CN106784777A - Alkaline earth metal vanadate electrode material and its preparation method and application - Google Patents
Alkaline earth metal vanadate electrode material and its preparation method and application Download PDFInfo
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- CN106784777A CN106784777A CN201710089238.XA CN201710089238A CN106784777A CN 106784777 A CN106784777 A CN 106784777A CN 201710089238 A CN201710089238 A CN 201710089238A CN 106784777 A CN106784777 A CN 106784777A
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- vanadate
- earth metal
- alkaline earth
- obtains
- strontium
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- 229910052784 alkaline earth metal Inorganic materials 0.000 title claims abstract description 23
- -1 Alkaline earth metal vanadate Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000007772 electrode material Substances 0.000 title abstract description 27
- DNWNZRZGKVWORZ-UHFFFAOYSA-N calcium oxido(dioxo)vanadium Chemical compound [Ca+2].[O-][V](=O)=O.[O-][V](=O)=O DNWNZRZGKVWORZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- YMNMFUIJDSASQW-UHFFFAOYSA-N distrontium;oxygen(2-);vanadium Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[V].[V].[Sr+2].[Sr+2] YMNMFUIJDSASQW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 29
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 26
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 235000011187 glycerol Nutrition 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000009825 accumulation Methods 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 230000002441 reversible effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000002060 nanoflake Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- UPLPHRJJTCUQAY-WIRWPRASSA-N 2,3-thioepoxy madol Chemical compound C([C@@H]1CC2)[C@@H]3S[C@@H]3C[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@](C)(O)[C@@]2(C)CC1 UPLPHRJJTCUQAY-WIRWPRASSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical group O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to the preparation method and applications of a class alkaline earth metal vanadate, such material can be used as sodium-ion battery negative active core-shell material, and it is the micro-flowers spheroidal material of the nanometer sheet accumulation of calcium vanadate or strontium vanadate, and described calcium vanadate molecular formula is CaV4O9, described strontium vanadate molecular formula is SrV4O9, 2~3 μm of its diameter, described calcium vanadate or the nanometer sheet thickness of strontium vanadate are 10~30nm.The beneficial effects of the invention are as follows：Calcium vanadate and strontium vanadate electrode active material are prepared using hydro-thermal method combination Post isothermal treatment, these materials are used as new sodium-ion battery negative active core-shell material, electrochemical performance, shows specific capacity higher, good cyclical stability and excellent high rate performance；Tap density is big simultaneously, with greatly commercialization potential.Additionally, process is simple of the invention, with low cost, building-up process environmental protection is promoted beneficial to the marketization.
Description
Technical field
The invention belongs to nanometer material and electrochemical technology field, and in particular to the preparation side of a class alkaline earth metal vanadate
Method and its application, such material can be used as sodium-ion battery negative active core-shell materials.
Background technology
Fossil fuel reserves increasingly reduce caused energy crisis, and fossil energy excessively uses the environment for bringing
Problem becomes the two big difficult problems faced during social development.Under this background, the development of regenerative resource has been
As a kind of inevitable trend.The efficient utilization of regenerative resource how is realized, is following solution energy crisis and environmental pollution
The key point of two hang-ups.Unstable, discontinuous regenerative resource can effectively be collected and stored by large-scale energy-storage system,
Then stabilization, lasting output are realized when necessary.Large-scale energy-storage system is also considered as what regenerative resource was utilized on a large scale
Necessary condition, its correlative study is significant.Now, lithium ion battery as small portable electronic device accumulator
Part, its development is very fast in recent years.Lithium ion battery possesses good cycle, a series of significant advantages such as specific capacity is big,
But lithium resource is rare, cause the cost Continued of lithium ion battery, which has limited its application in large-scale energy-storage system.
Sodium-ion battery is the transmission that energy is carried out with sodium ion substitution lithium ion, and it has similar knot with lithium ion battery
Structure and similar electrochemical process.And sodium resource has the advantages that low cost, rich reserves, therefore sodium-ion battery is large-scale storage
One of best candidate of energy system, has obtained the extensive concern of researcher.However, sodium-ion battery is currently not yet realized
Large-scale commercial application, its one of the main reasons is not find suitable electrode material.Sodium ion compared to lithium ion, directly
Footpath is bigger, and sodium ion needs to overcome bigger potential barrier in charge and discharge process, causes diffusion rate to substantially reduce, and macroscopically shows
For battery charge and discharge process voltage polarizing is big；Meanwhile, sodium ion, can be to electrode material during electrode material insertion abjection
Structure cause compared with havoc, directly influence the cycle life of battery.Therefore, suitable electrode material is found for sodium ion
The commercialization of battery is most important.
