CN105154980B - A kind of anode material of lithium battery and preparation method thereof - Google Patents
A kind of anode material of lithium battery and preparation method thereof Download PDFInfo
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- CN105154980B CN105154980B CN201510344514.3A CN201510344514A CN105154980B CN 105154980 B CN105154980 B CN 105154980B CN 201510344514 A CN201510344514 A CN 201510344514A CN 105154980 B CN105154980 B CN 105154980B
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Abstract
The invention discloses a kind of anode material of lithium battery and preparation method thereof.Its active material of described anode material of lithium battery is octahedral bulk single crystal cpd, and its molecular formula is (NH3CH2CH2NH3)2{Li6 [V12B18O54(O H)8]}.Positive electrode is made after drying and processing in the active material after being mixed with conductive material, adhesives.The material is to use octahedral bulk single crystal cpd made from a step hydrothermal synthesis method, is a kind of anode material of lithium battery of brand new type.The present invention has carried out the test and analysis of cyclic voltammetry curve, charge-discharge performance and AC impedance to positive electrode respectively.Charging and discharging curve shows that the positive electrode has higher first discharge specific capacity (123.2 mAh/g), and the test of AC impedance shows that battery has good ionic conductance.
Description
Technical field
The invention belongs to the preparation field of battery electrode material, and in particular to a kind of anode material of lithium battery and its preparation side
Method.
Background technology
Energy shortage be increasingly becoming today's society the most core the problem of one of, be this people also effort exploration send out
Existing novel energy, to substitute non-renewable and increasingly depleted fossil energy.Up to the present, existing a variety of New Green Energies
Source is employed in social life, such as, lithium ion battery, battery, fuel cell and solar cell etc..Wherein, lithium
Ion battery in the past few decades in have been achieved for considerable progress, as the lithium battery of secondary cell in current society
Irreplaceable effect has been played in living.But, as the important component of new energy, the development circumstances of lithium battery exists
Being showed in requirement in face of today's society to new energy must show slightly weak.Chief reason is that lithium ion battery is just in recent years
The progress of pole material is limited, and that is used on present society mainly still rests on the rich lithium being made up of Co, Ni, Mn and Fe
Metal oxide（And the research of negative pole has been achieved for larger progress relatively in recent years）, such as cobalt acid lithium, LiMn2O4 with
And LiFePO4 etc..
Therefore, with a kind of brand-new synthesis path, the anode material of lithium battery of new structure is obtained, seeks breakthrough existing just
The qualitative thinking of pole material synthesis method, has become one of industry question of common concern.
The content of the invention
It is an object of the invention in view of the shortcomings of the prior art, providing a kind of anode material of lithium battery and preparation method thereof.
The active component of the anode material of lithium battery is octahedral bulk single crystal cpd, with excellent chemical property, such as higher head
Secondary charging and discharging capacity, good ionic conductivity.
In order to reach the object of the invention, the present invention is adopted the following technical scheme that：
A kind of anode material of lithium battery, its active material is octahedral bulk single crystal cpd, and its molecular formula is
(NH3CH2CH2NH3)2{Li6 [V12B18O54(OH)8]}。
The preparation method of described active material is：
（1）Ammonium metavanadate is taken, boric acid, lithium chloride, cobalt acetate, oxalic acid is placed in the reaction under high pressure that liner is polytetrafluoroethylene (PTFE)
In kettle, distilled water is added, is well mixed, magnetic agitation 30min；
（2）Then pH value is adjusted to 8.00 ~ 8.50 with ethylenediamine；
（3）After reactor is finally placed at 160 DEG C into constant temperature 120 hours, it is allowed to naturally cool to room temperature, suction filtration is obtained
The octahedral bulk single crystal cpd of brown.
Step（1）Middle ammonium metavanadate, boric acid, lithium chloride, cobalt acetate, the mass ratio of oxalic acid are：2:7:8:1:3.
Described anode material of lithium battery, is prepared from by following components according to parts by weight：(NH3CH2CH2NH3)2{Li6
[V12B18O54(OH)8] 80 ~ 85 parts of active material, 10 ~ 15 parts of conductive material, 5 ~ 10 parts of adhesives.
Described active material is using preceding needing to be pre-processed：It is placed in by crystalline material grind into powder, and by powder
Dried 24 hours in 120 DEG C of vacuum drying chamber.
