A kind of compound vanadic anhydride based material and its preparation method and application
Technical field
The invention belongs to electrochemical field, it is related to a kind of compound vanadic anhydride based material and preparation method thereof and uses
On the way.
Background technique
Mg secondary cell is considered as the new secondary battery of great potential.The composition core of Mg secondary cell is Mg negative
Pole, organic electrolyte solution and the positive electrode with good deintercalation magnesium ion performance.Begin to the research of magnesium ion deintercalation material
In last century the seventies, but so far and not formed industrialization production, most importantly following two technological difficulties limit magnesium two
The development of primary cell: on the one hand, for lithium ion, the radius of magnesium ion is small, charge density is big, and solvation is tighter
Weight, causes magnesium ion to be more difficult to be embedded into general positive electrode than lithium ion, and movement of the magnesium ion in positive electrode
Also very slowly;On the other hand, magnesium will form one layer of fine and close passivating film in most of electrolyte, prevent moving for magnesium ion
It moves, causes magnesium ion that can not carry out reversible deposition and dissolution, affect its chemical property.Since current lithium and magnesium cell are equal
It has certain problems, people design a kind of lithium magnesium hybrid battery, and one kind is born with positive electrode, lithium magnesium composite electrolyte, magnesium
The battery system of pole, most important of which is that the selection of high performance positive electrode and related preparation problem.
The V of two rhombic systems2O5By VO in layer5Cubic pyramid composition, VO5Cubic pyramid occupy often
One layer of Bian Hejiao.The distance of top V~O key will be long than the distance of other four directions, is equivalent to the distance of a double bond.
V2O5Layer structure illustrate the two dimensional character of this material;However, V2O5Structure can also be considered as distortion VO6Octahedral
Body.Six V~O key lengths are very big, this enables foreign atom to be embedded in it similar in the gap of perovskite.Its is open
Layer structure provide good spatial channel for the deintercalation of lithium ion, the vanadic anhydride of 1mol layer structure can be embedded in
2mol Li+, theoretical capacity can achieve 294mAh/g, and vanadic anhydride is resourceful, easily prepared, be a kind of great
The magnesium lithium hybrid battery positive electrode of potentiality.However, vanadic anhydride is as positive electrode, there is also electronic conductivity is low
(10-2~10-3S/cm), ion diffusivity slow (10-12~10-13cm2/ s) the problems such as, this causes vanadic anhydride positive electrode to exist
Cycle performance and high rate performance are all poor in charge and discharge process.
CN108483496A discloses a kind of vanadium dioxide nano flaky material preparation method, the preparation method include with
Acidic materials: (1) being added drop-wise in the aqueous solution of vanadium source by lower step, and the solution after increasing temperature to acidic materials are added dropwise carries out
Stirring;(2) ripening is carried out to obtained product after step (1) stirring, it is thick obtains vanadium dioxide nano flaky material
Product;(3) the vanadium dioxide nano flaky material crude product that step (2) obtains is heat-treated, obtains vanadium dioxide nano sheet
Material.The scantling is uniform, even particle distribution, when as lithium magnesium hybrid battery positive electrode, the reversible ratio of first charge-discharge
Capacity is high.But the material system of the method preparation is single, electric conductivity and structural stability also need to further strengthen.
CN108155359A discloses a kind of vanadic anhydride/graphene/hollow carbon sphere nanocomposite anode electrode
Piece and its lithium-ion button battery preparation method.Hollow carbon sphere is introduced in vanadic anhydride/graphene composite material, by five oxygen
Change the superior electric conductivity of two vanadium/graphene and pore structure hollow carbon sphere abundant combines, the two generates synergistic effect, a side
Polymerization reaction can occur between face graphene oxide and hollow carbon sphere, thus have bonding action between hollow carbon sphere and graphene,
Uniform graphene-hollow carbon sphere composite construction can be formed, the presence of another aspect hollow carbon sphere has been also prevented from graphene sheet layer
Stacking again, be conducive to obtain the less graphene of the number of plies, vanadic anhydride/graphene anode material electricity be greatly improved
Performance, 100 times charging and discharging capacity is up to 683mAh/g.But the method still has the single problem of system.