In recent years, the research of sodium ion battery electrode material has had made great progress, especially the development of positive electrode.
But negative material aspect still suffers from larger challenge.When hard carbon is as sodium-ion battery negative pole, its first coulombic efficiency it is low, and
Because there is potential safety hazard close to zero volt in current potential；When ti-based compound is as sodium-ion battery negative pole, because storage sodium site has
Limit and cause capacity too low；Other are based on the material of conversion reaction or alloying reaction due to inevitable in charge and discharge process
Volumetric expansion it is big, cause the easy efflorescence of electrode material then to make the capacity of battery that rapid decay occurs, therefore be more difficult to reality
Apply on border.Therefore, new high-performance negative material is developed significant for the development and industrialization of sodium-ion battery.
Alkaline earth metal vanadate, it works as sodium-ion battery negative active core-shell material, its preparation method and correlative study
Also it is rarely reported at present.
The content of the invention
The present invention is directed to above-mentioned existing scientific and technical problem, there is provided a kind of alkaline earth metal vanadate electrode active material
Preparation method, its preparation process is simple, meets the requirement of Green Chemistry, and the calcium vanadate and strontium vanadate material of gained are used as sodium ion
With specific capacity higher during GND active material, excellent high rate performance and super good cycle performance, are that a class is potential
Commercial sodium-ion battery negative active core-shell material.
The present invention solves the technical scheme that is used of above-mentioned technical problem：Alkaline earth metal vanadate material, it is vanadic acid
The micro-flowers spheroidal material that the nanometer sheet of calcium or strontium vanadate is piled up, described calcium vanadate molecular formula is CaV4O9, described vanadium
Sour strontium molecular formula is SrV4O9, 2~3 μm of its diameter, described calcium vanadate or the nanometer sheet thickness of strontium vanadate be 10~
30nm。
The preparation method of described alkaline earth metal vanadate material, includes following steps：
1) weigh calcium source or barium source is added in glycerine, add deionized water, stir, obtain milky clear molten
Liquid；
2) vanadium source is weighed in proportion to be added in deionized water, add H2O2Solution, stirs 40~90 minutes, obtains orange red
Color solution；
3) by step 1) in the solution that obtains be added to step 2) in the solution that obtains, continue to stir 1.5~3 hours；
4) by step 3) in the solution that obtains be transferred in reactor, carry out hydro-thermal reaction, then take out reactor nature
Room temperature is cooled to, black product is obtained；
5) by step 4) the black product centrifuge washing that obtains, drying；
6) by step 5) desciccate that obtains is sintered heat treatment, then natural cooling, and taking-up obtains final product CaV4O9Or
SrV4O9Sample.
By such scheme, step 1) described in calcium source and barium source be respectively Ca (OH)2With Sr (OH)2；Step 2) described in
Vanadium source be V2O5。
By such scheme, step 1) in reaction system, described glycerine and the volume ratio of deionized water is 1:3~1:
1。
By such scheme, step 4) in hydrothermal temperature be 190~210 DEG C, the hydro-thermal reaction time be 2~5 days.
By such scheme, step 6) in the sintering atmosphere that uses be Ar or N2Deng inert atmosphere, heating rate is 2~5 DEG C/
Min, heat treatment temperature is 350~450 DEG C, and heat treatment time is 3~6h.
Described alkaline earth metal vanadate material as sodium-ion battery negative active core-shell material application.
