CN104466127B - PMMA-coated hollow Sn-Ni alloy nanowire array and preparation method and application of PMMA-coated hollow Sn-Ni alloy nanowire array - Google Patents
PMMA-coated hollow Sn-Ni alloy nanowire array and preparation method and application of PMMA-coated hollow Sn-Ni alloy nanowire array Download PDFInfo
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Abstract
The invention discloses a PMMA-coated hollow Sn-Ni alloy nanowire array, a preparation method of the nanowire array, and application of the nanowire array in a lithium battery negative pole material. The method comprises the following steps: (1) preparing Ni nanowires by using a constant-current electrodeposition method by taking AAO as a template; (2) preparing a hollow Sn-Ni alloy nanowire array by virtue of current replacement reaction by taking the Ni nanowires as a template; and (3) in-situ generating a PMMA high polymer film of 20-30nm in a circular pore formed by a single nanowire and the AAO by utilizing an in-situ MMA bulk polymerization method, thereby obtaining the PMMA-coated hollow Sn-Ni alloy nanowire array. The prepared PMMA-coated hollow Sn-Ni alloy nanowire array serves as a negative pole and is used for assembling a lithium ion battery, and the reversible specific capacity of the PMMA-coated hollow Sn-Ni alloy nanowire array is maintained be 0.84mAhcm<-2> after 50 times of cycles based on the flexibility of high polymers and the buffer action of an internal hollow structure on volume expansion.
Description
Technical field
The present invention relates to nano material and its applied technical field, more particularly to a kind of hollow Sn-Ni conjunctions of PMMA claddings
Crystal structure, its preparation method and its application.
Background technology
Three-dimensional tinbase nano structure electrode has important work for development high power capacity of new generation, high-power lithium ion battery
With.Traditional two-dimensional film lithium ion battery has short lithium ion diffusion path, high specific capacity, excellent chemical property
And security performance, but its battery volume energy density is relatively low.In contrast, three-diemsnional electrode structure can make full use of space excellent
Gesture, while the diffusion length for keeping two-dimensional film lithium ion short, improves the energy storage capacity of battery.Simultaneously three-dimensional structure can
Increase electrode and the contact area of dielectric film, improve electrical conductivity.Nano-tube array has unique three-D space structure with
Hollow structure, three-D space structure substantially increases the contact area of electrode material and electrolyte, shortens the transmission of lithium ion
Path, hollow structure can then alleviate the volumetric expansion in charge and discharge process, improve the cyclical stability of battery.
However, three-dimensional structure nano line electrode under by stress or hot conditions it may happen that deformation, due to draw ratio
Very big, the easy fracture of root of nano wire or mutually bonding and filming, three-dimensional manometer cable architecture is destroyed, and causes battery capacity
Decline, there is a problem that three-diemsnional electrode structural stability is poor.
The content of the invention
Three-dimensional structure nano wire is poor as lithium cell cathode material stability in order to solve the problems, such as prior art, this
A kind of bright hollow Sn-Ni alloy nanowire arrays, its preparation method and its application coated there is provided PMMA.
The technical scheme is that:
A kind of hollow Sn-Ni alloy nanowire arrays of PMMA claddings, including hollow Sn-Ni alloy nanowire arrays, institute
State hollow Sn-Ni alloy nanowire arrays outside to be coated by PMMA clads.
Preferably, the array heights of the hollow Sn-Ni alloy nanowire arrays are 8um-10um, adjacent two nano wire
Spacing is 60nm-70nm, and the cavity diameter of the hollow Sn-Ni alloy nano-wires is 260-280nm, the PMMA clads
Thickness is 20-30nm.
