CN106299301A - A kind of Li with excellent storage lithium performance3vO4the pattern of nano wire regulates and controls method mutually with thing - Google Patents

A kind of Li with excellent storage lithium performance3vO4the pattern of nano wire regulates and controls method mutually with thing Download PDF

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CN106299301A
CN106299301A CN201610850497.5A CN201610850497A CN106299301A CN 106299301 A CN106299301 A CN 106299301A CN 201610850497 A CN201610850497 A CN 201610850497A CN 106299301 A CN106299301 A CN 106299301A
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lithium
nano wire
performance
thing
pattern
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CN106299301B (en
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孙嬿
李春生
侴术雷
王云晓
王莉娜
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University of Wollongong
Suzhou University of Science and Technology
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University of Wollongong
North China University of Science and Technology
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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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a kind of Li with excellent storage lithium performance3VO4The pattern of nano wire regulates and controls method mutually with thing, belong to field of lithium ion battery material preparation, with vanadic anhydride and lithium carbonate as raw material, distilled water is solvent, high-temperature solid phase calcination United microwave radiation process is utilized to be prepared, including first sintering in air atmosphere, in microwave reactor, then carry out microwave exposure, easily-controllable, the energy-conserving and environment-protective fast, gentle of the method reaction rate.Gained nanowire diameter 80～240 nanometer, length 3～5 microns, compare Traditional bulk material, nano wire draw ratio is big, steady quality, purity height, low cost of manufacture, specific surface area significantly increase, significantly improve the contact area between material and electrolyte, make lithium ion battery have good high rate performance and stable charge-discharge performance, be suitable for preparing portable storage lithium dynamical battery.This technique is not only lithium vanadate Li3VO4Ion battery research and application provide important scientific research foundation, are that the rule explored between material microscopic appearance and performance boost provides reliable guarantee simultaneously.

Description

A kind of Li with excellent storage lithium performance3VO4The pattern of nano wire regulates and controls mutually with thing Method
[technical field]: the invention discloses a kind of Li with excellent storage lithium performance3VO4The pattern of nano wire and thing phase Regulation and control method, belongs to lithium ion battery negative technical field of nanometer material preparation.
[background technology]: Li3VO4Belong to light metal vanadate, because its special crystal structure makes this material at electrode material Material preparation and ionic conductor material synthesis field have extensive use.Especially, scientific research finds Li3VO4Unique molecular structure is constituted The necessary passage of ion migration, and specific energy density is high, security and stability is good, it is expected to send out in electrochemical cell preparation field Wave important function.
Collect through Literature Consult, existing prepare lithium vanadate Li3VO4Common method have: sol-gel process (Kim, W.T.； Jeong, Y.U.；Lee, Y.J.；Kim, Y.J.；Song, J.H.J.Power Sources 2013,244,557；Hu, S.； Song, Y.F.；Yuan, S.Y.；Liu, H.M.；Xu, Q.J.；Wang, Y.G.；Wang, C.X.；Xia, Y.Y.J.Power Sources 2016,303,333；Zhang, C.K.；Liu, C.F.；Nan, X.H.；Song, H.Q.；Liu, Y.G.；Zhang, C.P.；Cao, G.Z.A CS Appl.Mater.Interfaces2016,8 (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), ullrasonic spraying heat Solution (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), lyophilization Method (Zhao, D.；Cao, M.H.ACS Appl.Mater.Interfaces 2015,7 (45), 25084), self-template method (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 mostly its microstructure is that a micron block, small size are received Rice grain or the attached nano-particle material of carbon bag, also these methods there is also certain technical deficiency, such as: water/solvent-thermal method is Intermittent reaction, needs to react at high temperature under high pressure, higher to equipment requirements, is not suitable for producing continuously；And sol-gel process process Not easy-regulating, reaction time is longer；Energy consumption height, sintering time length and the nano junction in sintering process of high-temperature solid phase calcination method Structure lattice variations and reunion are serious, have a strong impact on chemical property；Additive method yet suffer to a certain extent complex process, The problems such as synthesis condition is harsh, material morphology is single.In order to promote material activity further, researchers begin to focus on to be received Meter level lithium vanadate Li3VO4Materials synthesis, the key problem of the more difficult preparation of nano material is Effective Regulation crystal growth rate and lures Lead material to grow along specific dimension.