When calcium vanadate and strontium vanadate are as anode material of lithium-ion battery, V as active element receiving and losing electrons, due to V's
Valence state is changeable, and the gain and loss of multiple electronics is capable of achieving in charge and discharge process, therefore its capacity can be higher relative to titanium base material.Separately
On the one hand, because V-O keys are stronger, V valence states in charge and discharge process cannot drop to 0 valency, therefore the overall Volume Changes phase of material
Material to conversion reaction type can be smaller.Additionally, alkaline-earth metal (Ca and Sr), as inactive elemental, is not involved in electrochemistry anti-
Answer, but the metal oxide (CaO and SrO) of nano-scale, the CaO and SrO of these nano-scales can be changed into during the course of the reaction
Can effectively buffer the Volume Changes in course of reaction, and inhibitory activity nano particle reunion so that electrode material has
Stability and activity higher.Meanwhile, micron floral structure can effectively improve electrode material tap density, make unit in actual production
The active material of more multimass can be loaded on the Copper Foil of area, the total capacity of battery is improved.And constitute the nanometer sheet of micro-flowers
Structure can bring nano effect, there is provided more avtive spots, shorten the diffusion length of sodium ion, so as to improve the power of reaction
Learn performance；
The beneficial effects of the invention are as follows：Calcium vanadate and strontium vanadate electrode active are prepared using hydro-thermal method combination Post isothermal treatment
Property material, these materials show ratio higher as new sodium-ion battery negative active core-shell material, electrochemical performance
Capacity, good cyclical stability and excellent high rate performance；Tap density is big simultaneously, with greatly commercialization potential.This
Outward, process is simple of the invention, with low cost, building-up process environmental protection, is promoted beneficial to the marketization.
Brief description of the drawings
Fig. 1 is the X-ray diffraction spectra figure (XRD) of the calcium vanadate electrode material of embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) and energy dispersion X-ray spectral element of the calcium vanadate electrode material of embodiment 1
Distribution map (EDS)；
Fig. 3 is the transmission electron microscope picture (TEM) of the calcium vanadate electrode material of embodiment 1 and the electron diffraction pattern of selected areas
Figure (SAED)；
Fig. 4 is XRD and the SEM figure of the strontium vanadate electrode material of embodiment 1；
Fig. 5 is the calcium vanadate electrode material of embodiment 1 in 100mA g-1Current density under and 0.01-3V potential regions in
Cycle performance of battery figure；
Fig. 6 is battery of the calcium vanadate electrode material of embodiment 1 under different current densities and in 0.01-3V potential regions
High rate performance figure；
Fig. 7 is the calcium vanadate electrode material of embodiment 1 in 1000mA g-1Current density under and 0.01-3V potential regions
Interior battery long circulating performance map；
Fig. 8 is the strontium vanadate electrode material of embodiment 1 in 100mA g-1Current density under and 0.01-3V potential regions in
Cycle performance of battery figure；
Fig. 9 is battery of the strontium vanadate electrode material of embodiment 1 under different current densities and in 0.01-3V potential regions
High rate performance figure；
Figure 10 is the strontium vanadate electrode material of embodiment 1 in 1000mA g-1Current density under and 0.01-3V potential regions
Interior battery long circulating performance map；
Specific embodiment
For a better understanding of the present invention, it is with reference to the embodiment content that the present invention is furture elucidated but of the invention
Content is not limited solely to the following examples.
Embodiment 1：
Alkaline earth metal vanadate electrode material is prepared and includes following steps：
1) 1.0mmol Ca (OH) are weighed2(or Sr (OH)2) be added in 10ml glycerine, 10ml deionized waters are added, use magnetic
Power agitator is stirred 60 minutes；
2) 2.0mmol V are weighed2O5It is added in 10ml deionized waters, adds the hydrogen peroxide of 5ml 30%, uses magnetic agitation
Device is stirred 60 minutes；
3) by step 1) in the solution that obtains be added to step 2) in the solution that obtains, it is small with magnetic stirrer 2
When；
4) by step 3) in the solution that obtains be transferred in 50ml reactors, hydro-thermal 2 days, naturally cold under the conditions of 200 DEG C
But to after room temperature, black product is taken out to obtain；
5) by step 4) the product centrifugation that obtains, with absolute ethanol washing 1~2 time, it is subsequently placed in 60~70 DEG C of bakings
Dried 12~24 hours in case；
6) by step 5) desciccate that obtains is heat-treated 5 hours for 400 DEG C in argon atmosphere, and heating rate is 5 DEG C/minute
Clock, is heat-treated relief sample natural cooling in argon atmosphere, takes out and obtains calcium vanadate (or strontium vanadate) sample.
