CN106299301B - A kind of Li with excellent storage lithium performance3VO4The pattern of nano wire mutually regulates and controls method with object - Google Patents
A kind of Li with excellent storage lithium performance3VO4The pattern of nano wire mutually regulates and controls method with object Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The present invention relates to a kind of Li with excellent storage lithium performance3VO4The pattern of nano wire mutually regulates and controls method with object, belong to field of lithium ion battery material preparation, using vanadic anhydride and lithium carbonate as raw material, distilled water is solvent, it is prepared using high-temperature solid phase calcination United microwave radiation process, it is sintered in air atmosphere including elder generation, then carries out microwave irradiation in microwave reactor, this method reaction rate is fast, mild easily-controllable, energy conservation and environmental protection.80~240 nanometers of gained nanowire diameter, 3~5 microns of length, compared to Traditional bulk material, nano wire draw ratio is big, quality is stable, with high purity, manufacturing cost is low, specific surface area significantly increases, significantly improve the contact area between material and electrolyte, make lithium ion battery that there is good high rate performance and stable charge-discharge performance, is suitble to prepare portable storage lithium dynamical battery.The technique is not only lithium vanadate Li3VO4Ion battery research provides important scientific research foundation with application, while providing reliable guarantee to explore the rule between material microscopic appearance and performance boost.
Description
[technical field]: the invention discloses a kind of Li with excellent storage lithium performance3VO4The pattern and object phase of nano wire
Regulation method belongs to negative electrode of lithium ion battery technical field of nanometer material preparation.
[background technique]: Li3VO4Belong to light metal vanadate, because its special crystal structure makes this substance in electrode material
Material preparation and ionic conductor material synthesis field have extensive use.Especially, scientific research finds Li3VO4Unique molecular structure is constituted
The necessary channel of Ion transfer, and specific energy density is high, security and stability is good, it is expected to it is sent out in electrochemical cell preparation field
Wave important function.
Summarize through Literature Consult, it is existing to prepare lithium vanadate Li3VO4Common method have: sol-gel method (Kim, W.T.；
Jeong, Y.U.；Lee, Y.J.；Kim, Y.J.；Song, J.H.J.Power Sources 2013,244,557；Hu, S.；
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C.P.；Cao, G.Z.A CS Appl.Mater.Interfaces 2016,8 (1), 680；Ni, S.B.；Lv, X.H.；Zhang,
J.C.；Ma, J.J.；Yang, X.L.；Zhang, L.L.Electrochem.Acta 2014,145,327；Liang, Z.Y.；
Zhao, Y.M.；Ouyang, L. Z.；Dong, Y.Z.；Kuang, Q.；Lin, X.H.；Liu, X.D.；Yan, L.J.Power
Sources 2014,252,244；Jian, Z.L.；Zheng, M.B.；Liang, Y.L.；Zhang, X.X.；Gheytani, S.；
