CN106784777B - 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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- CN106784777B CN106784777B CN201710089238.XA CN201710089238A CN106784777B CN 106784777 B CN106784777 B CN 106784777B CN 201710089238 A CN201710089238 A CN 201710089238A CN 106784777 B CN106784777 B CN 106784777B
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- 229910052784 alkaline earth metal Inorganic materials 0.000 title claims abstract description 22
- -1 Alkaline earth metal vanadate Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 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 35
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 238000009825 accumulation Methods 0.000 claims abstract description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 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
- 239000011575 calcium Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 235000011187 glycerol Nutrition 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052791 calcium Inorganic materials 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
- 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
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 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
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 25
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 25
- 238000000034 method Methods 0.000 abstract description 13
- 239000007773 negative electrode material Substances 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 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
- 239000000126 substance 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
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003860 storage Methods 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
- 230000003321 amplification Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000006182 cathode active 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
- 238000010586 diagram Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution 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
- 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
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
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- 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 kind of alkaline earth metal vanadate, such material can be used as sodium-ion battery negative electrode active material, be micro-flowers spheroidal material made of the nanometer sheet accumulation of calcium vanadate or strontium vanadate, and the calcium vanadate molecular formula is CaV4O9, the strontium vanadate molecular formula is SrV4O9, 2~3 μm of diameter, the nanometer sheet thickness of the calcium vanadate or strontium vanadate is 10~30nm.The beneficial effects of the present invention are: preparing calcium vanadate and strontium vanadate electrode active material using hydro-thermal method combination Post isothermal treatment, these materials are as novel sodium-ion battery negative electrode active material, electrochemical performance, show higher specific capacity, good cyclical stability and excellent high rate performance；Tap density is big simultaneously, has greatly commercialization potential.In addition, simple process and low cost of the invention, synthesis process is environmentally protective, is conducive to the marketization and promotes.
Description
Technical field
The invention belongs to nanometer material and electrochemical technology fields, and in particular to the preparation side of a kind of alkaline earth metal vanadate
Method and its application, such material can be used as sodium-ion battery negative electrode active material.
Background technique
Increasingly the reduce caused energy crisis and fossil energy of fossil fuel reserves excessively use bring environment
Problem becomes the two big difficult problems faced during social development.In this background, the development of renewable energy has been
As a kind of inevitable trend.The efficient utilization for how realizing renewable energy is the following solution energy crisis and environmental pollution
The key point of two hang-ups.Unstable, discontinuous renewable energy can effectively be collected and be stored by large-scale energy-storage system,
Then stable, lasting output is realized if necessary.Large-scale energy-storage system is also considered as what renewable energy utilized on a large scale
Necessary condition, correlative study are of great significance.Now, accumulator of the lithium ion battery as small portable electronic device
Part develops very fast in recent years.A series of significant advantages such as lithium ion battery has a good cycle, and specific capacity is big,
However lithium resource is rare, leads to the cost Continued of lithium ion battery, which has limited its applications in large-scale energy-storage system.
Sodium-ion battery is to replace lithium ion to carry out the transmission of energy with sodium ion, has similar knot with lithium ion battery
Structure and similar electrochemical process.And sodium resource has many advantages, such as at low cost, rich reserves, therefore sodium-ion battery is large-scale storage
One of the 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, one of the main reasons for this is that not finding suitable electrode material.Sodium ion is compared to lithium ion, directly
Diameter is bigger, and sodium ion needs overcome bigger potential barrier in charge and discharge process, causes diffusion rate to substantially reduce, macroscopically shows
It is big for battery charge and discharge process voltage polarizing；Meanwhile sodium ion electrode material be embedded in deviate from during, can be to electrode material
Structure cause the cycle life that battery is directly influenced compared with havoc.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.
However larger challenge is still suffered from terms of negative electrode material.When hard carbon is as sodium-ion battery cathode, coulombic efficiency is low for the first time, and
Since current potential is close to zero volt and there are security risks；When ti-based compound is as sodium-ion battery cathode, since storage sodium site has
It limits and causes capacity too low；Other materials based on conversion reaction or alloying reaction are due to inevitable in charge and discharge process
Volume expansion it is big, causing electrode material to be easy dusting then makes the capacity of battery that rapid decay occur, therefore is more difficult to reality
Border application.Therefore, novel high-performance negative electrode material is developed to be of great significance for the development and industrialization of sodium-ion battery.
