CN104993129A - Vanadium-based positive material for lithium ion batteries, and preparation method thereof - Google Patents
Vanadium-based positive material for lithium ion batteries, and preparation method thereof Download PDFInfo
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- CN104993129A CN104993129A CN201510258645.XA CN201510258645A CN104993129A CN 104993129 A CN104993129 A CN 104993129A CN 201510258645 A CN201510258645 A CN 201510258645A CN 104993129 A CN104993129 A CN 104993129A
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 57
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 47
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title abstract description 51
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000002127 nanobelt Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 230000014759 maintenance of location Effects 0.000 claims abstract description 5
- 239000010405 anode material Substances 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000011575 calcium Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 159000000007 calcium salts Chemical class 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 18
- 239000013077 target material Substances 0.000 abstract description 15
- DNWNZRZGKVWORZ-UHFFFAOYSA-N calcium oxido(dioxo)vanadium Chemical compound [Ca+2].[O-][V](=O)=O.[O-][V](=O)=O DNWNZRZGKVWORZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010891 electric arc Methods 0.000 abstract description 3
- 229910009112 xH2O Inorganic materials 0.000 abstract 1
- 230000004087 circulation Effects 0.000 description 18
- 239000002585 base Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000009830 intercalation Methods 0.000 description 8
- 230000002687 intercalation Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000123 polythiophene Polymers 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
-
- 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 invention discloses a vanadium-based positive material for lithium ion batteries, and a preparation method thereof. The molecular formula of the vanadium-based positive material is CaV6O16.xH2O (x is greater than 1 and smaller than 10). The positive material is a calcium vanadate ultra-long nanobelt, and is uniformly dispersed, the width is 100-500nm, and the length is 1-5mm. The preparation method is a room temperature arc discharge-hydrothermal synthesis two-step method, and concretely comprises the following steps: carrying out room temperature arc discharge to prepare a vanadium precursor solution, adjusting the pH value, and carrying out hydrothermal synthesis to obtain the target material. When the vanadium-based positive material prepared in the invention is applied in lithium ion batteries, the material has excellent rate performance, long life and cycle stability; and the discharge capacity of the material can reach 268mAh.g<-1> under a current density of 50mA.g<-1>. The capacity retention rate of the material after 1000 cycles under 2A.g<-1> can reach 83.6%, and the capacity retention rate of the material after 1000 cycles under 6A.g<-1> can reach 89.5%.
Description
Technical field
The present invention relates to technical field of material chemistry and high-energy battery field of material technology, be specifically related to a kind of novel high magnification and long circulation life lithium ion battery vanadium base anode material and preparation method thereof.
Background technology
Along with the application of lithium ion battery is to the expansion in the field such as electric automobile, intelligent grid, industry has had higher requirement to its chemical property.And positive electrode is the key of lithium ion battery development, it is not only the restraining factors of lithium ion battery price, is also the important decisive factor of lithium ion battery power density and energy density.Therefore, the exploitation of high power capacity, high-power lithium ion battery positive electrode, becomes study hotspot in recent years.Main flow positive electrode in the market, as the LiCoO of layer structure
2, olivine structural LiFePO
4vanadium etc., actual capacity is all at 170mAh g
-1below, and with high costs, be difficult to the actual demand meeting following extensive energy storage field.In recent years, the oxide of vanadium and vanadate thereof, day by day receive publicity because of advantages such as capacity are high, synthesis technique is simple, cost is low, become a kind of desirable potential alternative positive electrode that can meet tomorrow requirement.But because vanadium based material electron conduction is poor, material structure is unstable, cause that cyclical stability is poor and high rate performance is undesirable, cause its commercial applications and be subject to great limitation and challenge.Therefore, the vanadium based material of Development of New Generation high magnification, cycle performance excellence, seems very necessary.
