CN109841829A - A kind of porous SnO2The preparation method and application of the double salt ion cell positive materials of 1-dimention nano magnesium-lithium - Google Patents
A kind of porous SnO2The preparation method and application of the double salt ion cell positive materials of 1-dimention nano magnesium-lithium Download PDFInfo
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Abstract
A kind of porous SnO2The preparation method and application of the double salt ion cell positive materials of 1-dimention nano magnesium-lithium, the porous SnO21-dimention nano positive electrode diameter is in 100~300nm, and aperture is in 10~30nm;Preparation method includes the following steps, by a certain amount of SnCl2·2H2O is dissolved in the mixed solution being made of dehydrated alcohol and n,N-Dimethylformamide and is stirred at room temperature;A certain amount of PVP is dissolved in solution and continues to stir to get precursor solution A at room temperature;Atoleine is dissolved in precursor solution A and stirs to obtain precursor solution B;Precursor solution B is used for high-voltage electrostatic spinning, spinning product is subjected to double annealing, the porous SnO of final sample is obtained after its cooled to room temperature2;The present invention effectively inhibits the dusting of positive electrode, to improve the service life of the double salt ion batteries of magnesium-lithium;In addition, SnO2The porous structure of nanotube can be Li+The quick intercalation/deintercalation of ion provides channel, improves the kinetic characteristics of battery.
Description
Technical field
The present invention relates to secondary power battery material technical field, in particular to a kind of porous SnO21-dimention nano magnesium-lithium
The preparation method and application of double salt ion cell positive materials.
Background technique
Information, material, the energy are three big pillars of mankind's modern civilization, and the exploitation and utilization of the energy significantly affect the people's
The development of living standard and society.Energy revolution each time will certainly also promote the development of social economy and the modernization of the mankind
Process.
Currently, lithium ion battery has achieved extensive commercialization, occupied greatly in commercial rechargeable battery market
The market share.However, what the problems such as capacity of lithium ion battery is limited, shortage of resources, with high costs and security performance force not
It obtains and does not seek next " driving " future life of new ion battery.In the numerous ion batteries explored, Magnesium ion battery is because of it
Low in cost, cathode is without remarkable advantages such as dendritic growth, charging capacity height and by extensive concern.The theoretical volume of Magnesium ion battery
Capacity is 3833mAhcm-3, much higher than the theoretical volumetric capacity 2046mAhcm of ion battery-3, in large capacity vehicle mounted electric
Pond field shows great advantage.Magnesium is one of element material abundant in universe, and Magnesium ion battery is cheaper, great big rule
A possibility that mould is promoted.Therefore, the research and development of Magnesium ion battery are more and more deep in recent years, more and more extensive.
Although Magnesium ion battery is reported by correlative study, there is significant energy storage characteristic.But embedding at present/de- Mg2+Ion
The good high-voltage anode material of dynamic performance is limited, and the application of Magnesium ion battery receives serious obstruction.For this purpose, section
Worker is ground by the double salt battery systems of building lithium magnesium, significantly solves the problems, such as that Magnesium ion battery encounters some.By embedding lithium
Positive electrode, magnesium anode material and contain Mg2+And Li+The solid electrolyte of two kinds of ions, the double salt ion battery systems of building magnesium-lithium
System, make full use of the large capacity of magnesium cathode and quickly taken off without dendrite characteristic and lithium anode material/embedding lithium kinetic characteristics realize
Capacity safe high-efficiency energy-storage, so that low capacity of lithium ion battery, at high cost, Li dendrite and Magnesium ion battery deintercalation be effectively relieved
The problems such as dynamics, pushes the application of magnesium-based energy-storage battery.
Currently, SnO2Because of its relatively low operating voltage (its averaged discharge and charging voltage be respectively 0.3 and 0.5 V)
And receive great attention, it is attempted for lithium ion battery storage, can produce high specific energy value when being used in combination with high-voltage cathodes.