Alkaline earth metal vanadate is used as sodium-ion battery negative electrode active material, preparation method and correlative study work
It is also rarely reported at present.
Summary of the invention
The present invention provides a kind of alkaline earth metal vanadate electrode active material for above-mentioned existing scientific and technical problem
Preparation method, preparation process is simple, meets the requirement of Green Chemistry, and resulting calcium vanadate and strontium vanadate material are as sodium ion
Specific capacity with higher when battery cathode active material, excellent high rate performance and super good cycle performance are a kind of potential
Commercial sodium-ion battery negative electrode active material.
The technical proposal adopted by the invention to solve the above technical problems is that: alkaline earth metal vanadate material is vanadic acid
Micro-flowers spheroidal material made of the accumulation of the nanometer sheet of calcium or strontium vanadate, the calcium vanadate molecular formula are CaV4O9, the vanadium
Sour strontium molecular formula is SrV4O9, 2~3 μm of diameter, the nanometer sheet thickness of the calcium vanadate or strontium vanadate is 10~
30nm。
The preparation method of the alkaline earth metal vanadate material, includes following steps:
1) it weighs calcium source or barium source is added in glycerine, add deionized water, stir, it is molten to obtain milky clear
Liquid；
2) vanadium source is weighed in proportion to be added in deionized water, add H2O2Solution is stirred 40~90 minutes, is obtained orange red
Color solution；
3) solution obtained in step 1) is added in the solution that step 2) obtains, continues 1.5~3 hours of stirring；
4) solution obtained in step 3) is transferred in reaction kettle, carries out hydro-thermal reaction, then take out reaction kettle nature
It is cooled to room temperature, obtains black product；
5) the black product centrifuge washing for obtaining step 4), drying；
6) desciccate for obtaining step 5) is sintered heat treatment, then natural cooling, takes out up to CaV4O9Or
SrV4O9Sample.
According to the above scheme, calcium source described in step 1) and barium source are respectively Ca (OH)2With Sr (OH)2；Described in step 2)
Vanadium source be V2O5。
According to the above scheme, in step 1) reaction system, the volume ratio of the glycerine and deionized water is 1:3~1:
1。
According to the above scheme, hydrothermal temperature is 190~210 DEG C in step 4), and the hydro-thermal reaction time is 2~5 days.
According to the above scheme, the sintering atmosphere used in step 6) is Ar or N2Equal inert atmospheres, heating rate is 2~5 DEG C/
Min, heat treatment temperature are 350~450 DEG C, and heat treatment time is 3~6h.
Application of the alkaline earth metal vanadate material as sodium-ion battery negative electrode active material.
When calcium vanadate and strontium vanadate are as anode material of lithium-ion battery, V is as active element receiving and losing electrons, due to V's
Valence state is changeable, the gain and loss of multiple electronics can be achieved in charge and discharge process, therefore its capacity can be higher relative to titanium base material.Separately
On the one hand, since V-O key is stronger, V valence state in charge and discharge process can not drop to 0 valence, therefore the volume change phase of material entirety
It can be smaller to the material of conversion reaction type.In addition, alkaline-earth metal (Ca and Sr) is used as inactive elemental, it is anti-to be not involved in electrochemistry
It answers, but the metal oxide (CaO and SrO) of nano-scale, the CaO and SrO of these nano-scales can be become during the reaction
The volume change in reaction process, and the reunion of inhibitory activity nano particle can be effectively buffered, so that electrode material be made to have
Higher stability and activity.Meanwhile micron floral structure can effectively improve electrode material tap density, make unit in actual production
The active material that more multimass can be loaded on the copper foil of area, improves the total capacity of battery.And form the nanometer sheet of micro-flowers
Structure can bring nano effect, provide more active sites, shorten the diffusion length of sodium ion, to improve the power of reaction
Learn performance；
The beneficial effects of the present invention are: preparing calcium vanadate and strontium vanadate electrode active using hydro-thermal method combination Post isothermal treatment
Property material, these materials show higher ratio as novel sodium-ion battery negative electrode active material, electrochemical performance
Capacity, good cyclical stability and excellent high rate performance；Tap density is big simultaneously, has greatly commercialization potential.This
Outside, simple process and low cost of the invention, synthesis process is environmentally protective, is conducive to the marketization and promotes.