The preparation method of the hollow Sn-Ni alloy nanowire arrays of the PMMA claddings, comprises the following steps:
1)Constant current electrodeposition process prepares Ni nano-wire arrays
A. in a face metal spraying of porous anodic alumina template, metal spraying face conductive silver glue is covered in clean Copper Foil
On, expose the Copper Foil of porous anodic alumina template with silica gel sealing, it is vacuum dried after silica gel solidification;
B. with saturated calomel electrode as reference electrode, platinum electrode be to electrode, the porous anode oxygen to process in step a
Change aluminum alloy pattern plate be working electrode, under the electric current of 0.1-0.5 mA, galvanostatic deposition 1-4 h, deposition terminate after, spend respectively from
Sub- water and alcohol washes, wherein electrolyte by 10-30 g/L Ni2SO4·6H2The H of O, 20-50g/L3BO3With 20-40g/L's
Polyethylene glycol is constituted;
C. the porous anodic alumina template that deposition there are Ni nano wires is put in the NaOH solution of 0.1-0.5 M and is soaked
15-50min, to porous anodic alumina template micro- reaming is carried out, and is cleaned afterwards, is dried, and obtains the Ni nano wires of reaming, is preserved standby
With;
2)Electric current displacement method prepares hollow Sn-Ni alloy nanowire arrays
By the Ni nano wires of reaming, the SnSO of 0.01-0.1 M is put into4Immersion reaction 5-30 days, clear after taking-up in solution
Wash, dry hollow Sn-Ni alloy nanowire arrays;
3)PMMA coats hollow Sn-Ni alloy nanowire arrays
50-80mg initiator ammonium persulfates are dissolved in the methyl methacrylate monomer of 50-80ml, at 90-100 DEG C
Lower insulation 3-10min, is then incubated 10-30min at 80-85 DEG C, obtains PMMA solution;The PMMA solution for taking 5-10uL is dropped in
On porous anodic alumina template, PMMA solution impregnation porous anodic alumina template hole wall film forming will be many after solvent volatilization
Hole anodic oxidation aluminium formwork is placed in the NaOH solution of 1-4M and removes removing template, cleans, is dried, and obtains the hollow Sn-Ni of PMMA claddings
Alloy nanowire array.
Preferably, step 1)The thickness of Copper Foil is 10-25um in a, and Copper Foil uses the oxide and greasy dirt for front going to its surface.
Preferably, step 1)In b, first the porous anodic alumina template handled well is put in electrolyte before electrolysis ultrasonic
3-5min stands in the electrolytic solution 0.5-2h to remove the gas in porous anodic alumina template duct, then fills electrolyte
Sub-dip is moistened in porous anodic alumina template duct.
Application of the hollow Sn-Ni alloy nanowire arrays of the PMMA claddings in lithium cell cathode material.
Beneficial effects of the present invention are:
The hollow Sn-Ni alloy nanowire arrays of the made PMMA claddings of the present invention, preparation method is simple, and mild condition can
Control.The nanowire alignment of preparation is neat, and highly basically identical, diameter is homogeneous.PMMA coating films can increase hollow Sn-Ni alloys
The rigidity of nano-wire array, it is to avoid its lodging phenomenon, plays a part of barrier film, so as to strengthen the stable circulation performance of battery.Fill
Discharge performance test result shows that the hollow Sn-Ni alloy nanowire arrays after PMMA claddings have higher specific capacity and good
Cyclical stability, 50 times circulation after capacity remain at 0.84mAhcm-2, capacity is remained at after 200 circulations
0.8mAhcm-2, in addition to coulombic efficiency first is relatively low, remaining is nearly all in 90 more than %.PMMA coats hollow Sn-Ni alloy nanos
Linear array negative pole is expected to become a kind of new lithium ion battery negative material, before practical application area has extensive research
Scape.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the hollow Sn-Ni alloy nanowire arrays of the PMMA claddings prepared in embodiment 4;
Fig. 2 is the transmission electron microscope picture of the hollow Sn-Ni alloy nanowire arrays of the PMMA claddings prepared in embodiment 4;
Fig. 3 is the cycle performance curve of 50 circulations of battery of the assembling of embodiment 9;
Fig. 4 is the cycle performance curve of 200 circulations of battery of the assembling of embodiment 9.
