CN109306551A - A kind of boron doped titanic oxide nanofiber and preparation method thereof and application as lithium ion battery negative material - Google Patents
A kind of boron doped titanic oxide nanofiber and preparation method thereof and application as lithium ion battery negative material Download PDFInfo
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Abstract
The invention discloses a kind of boron doped titanic oxide nanofiber and preparation method thereof and as the application of lithium ion battery negative material.The diameter of boron doped titanic oxide nanofiber is nano-scale, length is micron-scale, and surface contains micropore.Preparation method is that ethyl alcohol, acetic acid, butyl titanate, butyl borate and polyvinylpyrrolidone mixed dissolution are obtained spinning solution;The spinning solution obtains polymer nanofiber by electrostatic spinning process;The polymer nanofiber obtains Detitanium-ore-type boron doped titanic oxide nanofiber, large specific surface area is conducive to the infiltration of electrolyte and the transmission of lithium ion, and boron doping is uniform, shows better electro-chemical activity by drying and calcination;It is used for lithium ion battery and shows excellent high rate performance and cycle performance.
Description
Technical field
The present invention relates to a kind of boron doped titanic oxide materials, and in particular to a kind of nanometer fibrous boron doping titanium dioxide
Titanium material further relates to a kind of method for preparing boron doped titanic oxide nanofiber by electrostatic spinning process.And B doping
TiO2Application of the nanofiber in high magnification long circulating lithium ion battery, belongs to lithium ion technical field of electronic materials.
Background technique
Negative electrode material used in commercial Li-ion battery is all graphite carbon material mostly, but graphite cathode material
Because intercalation potential is low, potential μAIt is minimum higher than the electronics of common electrolyte not occupy track (LUMO), SEI film easy to form,
Surface forms Li dendrite, causes security risk, and graphite surface defect is high again, and anisotropic character limits lithium ion in structure
Free diffusing in graphite-structure, big high rate performance is poor, requires to have on the fast charge and discharge product of high power in current EVs/HEVs etc.
Stern challenge.TiO2As lithium ion battery negative material, have that discharge platform high (1.7V), volume expansion is small (is less than
4%) the advantages that, environmentally protective at low cost.High intercalation potential can effectively avoid negative terminal surface and generate Li dendrite, to bring more
Add safe performance;Small cubic deformation makes material more stable during lithium ion deintercalation, to have longer make
With the service life, therefore TiO2Material is referred to as the most possible negative electrode material for replacing commercial graphite class material.
But TiO2Because itself poor electric conductivity limits its application in commercialization with due to leading lithium performance, in research
Common improved method has: 1. preparation nanometers or porous material;2. compound with the high conductive materials such as graphene, carbon nanotube;3.
It is doped with other metal ions, reduces TiO2Band gap width, so as to improve the electric conductivity of itself.The third method
It is middle to be doped preparation TiO with other metal ions2Nano material is referred to as most effective ameliorative way.By literature survey point
Analysis is learnt, finds existing Cr, Mo6+、Nb、Zr、Co、La、Mn、Fe、N、Sb、Ti3+、Ni、Sm3+Equal element dopings go to improve TiO2
Performance in lithium ion battery, but with B to TiO2The research being doped is very few, more has no that B adulterates TiO2Nanofiber.
Chinese patent (CN 103618076A) discloses a kind of boron doping sub-micron ball TiO2Electrode material and preparation method thereof and in lithium
Application in ion battery, electrode material TiO2Sub-micron ball electrode material, sub-micron ball is by rutile TiO2Nano particle
Composition has excellent electric conductivity and high rate performance as electrode material, but its cycle performance is to be improved.
Summary of the invention
For defect existing for boron doped titanic oxide material in the prior art, the first purpose of this invention is to be to mention
For a kind of boron doped anatase titanium dioxide material with nanometer fibrous pattern, boron doped titanic oxide material tool
There are nano-sized diameters and micron-scale length, and surface is rich in micropore, large specific surface area is conducive to infiltration and the lithium of electrolyte
The transmission of ion, and boron doping is uniform, titanium dioxide is Detitanium-ore-type, shows better electro-chemical activity.
Second object of the present invention is to be to provide a kind of easy to operate, at low cost to prepare the boron doping titanium dioxide
The method of titanium material, this method is realized using electrostatic spinning process, is conducive to industrialized production.
Third object of the present invention is to be to provide the application of the boron doped titanic oxide nanofiber, as
Lithium ion battery negative material application can obtain cycle performance and the superior lithium ion battery of high rate performance.
