CN108598365A - A kind of negative electrode for lithium secondary battery and preparation method thereof and its lithium secondary battery - Google Patents
A kind of negative electrode for lithium secondary battery and preparation method thereof and its lithium secondary battery Download PDFInfo
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- CN108598365A CN108598365A CN201810516819.1A CN201810516819A CN108598365A CN 108598365 A CN108598365 A CN 108598365A CN 201810516819 A CN201810516819 A CN 201810516819A CN 108598365 A CN108598365 A CN 108598365A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of negative electrode for lithium secondary battery and preparation method thereof and its lithium secondary battery, it belongs to field of chemical power source.The present invention is mainly by array of protrusions electrode skeleton, nanoscale alloy skeleton and active metal lithium are constituted, the material of the array of protrusions electrode skeleton of large aperture is Cu, Al, Sn, Fe, Co, Ni, Zn, any one in In, nanoscale alloy skeleton includes elemental lithium and non-elemental lithium, non- elemental lithium material includes Sn, Si, Cu, In, Al, Mg, Ge, Zn, at least one of Ni, active metal lithium is filled in the hole of nanoscale alloy skeleton, and come into full contact with the rich lithium alloy of composition with nanoscale alloy skeleton, rich lithium alloy is deposited in the hole of the array of protrusions electrode skeleton.The present invention can prevent structure destruction of nanometer skeleton in long-term cyclic process from causing caving in for electrode, fully inhibit the volume change of electrode to improve interface stability, further increase the chemical property of cathode of lithium.
Description
Technical field
The invention belongs to field of chemical power source；More particularly to a kind of negative electrode for lithium secondary battery and preparation method thereof and its lithium
Secondary cell.
Background technology
With the development of society, the demand to the secondary cell system of higher energy density is increasingly urgent.Lithium metal is
There is highest specific capacity (3860mAh/g) and most negative electrode potential (- 3.045V vs.SHE) in the negative material known, but
It is that easily with electrolyte complicated interfacial reaction occurs for lithium metal, leads to active lithium consumption, electrolyte dry-out and interface impedance
Gradually increase, then efficiency constantly reduces during charge and discharge cycles；Lithium ion is led in the nonuniform deposition of electrode surface
It sends a telegraph pole surface and generates a large amount of Li dendrites, the Li dendrite of continued propagation, which will penetrate battery diaphragm and be contacted with anode, leads to battery
Internal short-circuit causes security risk, if Li dendrite is broken into " the dead lithium " for losing electro-chemical activity from electrode, can cause electricity
The reduction of ultimate ratio capacity；In addition, volume change of the metal lithium electrode in charge and discharge process is very big, violent volume expansion and
Shrinking leads to the gradual dusting of electrode.Therefore, there is an urgent need for improve for the safety of lithium an- ode and cyclical stability.
The collector using the three-dimensional copper with sub-micron skeleton as cathode of lithium such as Yang, reduces current density, stablizes
Lithium an- ode.Kozen etc. forms the Al of 14nm thickness using atomic layer deposition method (ALD) on cathode of lithium surface2O3Film inhibits boundary
Face side reaction and lithium dendrite growth, but these methods prepare complexity, it is of high cost.
Application No. is in the patent of CN 201510394325.7 using lithium metal powder as cathode, powder porous electrode
Specific surface area is high, reduces current density, it is suppressed that lithium dendrite growth, but when heavy-current discharge, lithium powder electrode structure pattern
It changes greatly, cyclical stability reduces.It is proposed to use Li-Al alloys as cathode in US 4002492, also someone is with Li-Sn, Li-
Si alloys reduce negative reaction activity as cathode, inhibit lithium dendrite growth, but electrode body during alloying-removal alloying
Product variation is violent, causes electrode dusting, battery life short.
Therefore, there is an urgent need for developing a kind of simple cathode of lithium preparation method, safety and the cycle for improving lithium an- ode are steady
It is qualitative.
Invention content
It is an object of the present invention to provide a kind of negative electrode for lithium secondary battery and preparation method thereof and its lithium secondary batteries.
The invention is realized by the following technical scheme：
A kind of negative electrode for lithium secondary battery, the negative electrode for lithium secondary battery mainly by array of protrusions electrode skeleton,
Nanoscale alloy skeleton and active metal lithium are constituted, the material of the array of protrusions electrode skeleton of the large aperture be Cu, Al,
Any one in Sn, Fe, Co, Ni, Zn, In, the nanoscale alloy skeleton include elemental lithium and non-elemental lithium, described
Non- elemental lithium material includes at least one of Sn, Si, Cu, In, Al, Mg, Ge, Zn, Ni, and the active metal lithium, which is filled in, to be received
In the hole of meter level alloy skeleton, and the rich lithium alloy of composition is come into full contact with nanoscale alloy skeleton, the rich lithium alloy is heavy
Product is in the hole of the array of protrusions electrode skeleton.
