CN105304885B - A kind of aluminum secondary battery vanadium oxide positive electrode materials and preparation method thereof - Google Patents
A kind of aluminum secondary battery vanadium oxide positive electrode materials and preparation method thereof Download PDFInfo
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- CN105304885B CN105304885B CN201410336079.5A CN201410336079A CN105304885B CN 105304885 B CN105304885 B CN 105304885B CN 201410336079 A CN201410336079 A CN 201410336079A CN 105304885 B CN105304885 B CN 105304885B
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Abstract
The invention discloses a kind of aluminum secondary battery vanadium oxide positive electrode materials and preparation method thereof, method includes the following steps: (1) dissolves vfanadium compound, obtain vanadium ion solution；(2) vanadium ion solution and collector are subjected in closed container hydro-thermal reaction, reaction product is cleaned and is dried in vacuo after reaction, obtain the vanadium oxide positive electrode materials using collector as matrix.The barium oxide growth for the nanoparticle structure that method of the invention makes is on a current collector, so that not only having electrical contact well between the two, addition conductive agent and binder are not needed, and it is capable of increasing the surface area of barium oxide electrode material, improve the contact area of electrode material and electrolyte.
Description
Technical field
The present invention relates to aluminum secondary battery fields, and in particular, to a kind of aluminum secondary battery vanadium oxide positive electrode materials and
Preparation method.
Background technique
Advanced high-energy density secondary battery is effective to the development of next-generation electric car and renewable energy power generation
Using being vital.In recent years, the novel green secondary cell research based on new system, new material, new technology is constantly deep
Change, pass through constructing for light element polyelectron reaction system, it is expected to secondary cell be made to obtain energy more higher than conventional single electron system
Metric density.Aluminium is the most abundant metallic element of content on the earth, it has many advantages, such as light weight, pollution-free, cheap, because of it
Three electron transfer reactions can occur, theoretical electrochemistry specific capacity reaches 2980mAh/g, is only second to lithium in all metallic elements
(3870mAh/g)。
Since aluminium is a kind of very active metal, standard electrode potential is -1.68V, is lower than standard hydrogen-evolution overpotential, because
This aluminium ion is difficult to restore in aqueous solution, can generate strong evolving hydrogen reaction.So the electrolytic deposition and aluminium in aluminium are secondary
In the research and application of battery, non-aqueous solution electrolysis plastidome is generallyd use.And aluminium is easy film forming in neutral and organic electrolyte
And be passivated, lead to that electrode potential is substantially less than theoretical value and voltage behavior obviously lags, therefore aluminium is never successfully applied
In electrochemical energy storage and switch technology.In the 1970s, it is found that electrochemistry can occur in molten salt electrolyte for aluminium
Deposition, then using the aluminium electrode preparation research electrochemical behavior of secondary molten salt battery.Compared with aqueous electrolyte, fused salt tool
There is the features such as conductivity is high, and decomposition potential is high, and polarizability is low, the high-temperature molten salt aluminum secondary battery constituted has good reversibility,
The features such as theoretical specific energy is big.But high-temperature molten salt battery needs high temperature or to environmental requirement harshness, higher cost and is difficult to safeguard,
Limit the development of aluminum secondary battery.
Ionic liquid at room temperature is the substance being made of ion being in a liquid state at a temperature of room temperature or near room temperature, generally by having
Machine cation and inorganic anion composition.It not only has very low vapour pressure, has good dissolution to organic matter, inorganic matter
Property, and thermal stability and good flame resistance, also there is good ionic conductivity, stable electrochemical window is expected to become one kind
Safe and efficient secondary cell electrolyte.So far, ionic liquid has been widely studied as lithium-ion battery electrolytes.
It is nearest the study found that aluminum chloride type ionic liquid can be good at being used in aluminum secondary battery as electrolyte, make room temperature aluminium
The exploitation of secondary cell is possibly realized with application.The electrolyte being related in reported aluminum secondary battery is mainly aluminum chloride type
Ionic liquid, including AlCl3/[EMIM]Cl、AlCl3/ [BMIM] Cl and AlCl3/ [BMIM] Br etc..Aluminum chloride type ionic liquid
The characteristics of be itself contain aluminium ion, and form with the ratio of aluminium chloride and imidazolium halide salt change and change, already exist
It is studied in the electrolytic deposition field of aluminium.Metallic aluminium can only be deposited from acid melt, because of AlCl4 -With high degree of symmetry
Tetrahedral structure, electrochemically stable, the electrodeposition efficiency of aluminium is low.And Al in acid melt2Cl7 -Due to the asymmetry of its structure
Property, electro-chemical activity is high, being capable of effectively electric deposition aluminum.But the Al in acid chlorization aluminium profiles ionic liquid2Cl7 -Can with it is common
Binder PVDF reaction, therefore the ionic liquid of the type should not be used in the battery constituted using PVDF as the electrode of binder.