In order to achieve the above technical purposes, a diameter of the present invention provides a kind of boron doped titanic oxide nanofiber
Nano-scale, length are micron-scale, and surface contains micropore.
Boron doped titanic oxide material of the invention has nano-sized diameters and micron-scale length, and surface is rich in micro-
Hole substantially increases specific surface area, is used for lithium ion battery, is conducive to the infiltration of electrolyte and the transmission of lithium ion.
Preferred scheme, the molar ratio of titanium and boron is 10:1~10 in the boron doped titanic oxide nanofiber.
More preferably scheme, titanium dioxide is anatase crystal in the boron doped titanic oxide nanofiber.Anatase
The TiO of type2With higher embedding lithium coefficient, chemical property will be substantially better than rutile TiO2。
More preferably scheme, the diameter of the boron doped titanic oxide nanofiber is between 50~300nm, and length is 1
Between~100 microns.
The present invention provides a kind of preparation method of boron doped titanic oxide nanofiber, this method be by ethyl alcohol, acetic acid,
Butyl titanate, butyl borate and polyvinylpyrrolidone mixed dissolution obtain spinning solution;The spinning solution passes through Static Spinning
Silk technique, obtains polymer nanofiber;The polymer nanofiber obtains boron doped titanic oxide by drying and calcination
Nanofiber.
Technical solution of the present invention can not only obtain the boron doping two of nanometer fibrous pattern by electrostatic spinning process
Titanium oxide, and B can be obtained and adulterate more uniform titanium dioxide nano material.Polyvinylpyrrolidine during electrostatic spinning
Ketone plays an important role, and using its pyrrole group come coordination of metal ion, to play template action, is conducive to generate and receive
Rice threadiness B is titania-doped, meanwhile, the doping in situ of boron element is realized, to obtain the B doping two of doping more evenly
TiOx nano fibrous material.Relatively existing coprecipitation has apparent technical advantage.Polyvinylpyrrolidone is subsequent
Calcination process in remove, micropore can be formed on the titania-doped surface nanometer fibrous B, can be further improved material
Specific surface area, be more conducive to the infiltration of electrolyte and the transmission of lithium ion.
Preferred scheme, the mass ratio of ethyl alcohol, acetic acid and butyl titanate are (8~12): (1~3): 4.
The molar ratio of preferred scheme, butyl titanate and butyl borate is 10:1~10.More be selected as 10:1.5~
2.5, B element doping can inhibit crystal to grow up and change crystal structure to a certain extent, thus to the size and shape that make material
Some variations occur for looks, and when doping ratio is 10:2 or so, the boron doped titanic oxide nanofiber of preparation has bigger ratio
Surface area.
Preferred scheme, concentration of the polyvinylpyrrolidone in spinning solution are 0.04~0.06g/mL.When polyethylene pyrrole
When pyrrolidone concentration is too low, viscosity is too low, and when spinning can not form stable injection stream, and be easy to get the fiber for having pearl to save;When poly- second
When alkene pyrrolidone excessive concentration, viscosity is too big, and spinning solution cannot flow, and condenses easily at capillary exit, and spinning can not carry out.
Preferred scheme, the condition of the electrostatic spinning process are as follows: voltage is 18~20KV, and fltting speed is 1~3mL/
H, temperature are 25~60 DEG C, and ambient humidity is 10~30%.
Preferred scheme, the condition of the calcining are as follows: calcined 2~4 hours at 450~600 DEG C.When sintering temperature is too low,
When lower than 450 DEG C, phase change transition is not perfect, and the anatase purity of formation is low;When sintering temperature is crossed higher than 600 DEG C, anatase
Start to change to rutile.
The present invention also provides a kind of applications of boron doped titanic oxide nanofiber, as ion cathode material lithium
Using.
B of the invention adulterates TiO2The preparation method of nanofiber, comprising the following specific steps
1) dehydrated alcohol, acetic acid, butyl titanate and butyl borate are uniformly mixed, obtain presoma mixed liquor A,
The mass ratio of middle ethyl alcohol, acetic acid and butyl titanate is 10:3:4, wherein the molar ratio of butyl titanate and butyl borate is
10:1~10:10;
2) stirring in precursor liquid is added in polyvinylpyrrolidone to make it completely dissolved to obtain spinning solution;Wherein polyethylene
The ratio of pyrrolidones and precursor liquid is 0.05g/mL;Spinning solution is placed on electrostatic spinning machine, temperature is 30 DEG C, environmental wet
Degree is 20%, applies 19KV voltage, carries out spinning with the fltting speed of 2mL/h, obtains polymer nanofiber;
3) polymer nanofiber is dried for 24 hours at 80 DEG C, places in Muffle furnace and calcines 3 hours for 550 DEG C, obtain B doping
TiO2Nano-fiber material;
4) B of the invention adulterates TiO2The method that nanofiber is used to prepare lithium ion battery negative material: B is adulterated
TiO2Nano-fiber material is that 7:2:1 matches slurry according to mass ratio with acetylene black and PVDF, obtains B after coating drying and adulterates TiO2
Nanofiber anode material.