Specific embodiment
Embodiment 1
The preparation method of the Sn-Ni alloy nanowire arrays of PMMA claddings of the present invention, comprises the following steps:
1)Constant current electrodeposition process prepares Ni nano-wire arrays
A. porous anodic alumina template(AAO)Process
A diameter of 20 mm of clip, the Copper Foil that thickness is 15 μm, surpass respectively in the dilute hydrochloric acid solution and acetone of 1moL/L
Sound wave cleans 5 min, and to wash away the oxide and greasy dirt on its surface, then deionized water and alcohol are respectively washed 3-5 time,
4h is vacuum dried at 90 DEG C.
In the face metal spraying of porous anodic alumina template one, metal spraying face conductive silver glue is covered in the above-mentioned Copper Foil for processing
On, and the part with silica gel sealing in addition to AAO templates, do not allow Copper Foil to expose, after silica gel solidification, it is vacuum dried at 80 DEG C
4h。
B. electrolyte is prepared(Electrolyte by 15 g/L Ni2SO4·6H2The H of O, 35g/L3BO3With the poly- second two of 37g/L
Alcohol is constituted), the AAO templates handled well are put into in electrolyte ultrasound 3min to remove the gas in AAO templates duct, Ran Hou
1h is stood in electrolyte makes electrolyte fully infiltrate in AAO templates duct;With saturated calomel electrode as reference electrode, platinum electrode
It is the constant current under the electric current of 0.35 mA to electrode, with the AAO templates after ultrasonic in the electrolytic solution and standing as working electrode
2 h are deposited, after deposition terminates, respectively deionized water and alcohol are respectively cleaned 3-5 time.
C. the AAO templates that deposition there are Ni nano wires are put in the NaOH solution of 0.1M and soak 40min, to AAO templates
Micro- reaming is carried out, afterwards deionized water and alcohol respectively clean 3-5 time, are dried 5h in 100 DEG C of vacuum drying chamber, obtain reaming
Ni nano wires, save backup.
2)Electric current displacement method prepares hollow Sn-Ni alloy nanowire arrays
By the Ni nano wires of reaming, the SnSO of 0.1M is put into4Immersion reaction 5d, uses respectively deionization in solution after taking-up
Water and alcohol are respectively cleaned 3-5 time, are then dried 8h in 100 DEG C of vacuum drying chamber, obtain hollow Sn-Ni alloy nanos linear array
Row.
3)PMMA coats hollow Sn-Ni alloy nanowire arrays
Agitator, condenser pipe, thermometer are installed in the there-necked flask of 250mL.First plus 50mg BPO, MMA is added(It is single
Body)50 mL start stirring makes BPO(Initiator ammonium persulfate)In being dissolved in monomer, heating water bath is protected when temperature reaches 90 DEG C
Temperature 5 minutes, then makes material maintain 10 minutes or so at 80 DEG C, takes 5 μ L PMMA solution and drops in porous anodic alumina template
On, PMMA solution impregnation porous anodic alumina template hole wall film forming after solvent volatilization, porous anodic alumina template is put
Removing template is removed in 2M NaOH solution, cleaned, be dried, obtain the hollow Sn-Ni alloy nanowire arrays of PMMA claddings.
The array heights of the hollow Sn-Ni alloy nanowire arrays of the present embodiment gained PMMA claddings are 8-10um, adjacent
The spacing of two nano wires is 65-70nm, and the cavity diameter of hollow Sn-Ni alloy nano-wires is 260-262nm, PMMA clads
Thickness is 20-25nm.
Embodiment 2
The preparation method of the Sn-Ni alloy nanowire arrays of PMMA claddings of the present invention, comprises the following steps:
Step 1)With step 3)With embodiment 1.