Lan, Y.C.；Shi, Y.；Yao, Y.Chem.Commun.2015,51 (1), 229；Zhang, J.C.；Ni, S.B.；Ma,
J.J.；Yang, X.L.；Zhang, L.L.J.Power Sources 2016,301,41；Wei, H.Y.；Tsai, D.S.；
Hsieh, C.L.RSC Adv.2015,5 (85), 69176；Du, C.Q.；Wu, J.W.；Liu, J.；Yang, M.；Xu, Q.；
Tang, Z.Y.；Zhang, X.H.Electrochim.Acta 2015,152,473), water/solvent-thermal process method (Liu, J.；
Lu, P.J.；Liang, S.；Liu, J.；Wang, W.；Lei, M.；Tang, S.；Yang, Q.Nano Energy 2015,12,
709；Ni, S.B.；Zhang, J.C.；Ma, J.J.；Yang, X.L.；Zhang, L.L.J.Power Sources 2015,296,
377；Shi, Y.；Wang, J.Z.；Chou, S.L.；Wexler, D.；Li, H.J.；Ozawa, K.；Liu, H.K.；Wu,
Y.P.Nano Lett. 2013,13 (10), 4715；Li, Q.D.；Sheng, J.Z.；Wei, Q.L.；An, Q.Y.；Wei, X.J.；
Zhang, P.F.；Mai, L.Q.Nanoscale 2014,6 (19), 11072；Zhang, P.F.；Zhao, L.Z.；An, Q.Y.；
Wei, Q.L.；Zhou, L.；Wei, X.J.；Sheng, J.Z.；Mai, L.Q.Small 2016,12 (8), 1082；Ni, S.B.；
Lv, X.H.；Ma, J.J.；Yang, X.L.；Zhang, L.L.J.Power Sources 2014,248,122；Ni, S.B.；Lv,
X.H.；Ma, J.J.；Yang, X.L.；Zhang, L.L. Electrochem.Acta 2014,130,800；Shi, Y.；Gao,
J.；H.D.；Li, H.J.；Liu, H.K.；Wexler, D.；Wang, J.Z.；Wu, Y.P.Chem.Eur.J.2014,
20 (19), 5608), high-temperature solid phase calcination method (Zhang, C.K.；Song, H.Q.；Liu, C.F.；Liu, Y.G.；Zhang,
C.P.；Nan, X.H.；Cao, G.Z.Adv.Funct.Mater.2015,25 (23), 3497；Liang, Z.Y.；Zhao, Y.M.；
Dong, Y.Z.；Kuang, Q.；Lin, X.H.；Liu, X.D.；Yan, D.L.J.Electroanal. Chem.2015,745,1；
Chen, L.；Jiang, X.L.；Wang, N.N.；Yue, J.；Qian, Y.T.；Yang, J.Adv.Sci.2015,2 (9),
1500090；Ni, S.B.；Zhang, J.C.；Ma, J.J.；Yang, X. L.；Zhang, L.L.J.Mater.Chem.A 2015,3
(35), 17951；Liang, Z.Y.；Lin, Z.P.；Zhao, Y.M.；Dong, Y.Z.；Kuang, Q.；Lin, X.H.；Liu,
X.D.；Yan, D.L.J.Power Sources 2015,274,345；Huang, K.；Ling, Q.N.；Huang, C.H.；Bi,
K.；Wang, W. J.；Yang, T.Z.；Lu, Y.K.；Liu, J.；Zhang, R.；Fan, D.Y.；Wang, Y.G.；Lei, M.J.
Alloys Compd.2015,646,837；Li, H.Q.；Liu, X.Z.；Zhai, T.Y.；Li, D.；Zhou, H.S.
Adv.Energy Mater.2013,3,428；Li, Q.D.；Wei, Q.L.；Sheng, J.Z.；Yan, M.Y.；Zhou, L.；
Luo, W.；Sun, R.M.；Mai, L.Q.Adv.Sci.2015,2 (12), 1500284；Dong, B.；Jarkaneh, R.；Hull,
S.；Reeves-McLaren, N.；Biendicho, J.J.；West, A.R.J. Mater.Chem.A 2016,4 (4), 1408),
Ultrasonic spray pyrolysis (Kim, W.T.；Min, B.K.；Choi, H.C.；Lee, Y.J.；Jeong,
Y.U.J.Electrochem.Soc.2014,161 (9), A1302), coordination electrochemistry Reconstruction Method (Ni, S.B.；Zhang, J.C.；
Ma, J.J.；Yang, X.L.；Zhang, L.L.；Li, X. M.；Zeng, H.B.Adv.Mater.Interfaces 2016,3
(1), 1500340), aerosol processing (Ni, S.B.；Zhang, J.C.；Lv, X.H.；Yang, X.L.；Zhang, L.L.J.Power
Sources 2015,291,95；Tartaj, P.；Amarilla, J.M；Vazquez-Santos,
M.B.Chem.Mater.2016,28 (3), 986), freeze-drying (Zhao, D.；Cao, M.H.ACS
Appl.Mater.Interfaces 2015,7 (45), 25084), self-template methods (Li, Q.D.；Wei, Q.L.；Wang, Q.Q.；
Luo, W.；An, Q.Y.；Xu, Y. A.；Niu, C.J.；Tang, C.J.；Mai, L.Q.J.Mater.Chem.A 2015,3 (37),
18839), ball-milling method (Shao, G.Q.；Gan, L.；Ma, Y.；Li, H.Q.；Zhai, T.Y.J.Mater.Chem.A 2015,3
(21), 11253) etc..But its microstructure is mostly a micron block, small size nano particle or the attached nano-particle material of carbon packet,
Moreover there is also certain technical deficiencies for these methods, such as: water/solvent-thermal method is intermittent reaction, needs to react at high temperature under high pressure,