Due to SnO2Electrode low electronic conductivity and capacity be presented reduce, and often sent out in charge discharge reaction process
The large volume variation of raw metal Sn, swell increment are up to~300%, stress during circulating battery are easily caused to be difficult to discharge,
To eventually lead to the quick dusting of electrode material, battery capacity is caused significantly to decay, shortens the ion battery service life.
Summary of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of porous SnO21-dimention nano
The preparation method and application of the double salt ion cell positive materials of magnesium-lithium, by the porous knot of high-voltage electrostatic spinning means controlledly synthesis
The one-dimensional SnO of structure2Nanotube passes through SnO2Positive electrode volume is swollen caused by nanotube hole can be released effectively because of lithium ion insertion
Stress caused by swollen, effectively inhibits the dusting of positive electrode, to improve the use longevity of the double salt ion batteries of magnesium-lithium
Life;In addition, SnO2The porous structure of nanotube can be Li+The quick intercalation/deintercalation of ion provides channel, improves the power of battery
Learn characteristic.
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of porous SnO2The double salt ion cell positive materials of 1-dimention nano magnesium-lithium, the porous SnO21-dimention nano anode material
Diameter is expected in 100~300nm, and aperture is in 10~30nm;
A kind of porous SnO2The preparation method of the double salt ion cell positive materials of 1-dimention nano magnesium-lithium, and in particular to arrive:
Step 1:
By a certain amount of SnCl2·2H2O is dissolved in the mixed solution being made of dehydrated alcohol and n,N-Dimethylformamide
And 1~2h is stirred at room temperature;In the step one, dehydrated alcohol and n,N-Dimethylformamide liquor capacity be 1~
6ml;
Step 2:
A certain amount of PVP is dissolved in step 1 solution and continues 3~6h of stirring at room temperature, obtains precursor solution A;
Step 3:
After being dissolved in precursor solution A by the atoleine for accounting for 5~10% precursor solution A of quality and stir 24~48h
Obtain precursor solution B;
Step 4:
The spinning precursor solution B that step 3 obtains is used for high-voltage electrostatic spinning, specific spinning technique is as follows:
Flat mouth syringe needle with 0.5mm internal diameter is connected on syringe as spinning head, and the stainless steel plate of power ground is made
For fiber collecting board, keeping distance between spinning head and collecting board is 10~30cm and therebetween plus 15~30KV's
High pressure, setting injection flow rate pump is 5-10ml h-1Carry out electrostatic spinning, to electrostatic spinning after, by the film on receiver board
It collects and is made annealing treatment in air, annealing temperature is 500 DEG C, time 2h, and heating rate is 3.5 DEG C of min-1,
Sample is obtained after its cooled to room temperature;
Step 5:
The spinning product that step 4 is obtained carries out double annealing, and it is more to obtain final sample after its cooled to room temperature
Hole SnO2。
The SnCl2·2H2O, the proportionate relationship between dehydrated alcohol, n,N-Dimethylformamide is 4:3:3.
Sn Cl in the PVP and step 12·2H2O in mass ratio 1~2 is matched.
Annealing temperature is 900~1050 DEG C in the step five, and the time is 3~6h, and heating rate is 5 DEG C of min-1。
In the step three, the quality of atoleine is 0.05~1.5g.
A kind of porous SnO2The application of the double salt ion battery materials of 1-dimention nano magnesium-lithium, by the porous SnO of 70wt%2、
The conductive auxiliary agent (Super P) of 15wt% and the binder of 15wt% are put into mortar and are fully ground, the sample mud that will be mixed
Slurry blade coating is subsequently placed into 12h in 120 DEG C of vacuum drying ovens on copper foil, keeps it sufficiently dry, and fibreglass diaphragm is electricity
Pond diaphragm, is assembled into button cell;After assembled button cell is stood 12 hours, electrochemistry is carried out in LANDCT2100A
Performance test, test voltage are 0.01V~3.0V, current density 100mA/g.