Step 2)Electric current displacement method prepares hollow Sn-Ni alloy nanowire arrays
By the Ni nano wires of reaming, the SnSO of 0.1 M is put into4In solution immersion reaction 10d, spend respectively after taking-up from
Sub- water and alcohol are respectively cleaned 3-5 time, are then dried 8h in 100 DEG C of vacuum drying chamber, obtain hollow Sn-Ni alloy nanos linear array
Row.
The array heights of the hollow Sn-Ni alloy nanowire arrays of the present embodiment gained PMMA claddings are 8-10um, adjacent
The spacing of two nano wires is 60-65nm, and the cavity diameter of hollow Sn-Ni alloy nano-wires is 262-265nm, PMMA clads
Thickness be 20-25nm.
Embodiment 3
The preparation method of the Sn-Ni alloy nanowire arrays of PMMA claddings of the present invention, comprises the following steps:
Step 1)With step 3)With embodiment 1.
Step 2)Electric current displacement method prepares hollow Sn-Ni alloy nanowire arrays
By the Ni nano wires of reaming, the SnSO of 0.1 M is put into4In solution immersion reaction 15d, spend respectively after taking-up from
Sub- water and alcohol are respectively cleaned 3-5 time, are then dried 8h in 100 DEG C of vacuum drying chamber, obtain hollow Sn-Ni alloy nanos linear array
Row.
The array heights of the hollow Sn-Ni alloy nanowire arrays of the present embodiment gained PMMA claddings are 8-10um, adjacent
The spacing of two nano wires is 60-65nm, and the cavity diameter of hollow Sn-Ni alloy nano-wires is 265-270nm, PMMA clads
Thickness be 20-25nm.
Embodiment 4
The preparation method of the Sn-Ni alloy nanowire arrays of PMMA claddings of the present invention, comprises the following steps:
Step 1)With step 3)With embodiment 1.
Step 2)Electric current displacement method prepares hollow Sn-Ni alloy nanowire arrays
By the Ni nano wires of reaming, the SnSO of 0.1M is put into4Immersion reaction 25d, uses respectively deionization in solution after taking-up
Water and alcohol are respectively cleaned 3-5 time, are then dried 8h in 100 DEG C of vacuum drying chamber, obtain hollow Sn-Ni alloy nanos linear array
Row.ESEM is done to the Sn-Ni alloy nanowire arrays of the PMMA claddings obtained by the present embodiment(As a result it is as shown in Figure 1)Analysis
And transmission electron microscope(As a result it is as shown in Figure 2)Analysis.
The array heights of the hollow Sn-Ni alloy nanowire arrays of the present embodiment gained PMMA claddings are 8-10um, adjacent
The spacing of two nano wires is 60-65nm, and the cavity diameter of hollow Sn-Ni alloy nano-wires is 270-275nm, PMMA clads
Thickness be 20-25nm.
Embodiment 5
The preparation method of the Sn-Ni alloy nanowire arrays of PMMA claddings of the present invention, comprises the following steps:
Step 1)With step 3)With embodiment 1.
Step 2)Electric current displacement method prepares hollow Sn-Ni alloy nanowire arrays
By the Ni nano wires of reaming, the SnSO of 0.01 M is put into4In solution immersion reaction 25d, spend respectively after taking-up from
Sub- water and alcohol are respectively cleaned 3-5 time, are then dried 8h in 100 DEG C of vacuum drying chamber, obtain hollow Sn-Ni alloy nanos linear array
Row.
The array heights of the hollow Sn-Ni alloy nanowire arrays of the present embodiment gained PMMA claddings are 8-10um, adjacent
The spacing of two nano wires is 65-70nm, and the cavity diameter of hollow Sn-Ni alloy nano-wires is 260-263nm, PMMA clads
Thickness be 20-25nm.
Embodiment 6
The preparation method of the Sn-Ni alloy nanowire arrays of PMMA claddings of the present invention, comprises the following steps:
Step 1)With step 3)With embodiment 1.
