Embodiment
Embodiment 1: the preparation and the charge and discharge performance of amorphous silicon negative pole (anode) electrode
Be placed in the magnetic control sputtering device as shown in Figure 1 two commercially available silicon targets are parallel, silicon target is staggered relatively as negative electrode, and the stainless steel bell jar is as plus earth, the vertical target surface of externally-applied magnetic field.On the specimen holder between two silicon targets, put a slice Copper Foil, nickel foil, copper facing or/and the nickel plating iron foil as electrode current collecting body, is evacuated to 10 then
-4Below the Pa.Feed high-purity argon gas, make Ar Pressure reach 0.2Pa.Then, apply voltage to 300V to silicon target, Control current is 0.1A, and sputter was taken out collector after 2 hours, promptly gets negative pole of the present invention (anode) electrode, is 5 μ m through measuring its thickness.Because Copper Foil is identical with the copper facing collector, and nickel foil is also identical with nickel plating iron foil collector, and the apparent pattern after sputter on these four kinds of collectors is close substantially, therefore, has only provided the sputter situation on the Copper Foil here.Fig. 2 as can be seen, the Si comparison rule and very even that becomes to look has obvious gaps between the granule, its size is about 2 μ m.In addition, it can also be seen that have 4 granules to be agglomerated into a big particle, this bulky grain size is about 5 μ m.
This electrode and metal lithium sheet composition half-cell are measured its electrochemistry charge and discharge capacity in liquid electrolyte and pure solid polymer electrolyte.Electrolyte is respectively 1MLiPF
6(EC: DEC=1: 1V/V%) solution and PEO
Pure solid polymer electrolyte.Discharging and recharging standard is: at 1MLiPF
6(EC: DEC=1: 1V/V%) in the solution, 0.1mA/cm
2Discharge into OV, stop using 0.1mA/cm after 5 minutes
2Charge to 1.0V; At PEO
In the pure solid polymer electrolyte, with 0.05mA/cm
2Discharge into OV, stop using 0.05mA/cm after 5 minutes
2Charge to 1.0V.As can be seen from Figure 3, the Si electrode all has excellent cycle performance in two kinds of electrolyte.At 1MLiPF
6(EC: DEC=1: 1V/V%) in the electrolyte, the period 1 has peak capacity, reaches 4015mAh/g, and irreversible capacity seldom, has only 5% of initial capacity, since second round, in cycle period scope shown in Figure 3 (50 cycle), the capacity attenuation rate is very little, has only 23mAh/
, and the charge and discharge capacity in each cycle is basic identical, and promptly efficient is near 100%.At PEO
In the pure solid electrolyte, the capability value in first week is smaller, reaches 2680mAh/g, and along with the increase of cycle period, active material obtains activation gradually, and capacity increases gradually, and through 6 all after dates, capacity reaches maximum, a little less than at 1MLiPF
6(EC: DEC=1: the 1V/V%) capability value in the electrolyte.This is because under pure solid electrolyte situation, has only electrode surface could participate in electrochemical reaction, and the active material of body in mutually can not all touch electrolyte, so can't participate in electrochemical reaction.Along with the carrying out of circulation, the charge and discharge capacity is almost constant, and the capacity attenuation rate more is low to moderate 1.4mAh/
Above-mentioned example explanation, this Si electrode can be applied in lithium rechargeable battery and the polymer secondary battery.Polymer described here comprises pure solid type and gel-type two base polymers.
Embodiment 2: the preparation and the charge and discharge performance of amorphous state Si-Sn negative pole (anode) electrode
The preparation method of bianry alloy is identical with embodiment 1.With commercially available two silicon targets and two parallel respectively being placed in the magnetic control sputtering device of metal M target, on the specimen holder in the middle of four targets, put a slice Copper Foil, nickel foil, copper facing or/and the nickel plating iron foil as electrode current collecting body, is evacuated to 10 then
-4Below the Pa.Feed high-purity argon gas, make Ar Pressure reach 0.1Pa.Then, apply voltage to 200V to silicon target, Control current is 0.15A, and applying voltage for the metal Sn target is 200V, and electric current is 0.2A, and sputter was taken out collector after 3 hours, promptly got negative pole of the present invention (anode) electrode.Learn that through elementary analysis it consists of Si
0.7Sn
0.3, its thickness is 10 μ m.
