CN108117103A - A kind of vanadic acid cobalt compound and preparation method and application - Google Patents
A kind of vanadic acid cobalt compound and preparation method and application Download PDFInfo
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- CN108117103A CN108117103A CN201711431468.6A CN201711431468A CN108117103A CN 108117103 A CN108117103 A CN 108117103A CN 201711431468 A CN201711431468 A CN 201711431468A CN 108117103 A CN108117103 A CN 108117103A
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- vanadic acid
- acid cobalt
- cobalt compound
- preparation
- bipyridyls
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- -1 vanadic acid cobalt compound Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims abstract description 16
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000002604 ultrasonography Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 23
- 239000010941 cobalt Substances 0.000 claims description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 239000012456 homogeneous solution Substances 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001869 cobalt compounds Chemical class 0.000 claims 1
- SAXCKUIOAKKRAS-UHFFFAOYSA-N cobalt;hydrate Chemical compound O.[Co] SAXCKUIOAKKRAS-UHFFFAOYSA-N 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 11
- 239000007772 electrode material Substances 0.000 abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 abstract 2
- 150000004706 metal oxides Chemical class 0.000 abstract 2
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical class O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 23
- 239000000047 product Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910007966 Li-Co Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910001194 LixV2O5 Inorganic materials 0.000 description 2
- 229910008295 Li—Co Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 229910021276 Co2V2O7 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013124 LiNiVO4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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 vanadic acid cobalt compound, the molecular formula of the vanadic acid cobalt compound is CoV2O6.With and preparation method thereof, include the following steps：It is spare that ammonium metavanadate, cabaltous nitrate hexahydrate and 2,2 bipyridyls are weighed respectively；Cabaltous nitrate hexahydrate is positioned in beaker, deionized water is added in and stirs evenly, 2,2 bipyridyls weighed and ammonium metavanadate stirring is being added in, is obtaining mixed solution；By H3BO3It is added in above-mentioned mixed solution and adjusts pH, then heat；Cooling, ultrasound, drying, collection, obtain product；Product is calcined under air, obtains the vanadic acid cobalt compound.The vanadic acid cobalt compound of the present invention is prepared with 2,2 bipyridyls for template, has relatively low cost, environmental-friendly, higher discharge capacity and higher security；As electrode material, compared to single metal oxides, different metal oxide improves chemical property.
Description
Technical field
The invention belongs to battery material technical fields, specifically, are related to a kind of vanadic acid cobalt compound and preparation method thereof
With application.
Background technology
The energy is the driving source for the basic and human society fast development that we depend on for existence.Lithium battery is as 21 generation
The new energy of discipline is widely used in the different fields such as electronic component, medical instrument, household electrical appliance.At present, the lithium ion of industrialization
It is graphite-like Carbon anode that battery cathode, which mainly uses, and theoretical maximum capacity only has 372mAh/g.Therefore, we are urgent finds newly
Energy and material substitute conventional graphite, promote the chemical property of lithium ion battery.
Transition metal oxide has attracted more and more concerns, because it is suitable for lithium-ion electric as negative material
The advantages that pond has relatively low cost, environmental-friendly, higher theory and security.However, they are deposited in practical applications
It is poor in stability, the problems such as volume change is big, and capacity attenuation is big.Compared to single-phase oxide, mixed-metal oxides can assist
Include electrons/ions electrical conductivity, reversible capacity, mechanical stability with chemical property is improved.
Wherein vanadic acid salt, such as Co (VO3)2, Co2V2O7, LiNiVO4, RVO4(R=In, Cr, Fe, Al) is used as electrochemistry
The material of performance test, the results show α-Co (VO3)2Only 17% irreversible capacity.Vanadic acid cobalt is that a kind of chemical stability is excellent
Good, heat resistance and the good inorganic compound of crystal property have good optics, electrochemistry and catalysis characteristics, in optics device
Part, lithium ion battery, electrochemical sensor and catalyst field have good application prospect, cause the widely studied of people
Interest, it is different according to Co, V, O ratio in material, it can obtain a variety of with different compositions, the vanadic acid cobalt material of structure, China
For the fifth-largest vanadium resource state of the world, there is abundant navajoite resource.
For these reasons, it is special to propose the present invention.