Therefore, for the deficiency overcoming prior art to exist, prepare nanoscale and active high Li3VO4Material, this Bright patent provides a kind of Li with excellent storage lithium performance3VO4The pattern of nano wire regulates and controls method mutually with thing, high temperature solid-state is forged Burn and prepare in system with microwave irradiation technology integrated application to monodimension nanometer material, finally give Li3VO4The thing of nano-material Phase and the Effective Regulation of pattern.High-temperature solid phase calcination method United microwave radiotechnology, has that reaction rate is fast, reaction is gentle easily The advantages such as control, energy-conserving and environment-protective, product purity height and novel in shape.This process route is not only lithium vanadate Li3VO4Battery material grinds Study carefully and provide scientific research foundation with application, be the most also to explore the rule between material microscopic appearance and performance boost to provide reliable guarantor Barrier.
[summary of the invention]: the not enough or Improvement requirement for prior art, the present invention provides one to have excellent storage lithium performance Li3VO4The pattern of nano wire regulates and controls method mutually with thing, its objective is by high-temperature solid phase calcination United microwave radiotechnology system The standby highly active Li of small size3VO4Nano wire one-dimentional structure so that it is as excellent lithium ion battery material；This synthetic method is first First reaction raw materials is carried out compacting calcining, then the product after calcining is carried out microwave radiation processing, prepared Li3VO4Nano wire Draw ratio is big, activity is high, good stability, can be used for portable lithium storage materials and prepares；This high-temperature solid phase calcination United microwave spoke The technology of penetrating has given full play to the advantage of two kinds of mode of heatings, and operation safety, energy-conserving and environment-protective, process are easily-controllable, successfully solve Li3VO4 Nano wire one-dimensional material as lithium ion battery material apply present in technical bottleneck.
[technical scheme]: patent of the present invention provides a kind of Li with excellent storage lithium performance3VO4Nano wire Pattern regulates and controls method mutually with thing, and with vanadic anhydride and lithium carbonate as raw material, distilled water is solvent, utilizes high-temperature solid phase calcination to join Close microwave irradiation technology to synthesize, be achieved through the following technical solutions:
The first, at room temperature by lithium carbonate that purity is 99.9% and vanadic anhydride that purity is 99.9% by 3: 1 Stoichiometric proportion is sufficiently mixed, and is suppressed 10 minutes by solid-phase mixture under 10Mpa；
The second, the mixture after compacting is transferred in Muffle furnace, precalcining 3 hours in 550 DEG C of air atmospheres, then It is warming up to 900 DEG C calcine again 1～8 hour, obtains solid product A；
3rd, the solid product A after calcining 12 grams adds in 23.5 milliliters of distilled water, is sufficiently stirred for 10 minutes, then In being transferred to normal pressure and taking back the microwave reactor of flow cooling device, regulation microwave irradiation power is 100～1200W, heating temperature Spend 70～300 DEG C, microwave frequency 2450MHz, fully reaction 1～16 hour；
The 4th, products therefrom be cooled to room temperature, and centrifugation is with distilled water wash 4 times more dry in 70 DEG C of baking ovens Dry 24 hours, i.e. can get final Li3VO4Nanowire product.
Described Li3VO4The diameter of nano wire is only 80～240 nanometers, and length reaches 3～5 microns, and product structure is stable, major diameter Ratio is big, purity is high, specific surface area dramatically increases.
Described Li3VO4It is to be less than in the anhydrous and oxygen-free glove box of 1ppm at water and oxygen index that nano wire assembles lithium ion battery Carrying out, the negative pole related in assembling selects high purity lithium sheet；Select the carbon that volume ratio is 1: 1 containing 1mol/L lithium hexafluoro phosphate 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 barrier film；Show through battery testing: Li3VO4Nano wire The lithium ion battery assembled makes electrolyte and Nanowire contacts enlarged areas because of the high-specific surface area of this material, during lithium ion diffusion Between be obviously reduced, electro-chemical test demonstrates good high rate performance and stable charge-discharge performance: nano-material obtains The first week specific discharge capacity obtained is 400mAh g-1With 1.3～0.6V continuous discharge platforms, within the 3rd～200 week, reversible capacity is 240mAh g-1, and have～the discharge capacitance of 99.7%, hence it is evident that it is better than in this patented technology background other side related to The block of method synthesis and nano-particle material, be further characterized by the novelty of this patent, practicality and novelty；This is one-dimensional in a word Nano material represents advance and the beneficial effect of excellence.