Barium oxide is the typical embedded type compound with layer structure, because it is high with theoretical specific capacity, resource is rich
Rich, lower-price characteristic, becomes one of lithium ion battery electrode material of new generation.Recent studies have found that it is used as the secondary electricity of aluminium
The insertion reaction of aluminium, specific discharge capacity with higher can occur for pond positive electrode.Cornell University Jayaprakash et al. will
The barium oxide nano wire of hydro-thermal reaction synthesis is as positive electrode, by AlCl3With the molar ratio of [EMIm] Cl be 1.1:1 from
Sub- liquid constitutes secondary aluminium ion battery as electrolyte, using metallic aluminium as cathode.Constant current charge-discharge survey is carried out to battery
Examination, as a result, it has been found that, open-circuit voltage 1.8V, discharge voltage plateau is basically stable at 0.55V, and specific discharge capacity is within first week
305mAh/g.But when preparing anode electrode, barium oxide nano wire needs to add conductive agent, with binder mixed pulp
Coated on anode electrode can just be prepared on collector, on the one hand, the adhesive property and electric conductivity of binder are to be improved,
And the wellability of acid chlorization aluminium profiles il electrolyte is poor, it is incompatible with binder, be unfavorable for barium oxide nano wire with
Electrical contact between conducting base is also unfavorable for keeping the stability of anode electrode；On the other hand, the barium oxide nano wire
Conductivity is very low so that ion telescopiny slowly and only one layer of surface participations insertion reaction, be unfavorable for anode electrode and
Contact between electrolyte.
Summary of the invention
The purpose of the invention is to overcome acid chlorization aluminium profiles ionic liquid in the aluminum secondary battery of the prior art to be electrolysed
Liquid wellability is poor, incompatible with binder, the electrical contact being unfavorable between barium oxide nano wire and conducting base and vanadium oxygen
Compound nano wire conductivity is low, is unfavorable for the defect of the contact between anode electrode and electrolyte, and it is secondary to provide a kind of new aluminium
Battery vanadium oxide positive electrode materials and preparation method thereof, between the vanadium oxide positive electrode materials and conducting base and anode electrode
Good electrical contact is all had between electrolyte.
The present inventor has been surprisingly found that under study for action, (leads in the collector with large scale tridimensional network
Electric matrix) on using hydro-thermal in-situ deposition barium oxide method (that is, allowing barium oxide directly to synthesize and being deposited on collector
On) aluminum secondary battery vanadium oxide positive electrode materials are prepared, the channel that collector can not only be kept netted is conducive to electrolyte and exists
Its internal migration and diffusion, further increase the contact between positive electrode and electrolyte and the utilization rate of positive electrode, and
Barium oxide as active material and between the conducting base as collector have well electrical contact, do not need addition appoint
What conductive agent and binder, and it is able to maintain the stability of good anode electrode.
Therefore, to achieve the goals above, on the one hand, the present invention provides a kind of aluminum secondary battery vanadium oxide positive electrode materials
The preparation method of material, method includes the following steps:
(1) vfanadium compound is dissolved, obtains vanadium ion solution；
(2) vanadium ion solution and collector are subjected in closed container hydro-thermal reaction, carry out reaction product after reaction
Cleaning and vacuum drying, obtain the vanadium oxide positive electrode materials using collector as matrix.
On the other hand, the present invention provides the aluminum secondary battery vanadium oxide positive electrode materials that the above method is prepared.
Method of the invention is by first preparing vanadium ion solution, the method for then using hydro-thermal in-situ deposition, by vanadium ion
For solution heat resolve at the barium oxide nano particle and water of unformed shape, the nanoparticle structure made is grown in collector
On, addition conductive agent and binder are not needed, that is, may make not only has electrical contact well between the two, is able to maintain good
Anode electrode stability, and be capable of increasing the surface area of vanadium oxide positive electrode materials, improve positive electrode and electrolyte
Contact area, diffusion length needed for shortening aluminium ion and electronics so as to improve the specific discharge capacity of battery, and improves
Its stable circulation performance.In a preferred embodiment of the invention, it will be obtained after vacuum drying using collector as base
The vanadium oxide positive electrode materials of body are heat-treated (condition of heat treatment includes: that temperature is 300-600 DEG C, time 1-6h),
So that barium oxide turns to crystalline structure by amorphous structure, be conducive to the raising of barium oxide crystallinity, can further mention
The specific discharge capacity and cyclical stability of high battery.Meanwhile hydro-thermal reaction is carried out in closed container, make reaction relatively high
It is carried out under temperature and pressure, reaction speed is very fast, and the viscosity of hydrothermal solution is low compared with the viscosity under normal temperature and pressure, the expansion of reactive component
It dissipates comparatively fast, the diffusion region near crystal growth interface is narrower, is more advantageous to the growth of crystal.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is the XRD spectrum of vanadium oxide positive electrode materials prepared by the embodiment of the present invention 1.
Fig. 2 is the SEM picture before vanadium oxide positive electrode materials calcining prepared by the embodiment of the present invention 1.
Fig. 3 is the calcined SEM picture of vanadium oxide positive electrode materials prepared by the embodiment of the present invention 1.