The high requirements on the equipment is not suitable for continuous production；And easy-regulating, reaction time be not longer for sol-gel method process；High temperature solid-state
The energy consumption of calcination method is high, sintering time is long and nanostructure lattice variations and reunion seriously, seriously affect electricity during the sintering process
Chemical property；Other methods still have that complex process, synthesis condition are harsh, material morphology is single etc. to a certain extent and ask
Topic.In order to further enhance material activity, researchers begin to focus on nanoscale lithium vanadate Li3VO4Materials synthesis, nanometer
The key problem of the more difficult preparation of material is that Effective Regulation crystal growth rate and induced material are grown along specific dimension.
Therefore, in order to overcome the shortcomings of the prior art, nanoscale and active high Li are prepared3VO4Material, this hair
Bright patent provides a kind of Li with excellent storage lithium performance3VO4The pattern of nano wire mutually regulates and controls method with object, and high temperature solid-state is forged
It burns with microwave irradiation technology integrated application into monodimension nanometer material preparation system, finally obtains Li3VO4The object of nano-material
The Effective Regulation of phase and pattern.High-temperature solid phase calcination method United microwave radiotechnology, has that reaction rate is fast, reaction is mild easy
Control, energy conservation and environmental protection, product purity height and the advantages such as novel in shape.The process route is not only lithium vanadate Li3VO4Battery material is ground
Study carefully and provides reliable guarantor with using offer scientific research foundation, while also to explore the rule between material microscopic appearance and performance boost
Barrier.
[summary of the invention]: for prior art deficiency or Improvement requirement, the present invention provides a kind of with excellent storage lithium performance
Li3VO4The pattern of nano wire mutually regulates and controls method with object, and the purpose is to pass through high-temperature solid phase calcination United microwave radiotechnology system
The Li of standby small size high activity3VO4Nano wire one-dimentional structure makes it as excellent lithium ion battery material；The synthetic method is first
Compacting calcining first is carried out to reaction raw materials, then calcined product is subjected to microwave radiation processing, prepared Li3VO4Nano wire
Draw ratio is big, activity is high, stability is good, can be used for portable lithium storage materials preparation；This high-temperature solid phase calcination United microwave spoke
The technology of penetrating has given full play to the advantages of two kinds of heating methods, and safe operation, energy conservation and environmental protection, process are easily-controllable, successfully solves Li3VO4
Nano wire one-dimensional material is as technical bottleneck present in lithium ion battery material application.