Compared with the prior art, technical solution of the present invention bring advantageous effects:
1) B of the invention adulterates TiO2With special nanofiber pattern, diameter is long within the scope of 50~300nm
Degree is about tens microns, and nanofiber surface makes it possess bigger specific surface area, be more conducive to there are many micropores
The infiltration of electrolyte and the transmission of lithium ion.
2) B of the invention adulterates TiO2Boron doping is uniform in nanofiber, can preferably improve TiO2Electric conductivity,
To show better chemical property.
3) present invention prepares B doping TiO by electrostatic spinning process2Nanofiber, it is easy to operate, and can be by existing
There is mature industrial equipment, cost is relatively low, is conducive to industrialized production.
4) B of the invention adulterates TiO2The relatively existing TiO of nanofiber2Or B adulterates TiO2, make in lithium ion battery
Used time shows better chemical property, and charging and discharging currents are big, and cycle-index is more, and good rate capability is specific as follows:
In terms of circulation, recycled under 2000mA/g electric current 5000 capacity be 167mAh/g, especially optimum condition under,
Recycling 8000 times still has 150mAh/g capacity, and current other are superior on the high current long-life and facilitate the anatase of preparation
TiO2。
On high rate performance, under 4A/g charging or discharging current, capacity still has 150mAh/g capacity.
Detailed description of the invention
[Fig. 1] is process flow chart of the invention;
[Fig. 2] is different proportion B doping TiO2The XRD analysis map of nanofiber;
[Fig. 3] is different proportion B doping TiO2The SEM of nanofiber schemes;
[Fig. 4] is different proportion B doping TiO2The XPS of nanofiber schemes;
[Fig. 5] is different proportion B doping TiO2The N of nanofiber2De contamination thermoisopleth;
[Fig. 6] is different proportion B doping TiO2Nanofiber 1000 primary cell of charge and discharge cycles under 2A/g (12C) electric current
Performance map;
[Fig. 7] is different proportion B doping TiO2Nanofiber respectively 200mA/g, 1A/g, 2A/g, 3A/g, 4A/g,
The high rate performance figure of battery under 200mA/g electric current.
Specific embodiment
Following embodiment is intended to further illustrate the content of present invention, rather than limits the claims in the present invention protection scope.
Embodiment 1
B of the present invention adulterates TiO2The preparation of nanofiber high magnification long circulating lithium ion battery negative material is tested
Process is as shown in Figure 1, comprising the following steps:
(1) ethyl alcohol, acetic acid, butyl titanate and butyl borate are uniformly mixed, obtain presoma mixed liquor A, wherein
The mass ratio of ethyl alcohol, acetic acid and butyl titanate be 10:3:4, wherein the molar ratio of titanium and boron be respectively 10:0,10:1,10:2,
10:10。
(2) stirring in precursor liquid A is added in polyvinylpyrrolidone to make it completely dissolved to obtain mixed liquor, wherein poly- second
The ratio of alkene pyrrolidone and precursor liquid A are 0.05g/mL.
(3) mixed liquor in (2) is placed in electrostatic spinning machine, temperature is 30 DEG C, and ambient humidity 20% applies 19kV
Voltage carries out spinning with the speed of 3mL/h, obtains nanofiber.
(4) polymer nanofiber is dried for 24 hours at 80 degree, places in Muffle furnace and calcine 3 hours for 550 DEG C, obtains difference
Ratio B adulterates TiO2Nano-fiber material.
(5) the different proportion B for being prepared into step (4) adulterates TiO2Nano-fiber material, acetylene black and PVDF are according to matter
Amount obtains different proportion B doping TiO than being that 7:2:1 matches slurry after coating drying2Nanofiber anode material.
(6) electrode material prepared by step (5) is assembled into button cell, carries out chemical property in blue electrical testing channel
Test.