Detailed description of the invention
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 electron diffraction pattern of transmission electron microscope picture (TEM) and selected areas of the calcium vanadate electrode material of embodiment 1
Scheme (SAED)；
Fig. 4 is the XRD diagram and 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 region 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 region
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 region
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 region 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 region
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 region
Interior battery long circulating performance map；
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1:
The preparation of alkaline earth metal vanadate electrode material includes following steps:
1) 1.0mmol Ca (OH) is weighed2(or Sr (OH)2) be added in 10ml glycerol, 10ml deionized water is added, magnetic is used
Power blender stirs 60 minutes；
2) 2.0mmol V is weighed2O5It is added in 10ml deionized water, adds 30% hydrogen peroxide of 5ml, use magnetic agitation
Device stirs 60 minutes；
3) solution obtained in step 1) is added in the solution that step 2) obtains, it is small with magnetic stirrer 2
When；
4) solution obtained in step 3) is transferred in 50ml reaction kettle, 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) product for obtaining step 4) is centrifugated, and is washed 1~2 time with dehydrated alcohol, is subsequently placed in 60~70 DEG C of bakings
It is 12~24 hours dry in case；
6) desciccate for obtaining step 5) is heat-treated 5 hours for 400 DEG C in argon atmosphere, and heating rate is 5 DEG C/minute
Clock, allows sample natural cooling in argon atmosphere after heat treatment, take out and obtain calcium vanadate (or strontium vanadate) sample.
By taking the product calcium vanadate of the present embodiment and strontium vanadate material as an example, structure is by x-ray diffractometer and scanning electron
Microscope determines.As shown in Figure 1, X-ray diffracting spectrum (XRD) shows that the object of product calcium vanadate is mutually CaV4O9, product spreads out
Penetrate peak to number with JCPDS: 01-070-4469 is compareed unanimously, and no any miscellaneous phase exists.
As shown in Fig. 2, scanning electron microscope (SEM) picture shows that products therefrom is that micron is flower-shaped, average diameter size is 2~3
μm, it is made 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 further demonstrates that micro-flowers are accumulated by nano flake, nanometer
For piece with a thickness of 10~30nm, selective electron diffraction style (SAED) map shows that product is monocrystalline substance.
The object phase of product strontium vanadate is with pattern as shown in figure 4, XRD shows that strontium vanadate object is mutually SrV4O9, the diffraction maximum of product
Number with JCPDS: 01-070-4468 is compareed unanimously, and no any miscellaneous phase exists.It is that micron is flower-shaped that SEM, which shows strontium vanadate also, size
At 2~3 μm, micro-flowers are made of nano flake, and nanometer sheet thickness is 10~30nm.
The electrochemical property test of calcium vanadate and strontium vanadate electrode material manufactured in the present embodiment be by assemble half-cell,
It is tested using button cell, metallic sodium piece is used to electrode.Constant current charge-discharge test shows calcium vanadate in 100mA g-1's
Under current density (as shown in Figure 5), reversible specific capacity is up to 330mAh g-1, after circulation 150 is enclosed, capacity does not have decaying 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 obviously declines
Subtract.Last current density returns 1.0Ag-1When remain to stablize circulation.
The long circulating performance of calcium vanadate is as shown in fig. 7, in 1000mA g-1Current density under recycle, followed by 1000 times
After ring, capacity retention ratio 77.2%, very excellent cyclical stability of having withdrawn deposit.