Fig. 4 is the calcined SEM picture of vanadium oxide positive electrode materials prepared by the embodiment of the present invention 2.
Fig. 5 is the calcined SEM picture of vanadium oxide positive electrode materials prepared by the embodiment of the present invention 3.
Fig. 6 is the calcined SEM picture of vanadium oxide positive electrode materials prepared by the embodiment of the present invention 4.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In a first aspect, the present invention provides a kind of preparation method of aluminum secondary battery vanadium oxide positive electrode materials, this method
The following steps are included:
(1) vfanadium compound is dissolved, obtains vanadium ion solution；
(2) vanadium ion solution and collector are subjected in closed container hydro-thermal reaction, carry out reaction product after reaction
Cleaning and vacuum drying, obtain the vanadium oxide positive electrode materials using collector as matrix.
In the method for the present invention step (1), under preferable case, the method for dissolving vfanadium compound includes: under stiring, in vanadium
The solution for being added in object and capable of dissolving vfanadium compound is closed, the time of stirring is 0.5-3h.Those skilled in the art should understand that
It is that, if vfanadium compound can be dissolved in water, described can to dissolve the solution of vfanadium compound can be water；If vfanadium compound does not dissolve in
Water, then described can to dissolve the solution of vfanadium compound can be aqueous hydrogen peroxide solution, oxalic acid aqueous solution, aqueous hydrochloric acid solution or ammonia
Aqueous solution.Therefore, the solution that can dissolve vfanadium compound can be water-soluble for water, aqueous hydrogen peroxide solution, oxalic acid aqueous solution, hydrochloric acid
Liquid or ammonia spirit.It is not special for the concentration of aqueous hydrogen peroxide solution, oxalic acid aqueous solution, aqueous hydrochloric acid solution or ammonia spirit
Restriction, as long as vfanadium compound can be dissolved, in order to preferably dissolve vfanadium compound, under preferable case, peroxidating
The concentration of aqueous solution of hydrogen is 15-30 weight %, and the concentration of oxalic acid aqueous solution is 5-12.5 weight %, and the concentration of aqueous hydrochloric acid solution is
15-37 weight %, the concentration of ammonia spirit are 15-28 weight %.The molten of vfanadium compound can be dissolved by being added in vfanadium compound
The prepared aqueous solution that can dissolve vfanadium compound can be added when liquid (in the case where being not water, such as oxalic acid solution)
(such as oxalic acid aqueous solution) can also be separately added into water and can dissolve the substance (such as oxalic acid) of vfanadium compound.
In the method for the present invention step (1), the present inventor has found under study for action, with hydrogen peroxide aqueous dissolution vanadium
When compound, the time of stirring has an impact to the deposition of barium oxide on collector, and mixing time is too long, can reduce collector
The deposition of upper barium oxide, this may be because with stirring progress, hydrogen peroxide is light-exposed and with the presence of barium oxide
In the case where be constantly catalytically decomposed, long agitation decomposes excessive hydrogen peroxide completely, and generate pervanadic acid not
Stablize, will be slow resolve into vanadic anhydride and oxygen at room temperature, eventually lead to vanadic anhydride precipitation, vanadium ion solution is dense
Degree reduces, to reduce barium oxide in the deposition of collection liquid surface.In the case of it is therefore preferable that, the time of stirring is 0.5-
3h。
In the method for the present invention step (1), when dissolving vfanadium compound, water is preferably deionized water.For the method for stirring
There is no particular limitation, can be various stirrings commonly used in the art method, such as can for electric stirring, magnetic agitation,
Glass bar stirring etc., under preferable case, the method for stirring is magnetic agitation.For the speed of stirring, there is no particular limitation, only
It wants that vfanadium compound can be made to dissolve, such as can be 100-300rpm.Temperature when for dissolution vfanadium compound is without spy
Other restriction can be 10-40 DEG C.
In the method for the present invention step (1), for vfanadium compound, there is no particular limitation, can be commonly used in the art various
Vfanadium compound.Under preferable case, vfanadium compound is vanadic anhydride, vanadium dioxide, vanadium trioxide, vanadium oxalate, vanadyl oxalate
With one of ammonium metavanadate or a variety of.
In the method for the present invention step (1), the present inventor is under study for action it has furthermore been found that when what is be added can dissolve
When the solution of vfanadium compound is the aqueous solutions such as aqueous hydrogen peroxide solution, oxalic acid aqueous solution, aqueous hydrochloric acid solution or ammonia spirit, increase
The amount that the solute in the aqueous solution of vfanadium compound can be dissolved, allow to dissolve vfanadium compound aqueous solution in solute relative to
Vfanadium compound is excessive, is conducive to barium oxide in the uniform deposition of collection liquid surface.In the case of it is therefore preferable that, vfanadium compound with
The molar ratio that solute in the aqueous solution of vfanadium compound can be dissolved is 1:5-25, further preferably 1:10-24.