[technical solution of the present invention]: the invention patent provides a kind of Li with excellent storage lithium performance3VO4Nano wire
Pattern mutually regulates and controls method with object, and using vanadic anhydride and lithium carbonate as raw material, distilled water is solvent, is joined using high-temperature solid phase calcination
It closes microwave irradiation technology to be synthesized, be achieved through the following technical solutions:
The first, at room temperature by purity be 99.9% lithium carbonate and purity be 99.9% vanadic anhydride by 3: 1
Stoichiometric ratio is sufficiently mixed, and suppresses solid-phase mixture 10 minutes at 10Mpa；
The second, pressed mixture is transferred in Muffle furnace, the precalcining 3 hours in 550 DEG C of air atmospheres, then
It is warming up to 900 DEG C to calcine again 1~8 hour, obtains solid product A；
12 grams of calcined solid product A are added in 23.5 milliliters of distilled water third, are sufficiently stirred 10 minutes, then
It is transferred to normal pressure and takes back in the microwave reactor of flow cooling device, adjusting microwave irradiation power is 100~1200W, heating temperature
70~300 DEG C, microwave frequency 2450MHz of degree sufficiently reacts 1~16 hour；
4th, products therefrom is cooled to room temperature, be centrifugated and be washed with distilled water 4 times, then done in 70 DEG C of baking ovens
Dry 24 hours, final Li can be obtained3VO4Nanowire product.
The Li3VO4The diameter of nano wire is only 80~240 nanometers, and length is up to 3~5 microns, and product structure is stable, major diameter
It is dramatically increased than big, with high purity, specific surface area.
The Li3VO4Nano wire assembling lithium ion battery is in the anhydrous and oxygen-free glove box of water and oxygen index less than 1ppm
It carries out, cathode involved in assembly selects high-purity lithium piece；Selecting the volume ratio containing 1mol/L lithium hexafluoro phosphate is 1: 1 carbon
Diethyl phthalate and ethylene carbonate mixed solvent are as electrolyte；Li3VO4Nano wire, Kynoar and conductive black according to
Weight ratio 8: 1: 1 carries out being mixed with electrode pastes；Select polypropylene as diaphragm；Show through battery testing: Li3VO4Nano wire
The lithium ion battery of assembling is because the high-specific surface area of the material expands electrolyte and Nanowire contacts area, when lithium ion is spread
Between be obviously reduced, good high rate performance and stable charge-discharge performance are shown in electro-chemical test: nano-material obtains
The first week specific discharge capacity obtained is 400mAh g-1With 1.3~0.6V continuous discharge platform, reversible capacity is within the 3rd~200 week
240mAh g-1, and with~99.7% discharge capacitance, hence it is evident that better than other sides involved in the patented technology background
The block and nano-particle material of method synthesis, further confirm novelty, practicability and the novelty of the patent；This is one-dimensional in a word
Nano material shows excellent advance and beneficial effect.
The Li3VO4Chemical equation involved in nano wire synthesis process is as follows:
3Li2CO3+V2O5→2Li3VO4+3CO2
[advantages of the present invention and effect]: the invention patent relates to a kind of Li with excellent storage lithium performance3VO4Nano wire
Pattern mutually regulate and control method with object, can obtain following the utility model has the advantages that the 1, present invention is using high-temperature solid phase calcination United microwave spoke
It penetrates technology and carries out material preparation, fast, easy to operate, the mild easily-controllable, energy conservation and environmental protection of this method reaction rate, product purity height and shape
Looks are novel；2, prepared product is nanowire structure, with Traditional bulk Li3VO4Material is compared, and nano wire draw ratio is big, quality
Stablize, with high purity, manufacturing cost is low, specific surface area dramatically increases；3, nano wire can significantly improve between material and electrolyte
Contact area, shorten lithium ion diffusion time, lithium ion battery made to have good high rate performance and stable charge and discharge electrical
Can, battery process performance boost is suitble to prepare portable storage lithium dynamical battery；3, high-temperature solid phase calcination United microwave heating process
It is not only Li3VO41-dimention nano battery material research with application provide scientific research foundation, while also for explore material microscopic appearance with
Rule between performance boost provides reliable guarantee.