The application of described anode material of lithium battery：Using lithium piece as negative pole, with 1mol/L LiPF6For electrolyte, assembling
Into button cell.
The beneficial effects of the present invention are：
1）The active material preparation method of the present invention is simple, and raw material is cheap and easy to get, it is easy to obtain；
2）The active material of the present invention is octahedral bulk single crystal cpd, is a kind of brand-new structure type, is used as lithium battery
Positive electrode is used, and lithium ion anode material can be made to possess excellent chemical property, such as higher first charge-discharge specific capacity,
Good ionic conductivity.
Brief description of the drawings
Fig. 1 is compound (NH3CH2CH2NH3)2{Li6 [V12B18O54(OH)8] crystal structure schematic diagram；
Fig. 2 is compound (NH3CH2CH2NH3)2{Li6 [V12B18O54(OH)8] XRD powder diagrams；
Fig. 3 is compound (NH3CH2CH2NH3)2{Li6 [V12B18O54(OH)8] infrared spectrum；
Fig. 4 is compound (NH3CH2CH2NH3)2{Li6 [V12B18O54(OH)8] UV, visible light solid diffusing reflection spectrum
Figure；
Fig. 5 is compound (NH3CH2CH2NH3)2{Li6 [V12B18O54(OH)8] thermogravimetric analysis spectrogram；
Fig. 6 is the cyclic voltammetry curve of battery；
Fig. 7 is the first charge-discharge curve of battery；
Fig. 8 is the charging and discharging curve of battery；
Fig. 9 is the cycle characteristics curve of battery；
Figure 10 is the AC impedance curve of battery.
Embodiment
The present invention further illustrates the present invention with the following example, but protection scope of the present invention is not limited to following reality
Apply example.
Embodiment 1
Anode material of lithium battery preparation method, comprises the following steps：
（1）The synthesis of active material：Weigh the g of ammonium metavanadate 0.2000, the g of boric acid 0.7000, the g of lithium chloride 0.8000, second
The sour g of cobalt 0.1000, the g of oxalic acid 0.3000, are placed in the autoclave that 25.00 ml liner is polytetrafluoroethylene (PTFE), add and steam
The ml of distilled water 10.00, is well mixed, and pH value is adjusted to 8.20 with ethylenediamine after magnetic agitation 30min.Finally reactor is placed in
Then constant temperature be allowed to naturally cool to room temperature after 120 hours at 160 DEG C.Suction filtration obtains the octahedral bulk single crystal cpd of brown
(it is about 70% to calculate yield by vanadium).Although the chemical composition of cobalt acetate is not emerged from the final result of experiment,
Be according to repeatedly test result indicates that, lack cobalt acetate just can not obtain the compound, cobalt acetate may rise in compound experiment
The effect of mineralizer.
（2）The pretreatment of active material：By crystalline material grind into powder, and powder is placed in 120 DEG C of vacuum drying
Dried 24 hours in case, farthest to remove the moisture in material；
（3）The preparation of positive electrode：In parts by weight, it is prepared from the following components, 80 ~ 85 parts of active material is led
10 ~ 15 parts of electric material, 5 ~ 10 parts of adhesives, the conductive material is acetylene black.
The single crystal diffraction parsing of active material
X-ray single crystal diffraction is current to determine that mono-crystalline structures are the most frequently used and effective method.Fig. 1 is in University of Fuzhou
The Rigaku R-Axis-Parid Weissenberge IP diffractometers at physical chemistry state key subject common test center
On, at a temperature of 293 (2) K, use graphite monochromatised Mo target K alpha rays (λ=0.71073) to exist with ω -2 θ scan modes
The collection of the measure and diffracted intensity data of crystal unit cell parameters is carried out in certain limit.Select I>2 σ (I) independent point diffraction,
For mono-crystalline structures parsing.
The crystallographic data of the compound of table 1
The sign of active material
（1）XRD powder diffractions are characterized
X-ray powder diffraction data are the Rigaku public affairs Mini-Flex in the chemical institute's experiment teaching center of University of Fuzhou
Gained is determined on II desk type powder diffractometer.Diffractometer uses X`Celerator detectors, Cu target K α (λ=1.54178) spoke
Penetrate, the θ of scanning range 2 is 5o ~ 55o, and scanning step is 0.02os-1, sweep speed is 0.1secstep-1.As shown in Figure 2
Test result show the XRD diffraction peaks of compound with by single crystal data simulate come peak position it is consistent, illustrate that powder is
Pure phase.