Step 2)Electric current displacement method prepares hollow Sn-Ni alloy nanowire arrays
By the Ni nano wires of reaming, the SnSO of 0.05 M is put into4In solution immersion reaction 25d, spend respectively after taking-up from
Sub- water and alcohol are respectively cleaned 3-5 time, are then dried 8h in 100 DEG C of vacuum drying chamber, obtain hollow Sn-Ni alloy nanos linear array
Row.
The array heights of the hollow Sn-Ni alloy nanowire arrays of the present embodiment gained PMMA claddings are 8-10um, adjacent
The spacing of two nano wires is 65-70nm, and the cavity diameter of hollow Sn-Ni alloy nano-wires is 265-270nm, PMMA clads
Thickness be 20-25nm.
Embodiment 7
The preparation method of the Sn-Ni alloy nanowire arrays of PMMA claddings of the present invention, comprises the following steps:
Step 1)With step 2)With embodiment 4.
Step 3)PMMA coats hollow Sn-Ni alloy nanowire arrays
Agitator, condenser pipe, thermometer are installed in the there-necked flask of 250mL.First plus 80mg BPO, MMA50 mL are added
Starting stirring makes BPO be dissolved in monomer, heating water bath, and when temperature reaches 90 DEG C 5 minutes are incubated, and then makes material at 80 DEG C
Maintain 10 minutes or so, take 5 μ L PMMA solution and drop on porous anodic alumina template, PMMA solution impregnation porous anode oxygen
Change aluminum alloy pattern plate hole wall film forming, after solvent volatilization, porous anodic alumina template be placed in 2M NaOH solution and remove removing template,
Clean, be dried, obtain the hollow Sn-Ni alloy nanowire arrays of PMMA claddings.
The array heights of the hollow Sn-Ni alloy nanowire arrays of the present embodiment gained PMMA claddings are 8-10um, adjacent
The spacing of two nano wires is 60-65nm, and the cavity diameter of hollow Sn-Ni alloy nano-wires is 270-275nm, PMMA clads
Thickness be 25-30nm.
Embodiment 8
The preparation method of the Sn-Ni alloy nanowire arrays of PMMA claddings of the present invention, comprises the following steps:
Step 1)With step 2)With embodiment 4.
Step 3)PMMA coats hollow Sn-Ni alloy nanowire arrays
Agitator, condenser pipe, thermometer are installed in the there-necked flask of 250mL.First plus 50mg BPO, MMA 80 is added
ML starts stirring makes BPO be dissolved in monomer, heating water bath, and when temperature reaches 90 DEG C 5 minutes are incubated, and then makes material 80
DEG C maintain 10 minutes or so, take 5 L PMMA solution and drop on porous anodic alumina template, PMMA solution impregnation porous anodes
Alumina formwork hole wall film forming, after solvent volatilization, porous anodic alumina template is placed in 2M NaOH solution and removes mould
Plate, cleans, is dried, and obtains the hollow Sn-Ni alloy nanowire arrays of PMMA claddings.
The array heights of the hollow Sn-Ni alloy nanowire arrays of the present embodiment gained PMMA claddings are 8-10um, adjacent
The spacing of two nano wires is 60-65nm, and the cavity diameter of hollow Sn-Ni alloy nano-wires is 270-275nm, PMMA clads
Thickness be 28-30nm.
Embodiment 9
Application of the hollow Sn-Ni alloy nanowire arrays of PMMA claddings in lithium cell cathode material:
To be dispersed with the copper sheet of the hollow Sn-Ni alloy nanowire arrays that the PMMA obtained by embodiment 1 is coated as electrode
Piece, assembles button half-cell.
Electrode, CR2032 types battery container and instrument are put into together in vacuum drying chamber, 6 h are dried at 120 DEG C,
To remove moisture, be then quickly transferred to glove box (< 1 × 10- 4% moisture,< 4 × 10-4% oxygen) middle assembling electricity
Pond.Lithium piece is that to electrode, barrier film is polypropylene microporous composite membrane (CeLgard 2400), add appropriate 1moL/L LiPF6/
EC+ DMC+ EMC (volume ratios 1:1:1) seal after electrolyte.