The research of current vanadium system positive pole intercalation materials of li ions mainly concentrates on the oxide of vanadium (as V
2o
5, VO
2deng), three vanadate are (as LiV
3o
8, NaV
3o
8deng).Vanadium based material is because having open layer structure, and easily embed more lithium ion (each unit can embed 2 and above lithium ion), capacity is higher, but cyclical stability and high rate performance in urgent need to be improved with improvement.The reason that cyclical stability is poor, main one side causes irreversible transition due to the multivalent state of vanadium in charge and discharge process, on the other hand due in charge and discharge process, the embedding of lithium ion inevitably brings distortion of lattice with deviating from, and material structure torsional deformation is even caved in; High rate performance deficiency lower mainly due to vanadium based material electronic conductivity.Bibliographical information majority concentrates on the research improving its cyclical stability, and small part is absorbed in lifting and the improvement of high rate performance.Research means mostly is the study on the modification such as Surface coating, doping, conducting polymer compound; Or utilize nano material technology, design new nanostructure and improve its chemical property.As Guo etc. [Journal of Power Sources. 247(2014) 117-126] utilizes polythiophene (PTh) to LiV
3o
8burden is carried out on surface, obtains the LiV of 15 wt.%
3o
8/ PTh compound.At 300 and 900 mA g
1current density under first discharge capacity reach 213.3 and 200.3mAh g respectively
1, after 50 circulations, capacity is without obvious decay.Song etc. [J. Mater. Chem. A. 3(2015) 3547 – 3558] replace LiV with metal M o
3o
8part V in layer, namely adulterates to V position.After doping Mo, effectively increase stability and the electron conduction of material crystal structure; Define Lacking oxygen simultaneously, improve lithium ion diffusion coefficient in the material.Cycle performance and the high rate performance of material all obtain obviously promoting and improving compared with not adulterating.Jouanne etc. [J. New Mater. Electrochem. Syst. 5(2002) 191-196] adopt ion-exchange to synthesize alkaline-earth metal ions to LiV
3o
8adulterating in middle lithium position, obtains Li
1.1-2ym
yh
zv
3o
8series intercalation materials of li ions (M=Mg, Ca, Ba; Y=0.05-0.2; Z=0.1).Though the material circulation performance after mixing is improved, sacrifice corresponding discharge capacity.Liu etc. [Energy Environ. Sci., 4(2011) 4000 – 4008], utilize the V of one dimension
2o
5overlong nanowire and two-dimensional graphene nanometer sheet (GNS) compound, prepare V
2o
5nanowires/GNS compound.When being applied to lithium electricity positive electrode, it shows very excellent high rate performance, 1.6 A g
– 1under current density, discharge capacity is up to 316 mAh g
– 1.But its cycle performance still urgently improves raising, under 0.4 current density, after 50 circulations, capacity is surplus 190 mAh g only
– 1.Except above-mentioned coated, doping and composite conductive polymer, designing special nanostructure is also improve a kind of effective means of vanadium base intercalation materials of li ions, as Wei etc. [Adv. Funct. Mater. 25(2015) 1773 – 1779] devises a kind of H
2v
3o
8the regulatable multi-layer nano volume structure of pattern, this nanometer roll structure effectively can discharge Lithium-ion embeding and deviate from the material structure stress that process produces, and the space simultaneously between volume provides cushion space in volumetric expansion process, slow down caving in of the structure that stress causes.Therefore the cyclical stability of material is greatly improved, as at 1.0 A g
– 1current density, tests under 2.0 4.0 V voltage windows, and after 500 circulations, capacity still can keep 80.6%.Wang etc. [Energy Environ. Sci., 5(2012) 6173] by design hydro-thermal-solid-phase sintering two-step method, prepare finely dispersed Na
1.08v
3o
8ultrathin nanometer sheet.The thickness in monolayer of this nanometer sheet is less than 10nm, highly shortened the diffusion length of lithium ion, and material shows excellent high rate performance, and 30C, 50C high magnification discharge capacity still can reach 95,75 mAh g respectively
– 1, but only give the performance of 200 circulations.
From the result by references of report, long circulation life and to have the vanadium-based materials of good high rate performance concurrently rarely found is more the lifting and the improvement that stress single aspect.And the technique improved is how comparatively complicated, is not suitable for large-scale production.Along with the development of nanometer technology and the application in energy storage material field thereof, find a kind of new vanadium base intercalation materials of li ions, and design special nanostructure from structure, unavoidably for reaching a shortcut of above requirement.The present invention is to find new vanadium base intercalation materials of li ions for target, and easier method synthesis of nano structure is means, utilizes brand-new technique to synthesize calcium vanadate overlength nanobelt.The length of nanobelt can reach grade, has effectively evaded reunion difficult problem during Application of micron.When the overlength calcium vanadate overlength nanobelt of synthesis is applied to anode material for lithium-ion batteries, show excellent high rate performance and long circulation life.