CN103855373A discloses a kind of preparation method of vanadic anhydride/graphene composite material, including walks as follows
It is rapid: graphite oxide to be added in acetone, 30~180min of ultrasound, form the suspension of 0.006~0.053mg/mL;To above-mentioned
Three isopropoxy vanadium oxides and distilled water are added in suspension, seals, aged at room temperature 2~5 days, obtains wet gel;Wherein, third
Ketone, three isopropoxy vanadium oxides, distilled water volume ratio be 5~15:1:2~5;Wet gel is taken out, anhydrous propanone is successively used
It is washed several times with hexamethylene, is dried, obtains xerogel;Obtained xerogel is placed in inert gas shielding atmosphere, in
500~700 DEG C of 1~10h of pyroreaction, obtain vanadic anhydride/graphene composite material.The method preparation process is more multiple
It is miscellaneous, it is restricted larger.
Such material there are aiming at the problem that, need to design a kind of compound vanadic anhydride based material as lithium magnesium from
Sub- cell positive material, so that material has excellent chemical property.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of compound vanadic anhydride based material and its
Preparation method and purposes so that vanadic anhydride based material achieve the effect that pattern with, be evenly distributed, as lithium magnesium mix
Cell positive material has the characteristics that charge and discharge reversible specific capacity is high.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of preparation methods of compound vanadic anhydride based material, which is characterized in that
The preparation method comprises the following steps:
(1) carbon source is dispersed in water to form dispersion liquid;
(2) vanadium source and doped chemical source are added in the dispersion liquid that step (1) obtains, progress hydro-thermal reaction obtains described
Compound vanadic anhydride based material.
Preparation method provided by the invention prepares dispersion liquid and vanadium source by carbon source and doped chemical source forms compound mix
Miscellaneous, two kinds of technological means improve the electric conductivity and structural stability of vanadic anhydride based material;And preparation method technique
Simply, reaction condition is mild, is suitable for industrialized production and pollution-free, low production cost.
Water of the present invention can be the water of deionized water, ultrapure water etc. type.
Preferably, carbon source described in step (1) is inorganic carbon source.
Preferably, the inorganic carbon source includes graphite, active carbon, graphene, nitrogen-doped graphene, graphene oxide, carbon
Any one in nanotube or porous carbon.
Preferably, the inorganic carbon source is graphene oxide.
Preferably, the concentration of carbon source is 0.05~1mol/L in dispersion liquid described in step (1), such as be can be
0.05mol/L, 0.1mol/L, 0.2mol/L, 0.5mol/L, 0.8mol/L or 1mol/L etc., but and it is only limitted to cited number
Value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, the carbon source concentration in step (1) described dispersion liquid is 0.1~0.5mol/L.
Preferably, it is dispersed under ultrasound condition and carries out described in step (1).
Preferably, the time of the ultrasound be 10~120min, such as can be 10min, 20min, 50min, 80min,
100min or 120min etc., preferably 30~300min.
Preferably, vanadium source described in step (2) includes any one in ammonium metavanadate, sodium metavanadate or vanadic anhydride
Or at least two combination.
Preferably, the doped chemical in doped chemical source described in step (2) includes nitrogen, fluorine element, element sulphur, phosphorus
In element or chlorine element any one or at least two combination.
Preferably, the P elements are by any one in elemental phosphorous, organic phosphorus compound or inorganic phosphorous compound or extremely
Few two kinds of combination provides.Preferably organic phosphorus compound.
Preferably, the organic phosphorus compound includes trimerization phosphonitrilic chloride, atriphos, adenosine diphosphate (ADP), phosphoric acid alkene
Keto-acid pyruvic acid, tetramethylol chloride, vinyl phosphoric acid dimethyl ester, hexachlorocyclotriph,sphazene, polydichlorophosphazenes, gathers phosphate
In alkoxy phosphonitrile, poly- aryloxy group phosphonitrile or poly- fluoro epoxy group phosphonitrile any one or at least two combination.
Preferably, the inorganic phosphorous compound includes any one in sodium phosphate, potassium phosphate or phosphoric acid or at least two
Combination.
Preferably, the element sulphur is by vulcanized sodium, sodium thiosulfate, thiocarbamide, mercaptan, thiophenol, thioether, disulphide, more
Sulfide, cyclic sulfide, diallyl sulfide, Allifridin, garlicin compound or diene
In propyl disulfide compound any one or at least two combination provide.
Preferably, the nitrogen is provided by ammonium nitrate.
Preferably, the fluorine element is provided by ammonium fluoride.
Preferably, the chlorine element is provided by ammonium chloride and/or hydrochloric acid.