Described Li3VO4The chemical equation related in nano wire building-up process is as follows:
3Li2CO3+V2O5→2Li3VO4+3CO2
[advantages of the present invention and effect]: patent of the present invention relates to a kind of Li with excellent storage lithium performance3VO4Nano wire Pattern regulate and control method mutually with thing, it is possible to obtain following beneficial effect: 1, the present invention uses high-temperature solid phase calcination United microwave spoke The technology of penetrating carries out material and prepares, and the method reaction rate is fast, simple to operate, gentle easily-controllable, energy-conserving and environment-protective, product purity are high and shape Looks are novel；2, prepared product is nano thread structure, with Traditional bulk Li3VO4Material is compared, and nano wire draw ratio is big, quality Stable, purity height, low cost of manufacture, specific surface area dramatically increase；3, nano wire can significantly improve between material and electrolyte Contact area, shorten lithium ion diffusion time, make lithium ion battery have good high rate performance and stable charge and discharge is electrical Can, battery process performance boost, it is suitable for preparing portable storage lithium dynamical battery；3, high-temperature solid phase calcination United microwave heating technique It is not only Li3VO4The research of 1-dimention nano battery material and application provide scientific research foundation, simultaneously the most also for explore material microscopic appearance with Rule between performance boost provides reliable guarantee.
[accompanying drawing explanation]:
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 figure
Fig. 3 is Li in embodiment 13VO420.0K times of SEM test figure of nano wire
Fig. 4 is Li in embodiment 13VO480.0K times of SEM test figure of nano wire
Fig. 5 is Li in embodiment 13VO4350K times of SEM test figure of nano wire
[detailed description of the invention]:
Describe the concrete principle of the present invention in detail below in conjunction with embodiment and accompanying drawing, but be not limited thereto:
Embodiment 1:
First, at room temperature by lithium carbonate that purity is 99.9% and vanadic anhydride that purity is 99.9% by 3: 1 Stoichiometric proportion is sufficiently mixed, and suppresses 10 minutes under 10Mpa pressure；Then the mixture suppressed is transferred to horse Not in stove, precalcining 3 hours in 550 DEG C of air atmospheres, then be rapidly heated to 900 DEG C calcine 5 hours；Secondly, by 12 grams of calcinings After product put in 23.5 milliliters of distilled water, be sufficiently stirred for 10 minutes, and be transferred to cool down the micro-of effect with atmospheric pressure reflux Wave radiation reaction unit carries out microwave heating, regulates microwave power 700W, heating-up temperature 100 DEG C, microwave frequency 2450MHz, Fully reaction 8 hours；Finally, reacted product is cooled to room temperature, centrifugation with distilled water wash 4 times, then 70 DEG C baking oven is dried 24 hours, i.e. can get final products.By XRD and SEM means of testing, thing phase and the pattern of product are entered Row is analyzed, and XRD test result (Fig. 1) shows that product is pure phase Li3VO4Material, all diffraction maximums all can be attributed to JCPDS No.24-667, and degree of crystallinity is high；SEM test result (Fig. 2～5) display product is regular nano thread structure, and nanowire diameter is 80～240 nanometers, a length of 3～5 microns, draw ratio is big, purity is high, specific surface area dramatically increases.Lithium ion battery assembles Carrying out in the anhydrous and oxygen-free glove box less than 1ppm at water and oxygen index, assembling process selects high purity lithium sheet to be negative pole, and selection contains There are the diethyl carbonate that volume ratio is 1: 1 of 1mol/L lithium hexafluoro phosphate and ethylene carbonate mixed liquor as electrolyte；Li3VO4 Nano wire, Kynoar and conductive black carry out being mixed with electrode pastes according to weight ratio 8: 1: 1；Selection polypropylene is made For barrier film；Li3VO4The lithium ion battery that nano wire assembles makes electrolyte and Nanowire contacts face because of the high-specific surface area of this material Long-pending expansion, lithium ion is obviously reduced diffusion time, demonstrates good high rate performance and stable charge and discharge in electro-chemical test Electrical property: first week specific discharge capacity that nano-material obtains is 400mAh g-1With 1.3～0.6V continuous discharge platforms, the 3rd ～200 weeks reversible capacities are 240mAhg-1, and have～the discharge capacitance of 99.7%, hence it is evident that it is better than this patented technology back of the body Scape relates to other method synthesis block and nano-particle material, be further characterized by the novelty of this patent, practicality and Novelty；This monodimension nanometer material represents advance and the beneficial effect of excellence in a word.