[Detailed description of the invention]
Fig. 1 is Li in embodiment 13VO4Nano wire X-ray diffraction (XRD) figure
Fig. 2 is Li in embodiment 13VO410.0K times of scanning electron microscope of nano wire (SEM) test chart
Fig. 3 is Li in embodiment 13VO420.0K times of SEM test chart of nano wire
Fig. 4 is Li in embodiment 13VO480.0K times of SEM test chart of nano wire
Fig. 5 is Li in embodiment 13VO4350K times of SEM test chart of nano wire
[specific embodiment]
Below with reference to embodiment and attached drawing the present invention will be described in detail concrete principle, however, it is not limited to this:
Embodiment 1:
Firstly, at room temperature by purity be 99.9% lithium carbonate and purity be 99.9% vanadic anhydride by 3: 1
Stoichiometric ratio is sufficiently mixed, and is suppressed 10 minutes under 10Mpa pressure；Then the mixture suppressed is transferred to horse
Not in furnace, precalcining 3 hours in 550 DEG C of air atmospheres, then be rapidly heated to 900 DEG C and calcine 5 hours；Secondly, 12 grams are calcined
Product afterwards is put into 23.5 milliliters of distilled water, is sufficiently stirred 10 minutes, and is transferred to the micro- of the cooling effect of atmospheric pressure reflux
It carries out microwave heating in wave radiation reaction unit, adjusts microwave power 700W, 100 DEG C of heating temperature, microwave frequency 2450MHz,
Sufficiently reaction 8 hours；Finally, the product after reaction is cooled to room temperature, be centrifugated and is washed with distilled water 4 times, then 70
It is 24 hours dry in DEG C baking oven, final products can be obtained.By XRD and SEM means of testing to the object phase of product and pattern into
Row analysis, XRD test result (Fig. 1) show that product is pure phase Li3VO4Material, all diffraction maximums can all be attributed to JCPDS
No.24-667, and crystallinity is high；SEM test result (Fig. 2~5) shows that product is regular nanowire structure, nanowire diameter
It is 80~240 nanometers, length is 3~5 microns, and draw ratio is big, with high purity, specific surface area dramatically increases.Lithium ion battery assembling
It is to be carried out in the anhydrous and oxygen-free glove box of water and oxygen index less than 1ppm, assembling process selects high-purity lithium piece to be negative pole, selects
The diethyl carbonate and ethylene carbonate mixed liquor that the volume ratio for containing 1mol/L lithium hexafluoro phosphate is 1: 1 are as electrolyte；
Li3VO4Nano wire, Kynoar and conductive black carry out being mixed with electrode pastes according to weight ratio 8: 1: 1；It selects poly-
Propylene is as diaphragm；Li3VO4The lithium ion battery of nano wire assembling makes electrolyte and nano wire because of the high-specific surface area of the material
Contact area expands, and lithium ion diffusion time is obviously reduced, and good high rate performance and stabilization are shown in electro-chemical test
Charge-discharge performance: nano-material obtain first week specific discharge capacity be 400mAh g-1With 1.3~0.6V type discharge level
Platform, the 3rd~200 week reversible capacity are 240mAh g-1, and with~99.7% discharge capacitance, hence it is evident that specially better than this
The block and nano-particle material of the synthesis of other methods involved in sharp technical background, further confirm the patent novelty,
Practicability and novelty；The monodimension nanometer material shows excellent advance and beneficial effect in a word.