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the object of this invention is to provide a kind of lithium ion battery vanadium base anode material, is novel high magnification and long circulation life material.Another object of the present invention is to provide a kind of preparation method of above-mentioned lithium ion battery vanadium base anode material, by two easier step synthesis techniques, prepare a kind of long circulation life, have the novel vanadium base lithium ion positive electrode for battery material of high-rate characteristics concurrently simultaneously, the difficult problem that synchronous solution current vanadium system intercalation materials of li ions cycle performance is poor, high rate performance is not good, with extensive energy storage demand in satisfied future.
Technical scheme: for achieving the above object, the technical solution used in the present invention is:
A kind of lithium ion battery vanadium base anode material, its chemical formula is CaV
6o
16xH
2o, 1<x<10.
Described lithium ion battery vanadium base anode material is overlength nanobelt, and width is 100 ~ 500nm, and length is 1 ~ 5mm.
Vanadium has multiple oxidation state, can form multiple ligand with oxygen coordination, and each ligand is interconnected by the mode on common drift angle or common limit, forms multiple V-O stratiform frame structure.Can hold various metals cation between this stratiform framework, adjacent levels is coupled together by ionic bond by metal cation.Metal cation does not very easily depart from its sites position in charge and discharge process, in fact plays and supports and the effect of stable crystal structure.Therefore, CaV
6o
16xH
2o(1<x<10) crystal structure is the layer-structure frame of the monocline that V-O construction unit is built, Ca and H
2o is embedded in the interlayer in frame structure.Such special crystal structure is conducive to the performance of its chemical property.On the one hand, the metal cation of divalence or multivalence is embedded in V-O stratiform frame structure, as alkaline-earth metal Ca, due to Ca Dai Liangge unit positive charge, comparatively can form stronger ionic bond by alkali metal ion (as Li, Na, K etc.) in interlayer like this, the crystal structure formed is more stable, and the cycle performance of material can correspondingly be improved.On the other hand, the hydrone in interlayer has expanded interlamellar spacing further, and the metal cation that effectively can make up divalence embeds rear because of stronger electrostatic effect, causes the slight shrinkage of interlamellar spacing.In crystal, the migration of lithium ion controls by diffusing step, and lithium ion diffusion admittance is larger, is more conducive to its deintercalation, and therefore the embedding of hydrone causes the expansion of interlamellar spacing to make material have the potential quality of high-rate characteristics.And the existence also corresponding hydrogen bond that brings of simultaneously hydrone, connect levels, crystal structure is tended towards stability more, effectively can resist lithium ion and embed the crystal lattice stress brought in process, thus ensure that the electrochemical cycle stability of material.
The preparation method of described lithium ion battery vanadium base anode material, takes calcium salt and adds in deionized water, and be stirred to and dissolve completely, preparation obtains calcium salt soln; Vanadium metal line is received two poles, and one of them electrode inserts in described calcium salt soln, and another electrode is placed in the interface of liquid level and air; Switch on power, by transformer, the voltage between two electrodes is transferred to suitable voltage; The electrode inserted in calcium salt soln dissolves gradually and enters in solution, and another electrode, at liquid-gas interface place, arcing events occurs, and under huge exothermic conditions, enters solution after frit reaction, finally obtains blackish green V
3+precursor solution; Aqueous slkali is utilized to regulate the pH of precursor solution; Then the autoclave that 100mL polytetrafluoroethylene is liner is proceeded to, hydro-thermal reaction; Naturally, after cooling, after repeatedly cleaning with deionized water and alcohol, be drying to obtain.
Described calcium salt is Ca(NO
3)
2, CaSO
4, CaCl
2in one.
Described calcium salt soln concentration is 0.01 ~ 1mol L
-1.
It is 100 ~ 220V that described voltage is adjusted to.
Described aqueous slkali is NaOH, KOH, Ca(OH)
2, NH
3h
2one in O.
Described pH value is adjusted to 5 ~ 10.
The temperature of described hydro-thermal reaction is 100 ~ 250 DEG C, and temperature retention time is 4h ~ 48h.
Described drying mode is that nature dries, forced air drying, one in freeze drying.
Preparation method of the present invention is easier two-step synthesis method, has prepared calcium vanadate overlength nanobelt, has had the advantage of its uniqueness when the one-dimentional structure of this overlength is applied to energy storage material field, effectively can evade a reunion difficult problem for nano material.The one-dimentional structure of this overlength and the divalent calcium ions of vanadium oxygen intercalation and hydrone play cooperative effect, obtain the vanadium base anode material of a kind of novel high magnification, long circulation life.