Shown in the chemical property such as Fig. 8,9 and 10 of strontium vanadate as sodium-ion battery cathode.Strontium vanadate is in 100mA g-1
Current density under (as shown in Figure 8), reversible specific capacity be 150mAh g-1, lower 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 corresponding electric current
When under density, capacity is undamped, is finally switched to 0.5A g-1When still be able to stablize 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 stablize, and recycle 2500 circle
Afterwards, capacity basically no attenuation, embodies very excellent long circulating stability.Although strontium vanadate capacity is lower than calcium vanadate,
Its cyclical stability is more excellent than calcium vanadate.Respectively different electrochemical characteristic makes them can be with for calcium vanadate and strontium vanadate
Meets the needs of different in actual conditions respectively.
Embodiment 2:
The preparation of alkaline earth metal vanadate electrode material includes following steps:
1) 1.0mmol Ca (OH) is weighed2(or Sr (OH)2) be added in 5ml glycerol, 15ml deionized water is added, magnetic is used
Power blender stirs 60 minutes；
2) 2.0mmol V is weighed2O5It is added in 10ml deionized water, adds 30% hydrogen peroxide of 5ml, use magnetic agitation
Device stirs 60 minutes；
3) solution obtained in step 1) is added in the solution that step 2) obtains, it is small with magnetic stirrer 2
When；
4) solution obtained in step 3) is transferred in 50ml reaction kettle, 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) product for obtaining step 4) is centrifugated, and is washed 1~2 time with dehydrated alcohol, is subsequently placed in 60~70 DEG C of bakings
It is 12~24 hours dry in case；
6) desciccate for obtaining step 5) is heat-treated 5 hours for 400 DEG C in argon atmosphere, and heating rate is 5 DEG C/minute
Clock, allows sample natural cooling in argon atmosphere after heat treatment, take out and obtain calcium vanadate (or strontium vanadate) sample.
The alkaline earth metal vanadate that the present embodiment obtains, XRD show that diffraction maximum is stronger, and crystallization degree is higher, and SEM, which is shown, to be received
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, the results showed that the active material performance that the embodiment obtains is similar to Example 1.
Embodiment 3:
The preparation of alkaline earth metal vanadate electrode material includes following steps:
1) 1.2mmol Ca (OH) is weighed2(or Sr (OH)2) be added in 10ml glycerol, 10ml deionized water is added, magnetic is used
Power blender stirs 40 minutes；
2) 2.0mmol V is weighed2O5It is added in 10ml deionized water, adds 30% hydrogen peroxide of 5ml, use magnetic agitation
Device stirs 40 minutes；
3) solution obtained in step 1) is added in the solution that step 2) obtains, it is small with magnetic stirrer 2
When；
4) solution obtained in step 3) is transferred in 50ml reaction kettle, 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) product for obtaining step 4) is centrifugated, and is washed 1~2 time with dehydrated alcohol, is subsequently placed in 60~70 DEG C of bakings
It is 12~24 hours dry in case；
6) desciccate for obtaining step 5) is heat-treated 5 hours for 450 DEG C in nitrogen atmosphere, and heating rate is 5 DEG C/minute
Clock, allows sample natural cooling in argon atmosphere after heat treatment, take out and obtain calcium vanadate (or strontium vanadate) sample.
By the present embodiment obtain calcium vanadate and strontium vanadate active material assemble sodium ion half-cell, using button cell into
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, 500 circle capacity of circulation basically no attenuation, show the calcium vanadate obtained in the embodiment and strontium vanadate also and have and is very excellent
Different chemical property.
Embodiment 4:
The preparation of alkaline earth metal vanadate electrode material includes following steps:
1) 2.0mmol Ca (OH) is weighed2(or Sr (OH)2) be added in 20ml glycerol, 20ml deionized water is added, magnetic is used
Power blender stirs 60 minutes；
2) 4.0mmol V is weighed2O5It is added in 20ml deionized water, adds 30% hydrogen peroxide of 10ml, stirred with magnetic force
Device is mixed to stir 60 minutes；
3) solution obtained in step 1) is added in the solution that step 2) obtains, it is small with magnetic stirrer 2
When；
4) solution obtained in step 3) is transferred in 100ml reaction kettle, 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) product for obtaining step 4) is centrifugated, and is washed 1~2 time with dehydrated alcohol, is subsequently placed in 60~70 DEG C of bakings
It is 12~24 hours dry in case；
6) desciccate for obtaining step 5) is heat-treated 5 hours for 400 DEG C in argon atmosphere, and heating rate is 5 DEG C/minute
Clock, allows sample natural cooling in argon atmosphere after heat treatment, take out and obtain calcium vanadate (or strontium vanadate) sample.
