fe 3BO 6, with iron hydroxide (Fe (OH) 3) and diboron trioxide (B 2O 3) introduce Fe for raw material 3BO 6Preparation technology.First step batching: Fe (OH) 3And B 2O 3(granularity 100～300 orders) all are AR, take by weighing 29.25g Fe (OH) 3, 3.20g B 2O 3The second step batch mixing: load weighted raw material is added high speed mixer (18000 rev/mins), mixed 8 minutes, it is mixed; The 3rd one-step forming: compound is poured in the steel die, utilized 500 tons of forcing presses, pressurize 20 minutes; The 4th step sintering: the molding massive thing is put into retort, insert in the heating furnace of argon shield, be incubated 45 minutes down, take out weighing, obtain Fe in 900 ℃ 3BO 6Quality is 24.41g.
Embodiment 4
Adopt the complex sintered prepared Fe of liquid phase 3BO 6, with iron chloride (FeCl 37H 2O) and boric acid (H 3BO 3) introduce Fe for raw material 3BO 6Preparation technology.First step batching: FeCl 37H 2O and H 3BO 3All be AR, take by weighing 79.02gFeCl 37H 2O, 5.64g H 3BO 3The reaction of second step coats: load weighted material is poured in the 1000ml beaker, and adding the 65g mass fraction is 25～28% concentrated ammonia liquors, stirs 3 hours.The 3rd goes on foot the crushing process that dewaters: mixed liquor is poured in the cucurbit, utilized rotary evaporator, in 80 ℃ of water-baths, distilled 8 hours, take out and pulverize; The 4th one-step forming: compound is poured in the steel die, utilized 500 tons of forcing presses, pressurize 20 minutes; The 5th step sintering reaction: the molding massive thing is put into retort, insert in the heating furnace of argon shield, be incubated 70 minutes down, take out weighing, obtain Fe in 850 ℃ 3BO 6Quality is 24.53g.
Embodiment 5
Adopt Fe 3BO 6The technology of preparation boron nitride nano-tube is got iron hydroxide (Fe (OH) 3) and boric acid (H 3BO 3) for preparing 19.71 according to embodiment 1 step, raw material restrains Fe 3BO 6In 1100 ℃ of aminating reactions 48 hours (perhaps 900 ℃ of aminating reactions 10 hours or 800 ℃ of aminating reactions are 30 hours), keeping the ammonia throughput is 0.3L/min, cools to room temperature with the furnace; Take out product with excessive 35wt.% salt soak; Through centrifugation, washing and dry, obtain white boron nitride nanometer pipe powder 1.52g again, calculating its yield is 85.1%.
Fig. 3 has provided the XRD spectra of boron nitride nano-tube sample.Meet finely with the XRD diffraction maximum of JCPDS standard card number (NO.45-1171) hexagonal boron nitride crystal.By each crystal face d value of XRD, calculating the product lattice constant is a=0.2505nm, c=1.0049nm, and with standard card a=0.2504nm, c=1.0000nm conforms to basically, shows that product is the hexagonal boron nitride structure.
Fig. 4 is the SEM photo of boron nitride nano-tube sample, and length of the scale is represented 1 μ m in the photo.Visible by photo, the boron nitride nanometer length of tube that is obtained greater than generally greater than 10 μ m, uniform diameter, external diameter is less than 150nm.The content of boron nitride nano-tube can estimate from photo that its content is greater than 90wt.%, and all the other are a spot of boron nitride fragment impurity.
Fig. 5 is the FTIR spectrogram of boron nitride nano-tube sample.As shown in the figure, significantly infrared absorption peak lays respectively at 3421,1379 and 801cm -1The absworption peak at three places.Be positioned at 1379cm -1And 801cm -1Absworption peak, then be respectively TO vibration mode and the flexural vibrations outward of N-B-N key face in the face of B-N key in the boron nitride.Hence one can see that, and product is a boron nitride.And be positioned at 3421cm -1The absworption peak at place is because the O-H and the N-H key chattering of sample surfaces adsorbed water.