Preferably, the concentration for the vanadic acid radical ion that vanadium source described in step (2) is formed in dispersion liquid is 1~10mol/L,
Such as can be 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, mol/L, 8mol/L, 9mol/L or
10mol/L etc..
Preferably, the concentration for the doped chemical that doped chemical source described in step (2) is formed in dispersion liquid be 0.05~
0.2mol/L, such as can be 0.05mol/L, 0.08mol/L, 0.1mol/L, 0.13mol/L, 0.16mol/L, 0.19mol/L
Or 0.2mol/L etc..
Preferably, vanadium source and doped chemical source are added in dispersion liquid under stirring in step (2).
Preferably, the rate of the stirring be 500~1500r/min, such as can be 500r/min, 600r/min,
700r/min, 800r/min, 900r/min, 1000r/min, 1200r/min, 1400r/min or 1500r/min etc., preferably
800~1000r/min.
Preferably, the temperature of hydro-thermal reaction described in step (2) be 160~220 DEG C, such as can be 160 DEG C, 170 DEG C,
180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C or 220 etc., preferably 170~190 DEG C;
Preferably, the time of hydro-thermal reaction described in step (2) be 2~48h, such as can be 2h, 5h, 10h, 15h,
25h, 30h, 38h, 40h or 48h etc..
It preferably, further include being obtained after being precipitated, be centrifuged, washed and being dried after hydro-thermal reaction described in step (2)
To the compound vanadic anhydride based material.
Preferably, the preparation method includes the following steps:
(1) it is 0.05~1mol/L dispersion liquid that by carbon source, ultrasonic disperse forms concentration in water in 10~120min;
(2) vanadium source and doped chemical source are added to dispersion in step (1) in the case where stirring rate is 500~1500r/min
In liquid, stirring is to being completely dissolved, so that the concentration of the vanadic acid radical ion formed in dispersion liquid is 1~10mol/L, doped chemical
Concentration is 0.05~0.2mol/L, carries out 2~48h of hydro-thermal reaction at being 160~220 DEG C in temperature, by precipitating, is centrifuged, washes
Wash and obtain after drying the compound vanadic anhydride based material.
Second aspect, the present invention provides a kind of compound five oxygen that preparation method as described in relation to the first aspect is prepared
Change two vanadium based materials, wherein the carbon-based material of high conductivity and the layer structure vanadic anhydride of oxygen place doped modification are formed well
Compound, this for material have good chemical property provide possibility.
The third aspect, the present invention provides a kind of compound vanadic anhydride based materials as described in relation to the first aspect to prepare
Purposes in lithium anode of magnesium ion battery material.
The present invention has been obtained compound vanadic anhydride based material of uniform size, has been reached and received by specific technique
Riceization and the dual purpose for improving material conductivity, and then solve the problems, such as lithium magnesium ion in positive deintercalation, while obtain it
Obtained excellent chemical property.
Compared with the existing technology, the invention has the following advantages:
(1) preparation method of compound vanadic anhydride based material provided by the invention, the preparation method simple process,
Reaction condition is mild, is suitable for industrialized production, and pollution-free, low production cost, passes through composite mixed two kinds of technological means
The electric conductivity and structural stability for improving vanadic anhydride based material, make it can be used for anode of magnesium ion battery material.
(2) when compound vanadic anhydride based material provided by the invention is applied to lithium magnesium hybrid battery, first charge-discharge
Reversible specific capacity is 200~250mAh/g, compared to the material that related other methods existing at present are prepared, is had more excellent
Performance, application value is higher.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
The present embodiment provides a kind of compound vanadic anhydride based material preparation method, the preparation method includes following step
It is rapid:
(1) graphene oxide powder and deionized water are taken, ultrasonic disperse is configured to dispersion liquid, and dispersion liquid concentration is
0.1mol/L, ultrasonic time 30min.
(2) it is dissolved in above-mentioned solution using vanadic anhydride and thiocarbamide as vanadium source, sulphur source, radical ion containing vanadic acid in solution
Concentration be 1mol/L, sulphur concentration 0.05mol/L, continue stirring to being completely dissolved, the rate of stirring is 500r/min.
(3) by above-mentioned homogeneous solution carry out hydro-thermal reaction, temperature be 180 DEG C, the time be 12h hydro-thermal reaction after sunk
It forms sediment, obtains compound vanadic anhydride based material after centrifuge washing is dry.