Beneficial effects of the present invention:
Invention enhances the electric conductivity of Magnesium ion battery, proportion of the present invention by control reaction dissolvent, reaction temperature
The size for improving substance, pattern and structure are spent with soaking time.A kind of porous SnO prepared by the present invention21-dimention nano magnesium-lithium
Double salt ion battery materials, have a large amount of hole quickly to spread Li+ ion in charge and discharge process;A large amount of hole can effectively delay
Positive electrode volume expansion caused by the insertion of Li+ ion is solved, stress is discharged, inhibits the dusting of positive electrode, improves the double salt of magnesium-lithium
The cycle life of double salt batteries is promoted while ion battery charge-discharge power.
Detailed description of the invention
Fig. 1 is the porous SnO of high-voltage electrostatic spinning preparation2The microstructure morphology of 1-dimention nano positive electrode.
Specific embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings.
Embodiment 1: the porous SnO of diameter 100nm, aperture 10nm2The double salt ion material anode preparations of 1-dimention nano magnesium-lithium;
Step 1:
By a certain amount of SnCl2·2H2O is dissolved in the mixed solution being made of dehydrated alcohol and n,N-Dimethylformamide
And 1h is stirred at room temperature;In the step one, dehydrated alcohol and n,N-Dimethylformamide liquor capacity are 1ml, wherein
SnCl2·2H2O, the proportionate relationship between dehydrated alcohol, n,N-Dimethylformamide is 4:3:3.
Step 2:
A certain amount of PVP is dissolved in above-mentioned solution to and continues to stir at room temperature 3h, the Sn in the PVP and step 1
Cl2·2H2O 1:1 in mass ratio proportion, obtains precursor solution A;
Step 3:
The atoleine of 5% (accounting for precursor solution A) is dissolved in precursor solution A and is stirred and obtains presoma afterwards for 24 hours
Solution B;
Step 4: (precursor solution B having been obtained in step 3, step 4 has used precursor solution B)
The spinning precursor solution B that step 3 obtains is used for high-voltage electrostatic spinning, specific spinning technique is as follows:
Flat mouth syringe needle with 0.5mm internal diameter is connected on syringe as spinning head, and the stainless steel plate of power ground is made
For fiber collecting board, distance between spinning head and collecting board is kept to be 30cm and add the high pressure of 30KV, setting therebetween
Injection flow rate pump is 5ml h-1Carry out electrostatic spinning, to electrostatic spinning after, by the film on receiver board collect and
It is made annealing treatment in air, annealing temperature is 500 DEG C, time 2h, and heating rate is 3.5 DEG C of min-1, to its natural cooling
Sample is obtained after to room temperature;
Step 5:
The spinning product that step 4 is obtained carries out double annealing, and annealing temperature is 900 DEG C, time 6h, heating rate
For 5 DEG C of min-1, the porous SnO of final sample is obtained after its cooled to room temperature2;
In the step three, the quality of atoleine is 0.05g.
Embodiment 2: the porous SnO of diameter 200nm, aperture 20nm2The double salt ion material anode preparations of 1-dimention nano magnesium-lithium;
Step 1:
By a certain amount of SnCl2·2H2O is dissolved in the mixed solution being made of dehydrated alcohol and n,N-Dimethylformamide
And 1h is stirred at room temperature;In the step one, dehydrated alcohol and n,N-Dimethylformamide liquor capacity are 1ml, wherein
SnCl2·2H2O, the proportionate relationship between dehydrated alcohol, n,N-Dimethylformamide is 4:3:3.