Embodiment 2:
Firstly, at room temperature by purity be 99.9% lithium carbonate and purity be 99.9% vanadic anhydride by 3: 1
Stoichiometric ratio is sufficiently mixed, and is suppressed 10 minutes under 10Mpa pressure；Then the mixture suppressed is transferred to horse
Not in furnace, precalcining 3 hours in 550 DEG C of air atmospheres, then be rapidly heated to 900 DEG C and calcine 3 hours；Secondly, 12 grams are calcined
Product afterwards is put into 23.5 milliliters of distilled water, is sufficiently stirred 10 minutes, is transferred to normal pressure and with the micro- of cooling effect that flow back
It carries out microwave heating in wave radiation reaction unit, adjusts microwave power 700W, 100 DEG C of heating temperature, microwave frequency 2450MHz,
Sufficiently reaction 5 hours；Finally, product after reaction is cooled to room temperature, be centrifugated and is washed with distilled water 4 times, then at 70 DEG C
It is 24 hours dry in baking oven, final products can be obtained.It is mutually carried out by pattern of SEM with the XRD means of testing to product with object
Analysis, what XRD test result showed to synthesize under this condition is still pure phase Li3VO4Material, all diffraction maximums can all be attributed to JCPDS
No.24-667, product crystallinity are high；SEM test result shows that product is nanowire structure, wherein nanowire diameter 150~280
Nanometer, 2.0~3.0 microns of length.Li-ion batteries piles are carried out in the anhydrous and oxygen-free glove box of water and oxygen index less than 1ppm
Dress selects in assembling high-purity lithium piece to be negative pole, the diethyl carbonate and carbon that the volume ratio containing 1mol/L lithium hexafluoro phosphate is 1: 1
Vinyl acetate mixed liquor is as electrolyte；Li3VO4Nano wire, Kynoar and conductive black according to weight ratio 8: 1: 1 into
Row is mixed with electrode pastes；Select polypropylene as diaphragm；Although nano wire draw ratio reduces, the lithium-ion electric prepared
Pond still shows preferable high rate performance and stable charge-discharge performance in electro-chemical test.
Embodiment 3:
Firstly, at room temperature by purity be 99.9% lithium carbonate and purity be 99.9% vanadic anhydride by 3:1's
Stoichiometric ratio is sufficiently mixed, and is suppressed 10 minutes under 10Mpa pressure；Then, the mixture suppressed is transferred to
In Muffle furnace, precalcining 3 hours in 550 DEG C of air atmospheres, then be rapidly heated to 900 DEG C and calcine 1 hour；Secondly, 12 grams are forged
Product after burning is put into 23.5 milliliters of distilled water, is sufficiently stirred 10 minutes, is transferred to normal pressure and with reflux refrigerating function
It carries out microwave heating in microwave radiation reaction unit, adjusts microwave power 700W, 100 DEG C of heating temperature, microwave frequency
2450MHz, sufficiently reaction 3 hours；Finally, the product after reaction is cooled to room temperature, be centrifugated and is washed with distilled water 4
It is secondary, then drying 24 hours in 70 DEG C of baking ovens, final products can be obtained.XRD test result explanation, it is resulting with this condition
Product is similarly pure phase Li3VO4Material, all diffraction maximums can all be attributed to JCPDS No.24-667, and crystallinity is high；SEM test
Product is nano-material as the result is shown, and wherein nanorod diameter is 200~320 nanometers, 1.0~1.8 microns of length.In water and
Oxygen index carries out lithium ion battery assembling in the anhydrous and oxygen-free glove box less than 1ppm, select high-purity lithium piece to be negative in assembling process
Pole, the diethyl carbonate and ethylene carbonate mixed liquor that the volume ratio for containing 1mol/L lithium hexafluoro phosphate is 1: 1 are as electrolyte；
Li3VO4Nanometer rods, Kynoar and conductive black carry out being mixed with electrode pastes according to weight ratio 8: 1: 1；It selects poly-
Propylene is as diaphragm；Electrochemical results explanation, nano material draw ratio have larger impact to battery performance, make under this condition
Standby lithium ion battery high rate performance and stable charge/discharge is poor compared with the performance of lithium ion battery prepared in embodiment 1.
To prove in the invention patent embodiment 1-3 using technical effect associated with synthesis in solid state and microwave radiation, work as guarantor
It holds the experiment presoma high temperature process heat step operation of early period but does not use microwave irradiation process, product cannot obtain this specially
The desired effect and novelty of sharp embodiment 1-3:
The comparative example of embodiment 1:
Firstly, at room temperature by purity be 99.9% lithium carbonate and purity be 99.9% vanadic anhydride by 3: 1
Stoichiometric ratio is sufficiently mixed, and is suppressed 10 minutes under 10Mpa pressure；Then the mixture suppressed is transferred to horse
Not in furnace, precalcining 3 hours in 550 DEG C of air atmospheres, then be rapidly heated to 900 DEG C and calcine 5 hours.The XRD of product tests table
Bright resulting materials, all diffraction maximums can all be attributed to JCPDS No.24-667, and crystallinity is high；But the block that pattern is 1-5 microns
Body material cannot get the synthetic effect of the nano wire of corresponding embodiment；The chemical property of the material is also obviously implemented than corresponding
The difference of example；Further demonstrate the importance and necessity of invention.