The content of the invention
In order to solve problem above existing in the prior art, the first object of the present invention provides a kind of vanadic acid cobalt chemical combination
Object, the molecular formula of the vanadic acid cobalt compound is CoV2O6。
The second object of the present invention provides a kind of preparation method of the vanadic acid cobalt compound, the preparation method
Include the following steps：
(1) weigh respectively purity be all higher than 99.9% ammonium metavanadate, cabaltous nitrate hexahydrate and 2,2- bipyridyls it is spare；
(2) cabaltous nitrate hexahydrate is positioned in beaker, adds in deionized water and stir 8-12 minutes, form homogeneous solution,
It adds 2, the 2- bipyridyls weighed and ammonium metavanadate stirs 25-35 minutes, obtain mixed solution；
(3) by H3BO3It is 4-6 to be added in above-mentioned mixed solution and adjust pH, then moves in hydrothermal reaction kettle solution and adds
Heat；
(4) room temperature is naturally cooling to, then ultrasound, drying, collection, obtain product；
(5) product is calcined under air, obtains the vanadic acid cobalt compound.
The vanadic acid cobalt compound of the present invention is with the vanadium based compound that 2,2- bipyridyls are template preparation, is used as lithium ion
Negative material shows good discharge capacity, illustrates outstanding cycle performance.
The present invention's prepares vanadic acid cobalt with 2,2- bipyridyls for template, has relatively low cost, environmental-friendly, higher puts
The advantages that capacitance and security performance, compared to single-phase oxide, mixed-metal oxides can improve chemical property, including
Electrons/ions electrical conductivity, reversible capacity, mechanical stability are preferable.
Vanadic acid cobalt prepared by the present invention take on a red color bulk crystal structure and color and luster, transparency it is preferable.
Further, ammonium metavanadate, cabaltous nitrate hexahydrate and 2,2- bipyridyl molar ratio are 6 in step (1):12:1.
Further, the molal volume of cabaltous nitrate hexahydrate and deionized water ratio is 12mmol in step (2):55ml.
Further, H in step (3)3BO3Molar ratio with cabaltous nitrate hexahydrate is 1:1.
Further, H in step (3)3BO3Molal volume ratio with water in hydrothermal reaction kettle is 2mmol：25ml.
Further, heating temperature is 160-180 DEG C in step (3), keeps 70-74h.
Further, drying is at 75 DEG C -85 DEG C, when drying 10-14 is small in step (4).
Further, when calcining is that calcining 3.5-4.5 is small at 580 DEG C -620 DEG C in step (5), heating rate 1.5-
2.5℃/min。
The third object of the present invention provides a kind of application of vanadic acid cobalt compound in lithium ion battery material,
Vanadic acid cobalt compound is used for lithium ion battery negative material, in 100mA g-1Current density under, initial charge/discharge capacity is
564mAh g-1With 856mAh g-1, coulombic efficiency 66%.
Compared with prior art, beneficial effects of the present invention are as follows:
(1) vanadic acid cobalt compound of the invention is prepared with 2,2- bipyridyls for template, has relatively low cost, environment
Close friend, higher discharge capacity and higher security；
(2) vanadic acid cobalt using the present invention is carried as electrode material compared to single-phase oxide or mixed-metal oxides
High chemical property, such as electrons/ions electrical conductivity, reversible capacity, mechanical stability；
(3) when vanadic acid cobalt of the invention is used for electrode material, in 100mAg-1Current density under, initial charge and discharge capacitance
It measures as 564 and 856mAh g-1, adjoint coulombic efficiency 66%；
(4) preparation method of vanadic acid cobalt of the invention is simple, and easily operated, material easily obtains, convenient for large-scale production.
Description of the drawings
It in order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention, for those of ordinary skill in the art, without creative efforts, can be with
Other attached drawings are obtained according to these attached drawings.
Fig. 1：The enlarged drawing of vanadic acid cobalt prepared by embodiment 1 under the microscope；
Fig. 2：XRD spectrum without calcining vanadic acid cobalt prepared by embodiment 1；
Fig. 3：The XRD spectrum of vanadic acid cobalt by calcining prepared by embodiment 1；
Fig. 4：Vanadic acid cobalt prepared by embodiment 1 applies the cyclic voltammetry curve in electrode material；
Fig. 5：Vanadic acid cobalt prepared by embodiment 1 applies the current charging and discharging curve in electrode material；
Fig. 6：Vanadic acid cobalt prepared by embodiment 1 applies the long circulating test chart in electrode material；
Fig. 7：Vanadic acid cobalt prepared by embodiment 1 applies the high rate performance figure in electrode material.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical scheme will be carried out below
Detailed description.Obviously, described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are obtained all on the premise of creative work is not made
Other embodiment belongs to the scope that the present invention is protected.