In the method for the present invention step (1), the present inventor is under study for action it has furthermore been found that in terms of vanadium, when step (1)
Obtained in vanadium ion solution concentration be 0.03-0.3mol/L, preferably 0.05-0.15mol/L when, be conducive to barium oxide
In the uniform deposition of collection liquid surface.Therefore, when water is added in vfanadium compound, the water of vfanadium compound and addition is controlled
Amount, so that the concentration of vanadium ion solution is 0.03-0.3mol/L, preferably 0.05-0.15mol/L in terms of vanadium；When in vanadium chemical combination
Aqueous solution (such as aqueous hydrogen peroxide solution, oxalic acid aqueous solution, aqueous hydrochloric acid solution or the ammonium hydroxide that can dissolve vfanadium compound are added in object
Solution) when, control vfanadium compound with can dissolve solute in the aqueous solution of vfanadium compound molar ratio be 1:5-25, preferably 1:
10-24, and the total volume of last solution is controlled, so that the concentration of vanadium ion solution is 0.03-0.3mol/L, preferably in terms of vanadium
For 0.05-0.15mol/L.
In the method for the present invention step (2), collector plays the effect of conducting base, and collector is not limited particularly
It is fixed, it can be various collectors commonly used in the art.Under preferable case, collector is nickel foam, foam copper, titanium foam, foam
Iron nickel, stainless (steel) wire or carbon cloth.
In the method for the present invention step (2), for closed container, there is no particular limitation, can be not anti-with vanadium ion solution
The various containers answered, such as can be the stainless steel cauldron of polytetrafluoroethyllining lining.
In the method for the present invention step (2), in order to be more advantageous to barium oxide in the uniform deposition of collection liquid surface, preferably feelings
Under condition, the mass ratio of vanadium ion solution and collector is 200:1-10:1, further preferably 100:1-20:1.Hair of the invention
Bright people has found under study for action, as above controls the amount of the vanadium ion solution and collector in closed container, barium oxide can be made to exist
Deposition on collector is 1-30mg/cm2, preferably 2-10mg/cm2。
In the method for the present invention step (2), in order to keep hydro-thermal reaction more abundant, barium oxide is more advantageous in afflux body surface
The uniform deposition in face, under preferable case, the condition of hydro-thermal reaction includes: that heating temperature is 180-205 DEG C, heating time 1-4
It.
In the method for the present invention step (2), in order to remove the water-solubility impurity and oil soluble impurity in reaction product, preferably feelings
Under condition, the condition of cleaning includes: to be respectively washed reaction product with deionized water and organic solvent.For with deionized water and organic
The sequence of solvent cleaning is not particularly limited, and can first be cleaned, can also first be cleaned with organic solvent with deionized water.For having
There is no particular limitation for solvent, can be that can remove the various organic solvents of oil soluble impurity in reaction product, such as can
Think dehydrated alcohol.For the number of cleaning, there is no particular limitation, as long as the water-solubility impurity in reaction product can be removed
With oil soluble impurity, such as can be 3-5 times.
In the method for the present invention step (2), under preferable case, vacuum drying condition includes: that drying temperature is 60-80 DEG C,
Drying time is 12-24h.
In the method for the present invention, in order to make the amorphous structure of barium oxide preferably turn to crystalline structure and make active material
Barium oxide is formed on collector strongerly, and further increases the specific discharge capacity and cyclical stability of battery,
Under preferable case, this method further includes obtaining step (2) using collector as the vanadium oxide positive electrode materials of matrix progress heat
Processing, it is further preferred that it is 300-600 DEG C that the condition of heat treatment, which includes: temperature, time 1-6h.Wherein, the side of heat treatment
Formula may include calcining in air or nitrogen or argon gas.
On the other hand, the invention also includes the aluminum secondary battery vanadium oxide positive electrode materials that the above method is prepared.
Before heat treatment, the vanadium oxide positive electrode materials that the present invention is prepared are the barium oxide of undefined structure
(VOX, X 1.9-2.5), it may be possible to one of vanadic anhydride, vanadium dioxide, vanadium trioxide and vanadium oxide are a variety of
Mixture；After heat treatment, barium oxide turns to crystalline structure by amorphous structure, obtains the barium oxide of high-crystallinity
Grain.
In the present invention, it will be prepared using collector as the combination of the vanadium oxide positive electrode materials of matrix and collector
As anode, metallic aluminium is as cathode, and acid chlorization aluminium profiles ionic liquid is as electrolyte, using fibreglass diaphragm, in argon
Aluminum secondary battery can be assembled into gas glove box.For the specific method of assembling, there is no particular limitation, can be this field
Common various methods, details are not described herein.
Embodiment
The present invention is further illustrated for embodiment below, but is not intended to limit the present invention.
In following embodiment, being scanned the scanning electron microscope used when Electronic Speculum observation is field emission scanning electron microscope (Hitachi
Hitachi S-4800)。
Using the structural form of Rigaku DMAX2400 type X-ray diffractometer characterization barium oxide.
Using inductive coupling plasma emission spectrograph (Profile, Leeman company, the U.S.) analysis barium oxide
Element composition.