（2）Infrared spectrum characterization
Infrared spectrum is the Perkin-Elmer Spectrum 2000 for using my school physical chemistry key discipline at room temperature
FT-IR spectrophotometers, using KBr tablettings, tested at room temperature, scanning range is 400-4000 cm-1, scanning 20
It is secondary.From figure 3, it can be seen that 3500cm-1The wide absworption peak nearby occurred belongs to ν as (O-H) vibration absorption peak, 3189 cm-1
The wide absworption peak nearby occurred belongs to ν as (N-H) vibration absorption peak, and absworption peak is wider, is probably due to existing in crystal
Caused by hydrogen bond.1638 cm-1Belong to δ (O-H) vibration absorption peak, 1347 cm-1Belong to BO3In ν (B-O) key vibration inhale
Receive peak, 1049 cm-1Belong to BO4The vibration absorption peak of δ (B-O) in tetrahedron, 937 cm-1Place belongs to ν (V=Ot) vibration
Absworption peak, 759 cm-1、693 cm-1It is respectively belonging to νas(V-Oμ)Antisymmetric stretching vibration absworption peak and νs(V-Oμ) symmetrically stretch
Contracting vibration absorption peak.400~600 cm-1Place belongs to the skeletal vibration peak of cluster unit.
（3）UV, visible light solid diffusing reflection spectrum is characterized
UV-DRS is the Perkin-Elmer Lambda900 in national chemical fertilizer catalyst research engineering center of University of Fuzhou
The test of type ultraviolet-visible spectrometer is obtained, and scanning wavelength scope is 200-800 nm.From fig. 4, it can be seen that occurring at 249nm
Transition peak belong to OμLotus between → V moves transition, and the transition peak occurred at 561 nm belongs to V (IV) d-d jumps
Move, the transition peak occurred at 733 nm belongs to V (IV) and moves transition to V (V) lotus.
（4）Thermogravimetric analysis is characterized
Thermogravimetric analysis is the temperature model on the Netzsch TGS-2 thermal analyzers of University of Fuzhou's chemical experimental center
Enclose for 30~800 DEG C, programming rate is 10 DEG C/min, in nitrogen atmosphere obtained by measure.From figure 5 it can be seen that
59.86-171.52 DEG C of weightlessness 7.65%, corresponding to 3 lattice watters and 6 Li in crystal+Water of coordination (theoretical value：
7.71%）；6 Li in 171.52-398 DEG C of weightlessness 9.85%, correspondence crystal+And the ethylenediamine molecule of 2 protonations（Theoretical value：
7.98%）.After 398 DEG C, [the V in crystal12B18O60]14- Cluster anions start slow decomposition, show curve it is gentle under
Drop.Thermal gravimetric analysis curve has also reflected the accuracy of material crystal structure from side.
The electrochemical property test of positive electrode and analysis
（1）The test and analysis of the cyclic voltammetry curve of battery
Battery has carried out cyclic voltammetry curve (CV) test, and voltage range is 2 ~ 4.5 V, and sweep speed is 1 mV/S,
It can be found that battery is primarily present two couples of redox peaks (3.95 V, 3.72 V) and (3.51 V, 3.32 V) from Fig. 6,
Wherein 3.51 V oxidation peak performance is not it is obvious that by consulting pertinent literature, the peak position of CV curves is belonged to just
The oxidation-reduction potential change of active material is in the material of pole：V4+ ——V3+。
（2）The abundant electrical testing of battery and analysis
Fig. 7 is the first charge-discharge curve of battery under the mA/g of current density 30, and battery has higher initial charge specific volume
Measure (125.3 mAh/g) and first discharge specific capacity (123.2 mAh/g).Fig. 8 and Fig. 9 is battery in 30 mA/g current densities
Under charging and discharging curve, as can be seen from the figure battery capacity attenuation in cyclic process is serious.Test result is shown, the 15th
Specific capacity is only 51.7 mA/g after individual circulation.Active substances in cathode materials structure there occurs that change is probably to cause capacity attenuation
The reason for.