Here the molal quantity of Si is 0.7, and the molal quantity of Sn is 0.3, in actual applications: Si
1-xM
xThe molal quantity X range of choice of bianry alloy active material M is 0.01-0.8, and the molal quantity of Si is 1-X.
Charge and discharge performance test: this electrode and metal lithium sheet composition half-cell are measured its electrochemistry charge and discharge capacity in liquid electrolyte and pure solid polymer electrolyte.Electrolyte is with to discharge and recharge standard identical with the content described in the embodiment 1.As can be seen from Figure 4, Si
0.7Sn
0.3Electrode all has excellent cycle performance in two kinds of electrolyte.At 1MLiPF
6(EC: DEC=1: 1V/V%) in the electrolyte, the period 1 has peak capacity, reaches 2623mAh/g, and irreversible capacity seldom, has only 2% of initial capacity, since second round, in cycle period scope shown in Figure 4 (50 cycle), the capacity attenuation rate is very little, has only 8.9mAh/
, and the charge and discharge capacity in each cycle is basic identical, and promptly efficient is near 100%.At PEO
In the pure solid electrolyte, the capability value in first week is smaller, reaches 2127mAh/g, and along with the increase of cycle period, active material obtains activation gradually, and capacity increases gradually.Along with the carrying out of circulation, the charge and discharge capacity is almost constant, and the capacity attenuation rate more is low to moderate 0.3mAh/
Above-mentioned example explanation, this Si
0.7Sn
0.3Electrode can be applied in lithium rechargeable battery and the polymer secondary battery, and polymer described here comprises pure solid type and gel-type two base polymers.
Embodiment 3: the preparation and the charge and discharge performance of amorphous state Si-Sb negative pole (anode) electrode
The preparation method of this alloy is identical with embodiment 2.Be evacuated to 10
-4Below the Pa, feed high-purity argon gas, make Ar Pressure reach 0.5Pa.Then, apply voltage to 100V to silicon target, Control current is 0.15A, and applying voltage for metal Sb target is 200V, and electric current is 0.3A, and sputter was taken out collector after 2 hours, promptly got negative pole of the present invention (anode) electrode.Learn that through elementary analysis it consists of Si
0.6Sb
0.4, its thickness is 15 μ m.
Its cycle life curve is similar to Fig. 4.Si
0.6Sb
0.4Electrode all has excellent cycle performance in two kinds of electrolyte.At 1MLiPF
6(EC: DEC=1: 1V/V%) in the electrolyte, the period 1 has peak capacity, reaches 2517mAh/g, and irreversible capacity is 2% of an initial capacity, and in 50 cycles, the capacity attenuation rate is very little, has only 9.1mAh/
, and the charge and discharge capacity in each cycle is basic identical, and promptly efficient is near 100%.At PEO
In the pure solid electrolyte, the capability value in first week is smaller, reaches 2011mAh/g, and along with the increase of cycle period, capacity reaches maximum, and the charge and discharge capacity is almost constant, and the capacity attenuation rate more is low to moderate 0.3mAh/
Embodiment 4: the preparation and the charge and discharge performance of amorphous state Si-Al negative pole (anode) electrode
The preparation method of this alloy is identical with embodiment 2.Be evacuated to 10
-4Below the Pa, feed high-purity argon gas, make Ar Pressure reach 1Pa.Then, apply voltage to 300V to silicon target, Control current is 0.2A, and applying voltage for metal A l target is 300V, and electric current is 0.1A, and sputter was taken out collector after 3 hours, promptly got negative pole of the present invention (anode) electrode, learnt that through elementary analysis it consists of Si
0.5Al
0.4, its thickness is 20 μ m.