B adulterates TiO2The structure and associated batteries performance characterization of nanofiber:
1) different proportion B adulterates TiO2The structural characterization of nano-fiber material:
Different proportion B adulterates TiO2The XRD spectrum of nano-fiber material as shown in Fig. 2, itself the result shows that different proportion B mixes
Miscellaneous TiO2The diffraction maximum and anatase TiO of nanofiber2Characteristic diffraction peak it is essentially identical, Ti and B molar ratio be 10:1,
When 10:2, B is not all shown2O3Or TiB2Peak exist, it may be possible to the doping that B forms amorphous crystal phase or B element replaces
Ti element or in TiO2Lattice among, it is more because excessive butyl borate is doped and added to but when Ti and B molar ratio are 10:10
Remaining B fails doping and enters, to have B in 2 θ=14.53,27.95 by calcining in its diffraction maximum2O3Crystal phase.Doping
Material lattice can be caused to change, changed so as to cause material diffraction maximum, different proportion B known to illustration mixes from Fig. 2
Miscellaneous TiO2Diffraction peaks broadening in varying degrees has occurred in (101) crystal face in nanofiber diffraction spectra, this has with crystal grain refinement
It closes, will lead to scantling reduction.
2) different proportion B adulterates TiO2The morphology characterization of nano-fiber material:
Different proportion B adulterates TiO2The shape appearance figure of nano-fiber material is as shown in figure 3, Fig. 3 (a), 3 (b), 3 (c), 3 (d)
Respectively Ti and B molar ratio are 10:0,10:1,10:2,10:10, the result shows that being mixed by different proportion B prepared by electrostatic spinning
Miscellaneous TiO2Material is at threadiness, and the diameter of fiber between 50~300nm, deposit by about tens microns of length, nanofiber surface
In many micropores, fiber size is smaller when wherein Ti and B molar ratio is 10:2, and diameter is 100nm or so, more can from small figure
The porous presence of material surface out, wherein Ti:B is that the surface micropore of 10:2 sample is more prominent, and the presence of micropore will lead to material
Material has bigger specific surface area, is more conducive to the infiltration of electrolyte and the transmission of lithium ion.
3) different proportion B adulterates TiO2The XPS of nano-fiber material is characterized:
Ti and B molar ratio are that the B of 10:0,10:2,10:10 adulterate TiO2The element of nano-fiber material forms and Valence States
For analysis map as shown in figure 4, showing that sample has tri- elements of B, O, Ti from figure, the peak B1s can be separated into two independent peaks,
It is located at 191.0 and 192.1eV, it means that in the TiO of B doping2There may be the changes of different boron elements in matrix
Form corresponds to B-O-Ti key by the peak of the 191.0eV compared with standard bond energy, and the peak of 192.1eV and B2O3Middle B-O-B
Key is related, and as can be seen from the figure the peak of B-O-B is main peak and the swarming of B-O-Ti is secondary peak, this indicates that B's is primarily present shape
Formula is B2O3And there is a small amount of B instead of TiO2The position of middle script Ti atom.
4) different proportion B adulterates TiO2The N of nanofiber2De contamination thermoisopleth
Ti and B molar ratio are that the B of 10:0,10:1,10:2,10:10 adulterate TiO2The N of nanofiber2De contamination thermoisopleth is such as
Shown in Fig. 5, the N of four samples2De contamination isothermal curve is to belong to IV according to IUPAC classification, in the inclined Y-axis of low-pressure area curve, this
Category feature curve shows material exists with micropore.Wherein Ti and B molar ratio are that the B of 10:0,10:1,10:2,10:10 are adulterated
TiO2The specific surface area of nanofiber is respectively 50.44,103.37,125.83,23.38m2g-1, B element is entrained in a certain degree
On crystal can be inhibited to grow up and change crystal structure, so that some variations, doping ratio occur to the size and pattern for making material
There is bigger specific surface area for the sample of 10:2.
5) different proportion B adulterates TiO2The cycle performance figure of nanofiber
To the TiO of different proportion B doping2Nanofiber sample is with 2A g-1High current carries out charge and discharge cycles test, knot
Fruit is as shown in fig. 6, wherein Ti and B molar ratio are that the B of 10:0,10:1,10:2,10:10 adulterate TiO2Nano-fiber material has
There is good cycle performance, after circulation 5000 times, capacity is respectively 31.1mAh g-1、79.4mAh g-1、167.6mAh g-1、
55mAh g-1, the sample of Ti and B molar ratio 10:2 is demonstrated by superior chemical property, still keeps after 5000 circulations
167.6mAh g-1Capacity.In Fig. 6 illustration, the cycles samples of Ti and B molar ratio 10:2 10000 times, after the circulation 8000
Still maintain 150mAh g-1High capacity, because the destruction capacity of material starts slowly to decay finally in circulation 8000-10000 times
For 90mAhg-1, in order to compare B doping effect, prepare pure B2O3Electrode, to pure B2O3Electrode carries out its electrochemistry of charge-discharge test
Performance test has figure it is found that its capacity is almost 0, and side demonstrates B doping and greatly improves TiO2Chemical property.