By taking the product calcium vanadate and strontium vanadate material of the present embodiment as an example, its structure is by x-ray diffractometer and scanning electron
Microscope determines.As shown in figure 1, X-ray diffracting spectrum (XRD) shows that the thing of product calcium vanadate is mutually CaV4O9, product spreads out
Peak is penetrated to be numbered with JCPDS:01-070-4469 controls are consistent, exist without any dephasign.
As shown in Fig. 2 ESEM (SEM) picture shows, products therefrom is that micron is flower-shaped, and average diameter size is 2~3
μm, it is made up of nanometer sheet.Energy dispersion X-ray spectral element distribution map shows that tri- kinds of elements of Ca, V, O are in nano wire sample
It is evenly distributed.
As shown in figure 3, transmission electron microscope (TEM) picture is further demonstrated that, micro-flowers are to be piled up to form by nano flake, nanometer
Piece thickness is 10~30nm, and SEAD style (SAED) collection of illustrative plates shows, product is monocrystalline material.
The thing phase of product strontium vanadate is with pattern as shown in figure 4, XRD shows that strontium vanadate thing is mutually SrV4O9, the diffraction maximum of product
Numbered with JCPDS：01-070-4468 controls are consistent, exist without any dephasign.SEM shows strontium vanadate also for micron is flower-shaped, size
At 2~3 μm, micro-flowers are made up of nano flake, and nanometer sheet thickness is 10~30nm.
The electrochemical property test of calcium vanadate manufactured in the present embodiment and strontium vanadate electrode material be by assembling half-cell,
Tested using button cell, metallic sodium piece is used to electrode.Constant current charge-discharge test shows that calcium vanadate is in 100mA g-1's
Under current density (as shown in Figure 5), reversible specific capacity is up to 330mAh g-1, after the circle of circulation 150, capacity does not have decay substantially.
As shown in fig. 6, calcium vanadate also embodies excellent high rate performance, current density can be from 0.1Ag-1It is gradually increased to
10A g-1, in 10Ag-1Specific capacity still can be stablized in 100mAh g under high current density-1More than.And current density is returned again
To 0.1Ag-1And 10Ag is increased to again-1Specific capacity is suitable with first time corresponding process during this, and nothing substantially declines
Subtract.Last current density returns 1.0Ag-1When remain to stable circulation.
The long circulating performance of calcium vanadate is as shown in fig. 7, in 1000mA g-1Current density under circulate, followed by 1000 times
After ring, capability retention is 77.2%, very excellent cyclical stability of having withdrawn deposit.
Strontium vanadate as sodium-ion battery negative pole chemical property such as Fig. 8,9 and 10 shown in.Strontium vanadate is in 100mA g-1
Current density under (as shown in Figure 8), reversible specific capacity be 150mAh g-1, it is relatively low compared to calcium vanadate.Strontium vanadate also have compared with
Good high rate performance (as shown in Figure 9), current density is from 0.1Ag-1It is gradually increased to 5.0A g-1, and turn again to phase induced current
When under density, capacity is undamped, is finally switched to 0.5A g-1When still be able to stable circulation.The long circulating performance of strontium vanadate is as schemed
Shown in 10, in 1000mA g-1Current density under, it is preceding 500 circle capacity constantly rises, hereafter in stabilization, and circulation 2500 enclose
Afterwards, capacity is substantially undamped, embodies very excellent long circulating stability.Although strontium vanadate Capacity Ratio calcium vanadate is low,
Its cyclical stability is more excellent than calcium vanadate.The each different electrochemical characteristic of calcium vanadate and strontium vanadate causes that they can be with
Different demands in actual conditions are met respectively.