（3）The ac impedance measurement of battery and analysis
Figure 10 is that battery has carried out AC impedance (EIS) test, and frequency range is in the KHz of 0.01 Hz ~ 100, and amplitude is 5
MV, it can be found that AC impedance spectroscopy includes the oblique line that a circular curve and a slope are about 45 ° from figure, wherein, circle
Curved line appears in high frequency region to intermediate frequency zone, and a diameter of 180 (ohm), and corresponding is the impedance of redox reaction, and oblique line
Appear in low frequency range, represent the impedance relevant with lithium ion diffusion, the slope of oblique line is close to 45 °, then Li+Inside active material
Diffusion resistance it is more suitable.
In a word, there is higher first discharge specific capacity (123.2 mAh/g) and good ion from the compounds of this invention
Conductivity can be seen that the new material and possess the condition as anode material of lithium battery completely, be new type lithium ion battery just
Pole material have found the research that hydrothermal synthesis method under a new direction, and a step temperate condition is also anode material of lithium battery
There is provided a kind of new route of synthesis.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, should all belong to the covering scope of the present invention.
Claims (6)
1. a kind of anode material of lithium battery, it is characterised in that：Its active material of described anode material of lithium battery is octahedra single
Crystallization compound, its molecular formula is (NH3CH2CH2NH3)2{Li6[V12B18O54(OH)8], determine that crystal structure experimental data is as follows：
Molecular formula：C4H28B18Li6N4O60V12；
Molecular weight：1938.6；
Crystallographic system：It is orthogonal；
Cell parameter：
A/ 18.886 (2),
B/ 18.886 (2),
C/ 18.886 (2),
α/° 90,
β/° 90,
γ/° 90,
Unit cell volume/3 6736.8 (14)
Diffraction experiment temperature/DEG C 20 (2)
Space group Pn-3
Structure cell molecular number Z 4
Number of electrons F (000) 4139 in unit cell
Diffraction index
-24 ≤ h ≤24
-24 ≤ k ≤ 19
-23 ≤ l≤ 24
Total diffraction counts out 59066
Independent diffraction counts out 2586
The diffraction for participating in refine is counted out (I> 2σ(I)) 2289
All equivalent point average deviation Rint 0.0595
Observable point diffraction residual error factor R 1 is worth (I> 2σ(I)) 0.0842
Observable point diffraction weighted residual factor wR (F2) values (I> 2σ(I)) 0.3197
The value 0.0904 of place point diffraction residual error factor R 1
Place the point diffraction weighted residual factor wR (F2) value 0.3343
It is fitted excellent value 1.013
The Tu Feng and figure paddy e -3 2.237 and -0.942 of Residual electron density.
2. anode material of lithium battery according to claim 1, it is characterised in that：The preparation method of described active material
For：
（1）Ammonium metavanadate is taken, boric acid, lithium chloride, cobalt acetate, oxalic acid is placed in the autoclave that liner is polytetrafluoroethylene (PTFE),
Distilled water is added, is well mixed, magnetic agitation 30min；
（2）Then pH value is adjusted to 8.00 ~ 8.50 with ethylenediamine；
（3）After reactor is finally placed at 160 DEG C into constant temperature 120 hours, it is allowed to naturally cool to room temperature, suction filtration obtains brown
Octahedral bulk single crystal cpd.
3. anode material of lithium battery according to claim 2, it is characterised in that：Step（1）Middle ammonium metavanadate, boric acid, chlorine
Changing lithium, cobalt acetate, the mass ratio of oxalic acid is：2:7:8:1:3.
4. anode material of lithium battery according to claim 1, it is characterised in that：By following components according to parts by weight preparation
Into (en)2{Li6[V12B18O54(OH)6] 80 ~ 85 parts of active material, 10 ~ 15 parts of conductive material, 5 ~ 10 parts of adhesives.
5. anode material of lithium battery according to claim 4, it is characterised in that：Described active material is using preceding progress
Pretreatment：Drying 24 hours in 120 DEG C of vacuum drying chamber are placed in by crystalline material grind into powder, and by powder.
6. a kind of application of anode material of lithium battery as claimed in claim 1, it is characterised in that：Using lithium piece as negative pole, with
1mol/L LiPF6For electrolyte, button cell is assembled into.
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| CN107221658A (en) * | 2017-06-13 | 2017-09-29 | 福州大学 | A kind of novel lithium battery positive electrode |
| CN107275607B (en) * | 2017-06-13 | 2019-12-17 | 福州大学 | Novel B, V, O cluster compound-containing lithium battery positive electrode material |
| CN109360980A (en) * | 2018-11-14 | 2019-02-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of positive electrode boric acid vanadium lithium and products thereof and application |
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