Its cycle life curve is similar to Fig. 4.Si
0.5Al
0.5Electrode all has excellent cycle performance in two kinds of electrolyte.At 1MLiPF
6(EC: DEC=1: 1V/V%) in the electrolyte, the period 1 has peak capacity, reaches 2422mAh/g, and irreversible capacity is 2% of an initial capacity.In 50 cycles, the capacity attenuation rate is very little, has only 8.5mAh/
, and the charge and discharge capacity in each cycle is basic identical, and promptly efficient is near 100%.At PEO
In the pure solid electrolyte, the capability value in first week is smaller, reaches 2011mAh/g, and along with the increase of cycle period, it is almost constant after the maximum that capacity reaches, and the capacity attenuation rate more is low to moderate 0.3mAh/
Embodiment 5: the preparation and the charge and discharge performance of amorphous state Si-In negative pole (anode) electrode
The preparation method of this alloy is identical with embodiment 2.Be evacuated to 10
-4Below the Pa, feed high-purity argon gas, make Ar Pressure reach 1.5Pa.Then, apply voltage to 400V to silicon target, Control current is 0.05A, and applying voltage for the metal In target is 400V, and electric current is 0.2A, and sputter was taken out collector after 2 hours, promptly got negative pole of the present invention (anode) electrode, learnt that through elementary analysis it consists of Si
0.4In
0.6, its thickness is 25 μ m.
Its cycle life curve is similar to Fig. 4.Si
0.4In
0.6Electrode all has excellent cycle performance in two kinds of electrolyte.At 1MLiPF
6(EC: DEC=1: 1V/V%) in the electrolyte, the period 1 has peak capacity, reaches 2318mAh/g, and irreversible capacity is 2% of an initial capacity.In 50 cycles, the capacity attenuation rate is very little, has only 8.3mAh/
, and the charge and discharge capacity in each cycle is basic identical, and promptly efficient is near 100%.At PEO
In the pure solid electrolyte, the capability value in first week is smaller, reaches 1921mAh/g, and along with the increase of cycle period, it is almost constant after the maximum that capacity reaches, and the capacity attenuation rate more is low to moderate 0.2mAh/
Embodiment 6: the preparation and the charge and discharge performance of amorphous state Si-Bi negative pole (anode) electrode
The preparation method of this alloy is identical with embodiment 2.Be evacuated to 10
-4Below the Pa, feed high-purity argon gas, make Ar Pressure reach 2Pa.Then, apply voltage to 500V to silicon target, Control current is 0.04A, and applying voltage for metal Bi target is 500V, and electric current is 1A, and sputter was taken out collector after 1.5 hours, promptly got negative pole of the present invention (anode) electrode, learnt that through elementary analysis it consists of Si
0.3Bi
0.7, its thickness is 30 μ m.
Its cycle life curve is similar to Fig. 4.Si
0.3The Bi0.7 electrode all has excellent cycle performance in two kinds of electrolyte.At 1MLiPF
6(EC: DEC=1: 1V/V%) in the electrolyte, the period 1 has peak capacity, reaches 2100mAh/g, and irreversible capacity is 2% of an initial capacity.In 50 cycles, the capacity attenuation rate is very little, has only 7.8mAh/
, and the charge and discharge capacity in each cycle is basic identical, and promptly efficient is near 100%.At PEO
In the pure solid electrolyte, the capability value in first week is smaller, reaches 1911mAh/g, and along with the increase of cycle period, it is almost constant after the maximum that capacity reaches, and the capacity attenuation rate more is low to moderate 02mAh/
Embodiment 7: the preparation and the charge and discharge performance of amorphous state Si-Ti negative pole (anode) electrode
The preparation method of this alloy is identical with embodiment 2.Be evacuated to 10
-4Below the Pa, feed high-purity argon gas, make Ar Pressure reach 3Pa.Then, apply voltage to 600V to silicon target, Control current is 0.05A, and applying voltage for the metal Ti target is 800V, and electric current is 0.2A, and sputter was taken out collector after 4 hours, promptly got negative pole of the present invention (anode) electrode, learnt that through elementary analysis it consists of Si
0.2Ti
0.8, its thickness is 40 μ m.