Vanadium pentoxide powder, oxalic acid, vanadyl oxalate powder and ammonium metavanadate powder are purchased from Chinese medicines group chemical reagent
Beijing Co., Ltd.
Fibreglass diaphragm is Whatman glass fiber filter paper GF/C (1822-047).
The measuring method of the deposition of barium oxide on a current collector are as follows: weigh the quality of collector before hydro-thermal reaction respectively
With vacuum drying/calcined collector for being deposited with barium oxide quality, the quality difference value of the two and collector it is apparent
(by taking embodiment 1 as an example, the apparent area of every nickel foam is 3 × 4cm to area2) ratio be barium oxide on a current collector
Deposition.
Embodiment 1
The present embodiment is for illustrating aluminum secondary battery vanadium oxide positive electrode materials and preparation method thereof of the invention.
30ml deionized water is added at 25 DEG C in 0.364g vanadium pentoxide powder and passes through magnetic agitation (150rpm)
It is mixed, aqueous hydrogen peroxide solution (vanadic anhydride and the hydrogen peroxide of 5ml30 weight % is added while magnetic agitation
Molar ratio be 1:22), continuation stirs 0.5h at 150rpm, and obtaining concentration is that the transparent of 0.11mol/L orange red crosses vanadium
Acid solution (concentration is in terms of vanadium).Then obtained pervanadic acid solution all (36.1g) is transferred to 50ml polytetrafluoroethyllining lining
Stainless steel cauldron in, be added four 3 × 4cm2Nickel foam (aperture 110PPI, thickness 1mm, every quality is 0.4g),
Heating reaction 3 days, are cooled to 25 DEG C after completion of the reaction at 190 DEG C, take out reaction product and are first washed 2 times with dehydrated alcohol, then
It is washed with deionized 2 times, it is then 20 hours dry at 70 DEG C in a vacuum drying oven, finally forged at 500 DEG C in air
4h is burnt, obtains the vanadium oxide positive electrode materials using nickel foam as matrix after being cut into the disk that diameter is 1cm.
After measured, deposition of the barium oxide in nickel foam is 2mg/cm2。
The XRD spectrum of vanadium oxide positive electrode materials prepared by embodiment 1 is as shown in Figure 1.It is sent out through inductively coupled plasma body
Spectrometer (ICP) test is penetrated, and combines Fig. 1 it is found that obtained vanadium oxide positive electrode materials are undefined structure before heat treatment
Barium oxide (VOX, X 2.48), it may be possible to one of vanadic anhydride, vanadium dioxide, vanadium trioxide and vanadium oxide
Or a variety of mixture；After being heat-treated in air, the good V of crystallinity has been obtained2O5Particle.
The vanadium oxide positive electrode materials being prepared before embodiment 1 is heat-treated are observed under scanning electron microscope, are scanned
Electron microscope (SEM figure) is shown in Fig. 2.From figure 2 it can be seen that the vanadium oxide positive electrode materials that embodiment 1 is prepared before being heat-treated
Nickel foam substrate surface, partial size about 400nm are grown in Nanoparticulate pattern.Fig. 3 is prepared after embodiment 1 is heat-treated
Vanadium oxide positive electrode materials SEM figure, from figure 3, it can be seen that heat treatment after vanadium oxide positive electrode materials pattern with
It is almost the same before heat treatment.
Embodiment 2
The present embodiment is for illustrating aluminum secondary battery vanadium oxide positive electrode materials and preparation method thereof of the invention.
At 25 DEG C, 0.364g vanadium pentoxide powder is weighed according to the ratio that molar ratio is 1:10 and 1.8g oxalic acid directly adds
Enter into 72ml deionized water, 3h is persistently stirred by magnetic agitation (200rpm) to transparent dark blue solution is formed, is obtained
Concentration is the vanadyl oxalate solution of 0.056mol/L (concentration is in terms of vanadium).Then obtained solution all (74.1g) is transferred to
In the stainless steel cauldron of 50ml polytetrafluoroethyllining lining, 3 × 4cm of two panels is added2Foam iron-nickel (aperture 110PPI, thickness
1mm, every quality are 0.4g), it is reacted 4 days in 180 DEG C of heating.It is cooled to 25 DEG C after completion of the reaction, it is first to take out reaction product
It is washed 2 times with dehydrated alcohol, then is washed with deionized 2 times, it is then 24 hours dry at 60 DEG C in a vacuum drying oven, finally
6h is calcined at 300 DEG C in argon gas, obtains the barium oxide using foam iron-nickel as matrix after being cut into the disk that diameter is 1cm
Positive electrode.
After measured, deposition of the barium oxide on foam iron-nickel is 6mg/cm2。
The vanadium oxide positive electrode materials that embodiment 2 is prepared emit light through X-ray diffraction and inductively coupled plasma body
Spectrometer (ICP) test, learns, obtained vanadium oxide positive electrode materials are the barium oxide of undefined structure before heat treatment
(VOX, X 1.9), it may be possible to one of vanadic anhydride, vanadium dioxide, vanadium trioxide and vanadium oxide or a variety of mixing
Object；After being heat-treated in argon gas, the good barium oxide particle (VO of crystallinity has been obtainedX, X 1.9).