The comparative example of embodiment 2:
Firstly, at room temperature by purity be 99.9% lithium carbonate and purity be 99.9% vanadic anhydride by 3: 1
Stoichiometric ratio is sufficiently mixed, and is suppressed 10 minutes under 10Mpa pressure；Then the mixture suppressed is transferred to horse
Not in furnace, precalcining 3 hours in 550 DEG C of air atmospheres, then be rapidly heated to 900 DEG C and calcine 3 hours.Target final product
The analysis of XRD spectra the result shows that: all characteristic diffraction peaks correspond to JCPDS card number No.24-667, and crystallinity is fine；It can
It is that the agglomerate body that the microstructure of the material is 1~4.5 micron cannot obtain the technical effect of embodiment 2 at all；This electrode
The cyclical stability and specific discharge capacity of material are not so good as embodiment 2；Sufficiently testified again invention novelty and
Practicability.
The comparative example of embodiment 3:
Firstly, at room temperature by purity be 99.9% lithium carbonate and purity be 99.9% vanadic anhydride by 3: 1
Stoichiometric ratio is sufficiently mixed, and is suppressed 10 minutes under 10Mpa pressure；Then, the mixture suppressed is transferred to
In Muffle furnace, precalcining 3 hours in 550 DEG C of air atmospheres, then be rapidly heated to 900 DEG C and calcine 1 hour；The XRD of synthetic material
The signal of the acquisition of test is shown: characteristic feature diffraction maximum is corresponding with standard card JCPDS No.24-667 perfect；But
The size of this block materials is 1~4.6 micron, and pattern cannot obtain technical characterstic described in embodiment 2；In addition, this nanometer
The capacity retention ratio of material is poor compared with embodiment 2；It has sufficiently testified the novelty and novelty of invention.
Claims (1)
1. a kind of Li with excellent storage lithium performance3VO4The pattern of nano wire mutually regulates and controls method with object, with vanadic anhydride and carbon
Sour lithium is raw material, and distilled water is solvent, is synthesized using high-temperature solid phase calcination United microwave radiotechnology, passes through following technology
Scheme is realized:
Firstly, at room temperature by purity be 99.9% lithium carbonate and purity be 99.9% vanadic anhydride by 3: 1 chemistry
Metering ratio is sufficiently mixed, and is suppressed 10 minutes under 10Mpa pressure；Then the mixture suppressed is transferred to Muffle furnace
In, precalcining 3 hours in 550 DEG C of air atmospheres, then be rapidly heated to 900 DEG C and calcine 5 hours；Secondly, calcined by 12 grams
Product is put into 23.5 milliliters of distilled water, is sufficiently stirred 10 minutes, and is transferred to the microwave spoke with the cooling effect of atmospheric pressure reflux
Penetrate and carry out microwave heating in reaction unit, adjust microwave power 700W, 100 DEG C of heating temperature, microwave frequency 2450MHz, sufficiently
Reaction 8 hours；Finally, the product after reaction is cooled to room temperature, be centrifugated and is washed with distilled water 4 times, then dried at 70 DEG C
It is 24 hours dry in case, final products can be obtained；Divided by object phase and pattern of XRD the and SEM means of testing to product
Analysis, XRD test result show that product is pure phase Li3VO4Material, all diffraction maximums can all be attributed to JCPDS No.24-667；SEM
It is 80~240 nanometers that test result display product, which is nanowire diameter, and length is 3~5 microns.
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