Chemical property survey is carried out using the compound vanadic anhydride based material of gained as lithium anode of magnesium ion battery material
Examination, the quality proportioning of pole piece are material: acetylene black: PVDF=8:1:1, and electrolyte is (0.2mol/L [Mg2Cl2(DME)4]
[AlCl4]2With 1.0mol/L LiTFSI) electrolyte.Using magnesium sheet as reference electrode, CR2025 type button cell is prepared.1~
3.0V voltage window under 0.1C multiplying power, recycles specific discharge capacity for the first time and charge specific capacity is respectively 265mAh/g and 250mAh/
g。
Embodiment 2
The present embodiment provides a kind of compound vanadic anhydride based material preparation method, the preparation method includes following step
It is rapid:
(1) graphite composite powder and deionized water are taken, ultrasonic disperse is configured to dispersion liquid, solution concentration 0.1mol/L, ultrasound
Time is 30min.
(2) it is dissolved in above-mentioned solution using vanadic anhydride and thiocarbamide as vanadium source sulphur source, radical ion containing vanadic acid in solution
Concentration be 1mol/L, sulphur concentration 0.05mol/L, continue stirring to being completely dissolved, the rate of stirring is 500r/min.
(3) by above-mentioned homogeneous solution carry out hydro-thermal reaction, temperature be 180 DEG C, the time be 12h hydro-thermal reaction after sunk
It forms sediment, obtains compound vanadic anhydride based material after centrifuge washing is dry.
Chemical property survey is carried out using the compound vanadic anhydride based material of gained as lithium anode of magnesium ion battery material
Examination, the quality proportioning of pole piece are material: acetylene black: PVDF=8:1:1, and electrolyte is (0.2mol/L [Mg2Cl2(DME)4]
[AlCl4]2With 1.0mol/L LiTFSI) electrolyte.Using magnesium sheet as reference electrode, CR2025 type button cell is prepared.1~
3.0V voltage window under 0.1C multiplying power, recycles specific discharge capacity for the first time and charge specific capacity is respectively 220mAh/g and 200mAh/
g。
Embodiment 3
The present embodiment provides a kind of compound vanadic anhydride based material preparation method, the preparation method includes following step
It is rapid:
(1) graphene oxide powder and deionized water are taken, ultrasonic disperse is configured to dispersion liquid, and dispersion liquid concentration is
0.1mol/L, ultrasonic time 30min.
(2) be dissolved in above-mentioned solution using vanadic anhydride and sodium phosphate as vanadium source phosphorus source, in solution root containing vanadic acid from
The concentration of son is 1mol/L, phosphorus concentration 0.05mol/L, continues stirring to being completely dissolved, the rate of stirring is 500r/min.
(3) by above-mentioned homogeneous solution carry out hydro-thermal reaction, temperature be 180 DEG C, the time be 12h hydro-thermal reaction after sunk
It forms sediment, obtains compound vanadic anhydride based material after centrifuge washing is dry.
Chemical property survey is carried out using the compound vanadic anhydride based material of gained as lithium anode of magnesium ion battery material
Examination, the quality proportioning of pole piece are material: acetylene black: PVDF=8:1:1, and electrolyte is (0.2mol/L [Mg2Cl2(DME)4]
[AlCl4]2With 1.0mol/L LiTFSI) electrolyte.Using magnesium sheet as reference electrode, CR2025 type button cell is prepared.1~
3.0V voltage window under 0.1C multiplying power, recycles specific discharge capacity for the first time and charge specific capacity is respectively 220mAh/g and 210mAh/
g。
Embodiment 4
The present embodiment provides a kind of compound vanadic anhydride based material preparation method, the preparation method includes following step
It is rapid:
(1) graphene oxide powder and water are taken, ultrasonic disperse is configured to dispersion liquid, solution concentration 0.05mol/L, ultrasound
Time is 120min.
(2) it is dissolved in above-mentioned solution using vanadic anhydride and thiocarbamide as vanadium source sulphur source, radical ion containing vanadic acid in solution
Concentration be 1mol/L, sulphur concentration 0.05mol/L, continue stirring to being completely dissolved, the rate of stirring is 500r/min.
(3) by above-mentioned homogeneous solution carry out hydro-thermal reaction, temperature be 220 DEG C, the time be 2h hydro-thermal reaction after precipitated,
Compound vanadic anhydride based material is obtained after centrifuge washing is dry.