Embodiment 2:
First, at room temperature by lithium carbonate that purity is 99.9% and vanadic anhydride that purity is 99.9% by 3: 1 Stoichiometric proportion is sufficiently mixed, and suppresses 10 minutes under 10Mpa pressure；Then the mixture suppressed is transferred to horse Not in stove, precalcining 3 hours in 550 DEG C of air atmospheres, then be rapidly heated to 900 DEG C calcine 3 hours；Secondly, by 12 grams of calcinings After product put in 23.5 milliliters of distilled water, be sufficiently stirred for 10 minutes, be transferred to normal pressure and micro-with reflux cooling effect Wave radiation reaction unit carries out microwave heating, regulates microwave power 700W, heating-up temperature 100 DEG C, microwave frequency 2450MHz, Fully reaction 5 hours；Finally, reaction afterproduct is cooled to room temperature, centrifugation with distilled water wash 4 times, then at 70 DEG C Baking oven is dried 24 hours, i.e. can get final products.By SEM with XRD means of testing, the pattern of product is carried out mutually with thing Analyzing, what XRD test result synthesized under the conditions of showing this is still pure phase Li3VO4Material, all diffraction maximums all can be attributed to JCPDS No.24-667, product degree of crystallinity is high；SEM test result display product is nano thread structure, wherein nanowire diameter 150～280 Nanometer, length 2.0～3.0 microns.At water and oxygen index, the anhydrous and oxygen-free glove box less than 1ppm carries out Li-ion batteries piles Dress, selecting high purity lithium sheet in assembling is negative pole, and the volume ratio containing 1mol/L lithium hexafluoro phosphate is diethyl carbonate and the carbon of 1: 1 Vinyl acetate mixed liquor is as electrolyte；Li3VO4Nano wire, Kynoar and conductive black enter according to weight ratio 8: 1: 1 Row is mixed with electrode pastes；Select polypropylene as barrier film；Although nano wire draw ratio reduces, but the lithium-ion electric prepared Pond still demonstrates preferable high rate performance and stable charge-discharge performance in electro-chemical test.
Embodiment 3:
First, at room temperature by lithium carbonate that purity is 99.9% and vanadic anhydride that purity is 99.9% by 3:1's Stoichiometric proportion is sufficiently mixed, and suppresses 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 calcine 1 hour；Secondly, 12 grams are forged Product after burning puts in 23.5 milliliters of distilled water, is sufficiently stirred for 10 minutes, is transferred to normal pressure and with reflux cooling function Microwave radiation reaction unit carries out microwave heating, regulates microwave power 700W, heating-up temperature 100 DEG C, microwave frequency 2450MHz, fully reaction 3 hours；Finally, reacted product is cooled to room temperature, centrifugation with distilled water wash 4 Secondary, then be dried 24 hours in 70 DEG C of baking ovens, i.e. can get final products.XRD test result illustrates, with this understanding gained Product is similarly pure phase Li3VO4Material, all diffraction maximums all can be attributed to JCPDS No.24-667, and degree of crystallinity is high；SEM tests Result display product is nano-material, and wherein nanorod diameter is 200～320 nanometers, length 1.0～1.8 microns.At water and Oxygen index carries out lithium ion battery assembling less than in the anhydrous and oxygen-free glove box of 1ppm, and it is negative for selecting high purity lithium sheet in assembling process Pole, the volume ratio containing 1mol/L lithium hexafluoro phosphate be 1: 1 diethyl carbonate and ethylene carbonate mixed liquor as electrolyte； Li3VO4Nanometer rods, Kynoar and conductive black carry out being mixed with electrode pastes according to weight ratio 8: 1: 1；Select poly- Propylene is as barrier film；Electrochemical results illustrates, nano material draw ratio has considerable influence to battery performance, makes under the conditions of this Standby lithium ion battery high rate performance and stable charge/discharge are poor compared with the performance of lithium ion battery of preparation in embodiment 1.