Beneficial effect: compared with prior art, the present invention has following significant advantage:
1) by two easy step synthesis techniques, novel high performance lithium ion battery vanadium base anode material is prepared.2) the vanadium base anode material of the present invention's synthesis is finely dispersed overlength nanobelt, and length can reach grade, has the advantage of its uniqueness when the one-dimentional structure of overlength is applied to energy storage material field, effectively can evade a reunion difficult problem for nano material.3) the vanadium base anode material that prepared by the present invention has long circulation life and has excellent high rate performance concurrently.4) difficult problem that vanadium base intercalation materials of li ions field cycle performance is poor, high rate performance is not enough is synchronously solved.Simultaneously, what the present invention proposed utilizes the metal cation of divalence or multivalence such as alkaline earth metal cation to be embedded in vanadium oxygen layer shape framework thus the vanadate of preparation, be applied to the thinking of lithium ion battery high-performance positive electrode, for the research of other high performance vanadium sill of Future Development provides reference.
Accompanying drawing explanation
Fig. 1 is room temperature arc discharge device schematic diagram;
Fig. 2 is embodiment 1, embodiment 2 prepares target material XRD curve chart;
Fig. 3 is that the EDS mapping that embodiment 1 prepares target material schemes;
Fig. 4 is the FE-SEM figure that embodiment 1 prepares target material;
Fig. 5 executes example 1 to prepare target material at 200mA g
1cycle performance figure under current density;
Fig. 6 executes the high rate performance figure that example 1 prepares target material;
Fig. 7 be execute example 1 prepare target material at 2A g
1, 6A g
1long circulation life figure under current density;
Fig. 8 is that embodiment 2 prepares target material at 2A g
1cycle life figure under current density;
The material that Fig. 9 is example 3, prepared by example 4, example 5 is respectively at 200mA g
1cycle performance figure under current density.
Embodiment
The invention will be further described by the following examples, and unrestricted the present invention.
Embodiment 1
Take the Ca(NO of 2.98 g
3)
2join in the deionized water of 250mL, be stirred to it and dissolve completely, preparation obtains 0.05mol L
-1ca(NO
3)
2solution.Take 0.3 g vanadium metal line and receive two poles, electrode 1 is inserted into Ca(NO
3)
2in solution, electrode 2 is placed in the interface of liquid level and air.Switch on power, by transformer, the voltage between two electrodes is transferred to 150V.Electrode 1 dissolves gradually and enters in solution, and electrode 2, at liquid-gas interface place, arcing events occurs, and electrode 2 melting under huge exothermic conditions enters solution, finally obtains the precursor solution (Fig. 1 is shown in by arc discharge device schematic diagram) of vanadium.With dilute NaOH solution, precursor solution pH is adjusted to 7.Proceeded to by solution in the autoclave that 100mL polytetrafluoroethylene is liner again, control liquor capacity 80mL, sealing is placed in baking oven, is warming up to 200 DEG C, insulation 24h.Naturally take out after cooling, deionized water, alcohol respectively clean several times, and namely freeze drying obtains target material.Fig. 2 is shown in by its XRD collection of illustrative plates, and from XRD, obtained product is the monocline CaV of pure phase
6o
16xH
2o (1<x<10).By EDS mapping(Fig. 3) in known product only containing Ca, V, O tri-kinds of elements.FE-SEM(Fig. 4) display, product is finely dispersed overlength nanobelt structure, and nanobelt width 100-500nm, length can reach 1mm-5mm.
By the target material, conductive carbon (Super P), the binding agent (Kynoar that prepare, PVDF) mix according to the ratio of 7:2:1, with 1-METHYLPYRROLIDONE (NMP) for solvent, ultrasonic disperse also stirs 5h, obtained slurry, adopt scraper to be evenly coated on aluminium foil, be completely placed in vacuum drying chamber 80 DEG C of dry 12h.Take metal lithium sheet as negative pole, 11mol L-1 LiPF
6eCE:MC:DMC(1:1:1, volume ratio) mixed liquor be electrolyte, in the glove box being full of high-purity Ar gas, assembling CR2032 type button cell.24h is left standstill, with LAND CT 2001A tester at room temperature to its test chemical property before battery testing.Adopt constant current charge-discharge pattern, voltage window 1.5 ~ 4.0V.Fig. 5 is that it is at 200mA g
1cycle performance under current density, the capacity of material is increased to about 240 mAh g gradually at first 40 times as seen from the figure
1in time, starts to stablize, and after 200 circulations, capacity is decayed without detail, and coulombic efficiency is close to 100%, embodies excellent embedding lithium invertibity.Fig. 6 is its high rate performance, and material is at 6A g as seen from the figure
1, 10A g
1under, material capacity still can release 103 mAh g
1, 78 mAh g
1capacity, when current density returns to 100 A g
1after, capacity also recovers substantially, and continues through 100 circulations, and capacity without obviously decay, shows very excellent high rate performance substantially.Fig. 7 is that material is at 2A g
1, 6A g
1after experiencing 1000 circulations under current density, material capacity conservation rate can reach 83.6% respectively, 89.5%(is relative to peak capacity), embody the long circulation life of this material excellence.From the above, the calcium vanadate overlength nanobelt prepared, shows high magnification and to hold concurrently long cycle life characteristics when being applied to anode material for lithium-ion batteries.