Its cycle life curve is similar to Fig. 4.Si
0.2Ti
0.8Electrode all has excellent cycle performance in two kinds of electrolyte.At 1MLiPF
6(EC: DEC=1: 1V/V%) in the electrolyte, the period 1 has peak capacity, reaches 1200mAh/g, and irreversible capacity is 1% of an initial capacity.In 50 cycles, the capacity attenuation rate is very little, has only 7.8mAh/
, and the charge and discharge capacity in each cycle is basic identical, and promptly efficient is near 100%.At PEO
In the pure solid electrolyte, the capability value in first week is smaller, reaches 1080mAh/g.Value among the more foregoing embodiment of this value is on the low side, be because have only Si to react with Li in such electrode material, and subgroup element only plays the effect of buffering lattice dilatation.Along with the increase of cycle period, capacity was almost constant after capacity reached maximum, and the capacity attenuation rate more is low to moderate 0.2mAh/
Embodiment 8: the preparation and the charge and discharge performance of amorphous state Si-V negative pole (anode) electrode
The preparation method of this alloy is identical with embodiment 2.Be evacuated to 10
-4Below the Pa, feed high-purity argon gas, make Ar Pressure reach 4Pa.Then, apply voltage to 700V to silicon target, Control current is 0.05A, and applying voltage for metal V target is 300V, and electric current is 0.1A, and sputter was taken out collector after 5 hours, promptly got negative pole of the present invention (anode) electrode, learnt that through elementary analysis it consists of Si
0.3V
0.7, its thickness is 35 μ m.
Its cycle life curve is similar to Fig. 4.Si
0.3V
0.7Electrode all has excellent cycle performance in two kinds of electrolyte.At 1MLiPF
6(EC: DEC=1: 1V/V%) in the electrolyte, the period 1 has peak capacity, reaches 1425mAh/g, and irreversible capacity is 2% of an initial capacity.In 50 cycles, the capacity attenuation rate is very little, has only 7.6mAh/
, and the charge and discharge capacity in each cycle is basic identical, and promptly efficient is near 100%.At PEO
In the pure solid electrolyte, the capability value in first week is smaller, reaches 1180mAh/g.Value among the more foregoing embodiment of this value is on the low side, and its reason is identical with the reason described in the embodiment 7.Along with the increase of cycle period, it is almost constant after the maximum that capacity reaches, and the capacity attenuation rate more is low to moderate 0.2mAh/
Embodiment 9: the preparation and the charge and discharge performance of amorphous state Si-Cr negative pole (anode) electrode
The preparation method of this alloy is identical with embodiment 2.Be evacuated to 10
-4Below the Pa, feed high-purity argon gas, make Ar Pressure reach 1Pa.Then, apply voltage to 400V to silicon target, Control current is 0.1A, and applying voltage for the Metal Cr target is 400V, and electric current is 0.1A, and sputter was taken out collector after 4 hours, promptly got negative pole of the present invention (anode) electrode, learnt that through elementary analysis it consists of Si
0.4Cr
0.6, its thickness is 28 μ m.
Its cycle life curve is similar to Fig. 4.Si
0.4Cr
0.6Electrode all has excellent cycle performance in two kinds of electrolyte.At 1MLiPF
6(EC: DEC=1: 1V/V%) in the electrolyte, the period 1 has peak capacity, reaches 1465mAh/g, and irreversible capacity is 1% of an initial capacity.In 50 cycles, the capacity attenuation rate is very little, has only 7.6mAh/
, and the charge and discharge capacity in each cycle is basic identical, and promptly efficient is near 100%.At PEO
In the pure solid electrolyte, the capability value in first week is smaller, reaches 1280mAh/g.Along with the increase of cycle period, it is almost constant after the maximum that capacity reaches, and the capacity attenuation rate more is low to moderate 0.2mAh/
Embodiment 10: the preparation and the charge and discharge performance of amorphous state Si-Mo negative pole (anode) electrode
The preparation method of this alloy is identical with embodiment 2.Be evacuated to 10
-4Below the Pa, feed high-purity argon gas, make Ar Pressure reach 1.5Pa.Then, apply voltage to 500V to silicon target, Control current is 0.1A, applying voltage for metal M o target is 200V, and electric current is 0.05A, and sputter was taken out collector after 3 hours, promptly get negative pole of the present invention (anode) material and electrode thereof, learn that through elementary analysis it consists of Si
0.5Mo
0.5, its thickness is 22 μ m.
