CN1731599A - Secondary battery negative pole (anode) and making method - Google Patents
Secondary battery negative pole (anode) and making method Download PDFInfo
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- CN1731599A CN1731599A CNA2005100127107A CN200510012710A CN1731599A CN 1731599 A CN1731599 A CN 1731599A CN A2005100127107 A CNA2005100127107 A CN A2005100127107A CN 200510012710 A CN200510012710 A CN 200510012710A CN 1731599 A CN1731599 A CN 1731599A
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Abstract
The invention discloses a negative/positive pole for lithium secondary battery and polymer secondary battery and method for making same. The inventive pole is prepared by covering Si or Si1-xMx on copper foil, nickel foil, coppering base or/and nickel iron foil coated base with magnetron sputtering process, wherein M is main group element of subgroup element. By controlling target source and power, the components of electrode can be controlled. The inventive method has the advantage of controlling the thickness of electrode active materials effectively.
Description
Technical field
The present invention relates to the secondary cell field, especially for the preparing technical field of lithium rechargeable battery or polymer secondary battery negative pole (anode) material and electrode thereof.
Background technology
Present commercial lithium ion/polymer cells all adopts carbon materials as negative material, the theoretical capacity of carbon material (is 372mAh/g by weight, volume and capacity ratio is 833mAh/cc) less than lithium metal (4010mAh/g, 9340mAh/cc) 1/10th, in order to seek the negative material of high power capacity, people have turned one's attention to other element that belongs to the 4th main group (IVA) with carbon together, and as Si and Sn etc., these two kinds of elements can generate the Li/M atomic ratio up to 4.4 alloy with lithium reaction.In the periodic table of elements, Si is the IVA family element of next-door neighbour C, theoretical weight specific energy and volume and capacity ratio are 10 times of carbon material, and embedding lithium current potential approaches carbon material, therefore become a main direction of studying of lithium ion battery of future generation and polymer battery negative material.At present the key issue that can such material of puzzlement practicability is in electrochemistry embedding/take off in the lithium process because the life-span of relatively lacking that bigger lattice dilatation rate causes.The cubical expansivity of carbon material is 12%, and Si's is 297%.So big expansion rate has caused active material efflorescence rapidly in the electrochemistry cyclic process in the electrode, and make between the active material particle and active material and conductive current collector between conductivity significantly reduce, thereby cause the life-span rapid attenuation of electrode.In order to address this problem, the researcher has carried out some trials, and as carry out methods such as little coating and formation multicomponent alloy outside the Si particle, purpose makes Si can be dispersed in the material exactly, can cushion lattice dilatation, thereby reduces cubical expansivity.Discover, between the active material that lattice dilatation causes and the contact problems between active material and the conductive current collector remain the main cause of electrode failure.Except the particle size influences lattice dilatation of active material, active material thickness also is a key factor that influences electrode and even cell integrated performance, if thickness is excessive, then will inevitably causes the electric conductivity variation owing to lattice dilatation between the active material, thereby make electrode failure.If but thickness is too small, then the volume energy of electrode and gravimetric specific energy will inevitably reduce, and at present, preparation method commonly used adopts the mode of pasting that active material is coated onto on the conductive current collector, adopt the thickness of this method control active material difficult, can only be accurate to 10 micron orders.
Summary of the invention
The purpose of this invention is to provide a class and be used for novel negative pole (anode) of lithium rechargeable battery and polymer secondary battery and preparation method thereof.By selecting appropriate preparation method to solve between the active material that lattice dilatation causes and the problem of the electrode failure that the poor electric conductivity between active material and the collector causes.
Technical scheme of the present invention be achieved in that this secondary battery negative pole be adopt magnetron sputtering method in Copper Foil, nickel foil, copper facing or/and cover Si or Si on the nickel plating iron foil matrix
1-xM
xThe bianry alloy active material is made, and wherein M is major element or subgroup element.
The Si of described secondary battery negative pole
1-xM
xThe major element of bianry alloy active material M representative comprises: Al, In, Sn, Sb or Bi.
The Si of described secondary battery negative pole
1-xM
xThe subgroup element of bianry alloy active material M representative comprises: Ti, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Ag or Zn.
The Si of described secondary battery negative pole
1-xM
xThe X scope of bianry alloy active material is the 0.01-0.8 molal quantity.
The Si of described secondary battery negative pole or Si
1-xM
xThe bianry alloy active material is that nanoscale is amorphous.
The Si that the surface covers of described secondary battery negative pole or Si
1-xM
xThe thickness of bianry alloy is 0.01-50 μ m.
The manufacture method of described secondary battery negative pole comprises the steps:
A, silicon target or silicon target and metal M target are put into magnetic control sputtering device respectively, then with Copper Foil, nickel foil, copper facing or/and the nickel plating iron foil put between silicon target or silicon target and the metal M target;
B, be lower than 10 in vacuum degree
-4Under the situation of Pa, feed high-purity argon gas, and the control Ar Pressure is 0.1-5Pa;
C, regulation voltage are to 100-800V, and electric current is to 0.01-5A, and sputtering time is 0.5-10 hour;
Take out Copper Foil after D, sputter finish, obtain electrode of the present invention, the active material thickness that is plated is 0.01-50 μ m.
The preparation method of amorphous state Si electrode is among the preparation method of described secondary battery negative pole: with two parallel being placed in the magnetic control sputtering device of silicon target, 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 0.1-5Pa; Apply voltage to 100-800V to silicon target, Control current is 0.01-5A, takes out collector after sputter 0.5-10 hour, promptly.