The vanadium oxide positive electrode materials that embodiment 2 is prepared are observed under scanning electron microscope, wherein after heat treatment
The SEM figure for the vanadium oxide positive electrode materials being prepared is shown in Fig. 4, from fig. 4, it can be seen that embodiment 2 is prepared after being heat-treated
Barium oxide particle be grown in foam iron-nickel matrix surface, partial size about 3um in flower-shaped.It should be noted simultaneously that embodiment 2
Almost the same after the pattern of vanadium oxide positive electrode materials before heat treatment and heat treatment, details are not described herein.
Embodiment 3
The present embodiment is for illustrating aluminum secondary battery vanadium oxide positive electrode materials and preparation method thereof of the invention.
At 25 DEG C, 0.702g ammonium metavanadate is weighed according to the ratio that molar ratio is 1:5 and 2.7g oxalic acid is added directly into
In 40ml deionized water.1h is persistently stirred by magnetic agitation (150rpm) until forming clear solution, obtaining concentration is
(the NH of 0.15mol/L4)2[(VO)2(C2O4)3] solution (concentration is in terms of vanadium).Then by all (43.4g) transfers of obtained solution
Into the stainless steel cauldron of 50ml polytetrafluoroethyllining lining, four 3 × 4cm are added2Foam copper (aperture 110PPI, thickness
1mm, every quality are 0.4g), and heating reaction 1 day, is cooled to 25 DEG C after completion of the reaction at 205 DEG C, and it is first to take out reaction product
It is washed with deionized 2 times, then washs 2 times with dehydrated alcohol, it is then 12 hours dry at 80 DEG C in a vacuum drying oven, finally
Calcine 1h at 600 DEG C in nitrogen, be cut into after the disk that diameter is 1cm obtain using foam copper as the barium oxide of matrix just
Pole material.
After measured, deposition of the barium oxide on foam copper is 10mg/cm2。
The vanadium oxide positive electrode materials that embodiment 3 is prepared emit light through X-ray diffraction and inductively coupled plasma body
Spectrometer (ICP) test, learns, obtained vanadium oxide positive electrode materials are the barium oxide of undefined structure before heat treatment
(VOX, X 2.17), it may be possible to one of vanadic anhydride, vanadium dioxide, vanadium trioxide and vanadium oxide are a variety of mixed
Close object；After being heat-treated in nitrogen, the good barium oxide particle (VO of crystallinity has been obtainedX, X 2.17).
The vanadium oxide positive electrode materials that embodiment 3 is prepared are observed under scanning electron microscope, wherein after heat treatment
The SEM figure for the vanadium oxide positive electrode materials being prepared is shown in Fig. 5, from fig. 5, it can be seen that embodiment 3 is prepared after being heat-treated
Barium oxide particle in must shape be grown in foam copper matrix surface.It should be noted simultaneously that the vanadium before the heat treatment of embodiment 3
Almost the same after the pattern of oxide anode material and heat treatment, details are not described herein.
Embodiment 4
The present embodiment is for illustrating aluminum secondary battery vanadium oxide positive electrode materials and preparation method thereof of the invention.
At 25 DEG C, 40ml deionized water is added in 0.49g vanadyl oxalate powder and is held by magnetic agitation (150rpm)
Continuous stirring 2h, obtains the blue vanadium ion solution that concentration is 0.05mol/L (concentration is in terms of vanadium).Then by solution whole
(40.49g) is transferred in the stainless steel cauldron of 50ml polytetrafluoroethyllining lining, and four 3 × 4cm are added2Stainless (steel) wire (1000
Mesh, every quality are 0.5g), it is reacted 1 day in 180 DEG C of heating, is cooled to 25 DEG C after completion of the reaction, taken out reaction product and first use
Dehydrated alcohol washs 2 times, then is washed with deionized 2 times, then 12 hours dry at 80 DEG C in a vacuum drying oven, finally exists
Calcine 6h at 300 DEG C in air, be cut into after the disk that diameter is 1cm obtain using stainless (steel) wire as the barium oxide of matrix just
Pole material.
After measured, deposition of the barium oxide on stainless (steel) wire is 0.5mg/cm2。
The vanadium oxide positive electrode materials that embodiment 4 is prepared emit light through X-ray diffraction and inductively coupled plasma body
Spectrometer (ICP) test, learns, obtained vanadium oxide positive electrode materials are the barium oxide of undefined structure before heat treatment
(VOX, X 1.95), it may be possible to one of vanadic anhydride, vanadium dioxide, vanadium trioxide and vanadium oxide are a variety of mixed
Close object；After being heat-treated in air, barium oxide has obtained the good V of crystallinity through oxidation2O5Particle.
The vanadium oxide positive electrode materials that embodiment 4 is prepared are observed under scanning electron microscope, wherein after heat treatment
The SEM figure for the vanadium oxide positive electrode materials being prepared is shown in Fig. 6, from fig. 6, it can be seen that embodiment 4 is prepared after being heat-treated
Barium oxide particle be grown in stainless (steel) wire matrix surface in the form of sheets.It should be noted simultaneously that before embodiment 4 is heat-treated
Almost the same after the pattern of vanadium oxide positive electrode materials and heat treatment, details are not described herein.