Using LAND battery test systems(CT2001 A)Battery to being assembled carries out constant current charge-discharge test(Survey
Test result is as shown in Figure 3, Figure 4), test voltage scope is 0.002-3 V, and current density is 1-5 mAcm-2.Charge-discharge performance is surveyed
Test result shows that the hollow Sn-Ni alloy nanowire arrays after coating have higher specific capacity and good cyclical stability,
Capacity remains at 0.84mAhcm after 50 circulations-2, capacity remains at 0.8mAhcm after 200 circulations-2, except coulomb first
Less efficient outer, remaining is nearly all in 90 more than %.
Claims (3)
1. the preparation method of the hollow Sn-Ni alloy nanowire arrays of a kind of PMMA cladding, it is characterised in that including following step
Suddenly:
1)Constant current electrodeposition process prepares Ni nano-wire arrays
A. in a face metal spraying of porous anodic alumina template, metal spraying face conductive silver glue is covered on clean Copper Foil, is used
Silica gel sealing exposes the Copper Foil of porous anodic alumina template, is vacuum dried after silica gel solidification;
B. with saturated calomel electrode as reference electrode, platinum electrode be to electrode, the porous anodic aluminium oxide to process in step a
Template is working electrode, under the electric current of 0.1-0.5 mA, galvanostatic deposition 2-4 h, and after deposition terminates, difference deionized water
And alcohol washes, wherein electrolyte by 10-30 g/L Ni2SO4·6H2The H of O, 20-50g/L3BO3With the poly- second of 20-40g/L
Glycol is constituted;First the porous anodic alumina template handled well is put into in electrolyte ultrasound 3-5min to remove porous before electrolysis
Gas in anodic oxidation aluminium formwork duct, 0.5-2h is then stood in the electrolytic solution makes electrolyte fully infiltrate porous anode
In alumina formwork duct;
C. the porous anodic alumina template that deposition there are Ni nano wires is put in the NaOH solution of 0.1-0.5 M and soaks 15-
50min, to porous anodic alumina template micro- reaming is carried out, and is cleaned afterwards, is dried, and obtains the Ni nano wires of reaming, is saved backup;
2)Electric current displacement method prepares hollow Sn-Ni alloy nanowire arrays
By the Ni nano wires of reaming, the SnSO of 0.01-0.1 M is put into4Immersion reaction 5-30 days in solution, clean after taking-up, do
It is dry to obtain hollow Sn-Ni alloy nanowire arrays;
3)PMMA coats hollow Sn-Ni alloy nanowire arrays
50-80mg initiator ammonium persulfates are dissolved in the methyl methacrylate monomer of 50-80ml, are protected at 90-100 DEG C
Warm 3-10min, is then incubated 10-30min at 80-85 DEG C, obtains PMMA solution;The PMMA solution for taking 5-10 μ L drops in porous
On anodic oxidation aluminium formwork, PMMA solution impregnation porous anodic alumina template hole wall film forming, after solvent volatilization, by porous sun
Pole alumina formwork is placed in the NaOH solution of 1-4M and removes removing template, cleans, is dried, and obtains the hollow Sn-Ni alloys of PMMA claddings
Nano-wire array.
2. the preparation method of the hollow Sn-Ni alloy nanowire arrays of PMMA as claimed in claim 1 cladding, it is characterised in that
Step 1)The thickness of Copper Foil is 10-25 μm in a, and Copper Foil uses the oxide and greasy dirt for front going to its surface.
3. by the preparation method gained PMMA claddings of the hollow Sn-Ni alloy nanowire arrays of PMMA claddings described in claim 1
Application of the hollow Sn-Ni alloy nanowire arrays in lithium cell cathode material.
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