Step 2:
A certain amount of PVP is dissolved in above-mentioned solution and is continued in stirring 4.5h, the PVP and step 1 at room temperature
Sn Cl2·2H2O 1:1 in mass ratio proportion, obtains precursor solution A;
Step 3:
The atoleine of 8% (accounting for precursor solution A) is dissolved in precursor solution A and obtains presoma after stirring 36h
Solution B;
Step 4: (precursor solution B having been obtained in step 3, step 4 has used precursor solution B)
The spinning precursor solution B that step 3 obtains is used for high-voltage electrostatic spinning, specific spinning technique is as follows:
Flat mouth syringe needle with 0.5mm internal diameter is connected on syringe as spinning head, and the stainless steel plate of power ground is made
For fiber collecting board, distance between spinning head and collecting board is kept to be 20cm and add the high pressure of 20KV, setting therebetween
Injection flow rate pump is 8ml h-1Carry out electrostatic spinning, to electrostatic spinning after, by the film on receiver board collect and
It is made annealing treatment in air, annealing temperature is 500 DEG C, time 2h, and heating rate is 3.5 DEG C of min-1, to its natural cooling
Sample is obtained after to room temperature;
Step 5:
The spinning product that step 4 is obtained carries out double annealing, and annealing temperature is 980 DEG C, time 4.5h, heating speed
Degree is 5 DEG C of min-1, the porous SnO of final sample is obtained after its cooled to room temperature2;
In the step three, the quality of atoleine is 1.0g.
Embodiment 3: the porous SnO of diameter 300nm, aperture 30nm2The double salt ion material anode preparations of 1-dimention nano magnesium-lithium;
Step 1:
By a certain amount of SnCl2·2H2O is dissolved in the mixed solution being made of dehydrated alcohol and n,N-Dimethylformamide
And 1h is stirred at room temperature;In the step one, dehydrated alcohol and n,N-Dimethylformamide liquor capacity are 1ml, wherein
SnCl2·2H2O, the proportionate relationship between dehydrated alcohol, n,N-Dimethylformamide is 4:3:3.
Step 2:
A certain amount of PVP is dissolved in above-mentioned solution to and continues to stir at room temperature 6h, the Sn in the PVP and step 1
Cl2·2H2O 1:1 in mass ratio proportion, obtains precursor solution A;
Step 3:
The atoleine of 10% (accounting for precursor solution A) is dissolved in precursor solution A and obtains presoma after stirring 48h
Solution B;
Step 4: (precursor solution B having been obtained in step 3, step 4 has used precursor solution B)
The spinning precursor solution B that step 3 obtains is used for high-voltage electrostatic spinning, specific spinning technique is as follows:
Flat mouth syringe needle with 0.5mm internal diameter is connected on syringe as spinning head, and the stainless steel plate of power ground is made
For fiber collecting board, distance between spinning head and collecting board is kept to be 10cm and add the high pressure of 15KV, setting therebetween
Injection flow rate pump is 10ml h-1Carry out electrostatic spinning, to electrostatic spinning after, by the film on receiver board collect and
It is made annealing treatment in air, annealing temperature is 500 DEG C, time 2h, and heating rate is 3.5 DEG C of min-1, to its natural cooling
Sample is obtained after to room temperature;
Step 5:
The spinning product that step 4 is obtained carries out double annealing, and annealing temperature is 1050 DEG C, time 3h, heating rate
For 5 DEG C of min-1, the porous SnO of final sample is obtained after its cooled to room temperature2;
In the step three, the quality of atoleine is 0.05g.
It is as shown in Figure 1 the double salt ion cell positive material shape appearance figures of 1-dimention nano magnesium-lithium.
By figure result as it can be seen that the double salt ion batteries of 1-dimention nano magnesium-lithium of the porous SnO2 of diameter 250nm, aperture 25nm just
Pole nano material even thickness, diameter is in 250nm or so, and porous structure, uniform diameter, probably in 25nm is presented in port pattern
Left and right.The porous SnO2 monodimension nanometer material can be de- for the insertion of positive lithium ion in the bis- salt battery charge and discharge process of Mg-Li
A large amount of quick diffusion admittances are provided out, and porous structure can significantly alleviate positive electrode because the intercalation/deintercalation of lithium ion is made
At material expansion/contraction alleviate the dusting of positive electrode to be released effectively the stress in material, improve double salt electricity
The cycle life in pond.