Its cycle life curve is similar to Fig. 4.Si
0.3Mo
0.7Electrode all has excellent cycle performance in two kinds of electrolyte.At 1MLiPF
6(EC: DEC=1: 1V/V%) in the electrolyte, the period 1 has peak capacity, reaches 1535mAh/g, and irreversible capacity is 1.4% of an initial capacity.In 50 cycles, the capacity attenuation rate is very little, has only 6.6mAh/
, and the charge and discharge efficient in each cycle is near 100%.At PEO
In the pure solid electrolyte, the capability value in first week is smaller, reaches 1320mAh/g.Along with the increase of cycle period, it is almost constant after the maximum that capacity reaches, and the capacity attenuation rate more is low to moderate 0.2mAh/
Embodiment 11: the preparation and the charge and discharge performance of amorphous state Si-W negative pole (anode) electrode
The preparation method of this alloy is identical with embodiment 2.Be evacuated to 10
-4Below the Pa, feed high-purity argon gas, make Ar Pressure reach 0.2Pa.Then, apply voltage to 650V to silicon target, Control current is 0.05A, applying voltage for metal W target is 200V, and electric current is 0.05A, and sputter was taken out collector after 2 hours, promptly get negative pole of the present invention (anode) material and electrode thereof, learn that through elementary analysis it consists of Si
0.6W
0.4, its thickness is 18 μ m.
Its cycle life curve is similar to Fig. 4.Si
0.8W
0.4Electrode all has excellent cycle performance in two kinds of electrolyte.At 1MLiPF
6(EC: DEC=1: 1V/V%) in the electrolyte, the period 1 has peak capacity, reaches 1682mAh/g, and irreversible capacity is 1.2% of an initial capacity.In 50 cycles, the capacity attenuation rate is very little, has only 6.4mAh/
, and the charge and discharge efficient in each cycle is near 100%.At PEO
In the pure solid electrolyte, the capability value in first week is smaller, reaches 1420mAh/g.Along with the increase of cycle period, it is almost constant after the maximum that capacity reaches, and the capacity attenuation rate more is low to moderate 0.2mAh/
Embodiment 12: the preparation and the charge and discharge performance of amorphous state Si-Hn negative pole (anode) electrode
The preparation method of this alloy is identical with embodiment 2.Be evacuated to 10
-4Below the Pa, feed high-purity argon gas, make Ar Pressure reach 0.5Pa.Then, apply voltage to 650V to silicon target, Control current is 0.1A, applying voltage for metal M n target is 200V, and electric current is 0.05A, and sputter was taken out collector after 3 hours, promptly get negative pole of the present invention (anode) material and electrode thereof, learn that through elementary analysis it consists of Si
0.7Mn
0.3, its thickness is 18 μ m.
Its cycle life curve is similar to Fig. 4.Si
0.7Mn
0.3Electrode all has excellent cycle performance in two kinds of electrolyte.At 1MLiPF
6(EC: DEC=1: 1V/V%) in the electrolyte, the period 1 has peak capacity, reaches 1722mAh/g, and irreversible capacity is 1.4% of an initial capacity.In 50 cycles, the capacity attenuation rate is very little, has only 6.5mAh/
, and the charge and discharge efficient in each cycle is near 100%.At PEO
In the pure solid electrolyte, the capability value in first week is smaller, reaches 1537mAh/g.Along with the increase of cycle period, it is almost constant after the maximum that capacity reaches, and the capacity attenuation rate more is low to moderate 0.2mAh/
Embodiment 13: the preparation and the charge and discharge performance of amorphous state Si-Fe negative pole (anode) electrode
The preparation method of this alloy is identical with embodiment 2.Be evacuated to 10
-4Below the Pa, feed high-purity argon gas, make Ar Pressure reach 0.4Pa.Then, apply voltage to 700V to silicon target, Control current is 0.1A, and applying voltage for metal Fe target is 200V, and electric current is 0.02A, and sputter was taken out collector after 4 hours, promptly got negative pole of the present invention (anode) electrode, learnt that through elementary analysis it consists of Si
0.8Fe
0.2, its thickness is 12 μ m.