The amount of the preparation-obtained product of the embodiment is twice of embodiment 1, and the product of acquisition is to deposit phase, pattern
For micro-flowers made of nano flake accumulation.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, close with embodiment 1.Explanation
The preparation method has the potentiality of amplification.
Claims (5)
1. the preparation method of alkaline earth metal vanadate material, the alkaline earth metal vanadate material are calcium vanadate or vanadic acid
Micro-flowers spheroidal material made of the nanometer sheet accumulation of strontium, the calcium vanadate molecular formula are CaV4O9, the strontium vanadate molecule
Formula is SrV4O9, 2~3 μm of diameter, the nanometer sheet thickness of the calcium vanadate or strontium vanadate is 10~30nm, includes
Following steps:
1) it weighs 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 is stirred 40~90 minutes, is obtained orange red molten
Liquid；
3) solution obtained in step 1) is added in the solution that step 2) obtains, continues 1.5~3 hours of stirring；
4) solution obtained in step 3) is transferred in reaction kettle, carries out hydro-thermal reaction, then takes out reaction kettle natural cooling
To room temperature, black product is obtained；
5) the black product centrifuge washing for obtaining step 4), drying；
6) desciccate for obtaining step 5) is sintered heat treatment, then natural cooling, takes out up to CaV4O9Or SrV4O9
Sample.
2. the preparation method of alkaline earth metal vanadate material according to claim 1, it is characterised in that described in step 1)
Calcium source and barium source are respectively Ca (OH)2With Sr (OH)2；Vanadium source described in step 2) is V2O5。
3. the preparation method of alkaline earth metal vanadate material according to claim 1, it is characterised in that step 1) reaction system
In, the volume ratio of the glycerine and deionized water is 1:3~1:1.
4. the preparation method of alkaline earth metal vanadate material according to claim 1, it is characterised in that hydro-thermal is anti-in step 4)
Answering temperature is 190~210 DEG C, and the hydro-thermal reaction time is 2~5 days.
5. the preparation method of alkaline earth metal vanadate material according to claim 1, it is characterised in that used in step 6)
Sintering atmosphere is Ar or N2Inert atmosphere, heating rate are 2~5 DEG C/min, and heat treatment temperature is 350~450 DEG C, when heat treatment
Between be 3~6h.
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| 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 |
| CN107863503B (en) * | 2017-10-12 | 2020-09-11 | 合肥国轩高科动力能源有限公司 | Preparation method of modified lithium iron silicate cathode material |
| CN109553134B (en) * | 2019-01-23 | 2021-02-02 | 陕西科技大学 | Flower cluster-shaped calcium vanadate microsphere and preparation method thereof |
| CN111268727B (en) * | 2020-02-17 | 2022-12-02 | 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 |
| CN111628163B (en) * | 2020-05-12 | 2021-06-08 | 青岛大学 | De-intercalation type vanadium-based negative electrode material and preparation method thereof |
| CN112420982A (en) * | 2020-11-02 | 2021-02-26 | 四川大学 | Electrode piece of perovskite vanadate blending active material |
| CN112374537A (en) * | 2020-11-02 | 2021-02-19 | 四川大学 | Preparation method of metal vanadate nano composite material |
| CN112670494B (en) * | 2021-01-20 | 2023-06-20 | 广东工业大学 | Vanadate electrode material and preparation method and application thereof |
| CN113277557B (en) * | 2021-05-14 | 2023-10-24 | 宁德新能源科技有限公司 | Amorphous calcium vanadate, preparation method thereof, battery cathode and battery |
| CN114604895B (en) * | 2022-04-12 | 2023-06-16 | 四川大学 | Polyoxometalate Sr 2 xV 2 O 7 H 2 O and preparation method and application thereof |
| CN114853065A (en) * | 2022-05-26 | 2022-08-05 | 三峡大学 | W-doped V 2 O 5 Preparation method of self-assembled nano-sheet ball electrode material |
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