Claims (7)
1. a kind of porous SnO2The double salt ion cell positive materials of 1-dimention nano magnesium-lithium, which is characterized in that the porous SnO2It is one-dimensional
Nano anode material diameter is in 100~300nm, and aperture is in 10~30nm.
2. a kind of porous SnO2The preparation method of the double salt ion cell positive materials of 1-dimention nano magnesium-lithium, which is characterized in that including
Following steps:
Step 1:
By a certain amount of SnCl2·2H2O be dissolved in the mixed solution being made of dehydrated alcohol and n,N-Dimethylformamide and
1~2h is stirred at room temperature;In the step one, dehydrated alcohol and n,N-Dimethylformamide liquor capacity are 1~6ml;
Step 2:
A certain amount of PVP is dissolved in step 1 solution and continues 3~6h of stirring at room temperature, obtains precursor solution A;
Step 3:
The atoleine for accounting for 5~10% precursor solution A of quality is dissolved in precursor solution A and is obtained after stirring 24~48h
Precursor solution B;
Step 4:
The spinning precursor solution B that step 3 obtains is used for high-voltage electrostatic spinning, specific spinning technique is as follows:
Flat mouth syringe needle with 0.5mm internal diameter is connected on syringe as spinning head, and the stainless steel plate of power ground is as fine
Collecting board is tieed up, distance between spinning head and collecting board is kept to be 10~30cm and add the high pressure of 15~30KV therebetween,
Setting injection flow rate pump is 5-10ml h-1Carry out electrostatic spinning, to electrostatic spinning after, the film on receiver board is gathered up
Come and made annealing treatment in air, annealing temperature is 500 DEG C, time 2h, and heating rate is 3.5 DEG C of min-1, certainly to it
Sample is obtained after being so cooled to room temperature;
Step 5:
The spinning product that step 5 is obtained carries out double annealing, and it is porous to obtain final sample after its cooled to room temperature
SnO2。
3. a kind of porous SnO according to claim 22The preparation side of the double salt ion cell positive materials of 1-dimention nano magnesium-lithium
Method, which is characterized in that the SnCl2·2H2O, the proportionate relationship between dehydrated alcohol, n,N-Dimethylformamide is 4:3:
3。
4. a kind of porous SnO according to claim 22The preparation side of the double salt ion cell positive materials of 1-dimention nano magnesium-lithium
Method, which is characterized in that the Sn Cl in the PVP and step 12·2H2O in mass ratio 1~2 is matched.
5. a kind of porous SnO according to claim 22The preparation side of the double salt ion cell positive materials of 1-dimention nano magnesium-lithium
Method, which is characterized in that annealing temperature is 900~1050 DEG C in the step five, and the time is 3~6h, and heating rate is 5 DEG C
min-1。
6. a kind of porous SnO according to claim 22The preparation side of the double salt ion cell positive materials of 1-dimention nano magnesium-lithium
Method, which is characterized in that in the step three, the quality of atoleine is 0.05~1.5g.
7. a kind of porous SnO2The application of the double salt ion battery materials of 1-dimention nano magnesium-lithium, which is characterized in that by the more of 70wt%
Hole SnO2, the conductive auxiliary agent of 15wt% and the binder of 15wt% be put into mortar and be fully ground, the sample mud that will be mixed
With blade coating on copper foil, it is subsequently placed into 12h in 120 DEG C of vacuum drying ovens, keeps it sufficiently dry, fibreglass diaphragm is battery
Diaphragm is assembled into button cell;After assembled button cell is stood 12 hours, electrochemistry is carried out in LANDCT2100A
It can test, test voltage is 0.01V~3.0V, current density 100mA/g.
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Cited By (1)
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