6) different proportion B adulterates TiO2The cycle performance figure of nanofiber
To the TiO of different proportion B doping2Nanofiber sample with the electric current of 0.2A/g, 1A/g, 2A/g, 3A/g, 4A/g into
Then electric current is restored to 0.2A/g and carries out 30 charge and discharge cycles tests, test knot again by 30 charge and discharge cycles tests of row
Fruit is as shown in fig. 7, Ti and B molar ratio are that 10:2 sample starts under 0.2A/g electric current with 230mAh/g capacity, with electric current
It increases, there remains the charge/discharge capacity of 150mAh/g in 4A/g, become the best sample of high rate performance.Wherein molar ratio is
For 10:10 sample almost without capacity attenuation under 2A/g, 3A/g, 4A/g electric current, capacity is maintained at 100mAh/g or so, has more
Add excellent high rate performance, and compares pure TiO2, molar ratio 10:1 material, there is approximate specific volume under 0.2A/g charging and discharging currents
Amount, with the increase of electric current, pure TiO2The decaying of material is gradually increased, known to comparison attenuation rate (known to table 1), the sample of B doping
Attenuation rate of the specific capacity of product under different electric currents is respectively less than pure TiO2Sample, it was demonstrated that B doping is to TiO2Performance has great
Improve left and right.
1 difference B doping ratio TiO of table2High rate performance attenuation rate analytical data
Claims (10)
1. a kind of boron doped titanic oxide nanofiber, it is characterised in that: diameter is nano-scale, length is micron-scale, and
Surface contains micropore.
2. a kind of boron doped titanic oxide nanofiber according to claim 1, it is characterised in that:
The molar ratio of titanium and boron is 10:1~10 in the boron doped titanic oxide nanofiber.
3. a kind of boron doped titanic oxide nanofiber according to claim 1 or 2, it is characterised in that:
Titanium dioxide is anatase crystal in the boron doped titanic oxide nanofiber;
The diameter of the boron doped titanic oxide nanofiber is between 50~300nm, and length is between 1~100 micron.
4. a kind of described in any item preparation methods of boron doped titanic oxide nanofiber of claims 1 to 3, feature exist
In: ethyl alcohol, acetic acid, butyl titanate, butyl borate and polyvinylpyrrolidone mixed dissolution are obtained into spinning solution;The spinning
Silk liquid obtains polymer nanofiber by electrostatic spinning process;The polymer nanofiber is obtained by drying and calcination
Boron doped titanic oxide nanofiber.
5. a kind of preparation method of boron doped titanic oxide nanofiber according to claim 4, it is characterised in that: second
The mass ratio of alcohol, acetic acid and butyl titanate is (8~12): (1~3): 4.
6. a kind of preparation method of boron doped titanic oxide nanofiber according to claim 4, it is characterised in that: metatitanic acid
The molar ratio of four butyl esters and butyl borate is 10:1~10.
7. a kind of preparation method of boron doped titanic oxide nanofiber according to claim 4, it is characterised in that: poly- second
Concentration of the alkene pyrrolidone in spinning solution is 0.04~0.06g/mL.
8. according to a kind of described in any item preparation methods of boron doped titanic oxide nanofiber of claim 4~7, feature
It is: the condition of the electrostatic spinning process are as follows: voltage is 18~20KV, and fltting speed is 1~3mL/h, and temperature is 25~60
DEG C, ambient humidity is 10~30%.
9. according to a kind of described in any item preparation methods of boron doped titanic oxide nanofiber of claim 4~7, feature
It is: the condition of the calcining are as follows: calcined 2~4 hours at 450~600 DEG C.
10. a kind of described in any item applications of boron doped titanic oxide nanofiber of claims 1 to 3, it is characterised in that: make
For the application of ion cathode material lithium.
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CN111575833A (en) * | 2020-05-18 | 2020-08-25 | 湖北工程学院 | Preparation method of titanium dioxide nanofiber containing temperature-sensitive material |
CN113991055A (en) * | 2021-09-30 | 2022-01-28 | 内蒙古科技大学包头医学院 | Self-supporting nanofiber paper and preparation method thereof |
CN114149024A (en) * | 2021-11-30 | 2022-03-08 | 陕西科技大学 | Boron-doped porous titanium dioxide/carbon fiber negative electrode material and preparation method thereof |
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