For proving, patent Example 1-3 of the present invention uses technique effect associated with solid phase synthesis and microwave radiation, work as guarantor Holding the experiment presoma high temperature process heat step operation of early stage but do not use microwave irradiation operation, product can not obtain this specially The Expected Results of profit embodiment 1-3 and novelty:
The comparative example of embodiment 1:
First, at room temperature by lithium carbonate that purity is 99.9% and vanadic anhydride that purity is 99.9% by 3: 1 Stoichiometric proportion is sufficiently mixed, and suppresses 10 minutes under 10Mpa pressure；Then the mixture suppressed is transferred to horse Not in stove, precalcining 3 hours in 550 DEG C of air atmospheres, then be rapidly heated to 900 DEG C calcine 5 hours.The XRD of product tests table Bright resulting materials, all diffraction maximums all can be attributed to JCPDS No.24-667, and degree of crystallinity is high；But the block that pattern is 1-5 micron Body material, can not get the synthetic effect of the nano wire of corresponding embodiment；The chemical property of this material is the most substantially implemented than correspondence The difference of example；Further demonstrate the importance and necessity of invention.
The comparative example of embodiment 2:
First, at room temperature by lithium carbonate that purity is 99.9% and vanadic anhydride that purity is 99.9% by 3: 1 Stoichiometric proportion is sufficiently mixed, and suppresses 10 minutes under 10Mpa pressure；Then the mixture suppressed is transferred to horse Not in stove, precalcining 3 hours in 550 DEG C of air atmospheres, then be rapidly heated to 900 DEG C calcine 3 hours.Target end product The analysis result of XRD spectra shows: all characteristic diffraction peak correspondence JCPDS card No.24-667, and degree of crystallinity is fine；Can It is that the microstructure of this material is the agglomerate body of 1～4.5 micron, can not obtain the technique effect of embodiment 2 at all；This electrode The cyclical stability of material and specific discharge capacity are all not as embodiment 2；Fully again testified invention novelty and Practicality.
The comparative example of embodiment 3:
First, at room temperature by lithium carbonate that purity is 99.9% and vanadic anhydride that purity is 99.9% by 3: 1 Stoichiometric proportion is sufficiently mixed, and suppresses 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 calcine 1 hour；The XRD of synthetic material The signal of the acquisition of test shows: typical characteristic 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 can not obtain the technical characterstic described by embodiment 2；It addition, this nanometer The capability retention of material relatively embodiment 2 is poor；The novelty of invention of fully having testified and novelty.

Claims (4)

  1. Patent the most of the present invention provides a kind of Li with excellent storage lithium performance3VO4The pattern of nano wire regulates and controls method mutually with thing, with Vanadic anhydride and lithium carbonate are raw material, and distilled water is solvent, utilize high-temperature solid phase calcination United microwave radiotechnology to close Become, be achieved through the following technical solutions:
    The first, at room temperature by lithium carbonate that purity is 99.9% and vanadic anhydride that purity is 99.9% by 3: 1 chemistry Metering ratio is sufficiently mixed, and is suppressed 10 minutes by solid-phase mixture under 10Mpa；
    The second, being transferred in Muffle furnace by the mixture after compacting, in 550 DEG C of air atmospheres, precalcining 3 hours, then heat up Calcine again 1～8 hour to 900 DEG C, obtain solid product A；
    3rd, the solid product A after calcining 12 grams adds in 23.5 milliliters of distilled water, is sufficiently stirred for 10 minutes, then shifts To normal pressure and take back flow cooling device microwave reactor in, regulation microwave irradiation power be 100～1200W, heating-up temperature 70 ～300 DEG C, microwave frequency 2450MHz, fully reaction 1～16 hour；
    4th, products therefrom is cooled to room temperature, centrifugation with distilled water wash 4 times, then in 70 DEG C of baking ovens, it is dried 24 Hour, i.e. can get final Li3VO4Nanowire product.