Embodiment 2
Take the Ca(NO of 2.98 g
3)
2join in the deionized water of 250mL, be stirred to it and dissolve completely, preparation obtains 0.05mol L
-1ca(NO
3)
2solution.Take 0.3g vanadium metal line and receive two poles, electrode 1 is inserted into Ca(NO
3)
2in solution, electrode 2 is placed in the interface of liquid level and air.Switch on power, by transformer, the voltage between two electrodes is transferred to 150V.Electrode 1 dissolves gradually and enters in solution, and electrode 2, at liquid-gas interface place, arcing events occurs, and electrode 2 melting under huge exothermic conditions enters solution, finally obtains the precursor solution of vanadium.With dilute NaOH solution, described precursor solution pH is adjusted to 6.Proceeded to by solution in the autoclave that 100mL polytetrafluoroethylene is liner again, control liquor capacity 80mL, sealing is placed in baking oven, is warming up to 200 DEG C, insulation 24h.Naturally take out after cooling, deionized water, alcohol respectively clean several times, and namely freeze drying obtains target material.Fig. 2 is its XRD collection of illustrative plates, and known pH is 6 obtained material XRD characteristic peaks compared with pH is that 6 obtained materials are weak, illustrate crystallinity than pH be 7 low.
Cell making process is with embodiment 1.Fig. 8 is that the obtained material of this example is at 2A g
1cycle life figure under current density, material capability retention after 700 circulations can reach 83.8%(relative to peak capacity).Relative to high crystalline target material (as embodiment 1), cycle performance is slightly poorer, and it is relatively poor that main cause is attributable to low-crystalline crystal structural stability.
Embodiment 3
Take the Ca(NO of 5.96 g
3)
2join in the deionized water of 250mL, be stirred to it and dissolve completely, preparation obtains 0.1 mol L
-1ca(NO
3)
2solution.Take 0.3 g vanadium metal line and receive two poles, electrode 1 is inserted into Ca(NO
3)
2in solution, electrode 2 is placed in the interface of liquid level and air.Switch on power, by transformer, the voltage between two electrodes is transferred to 150V.Electrode 1 dissolves gradually and enters in solution, and electrode 2, at liquid-gas interface place, arcing events occurs, and electrode 2 melting under huge exothermic conditions enters solution, finally obtains the precursor solution of vanadium.With dilute NaOH solution, described precursor solution pH is adjusted to 7.Proceeded to by solution in the autoclave that 100mL polytetrafluoroethylene is liner again, control liquor capacity 80mL, sealing is placed in baking oven, is warming up to 200 DEG C, insulation 18h.Naturally take out after cooling, deionized water, alcohol respectively clean several times, and namely freeze drying obtains target material.
Cell making process is with embodiment 1.Fig. 9 is that the obtained material of this example is at 200mA g
1cycle performance under current density, incipient stage capacity increases gradually, until stable capacity 238 mAh g
1, following cycle is without obvious capacity attenuation, substantially similar with example 1.
Embodiment 4
Take the Ca(NO of 2.98 g
3)
2join in the deionized water of 250mL, be stirred to it and dissolve completely, preparation obtains 0.05mol L
-1ca(NO
3)
2solution.Take 0.3 g vanadium metal line and receive two poles, electrode 1 is inserted into Ca(NO
3)
2in solution, electrode 2 is placed in the interface of liquid level and air.Switch on power, by transformer, the voltage between two electrodes is transferred to 200V.Electrode 1 dissolves gradually and enters in solution, and electrode 2, at liquid-gas interface place, arcing events occurs, and electrode 2 melting under huge exothermic conditions enters solution, finally obtains the precursor solution of vanadium.With dilute NaOH solution, described precursor solution pH is adjusted to 7.Proceeded to by solution in the autoclave that 100mL polytetrafluoroethylene is liner again, control liquor capacity 80mL, sealing is placed in baking oven, is warming up to 180 DEG C, insulation 24h.Naturally take out after cooling, deionized water, alcohol respectively clean several times, and namely freeze drying obtains target material.