Embodiment 1
The preparation method of vanadic acid cobalt compound, includes the following steps：
(1) ammonium metavanadate 0.6mmol, cabaltous nitrate hexahydrate 1.2mmol and 2 that purity is all higher than 99.9% are weighed respectively,
2- bipyridyls 1.0mmol is spare；
(2) cabaltous nitrate hexahydrate weighed is positioned in beaker, adds in 5.5ml deionized waters and stir 10 minutes, formed
Homogeneous solution is adding in 2, the 2- bipyridyls that weigh and ammonium metavanadate stirs 30 minutes, is obtaining mixed solution；
(3) by 1.2mmol H3BO3It is 4.5 to be added in above-mentioned mixed solution and adjust pH, and solution then is moved to 15ml water
170 DEG C are heated in thermal response kettle, keeps 72h；
(4) room temperature is naturally cooling to, is then collected after ultrasound, 80 DEG C of drying 12h, obtains product；
(5) by product, 600 DEG C of calcining 4h, heating rate are 2 DEG C/min in air atmosphere, obtain the vanadic acid cobalt
Close object.
Vanadic acid cobalt compound manufactured in the present embodiment can significantly observe under the microscope red bulk crystals and color and luster,
Transparency is good, as shown in Figure 1.It is drawn through XRD detection and analysis, the vanadic acid cobalt compound manufactured in the present embodiment without calcining
Diffraction maximum match with the diffraction maximum that computer mould is drawn up, as shown in Figure 2.Vanadic acid cobalt after calcining prepared by this implementation
The sample of compound through XRD analysis the result shows that, except * mark diffraction maximum position correspond to HxV2O5Standard card JCPDS NO
Outside 45-0429, remaining diffraction maximum can correspond to CoV well2O6Standard card JCPDS NO 38-0090, as shown in Figure 3.
Battery is made in vanadic acid cobalt compound manufactured in the present embodiment as follows：
(1) by vanadic acid cobalt sample obtained and carbon black and Kynoar in mass ratio 7:2:After 1 ratio mixing fully
Grinding, wears into slurry by solvent of N-Methyl pyrrolidone, coated on copper foil, 6h is dried in vacuo at 120 DEG C；
(2) using lithium metal as to electrode, Celgard films are membrane, dissolved with LiPF6The EC+DMC+DEC of (1mol/L)
(volume ratio 1：1：1) it is electrolyte, CR2032 type batteries is assembled into the glove box of argon atmosphere；
(3) after standing 6h, LANHE CT2001A test systems is selected to carry out constant current charge-discharge test, test voltage is selected
3-0.01V。
Fig. 4 describes CoV manufactured in the present embodiment2O6 materials are in voltage range 0.01V-3V with the scanning speed of 0.5mV/s
Spend the cyclic voltammetry curve carried out.In first cathodic scan, two reduction peaks are concentrated mainly on 0.32V and 2.42V,
Corresponding to CoV2O6Crystal structure is disintegrated, and forms CoO and LixV2O5And the SEI films formed on fresh surface；It is laggard
One step is reduced into metal Co, forms Li-Co alloys.Another side, the anodic scan of a cycle show that two anode peaks exist
1.48V and 2.73V, the former is attributed to the de- alloy reaction of Li-Co, and lithium ion is from LixV2O5Abjection and Li2The decomposition of O, and
Co (0) is oxidized to CoO.It is saved in the two the cycling of anode peak below, simply peak position is slightly offset.
In the cathodic scan of two circles, cathode peak equally occurs shifting (0.32 → 0.38V), and peak shape becomes sharp keen, another peak position quilt
It is complete to retain；It is basically identical with the second circle in the scanning of the 3rd circle, illustrate the structural intergrity of material or preferable,
There is a slight cathode peak in 0.28V or so, shows a simpler reduction reaction, is attributed to swashing for the first two cycle
Active should.The material is in 100mA g-1Current density under voltage range 0-3V constant current charge-discharge curve.As shown in figure 5,
In first time discharge curve, voltage quickly falls to 0.75V and a platform occurs, then occurs second in 0.4V or so
Platform gradually decreases to discharge capacity 856mAh g-1, it is considered that this process be irreversible procedure, the decomposition including electrolyte
With the formation of SEI films, interface lithium storage is defined as, therefore initial charge/discharge capacity is 564mAh g-1With 856mAh g-1, phase
When in 5.4mol and 8.2mol Li+Deviate from/be inserted into material, adjoint coulombic efficiency 66%.