Embodiment 2：
Alkaline earth metal vanadate electrode material is prepared and includes following steps：
1) 1.0mmol Ca (OH) are weighed2(or Sr (OH)2) be added in 5ml glycerine, 15ml deionized waters are added, use magnetic
Power agitator is stirred 60 minutes；
2) 2.0mmol V are weighed2O5It is added in 10ml deionized waters, adds the hydrogen peroxide of 5ml 30%, uses magnetic agitation
Device is stirred 60 minutes；
3) by step 1) in the solution that obtains be added to step 2) in the solution that obtains, it is small with magnetic stirrer 2
When；
4) by step 3) in the solution that obtains be transferred in 50ml reactors, hydro-thermal 4 days, naturally cold under the conditions of 200 DEG C
But to after room temperature, black product is taken out to obtain；
5) by step 4) the product centrifugation that obtains, with absolute ethanol washing 1~2 time, it is subsequently placed in 60~70 DEG C of bakings
Dried 12~24 hours in case；
6) by step 5) desciccate that obtains is heat-treated 5 hours for 400 DEG C in argon atmosphere, and heating rate is 5 DEG C/minute
Clock, is heat-treated relief sample natural cooling in argon atmosphere, takes out and obtains calcium vanadate (or strontium vanadate) sample.
The alkaline earth metal vanadate that the present embodiment is obtained, XRD displays diffraction maximum is stronger, and crystallization degree is higher, and SEM shows and receives
Rice piece is smaller.The alkaline earth metal vanadate material that the present embodiment is obtained assembles sodium ion half-cell, is carried out using button cell
Test, as a result shows that the active material performance that the embodiment is obtained is similar to Example 1.
Embodiment 3：
Alkaline earth metal vanadate electrode material is prepared and includes following steps：
1) 1.2mmol Ca (OH) are weighed2(or Sr (OH)2) be added in 10ml glycerine, 10ml deionized waters are added, use magnetic
Power agitator is stirred 40 minutes；
2) 2.0mmol V are weighed2O5It is added in 10ml deionized waters, adds the hydrogen peroxide of 5ml 30%, uses magnetic agitation
Device is stirred 40 minutes；
3) by step 1) in the solution that obtains be added to step 2) in the solution that obtains, it is small with magnetic stirrer 2
When；
4) by step 3) in the solution that obtains be transferred in 50ml reactors, hydro-thermal 2 days, naturally cold under the conditions of 190 DEG C
But to after room temperature, black product is taken out to obtain；
5) by step 4) the product centrifugation that obtains, with absolute ethanol washing 1~2 time, it is subsequently placed in 60~70 DEG C of bakings
Dried 12~24 hours in case；
6) by step 5) desciccate that obtains is heat-treated 5 hours for 450 DEG C in nitrogen atmosphere, and heating rate is 5 DEG C/minute
Clock, is heat-treated relief sample natural cooling in argon atmosphere, takes out and obtains calcium vanadate (or strontium vanadate) sample.
Calcium vanadate and strontium vanadate active material the assembling sodium ion half-cell that the present embodiment is obtained, are entered using button cell
Row test.Constant current charge-discharge test shows in 100mA g-1Current density under, calcium vanadate reversible discharge specific capacity is reachable
356mAh g-1, strontium vanadate reversible discharge specific capacity is up to 220mAh g-1, slightly above embodiment 1.In 1000mA g-1Electric current
Under density, the circle capacity of circulation 500 is substantially undamped, shows the calcium vanadate and strontium vanadate of acquisition in the embodiment also with very excellent
Different chemical property.
Embodiment 4：
Alkaline earth metal vanadate electrode material is prepared and includes following steps：
1) 2.0mmol Ca (OH) are weighed2(or Sr (OH)2) be added in 20ml glycerine, 20ml deionized waters are added, use magnetic
Power agitator is stirred 60 minutes；
2) 4.0mmol V are weighed2O5It is added in 20ml deionized waters, adds the hydrogen peroxide of 10ml 30%, is stirred with magnetic force
Device is mixed to stir 60 minutes；
3) by step 1) in the solution that obtains be added to step 2) in the solution that obtains, it is small with magnetic stirrer 2
When；
4) by step 3) in the solution that obtains be transferred in 100ml reactors, hydro-thermal 2 days, naturally cold under the conditions of 200 DEG C
But to after room temperature, black product is taken out to obtain；
5) by step 4) the product centrifugation that obtains, with absolute ethanol washing 1~2 time, it is subsequently placed in 60~70 DEG C of bakings
Dried 12~24 hours in case；
6) by step 5) desciccate that obtains is heat-treated 5 hours for 400 DEG C in argon atmosphere, and heating rate is 5 DEG C/minute
Clock, is heat-treated relief sample natural cooling in argon atmosphere, takes out and obtains calcium vanadate (or strontium vanadate) sample.