Cell making process is with embodiment 1.Fig. 9 is that the obtained material of this example is at 200mA g
1cycle performance under current density, incipient stage capacity increases gradually, until stable capacity 243 mAh g
1, following cycle is without obvious capacity attenuation.
Embodiment 5
Take the Ca(NO of 2.98 g
3)
2join in the deionized water of 250mL, be stirred to it and dissolve completely, preparation obtains 0.05mol L
-1ca(NO
3)
2solution.Take 0.3 g vanadium metal line and receive two poles, electrode 1 is inserted into Ca(NO
3)
2in solution, electrode 2 is placed in the interface of liquid level and air.Switch on power, by transformer, the voltage between two electrodes is transferred to 150V.Electrode 1 dissolves gradually and enters in solution, and electrode 2, at liquid-gas interface place, arcing events occurs, and electrode 2 melting under huge exothermic conditions enters solution, finally obtains the precursor solution of vanadium.Use NH
3h
2described precursor solution pH is adjusted to 7 by O.Proceeded to by solution in the autoclave that 100mL polytetrafluoroethylene is liner again, control liquor capacity 80mL, sealing is placed in baking oven, is warming up to 200 DEG C, insulation 24h.Naturally take out after cooling, deionized water, alcohol respectively clean several times, and namely forced air drying obtains target material.
Cell making process is with embodiment 1.Fig. 9 is that the obtained material of this example is at 200mA g
1cycle performance under current density, incipient stage capacity increases gradually, until stable capacity 232 mAh g
1, following cycle is without obvious capacity attenuation.
Claims (10)
1. a lithium ion battery vanadium base anode material, is characterized in that, its chemical formula is CaV
6o
16xH
2o, 1<x<10.
2. lithium ion battery vanadium base anode material according to claim 1, is characterized in that, described lithium ion battery vanadium base anode material is overlength nanobelt, and width is 100 ~ 500nm, and length is 1 ~ 5mm.
3. the preparation method of vanadium base anode material of the lithium ion battery described in claim 1 or 2, is characterized in that, takes calcium salt and adds in deionized water, and be stirred to and dissolve completely, preparation obtains calcium salt soln; Vanadium metal line is received two poles, and one of them electrode inserts in described calcium salt soln, and another electrode is placed in the interface of liquid level and air; Switch on power, by transformer, the voltage between two electrodes is transferred to suitable voltage; The electrode inserted in calcium salt soln dissolves gradually and enters in solution, and another electrode, at liquid-gas interface place, arcing events occurs, and under huge exothermic conditions, enters solution after frit reaction, finally obtains blackish green V
3+precursor solution; Aqueous slkali is utilized to regulate the pH of precursor solution; Then proceed to the autoclave that 100mL polytetrafluoroethylene is liner, control liquor capacity is 80ml, hydro-thermal reaction; Naturally after cooling, with deionized water and alcohol washes several times after, be drying to obtain.
4. the preparation method of lithium ion battery vanadium base anode material according to claim 3, is characterized in that, described calcium salt is Ca(NO
3)
2, CaSO
4, CaCl
2in one.
5. the preparation method of lithium ion battery vanadium base anode material according to claim 3, is characterized in that, described calcium salt soln concentration is 0.01 ~ 1mol L
-1.
6. the preparation method of lithium ion battery vanadium base anode material according to claim 3, is characterized in that, it is 100 ~ 220V that described voltage is adjusted to.
7. the preparation method of lithium ion battery vanadium base anode material according to claim 3, is characterized in that, described aqueous slkali is NaOH, KOH, Ca(OH)
2, NH
3h
2one in O.
8. the preparation method of lithium ion battery vanadium base anode material according to claim 3, it is characterized in that, described pH value is adjusted to 5 ~ 10.
9. the preparation method of lithium ion battery vanadium base anode material according to claim 3, is characterized in that, the temperature of described hydro-thermal reaction is 100 ~ 250 DEG C, and temperature retention time is 4h ~ 48h.
10. the preparation method of lithium ion battery vanadium base anode material according to claim 3, is characterized in that, described drying mode is that nature dries, forced air drying, one in freeze drying.
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| CN112374537A (en) * | 2020-11-02 | 2021-02-19 | 四川大学 | Preparation method of metal vanadate nano composite material |
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