In second and third circle Xun Huan, discharge capacity is decayed, but coulombic efficiency increases, more than 85%.Fig. 6
Material is disclosed in 100mA g-1Under cyclic curve and coulombic efficiency, cycle 100 times after still have 222mAh g-1Can inverse put
Capacitance, cycle efficieny are not less than 98%, illustrate that the cyclicity of the material is good.Fig. 7 is electrode material in 100mAg-1、
200mAg-1、400mA g-1、800mA g-1Current density under high rate performance, respectively reach 373mAh g-1、292mAh g-1、254mAh g-1、228mAh g-1Discharge capacity, when electric current return to 100mA g-1When, discharge capacity is 257mAh g-1、
284mAh g-1、302mAh g-1, very close initial value shows at higher current densities without apparent capacity attenuation, explanation
Material has excellent high rate performance.
Embodiment 2
The preparation method of vanadic acid cobalt compound, includes the following steps：
(1) ammonium metavanadate 1.2mmol, cabaltous nitrate hexahydrate 2.4mmol and 2 that purity is all higher than 99.9% are weighed respectively,
2- bipyridyls 2.0mmol is spare；
(2) cabaltous nitrate hexahydrate weighed is positioned in beaker, adds in 11ml deionized waters and stir 8 minutes, formed equal
Even solution is adding in 2, the 2- bipyridyls that weigh and ammonium metavanadate stirs 25 minutes, is obtaining mixed solution；
(3) by 2.4mmol H3BO3It is 4 to be added in above-mentioned mixed solution and adjust pH, and solution then is moved to 30ml hydro-thermals
160 DEG C are heated in reaction kettle, keeps 70h；
(4) room temperature is naturally cooling to, is then collected after ultrasound, 75 DEG C of drying 10h, obtains product；
(5) by product, 580 DEG C of calcining 3.5h, heating rate are 1.5 DEG C/min in air atmosphere, obtain the vanadic acid
Cobalt compound.
The vanadic acid cobalt chemical combination such as identical condition of embodiment 1 manufactured in the present embodiment has carried out XRD tests, result of the test and reality
It is basically identical to apply example 1.
Using the method for embodiment 1, electrode material is made in the vanadic acid cobalt chemical combination of the present embodiment, has carried out Xun Huan volt respectively
It is basically identical with embodiment 1 to pacify curve, constant current charge-discharge curve, long circulating test and high rate performance test, result.
Embodiment 3
The preparation method of vanadic acid cobalt compound, includes the following steps：
(1) ammonium metavanadate 1.2mmol, cabaltous nitrate hexahydrate 2.4mmol and 2 that purity is all higher than 99.9% are weighed respectively,
2- bipyridyls 2.0mmol is spare；
(2) cabaltous nitrate hexahydrate weighed is positioned in beaker, adds in 11ml deionized waters and stir 12 minutes, formed equal
Even solution is adding in 2, the 2- bipyridyls that weigh and ammonium metavanadate stirs 35 minutes, is obtaining mixed solution；
(3) by 2.4mmol H3BO3It is 6 to be added in above-mentioned mixed solution and adjust pH, and solution then is moved to 30ml hydro-thermals
180 DEG C are heated in reaction kettle, keeps 74h；
(4) room temperature is naturally cooling to, is then collected after ultrasound, 85 DEG C of drying 14h, obtains product；
(5) by product, 620 DEG C of calcining 4.5h, heating rate are 2.5 DEG C/min in air atmosphere, obtain the vanadic acid
Cobalt compound.
The vanadic acid cobalt chemical combination such as identical condition of embodiment 1 manufactured in the present embodiment has carried out XRD tests, result of the test and reality
It is basically identical to apply example 1.
Using the method for embodiment 1, electrode material is made in the vanadic acid cobalt chemical combination of the present embodiment, has carried out Xun Huan volt respectively
It is basically identical with embodiment 1 to pacify curve, constant current charge-discharge curve, long circulating test and high rate performance test, result.