Chemical property survey is carried out using the compound vanadic anhydride based material of gained as lithium anode of magnesium ion battery material
Examination, the quality proportioning of pole piece are material: acetylene black: PVDF=8:1:1, and electrolyte is (0.2mol/L [Mg2Cl2(DME)4]
[AlCl4]2With 1.0mol/L LiTFSI) electrolyte.Using magnesium sheet as reference electrode, CR2025 type button cell is prepared.1~
3.0V voltage window under 0.1C multiplying power, recycles specific discharge capacity for the first time and charge specific capacity is respectively 250mAh/g and 220mAh/
g。
Embodiment 5
The present embodiment provides a kind of compound vanadic anhydride based material preparation method, the preparation method includes following step
It is rapid:
(1) active carbon and deionized water are taken, ultrasonic disperse is configured to dispersion liquid, solution concentration 1mol/L, ultrasonic time
For 10min.
(2) it is dissolved in above-mentioned solution using sodium metavanadate and thioether as vanadium source sulphur source, the radical ion containing vanadic acid in solution
Concentration is 10mol/L, sulphur concentration 0.05mol/L, continues stirring to being completely dissolved, the rate of stirring is 1500r/min.
(3) by above-mentioned homogeneous solution carry out hydro-thermal reaction, temperature be 160 DEG C, the time be 48h hydro-thermal reaction after sunk
It forms sediment, obtains compound vanadic anhydride based material after centrifuge washing is dry.
Chemical property survey is carried out using the compound vanadic anhydride based material of gained as lithium anode of magnesium ion battery material
Examination, the quality proportioning of pole piece are compound vanadic anhydride material: acetylene black: PVDF=8:1:1, and electrolyte is (0.2mol/L
[Mg2Cl2(DME)4][AlCl4]2With 1.0mol/L LiTFSI) electrolyte.Using magnesium sheet as reference electrode, CR2025 type knob is prepared
Detain battery.Under 1~3.0V voltage window, 0.1C multiplying power, recycles specific discharge capacity for the first time and charge specific capacity is respectively
240mAh/g and 230mAh/g.
Embodiment 6
In the present embodiment, other than the vanadic anhydride in step (1) is changed to ammonium metavanadate, other conditions with implementation
Example 1 is identical.
Embodiment 7
In the present embodiment, other than the mixing time in step (2) is changed to 1000r/min, other conditions with implementation
Example 1 is identical.
Embodiment 8
In the present embodiment, other than the ultrasonic time in step (1) is changed to 60min, other conditions with 1 phase of embodiment
Together.
Comparative example 1
In this comparative example, other than the water in step (1) is replaced with ethyl alcohol, other conditions are same as Example 1.
Preparation method described in this comparative example cannot get size uniformly compound vanadic anhydride based material.
Comparative example 2
In this comparative example, other than the ultrasound in step (1) is replaced with simple agitation, other conditions with embodiment 1
It is identical.
Preparation method described in this comparative example cannot get size uniformly compound vanadic anhydride based material.
Comparative example 3
In this comparative example, step is added without other doped chemicals in (2), and other conditions are same as Example 1.
It is relatively poor that preparation method described in this comparative example obtains material electrochemical performance, first discharge specific capacity is only
190mAh/g。
By embodiment 1-8 and comparative example 1-3 can be seen that preparation method of the present invention be by solvent selection,
What numerous process conditions synthesis such as the selection and heat treatment of reactant were prepared, when any one step missing or technique hair
Changing, uniform, structure, which is not achieved, in size to stablize, and cannot all obtain compound vanadic anhydride based material.
And the compound vanadic anhydride based material that 1-8 of the embodiment of the present invention is prepared is used for anode of magnesium ion battery material
Material, the positive electrode have excellent chemical property, and first charge-discharge reversible specific capacity is up to 200~250mAh/g.
The Applicant declares that the present invention is explained by the above embodiments compound vanadic anhydride based material of the invention and
Preparation method and use, but the invention is not limited to above-mentioned method detaileds, that is, it is above-mentioned not mean that the present invention must rely on
Method detailed could be implemented.It should be clear to those skilled in the art, any improvement in the present invention, produces to the present invention
The equivalence replacement of each raw material of product and addition, the selection of concrete mode of auxiliary element etc., all fall within protection scope of the present invention and
Within the open scope.