Embodiment 5
According to the method for embodiment 1, unlike, be added 1ml30 weight % aqueous hydrogen peroxide solution (vanadic anhydride with
The molar ratio of hydrogen peroxide is 1:4.4).
After measured, deposition of the barium oxide in nickel foam is 1mg/cm2。
Embodiment 6
According to the method for embodiment 1, unlike, 100ml deionized water is added in vanadium pentoxide powder, obtains dense
Degree is the transparent orange red pervanadic acid solution of 0.038mol/L (concentration is in terms of vanadium).
After measured, deposition of the barium oxide in nickel foam is 1mg/cm2。
Embodiment 7
According to the method for embodiment 1, unlike, after aqueous hydrogen peroxide solution is added, continue to stir 4h.
After measured, deposition of the barium oxide in nickel foam is 1mg/cm2。
Embodiment 8
According to the method for embodiment 1, unlike, it is 1cm that 4 areas, which are added,2Nickel foam disk (aperture 110PPI, it is thick
1mm is spent, every quality is 0.03g).
After measured, deposition of the barium oxide in nickel foam is 20mg/cm2。
Embodiment 9
According to the method for embodiment 1, unlike, the heating reaction 12h at 190 DEG C is added after nickel foam.
After measured, deposition of the barium oxide in nickel foam is 0.5mg/cm2。
Embodiment 10
According to the method for embodiment 1, it unlike, after 70 DEG C 20 hours dry, without calcining, is directly cut into straight
Diameter is the disk of 1cm.
After measured, deposition of the barium oxide in nickel foam is 2mg/cm2。
Embodiment 11
According to the method for embodiment 1, it unlike, after 70 DEG C 20 hours dry, is calcined at 150 DEG C in air
4h。
After measured, deposition of the barium oxide in nickel foam is 2mg/cm2。
The XRD spectrum for the vanadium oxide positive electrode materials that embodiment 5-9 and embodiment 11 are prepared with 1 class of embodiment
Seemingly, the XRD spectrum for the vanadium oxide positive electrode materials that embodiment 10 is prepared is referring to the map before calcining in Fig. 1.And through inductance
Coupled plasma optical emission spectrometer (ICP) test learns, the barium oxide that embodiment 5-9 and embodiment 11 are prepared is just
Be the barium oxide of undefined structure before the material heat treatment of pole, it may be possible to vanadic anhydride, vanadium dioxide, vanadium trioxide and
One of vanadium oxide or a variety of mixtures；After heat treatment, the good barium oxide of crystallinity has been obtained.Embodiment 10
The vanadium oxide positive electrode materials being prepared still are the barium oxide of undefined structure.
By the vanadium oxide positive electrode materials being prepared before embodiment 5-11 heat treatment and after heat treatment under scanning electron microscope
It is observed, SEM figure is similar to Example 1 respectively, that is, the vanadium oxide positive electrode materials (packet that embodiment 5-11 is prepared
Include through Overheating Treatment and without the vanadium oxide positive electrode materials of Overheating Treatment) afflux body surface is grown in Nanoparticulate pattern
Face.
Test example
It is secondary as aluminium using the combination of the embodiment 1-11 vanadium oxide positive electrode materials being prepared and collector respectively
Anode, using metal aluminium flake as cathode, with acid chlorization aluminium profiles imidazolium ionic liquid AlCl3/ [BMIM] Cl=1.1:1
(molar ratio) is assembled into aluminium secondary button cell (2025 types using fibreglass diaphragm for electrolyte in argon gas glove box
Number), constant current charge-discharge performance test is carried out on LAND CT2001A tester (being purchased from Wuhan Land Electronic Co., Ltd.),
Charging/discharging voltage range is 2.5-0.02V, and charging and discharging currents density is 44.2mA/g.Wherein, the vanadium oxygen of embodiment 1-11 preparation
Putting after the first discharge specific capacity (in terms of the quality of positive electrode) of the battery that compound positive electrode is assembled into and circulation 50 times
Electric specific capacity (in terms of the quality of positive electrode) is shown in Table 1.
Table 1
Aluminum secondary battery vanadium oxide positive electrode materials of the invention, barium oxide nanoparticle structure are grown directly upon afflux
On body, addition conductive agent and binder are not needed, that is, may make not only has electrical contact well between the two, is able to maintain good
The stability of good anode electrode, and it is capable of increasing the surface area of vanadium oxide positive electrode materials, improve positive electrode and electrolysis
The contact area of liquid, diffusion length needed for shortening aluminium ion and electronics, meanwhile, aluminum secondary battery of the invention is with higher
Specific discharge capacity and excellent stable circulation performance.
Embodiment 1 and embodiment 5 are compared it is found that vfanadium compound and solute in the aqueous solution of vfanadium compound can be dissolved
When molar ratio is 1:10-24, barium oxide is more advantageous in the uniform deposition of collection liquid surface, and can further increase battery
Specific discharge capacity and stable circulation performance.