Its cycle life curve is similar to Fig. 4.Si
0.8Fe
0.2Electrode all has excellent cycle performance in two kinds of electrolyte.At 1NLiPF
6(EC: DEC=1: 1V/V%) in the electrolyte, the period 1 has peak capacity, reaches 1812mAh/g, and irreversible capacity is 1.5% of an initial capacity.In 50 cycles, the capacity attenuation rate is very little, has only 6.1mAh/
, and the charge and discharge efficient in each cycle is near 100%.At PEO
In the pure solid electrolyte, the capability value in first week is smaller, reaches 1623mAh/g.Along with the increase of cycle period, it is almost constant after the maximum that capacity reaches, and the capacity attenuation rate more is low to moderate 0.2mAh/
Embodiment 14: the preparation and the charge and discharge performance of amorphous state Si-CO negative pole (anode) electrode
The preparation method of this alloy is identical with embodiment 2.Be evacuated to 10
-4Below the Pa, feed high-purity argon gas, make Ar Pressure reach 1Pa.Then, apply voltage to 400V to silicon target, Control current is 0.2A, applying voltage for the metal Co target is 150V, and electric current is 0.02A, and sputter was taken out collector after 2 hours, promptly get negative pole of the present invention (anode) material and electrode thereof, learn that through elementary analysis it consists of Si
0.9Co
0.1, its thickness is 16 μ m.
Its cycle life curve is similar to Fig. 4.Si
0.9Co
0.1Electrode all has excellent cycle performance in two kinds of electrolyte.At 1MLiPF
6(EC: DEC=1: 1V/V%) in the electrolyte, the period 1 has peak capacity, reaches 2012mAh/g, and irreversible capacity is 1.6% of an initial capacity.In 50 cycles, the capacity attenuation rate is very little, has only 6.2mAh/
, and the charge and discharge efficient in each cycle is near 100%.At PEO
In the pure solid electrolyte, the capability value in first week is smaller, reaches 1888mAh/g.Along with the increase of cycle period, it is almost constant after the maximum that capacity reaches, and the capacity attenuation rate more is low to moderate 0.2mAh/
Embodiment 15: the preparation and the charge and discharge performance of amorphous state Si-Ni negative pole (anode) electrode
The preparation method of this alloy is identical with embodiment 2.Be evacuated to 10
-4Below the Pa, feed high-purity argon gas, make Ar Pressure reach 0.6Pa.Then, apply voltage to 400V to silicon target, Control current is 0.3A, applying voltage for metal Ni target is 150V, and electric current is 0.03A, and sputter was taken out collector after 2 hours, promptly get negative pole of the present invention (anode) material and electrode thereof, learn that through elementary analysis it consists of Si
0.95Ni
0.15, its thickness is 10 μ m.
Its cycle life curve is similar to Fig. 4.Si
0.95Ni
0.15Electrode all has excellent cycle performance in two kinds of electrolyte.At 1MLiPF
6(EC: DEC=1: 1V/V%) in the electrolyte, the period 1 has peak capacity, reaches 2412mAh/g, and irreversible capacity is 1.4% of an initial capacity.In 50 cycles, the capacity attenuation rate is very little, has only 5.2mAh/
, and the charge and discharge efficient in each cycle is near 100%.At PEO
In the pure solid electrolyte, the capability value in first week is smaller, reaches 2288mAh/g.Along with the increase of cycle period, it is almost constant after the maximum that capacity reaches, and the capacity attenuation rate more is low to moderate 0.2mAh/
Embodiment 16: the preparation and the charge and discharge performance of amorphous state Si-Cu negative pole (anode) electrode
The preparation method of this alloy is identical with embodiment 2.Be evacuated to 10
-4Below the Pa, feed high-purity hydrogen, make Ar Pressure reach 0.8Pa.Then, apply voltage to 500V to silicon target, Control current is 0.2A, and applying voltage for metal Cu target is 180V, and electric current is 0.06A, and sputter was taken out collector after 3 hours, promptly got negative pole of the present invention (anode) electrode, learnt that through elementary analysis it consists of Si
0.75Cu
0.25, its thickness is 13 μ m.