The above description is merely a specific embodiment, but protection scope of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can readily occur in change or replacement, should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. a kind of vanadic acid cobalt compound, which is characterized in that the molecular formula of the vanadic acid cobalt compound is CoV2O6。
2. a kind of preparation method of vanadic acid cobalt compound described in claim 1, which is characterized in that the preparation method includes
Following steps：
(1) weigh respectively purity be all higher than 99.9% ammonium metavanadate, cabaltous nitrate hexahydrate and 2,2- bipyridyls it is spare；
(2) cabaltous nitrate hexahydrate is positioned in beaker, adds in deionized water and stir 8-12 minutes, form homogeneous solution, adding
Enter 2, the 2- bipyridyls weighed and ammonium metavanadate stirs 25-35 minutes, obtain mixed solution；
(3) by H3BO3It is 4-6 to be added in above-mentioned mixed solution and adjust pH, then moves in hydrothermal reaction kettle solution and heats；
(4) room temperature is naturally cooling to, then ultrasound, drying, collection, obtain product；
(5) product is calcined under air, obtains the vanadic acid cobalt compound.
3. the preparation method of vanadic acid cobalt compound according to claim 2, which is characterized in that ammonium metavanadate in step (1),
Cabaltous nitrate hexahydrate and 2,2- bipyridyls molar ratio are 6:12:1.
4. the preparation method of vanadic acid cobalt compound according to claim 2, which is characterized in that six hydration nitre in step (2)
The molal volume of sour cobalt and deionized water ratio is 12mmol:55ml.
5. the preparation method of vanadic acid cobalt compound according to claim 2, which is characterized in that H in step (3)3BO3With six
The molar ratio of nitric hydrate cobalt is 1:1.
6. the preparation method of the vanadic acid cobalt compound according to claim 2 or 5, which is characterized in that H in step (3)3BO3With
The molal volume ratio of water is 2mmol in hydrothermal reaction kettle：25ml.
7. the preparation method of vanadic acid cobalt compound according to claim 2, which is characterized in that heating temperature in step (3)
For 160-180 DEG C, 70-74h is kept.
8. the preparation method of vanadic acid cobalt compound according to claim 2, which is characterized in that in step (4) drying be
At 75 DEG C -85 DEG C, when drying 10-14 is small.
9. the preparation method of vanadic acid cobalt compound according to claim 2, which is characterized in that in step (5) calcining be
When calcining 3.5-4.5 is small at 580 DEG C -620 DEG C, heating rate is 1.5-2.5 DEG C/min.
A kind of 10. application of vanadic acid cobalt compound described in claim 1 in lithium ion battery material, which is characterized in that vanadium
Sour cobalt compound is used for lithium ion battery negative material, in 100mA g-1Current density under, initial charge/discharge capacity is
564mAh g-1With 856mAh g-1, coulombic efficiency 66%.
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| CN109455770A (en) * | 2018-11-05 | 2019-03-12 | 青岛科技大学 | A kind of electrode material vanadic acid cobalt, preparation method and application |
| CN109534401A (en) * | 2018-11-12 | 2019-03-29 | 青岛科技大学 | A kind of preparation method of copper vanadate, the copper vanadate that this method is prepared and its application in lithium ion battery |
| CN109574822A (en) * | 2019-01-22 | 2019-04-05 | 天津师范大学 | A series of four aryl spiro-compounds and the preparation method and application thereof |
| CN109694322A (en) * | 2019-01-22 | 2019-04-30 | 天津师范大学 | Application of the four aryl loop coil polyacid compounds on lithium ion battery |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109455770A (en) * | 2018-11-05 | 2019-03-12 | 青岛科技大学 | A kind of electrode material vanadic acid cobalt, preparation method and application |
| CN109455770B (en) * | 2018-11-05 | 2021-02-02 | 青岛科技大学 | Electrode material cobalt vanadate, and preparation method and application thereof |
| CN109534401A (en) * | 2018-11-12 | 2019-03-29 | 青岛科技大学 | A kind of preparation method of copper vanadate, the copper vanadate that this method is prepared and its application in lithium ion battery |
| CN109534401B (en) * | 2018-11-12 | 2021-08-27 | 青岛科技大学 | Preparation method of copper vanadate, copper vanadate prepared by method and application of copper vanadate in lithium ion battery |
| CN109574822A (en) * | 2019-01-22 | 2019-04-05 | 天津师范大学 | A series of four aryl spiro-compounds and the preparation method and application thereof |
| CN109694322A (en) * | 2019-01-22 | 2019-04-30 | 天津师范大学 | Application of the four aryl loop coil polyacid compounds on lithium ion battery |
| CN109694322B (en) * | 2019-01-22 | 2021-05-04 | 天津师范大学 | Application of tetraaryl spiro polyacid compound in lithium ion battery |
| CN109574822B (en) * | 2019-01-22 | 2021-12-21 | 天津师范大学 | Series of tetraaryl spiro-compounds, preparation method and application thereof |
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