The amount of the preparation-obtained product of the embodiment is the twice of embodiment 1, and the product of acquisition is deposits phase, pattern
For the micro-flowers that nano flake is piled up.Calcium vanadate and strontium vanadate active material the assembling sodium ion half that the present embodiment is obtained
Battery, is tested using button cell.Constant current charge-discharge test shows in 100mA g-1Current density under, calcium vanadate is reversible
Specific discharge capacity is up to 327mAh g-1, strontium vanadate reversible discharge specific capacity is up to 158mAh g-1, it is close with embodiment 1.Explanation
The preparation scheme has the potentiality amplified.
Claims (7)
1. alkaline earth metal vanadate material, it is the micro-flowers spheroidal material piled up of nanometer sheet of calcium vanadate or strontium vanadate,
Described calcium vanadate molecular formula is CaV4O9, described strontium vanadate molecular formula is SrV4O9, 2~3 μm of its diameter is described
The nanometer sheet thickness of calcium vanadate or strontium vanadate is 10~30nm.
2. the preparation method of the alkaline earth metal vanadate material described in claim 1, includes following steps：
1) weigh calcium source or barium source is added in glycerine, add deionized water, stir, obtain milky clear transparent solutions；
2) vanadium source is weighed in proportion to be added in deionized water, add H2O2Solution, stirs 40~90 minutes, obtains orange red molten
Liquid；
3) by step 1) in the solution that obtains be added to step 2) in the solution that obtains, continue to stir 1.5~3 hours；
4) by step 3) in the solution that obtains be transferred in reactor, carry out hydro-thermal reaction, then take out reactor natural cooling
To room temperature, black product is obtained；
5) by step 4) the black product centrifuge washing that obtains, drying；
6) by step 5) desciccate that obtains is sintered heat treatment, then natural cooling, and taking-up obtains final product CaV4O9Or SrV4O9
Sample.
3. the preparation method of the alkaline earth metal vanadate material as described in claim 2, it is characterised in that step 1) described in
Calcium source and barium source are respectively Ca (OH)2With Sr (OH)2；Step 2) described in vanadium source be V2O5。
4. the preparation method of the alkaline earth metal vanadate material as described in claim 2, it is characterised in that step 1) reaction system
In, described glycerine and the volume ratio of deionized water is 1:3~1:1.
5. the preparation method of the alkaline earth metal vanadate material as described in claim 2, it is characterised in that step 4) in hydro-thermal it is anti-
It is 190~210 DEG C to answer temperature, and the hydro-thermal reaction time is 2~5 days.
6. the preparation method of the alkaline earth metal vanadate material as described in claim 2, it is characterised in that step 6) in use
Sintering atmosphere is Ar or N2Deng inert atmosphere, heating rate is 2~5 DEG C/min, and heat treatment temperature is 350~450 DEG C, heat treatment
Time is 3~6h.
7. the alkaline earth metal vanadate material described in claim 1 as sodium-ion battery negative active core-shell material application.
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| CN107863503A (en) * | 2017-10-12 | 2018-03-30 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of modified ferric metasilicate lithium positive electrode material |
| WO2019050472A1 (en) * | 2017-09-08 | 2019-03-14 | National University Of Singapore | A method of producing a nanomaterial from a vanadium source and related nanomaterials |
| CN109553134A (en) * | 2019-01-23 | 2019-04-02 | 陕西科技大学 | A kind of flowers shape calcium vanadate microballoon and preparation method thereof |
| CN111268727A (en) * | 2020-02-17 | 2020-06-12 | 河南科技大学 | Calcium vanadate composite material and preparation method and application thereof |
| CN111320206A (en) * | 2020-03-02 | 2020-06-23 | 吉林师范大学 | 2D-CaV for lithium ion and sodium ion battery4O9Nano sheet material and preparation method thereof |
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| CN113690405A (en) * | 2020-11-02 | 2021-11-23 | 四川大学 | Electrode piece of perovskite vanadate blending active material |
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