Claims (4)

1.Fe 3BO 6Ammonification prepares the method for boron nitride nano-tube, it is characterized in that taking dry mixing process or liquid phase combination process to mix raw material iron containing compounds and boron-containing compound, and described dry mixing process is that load weighted raw material is added high speed mixer; Mixed 3～30 minutes, it is mixed, described liquid phase combination process is with the concentrated ammonia liquor that adds 25～28wt.% in the load weighted raw material; Mix and stirred 1～5 hour, the gained mixed liquor is poured in the cucurbit, utilize rotary evaporator; In 60～90 ℃ of water-baths, distilled 4～12 hours, take out pulverizing and get final product; Described iron containing compounds is any one in ferric nitrate, iron hydroxide and the iron chloride, and described boron-containing compound is boric acid or boron oxide, obtains mixed material; Be pressed, prepared Fe in 5～90 minutes 700～900 ℃ of following insulation reaction then 3BO 6, directly with Fe 3BO 6800～1200 ℃ of following ammonifications 5～50 hours, products therefrom soaked through the concentrated hydrochloric acid of 35～38wt.% again, centrifugation then, and washing and dry can obtain boron nitride nano-tube.
2. by the described Fe of claim 1 3BO 6Ammonification prepares the method for boron nitride nano-tube, and the mol ratio that it is characterized in that Fe in described iron containing compounds and the boron-containing compound: B is 3: 1.
3. by the described Fe of claim 1 3BO 6Ammonification prepares the method for boron nitride nano-tube, it is characterized in that described boron oxide is an industrial goods diboron trioxide powder, and granularity is 100～300 orders.
4. by the described Fe of claim 1 3BO 6Ammonification prepares the method for boron nitride nano-tube, it is characterized in that described compression moulding is that mixed material is poured in the steel die, utilizes the pressurize 10～90 minutes of colding pressing of 500 tons of pressure of forcing press.
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US20120237704A1 (en) 2011-03-17 2012-09-20 Honeywell Federal Manufacturing & Technologies, Llc Controlled lowering of a polymers glass transition temperature
CN105531223A (en) * 2013-06-14 2016-04-27 耶迪特普大学 A production method for the boron nitride nanotubes
CN107641789B (en) * 2016-07-22 2020-03-27 中国科学院苏州纳米技术与纳米仿生研究所 Boron nitride nanosheet continuous film, and preparation method and application thereof
CN107640751B (en) * 2016-07-22 2020-03-27 中国科学院苏州纳米技术与纳米仿生研究所 One-dimensional boron nitride nano material and preparation method thereof
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101580236A (en) * 2009-06-16 2009-11-18 武汉工程大学 Method for preparing boron nitride nanotubes by annealing of inorganic boracic precursor
CN101580235A (en) * 2009-06-17 2009-11-18 武汉工程大学 Process for purifying and recovering boron nitride nanotube crude product

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101580236A (en) * 2009-06-16 2009-11-18 武汉工程大学 Method for preparing boron nitride nanotubes by annealing of inorganic boracic precursor
CN101580235A (en) * 2009-06-17 2009-11-18 武汉工程大学 Process for purifying and recovering boron nitride nanotube crude product

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
C.C. Tang et al..Effective growth of boron nitride nanotubes.《Chemical Physics Letters》.2002,第356卷(第3-4期),254-258页.
C.C. Tang et al..Effective growth of boron nitride nanotubes.《Chemical Physics Letters》.2002,第356卷(第3-4期),254-258页. *
Hua Chen et al..Over 1.0 mm-long boron nitride nanotubes.《Chemical Physics Letters》.2008,第463卷(第1-3期),130-133页. *
徐丽娜等.氮化硼纳米管的研究进展.《应用化学》.2004,第21卷(第9期),872-877页. *

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