  2. A kind of Li with excellent storage lithium performance3VO4The pattern of nano wire regulates and controls method mutually with thing, It is characterized in that: described Li3VO4The diameter of nano wire is only 80～240 nanometers, and length reaches 3～5 microns, product structure is stable, Draw ratio is big, purity is high, specific surface area dramatically increases.
  3. A kind of Li with excellent storage lithium performance3VO4The pattern of nano wire regulates and controls method mutually with thing, It is characterized in that: described Li3VO4It is the anhydrous and oxygen-free glove less than 1ppm at water and oxygen index that nano wire assembles lithium ion battery Carrying out in case, the negative pole related in assembling selects high purity lithium sheet；Selecting the volume ratio containing 1mol/L lithium hexafluoro phosphate is 1: 1 Diethyl carbonate and ethylene carbonate mixed solvent as electrolyte；Li3VO4Nano wire, Kynoar and conductive black Carry out being mixed with electrode pastes according to weight ratio 8: 1: 1；Select polypropylene as barrier film；Show through battery testing: Li3VO4Receive The lithium ion battery that rice noodle assembles makes electrolyte and Nanowire contacts enlarged areas because of the high-specific surface area of this material, and lithium ion expands The scattered time is obviously reduced, and demonstrates good high rate performance and stable charge-discharge performance in electro-chemical test: nanometer wire rod First week specific discharge capacity that material obtains is 400 mAh g-1With 1.3～0.6V continuous discharge platforms, the 3rd～200 week reversible appearance Amount is 240 mAh g-1, and have～the discharge capacitance of 99.7%, hence it is evident that be better than this patented technology background relates to The block of other method synthesis and nano-particle material, be further characterized by the novelty of this patent, practicality and novelty；In a word This monodimension nanometer material represents advance and the beneficial effect of excellence.
  4. A kind of Li with excellent storage lithium performance3VO4The pattern of nano wire regulates and controls method mutually with thing, It is characterized in that: described Li3VO4The chemical equation related in nano wire building-up process is as follows:
    3Li2CO3+V2O5→2Li3VO4+3CO2。
CN201610850497.5A 2016-09-27 2016-09-27 A kind of Li with excellent storage lithium performance3VO4The pattern of nano wire mutually regulates and controls method with object Active CN106299301B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111943265A (en) * 2020-08-10 2020-11-17 苏州科技大学 High performance liquid phase synthesis LiVO2Microstructure control method of nano-sheet and nano-sphere battery material
CN111977688A (en) * 2020-08-10 2020-11-24 苏州科技大学 Controllable preparation NaVO2Method for preparing nano-sphere sodium storage electrode material
CN115535973A (en) * 2022-10-28 2022-12-30 四川蜀旺新能源股份有限公司 Preparation and application of vanadium-tungsten bimetallic selenide material

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CN103496741A (en) * 2013-09-25 2014-01-08 三峡大学 Li3VO4 negative electrode material prepared by solid-phase reaction method

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CN103496741A (en) * 2013-09-25 2014-01-08 三峡大学 Li3VO4 negative electrode material prepared by solid-phase reaction method

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111943265A (en) * 2020-08-10 2020-11-17 苏州科技大学 High performance liquid phase synthesis LiVO2Microstructure control method of nano-sheet and nano-sphere battery material
CN111977688A (en) * 2020-08-10 2020-11-24 苏州科技大学 Controllable preparation NaVO2Method for preparing nano-sphere sodium storage electrode material
CN111977688B (en) * 2020-08-10 2023-09-22 苏州科技大学 Controllable NaVO preparation 2 Method for preparing nanosphere sodium storage electrode material
CN111943265B (en) * 2020-08-10 2023-11-17 苏州科技大学 LiVO (LiVO) synthesized by high-efficiency liquid phase 2 Microstructure control method of nanosheet and nanosphere battery material
CN115535973A (en) * 2022-10-28 2022-12-30 四川蜀旺新能源股份有限公司 Preparation and application of vanadium-tungsten bimetallic selenide material
CN115535973B (en) * 2022-10-28 2023-06-09 四川蜀旺新能源股份有限公司 Preparation and application of vanadium-tungsten bimetallic selenide material

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