Embodiment 1 and embodiment 6 are compared it is found that in terms of vanadium, when the concentration of vanadium ion solution is 0.05-0.15mol/L,
Barium oxide is more advantageous in the uniform deposition of collection liquid surface, and the specific discharge capacity and circulation of battery can be further increased
Stability.
Embodiment 1 and embodiment 7 are compared it is found that with hydrogen peroxide aqueous dissolution vfanadium compound, when the time of stirring
When for 0.5-3h, barium oxide is more advantageous in the uniform deposition of collection liquid surface, and can further increase the electric discharge of battery
Specific capacity and stable circulation performance.
Embodiment 1 and embodiment 8 are compared it is found that the mass ratio of vanadium ion solution and collector be 100:1-20:1 when,
The specific discharge capacity and stable circulation performance of battery can be further increased.
Embodiment 1 and embodiment 9 are compared it is found that extend the time of the hydro-thermal reaction in closed container, when heated between
When being 1-4 days, so that reaction is more abundant, barium oxide is more advantageous in the uniform deposition of collection liquid surface, and can be further
Improve the specific discharge capacity and stable circulation performance of battery.
Embodiment 1 and embodiment 10-11 are compared it is found that by being obtained after vacuum drying using collector as the vanadium oxygen of matrix
Compound positive electrode is heat-treated and the temperature being heat-treated is 300-600 DEG C, when the time is 1-6h, although not will increase vanadium oxygen
The deposition of compound on a current collector is still but conducive to the raising of the crystallinity of barium oxide, can further increase battery
Specific discharge capacity and stable circulation performance.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (5)
1. a kind of preparation method of aluminum secondary battery vanadium oxide positive electrode materials, which is characterized in that method includes the following steps:
(1) vfanadium compound is dissolved, obtains the vanadium ion solution that concentration is 0.05-0.15mol/L；
(2) vanadium ion solution and collector are subjected in closed container hydro-thermal reaction, clean reaction product after reaction
And vacuum drying, obtain the vanadium oxide positive electrode materials using collector as matrix；
Wherein, in step (1), the method for dissolving vfanadium compound includes: that under stiring, vanadium can be dissolved by being added in vfanadium compound
The solution of compound, the time of the stirring are 0.5-3h；
The solution that vfanadium compound can be dissolved is water, aqueous hydrogen peroxide solution, oxalic acid aqueous solution, aqueous hydrochloric acid solution or ammonium hydroxide
Solution；
In step (2), the mass ratio of the vanadium ion solution and the collector is 100:1-20:1；
The condition of the hydro-thermal reaction includes: that heating temperature is 180 DEG C to less than 205 DEG C, and heating time is 1-4 days；
Deposition of the barium oxide on the collector is 2-10mg/cm2；
(3) it is heat-treated what step (2) obtained by the vanadium oxide positive electrode materials of matrix of collector, the heat treatment
Condition includes: that temperature is 300-600 DEG C, time 1-6h.
2. according to the method described in claim 1, wherein, in step (2), the vacuum drying condition includes: drying temperature
It is 60-80 DEG C, drying time 12-24h.
3. method according to claim 1 or 2, wherein the vfanadium compound is vanadic anhydride, vanadium dioxide, three oxygen
Change one of two vanadium, vanadium oxalate, vanadyl oxalate and ammonium metavanadate or a variety of.
4. method according to claim 1 or 2, wherein the collector is nickel foam, foam copper, titanium foam, foamed iron
Nickel, stainless (steel) wire or carbon cloth.
5. the aluminum secondary battery vanadium oxide positive electrode materials that method described in any one of claim 1-4 is prepared.
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| CN107500355B (en) * | 2017-08-30 | 2019-05-31 | 北京理工大学 | A kind of preparation method being layered lepidocrocite type nanometer strip vanadium dioxide |
| CN109616616B (en) * | 2019-01-07 | 2021-09-24 | 湘潭大学 | Preparation method of vanadium oxide nanobelt/foamed nickel composite self-supporting electrode material |
| CN112993217A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Preparation method of organic-inorganic hybrid material based on vanadium pentoxide and application of organic-inorganic hybrid material in zinc ion battery |
| CN113161522B (en) * | 2021-03-12 | 2022-07-19 | 广东工业大学 | Amorphous vanadium oxide/carbon composite material and preparation method and application thereof |
| CN114050245B (en) * | 2021-11-16 | 2023-12-15 | 中科南京绿色制造产业创新研究院 | Composite positive electrode material with spring-like lamellar structure, and preparation method and application thereof |
| CN114284485A (en) * | 2021-12-31 | 2022-04-05 | 齐鲁工业大学 | V-shaped groove2O3Preparation method of/C hollow nanosphere electrode material |
| CN114314650A (en) * | 2022-01-05 | 2022-04-12 | 黑龙江大学 | Method for efficiently recovering titanium oxide from vanadium-titanium waste catalyst |
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