Amorphous state Si among the preparation method of described secondary battery negative pole
1-xM
xThe bianry alloy electrode preparation method is: two silicon targets are placed in the magnetic control sputtering device as negative electrode is parallel respectively with two metal M targets, and the stainless steel bell jar is as plus earth, the vertical target surface of externally-applied magnetic field; 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; Be evacuated to 10
-4Below the Pa; Feed high-purity argon gas, make Ar Pressure reach 0.1-5Pa; Apply voltage to 100-800V to silicon target, Control current is 0.01-5A, and applying voltage for the metal M target is 100-800V, and electric current is 0.01-5A, takes out collector after sputter 0.5-10 hour, promptly.
The present invention adopt magnetron sputtering method at Copper Foil, nickel foil, copper facing or/and make the amorphous silicon base composite electric utmost point on the nickel plating iron foil matrix, by control target source and power can control electrode composition, when active material is in nanometer or amorphous state size, the absolute volume of ultrafine dust changes little, can make out of phase volumetric expansion even, thus the life-span that can improve electrode.What is more important adopts this method directly to be made into electrode, makes material and being made into one of electrode, and effectively the thickness of control electrode active material can be as accurate as 1 micron order.The present invention is applied to improve the specific energy of lithium rechargeable battery and polymer secondary battery greatly in lithium rechargeable battery and the polymer secondary battery.
Description of drawings
The magnetic control sputtering device schematic diagram that Fig. 1 the present invention adopts
Among the figure: 1, stainless steel bell jar 2, specimen holder 3, radome 4, regulated power supply 5, air inlet 6, gas outlet 7, sputtering target 8, magnetic pole 9, plasma
Fig. 2 is the Si of sputter on Copper Foil
0.7Sn
0.3The sem photograph of electrode
Fig. 3 is a Si electrode (Cu paper tinsel) with PEO
For the neutralization of the polymer battery of pure solid electrolyte with 1MLiPF
6(EC: DEC=1: 1V/V%) be cyclic curve in the half-cell of electrolyte
Fig. 4 is Si
0.7Sn
0.3Electrode (Cu paper tinsel) is with PEO
For the neutralization of the polymer battery of pure solid electrolyte with 1MLiPF
6(EC: DEC=1: 1V/V%) be cyclic curve in the half-cell of electrolyte
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.
Claims (9)
1, a kind of secondary battery negative pole is characterized in that: kind electrode be adopt magnetron sputtering method in Copper Foil, nickel foil, copper facing or/and cover Si or Si on the nickel plating iron foil matrix
1-xM
xThe bianry alloy active material is made, and wherein M is major element or subgroup element.
2, secondary battery negative pole according to claim 1 is characterized in that: Si
1-xM
xThe major element of bianry alloy active material M representative comprises: Al, In, Sn, Sb or Bi.
3, secondary battery negative pole according to claim 1 is characterized in that: Si
1-xM
xThe subgroup element of bianry alloy active material M representative comprises: Ti, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Ag or Zn.
4, secondary battery negative pole according to claim 1 is characterized in that: Si
1-xM
xThe X scope of bianry alloy active material is the 0.01-0.8 molal quantity.
5, according to claim 1 or 2 or 3 or 4 described secondary battery negative poles, it is characterized in that: Si or Si
1-xM
xThe bianry alloy active material is that nanoscale is amorphous.
6, secondary battery negative pole according to claim 1 is characterized in that kind electrode the surface Si that covers or Si
1-xM
xThe thickness of bianry alloy is 0.01-50 μ m.
7, the manufacture method of secondary battery negative pole according to claim 1, its feature comprises the steps:
A, silicon target or silicon target and metal M target are put into magnetic control sputtering device respectively, then with Copper Foil, nickel foil, copper facing or/and the nickel plating iron foil put between silicon target or silicon target and the metal M target;
B, be lower than 10 in vacuum degree
-4Under the situation of Pa, feed high-purity argon gas, and the control Ar Pressure is 0.1-5Pa;
C, regulation voltage are to 100-800V, and electric current is to 0.01-5A, and sputtering time is 0.5-10 hour;
Take out Copper Foil after D, sputter finish, obtain electrode of the present invention, the active material thickness that is plated is 0.01-50 μ m.
8, the preparation method of secondary battery negative pole according to claim 7, it is characterized in that: the preparation method of amorphous state Si electrode is with two parallel being placed in the magnetic control sputtering device of silicon target, 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 0.1-5Pa; Apply voltage to 100-800V to silicon target, Control current is 0.01-5A, takes out collector after sputter 0.5-10 hour, promptly.
9, the preparation method of secondary battery negative pole according to claim 7 is characterized in that: amorphous state Si
1-xM
xThe bianry alloy electrode preparation method is that two silicon targets are placed in the magnetic control sputtering device as negative electrode is parallel respectively with two metal M targets, and the stainless steel bell jar is as plus earth, the vertical target surface of externally-applied magnetic field; 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; Be evacuated to 10
-4Below the Pa; Feed high-purity argon gas, make Ar Pressure reach 0.1-5Pa; Apply voltage to 100-800V to silicon target, Control current is 0.01-5A, and applying voltage for the metal M target is 100-800V, and electric current is 0.01-5A, takes out collector after sputter 0.5-10 hour, promptly.
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