Its cycle life curve is similar to Fig. 4.Si
0.75Cu
0.25Electrode all has excellent cycle performance in two kinds of electrolyte.At 1MLiPF
6(EC: DEC=1: 1V/V%) in the electrolyte, the period 1 has peak capacity, reaches 1912mAh/g, and irreversible capacity is 1.4% of an initial capacity.In 50 cycles, the capacity attenuation rate is very little, has only 5.3mAh/
And the charge and discharge efficient in each cycle is near 100%.At PEO
In the pure solid electrolyte, the capability value in first week is smaller, reaches 1788mAh/g.Along with the increase of cycle period, it is almost constant after the maximum that capacity reaches, and the capacity attenuation rate more is low to moderate 0.2mAh/
Embodiment 17: the preparation and the charge and discharge performance of amorphous state Si-Ag negative pole (anode) electrode
The preparation method of this alloy is identical with embodiment 2.Be evacuated to 10
-4Below the Pa, feed high-purity argon gas, make Ar Pressure reach 1.2Pa.Then, apply voltage to 450V to silicon target, Control current is 0.15A, and applying voltage for metal A g target is 250V, and electric current is 0.1A, and sputter was taken out collector after 2.5 hours, promptly got negative pole of the present invention (anode) electrode, learnt that through elementary analysis it consists of Si
0.75Ag
0.25, its thickness is 18 μ m.
Its cycle life curve is similar to Fig. 4.Si
0.75Ag
0.25Electrode all has excellent cycle performance in two kinds of electrolyte.At 1MLiPF
6(EC: DEC=1: 1V/V%) in the electrolyte, the period 1 has peak capacity.Reach 1612mAh/g, irreversible capacity is 1.4% of an initial capacity.In 50 cycles, the capacity attenuation rate is very little, has only 5.5mAh/
, and the charge and discharge efficient in each cycle is near 100%.At PEO
In the pure solid electrolyte, the capability value in first week is smaller, reaches 1528mAh/g.Along with the increase of cycle period, it is almost constant after the maximum that capacity reaches, and the capacity attenuation rate more is low to moderate 0.2mAh/
Embodiment 18: the preparation and the charge and discharge performance of amorphous state Si-Zn negative pole (anode) electrode
The preparation method of this alloy is identical with embodiment 2.Be evacuated to 10
-4Below the Pa, feed high-purity argon gas, make Ar Pressure reach 0.2Pa.Then, apply voltage to 800V to silicon target, Control current is 0.05A, applying voltage for the Metal Zn target is 100V, and electric current is 0.12A, and sputter was taken out collector after 3.5 hours, promptly get negative pole of the present invention (anode) material and electrode thereof, learn that through elementary analysis it consists of Si
0.65Zn
0.35, its thickness is 15 μ m.
Its cycle life curve is similar to Fig. 4.Si
0.65Zn
0.35Electrode all has excellent cycle performance in two kinds of electrolyte.At 1MLiPF
6(EC: DEC=1: 1V/V%) in the electrolyte, the period 1 has peak capacity, reaches 1922mAh/g, and irreversible capacity is 1.5% of an initial capacity.In 50 cycles, the capacity attenuation rate is very little, has only 5.6mAh/
, and the charge and discharge efficient in each cycle is near 100%.At PEO
In the pure solid electrolyte, the capability value in first week is smaller, reaches 1768mAh/g.Along with the increase of cycle period, it is almost constant after the maximum that capacity reaches, and the capacity attenuation rate more is low to moderate 0.2mAh/
Manufacture method and secondary battery negative pole that listed examples of the present invention is intended to further to illustrate this secondary battery negative pole can be applied in lithium rechargeable battery and the polymer secondary battery, and scope of the present invention is not constituted any restriction, the embodiment of the invention or all can obtain this lithium rechargeable battery or polymer secondary battery negative pole (anode) material and the electrode itself thereof of being used for via claims of the present invention are described.