A kind of negative electrode for lithium secondary battery of the present invention, array of protrusions in the array of protrusions electrode skeleton
Cross sectional shape is any one of circle, polygon, five-pointed star, fan-shaped weight, and the diameter of section of the array of protrusions is 0.1 μm
~5 μm, the depth of section of array of protrusions is 1 μm~50 μm.
A kind of negative electrode for lithium secondary battery of the present invention, it is non-in the rich lithium alloy of the nanoscale alloy skeleton structure
Lithium ingredient is distributed for gradient.
A kind of negative electrode for lithium secondary battery of the present invention, the content of non-elemental lithium accounts for rich lithium in the rich lithium alloy
The 10%~30% of alloy total amount.
A kind of negative electrode for lithium secondary battery of the present invention, active metal lithium are excessive active metal lithium.
A kind of negative electrode for lithium secondary battery of the present invention, non-lithium ingredient distribution gradient, non-lithium ingredient is in electrode table
Face is enriched with, and concentration gradient reaches maximum.
A kind of negative electrode for lithium secondary battery of the present invention, structure have the following advantages：The array of protrusions electrode bone
Frame is three-dimensional collector (array electrode or foam electrode) with macropore gauge structure, carrier and electrode as rich lithium alloy
Supporter prevents structure destruction of nanometer skeleton in long-term cyclic process from causing caving in for electrode, and the cycle for improving electrode is steady
It is qualitative, and fully inhibit the volume change of electrode；The rich lithium alloy of the Nanoalloy skeleton structure, can sufficiently promote electric current
Being uniformly distributed in rich lithium alloy effectively slows down violent volume change of non-lithium material during removal lithium embedded, improves electricity
The stability of pole；The rich lithium alloy of the gradient distribution can effectively reduce the reactivity of interface cathode of lithium, improve interface
Stability further increases the chemical property of cathode of lithium.
A kind of negative electrode for lithium secondary battery of the present invention can be used in lithium secondary battery, solid state lithium battery, lithium air
Battery.
A kind of preparation method of negative electrode for lithium secondary battery of the present invention, includes the following steps：
Step a, template prepares array of protrusions electrode skeleton；
Step b, vacuum evaporation or magnetron sputtering prepare nanoscale alloy skeleton, filling active metal lithium.
The preparation method of a kind of negative electrode for lithium secondary battery of the present invention, in step a protrusions array electrode skeletons
The preparation of porous masterplate uses thickness for 20 μm of polycarbonate membrane, so that it injury mark is occurred by the bombardment of nuclear fission fragment,
Make trace corrosion at hole with chemical attack again, prepares porous masterplate.
A kind of preparation method of negative electrode for lithium secondary battery of the present invention utilizes the porous of preparation using platinum as substrate
Masterplate prepares array of protrusions electrode skeleton by electrochemical deposition or sol-gal process.
A kind of preparation method of negative electrode for lithium secondary battery of the present invention can utilize Porous Cu or foam copper to make
For array of protrusions electrode skeleton.
A kind of preparation method of negative electrode for lithium secondary battery of the present invention, in step b vacuum evaporation use more crucibles
Prepared by mode, using pure lithium and non-elemental lithium particle as evaporation source, substrate is array of protrusions electrode skeleton, the vacuum
Vacuum degree >=2 × 10 of room-2The output power of Pa, vacuum evaporation power supply are 50~150W, are added in evaporation source crucible non-
The content of elemental lithium is 10%~50%, and time of vacuum thermal evaporation is 15~30min, and substrate is away from evaporation source in vacuum evaporation room
The distance of crucible is 5~15cm.
A kind of preparation method of negative electrode for lithium secondary battery of the present invention, magnetron sputtering uses more targets in step b
Prepared by mode, in vacuum sputtering cabin Du≤5 × 10 Zhen Kong-3Pa, magnetic control sputtering device output power of power supply are 15~30W, are sputtered
Argon gas flow in journey is 15~25L/min, and the vacuum sputtering time is 20~60min.
A kind of preparation method of negative electrode for lithium secondary battery of the present invention, vacuum evaporation is with pure lithium and non-elemental lithium
For grain respectively as evaporation source, substrate is array collector, by adjusting deposited chamber vacuum degree, output power, evaporation source ratio, steaming
Plate time, the substrate parameters such as at a distance from evaporation source, the structure of regulation and control vapor deposition lithium alloy.When the present invention prepares gradient lithium alloy,
It is prepared using more crucible modes, there is the evaporation source of different element ratios in crucible, crucible is controlled by controlling different output power
Temperature, so that it is had a different evaporation rates, prepare the lithium alloy with non-elemental lithium concentration gradients.
A kind of preparation method of negative electrode for lithium secondary battery of the present invention, magnetron sputtering use magnetic control sputtering device (type
Number be JCP-350M2), substrate surface deposit suitable thickness rich lithium alloy.Output power, gas stream are sputtered by adjusting
The parameters such as amount, vacuum degree, sedimentation time regulate and control the microstructure of rich lithium alloy electrode.When the present invention prepares gradient lithium alloy, adopt
With the mode of more targets, by controlling constituent content, sputtering power in different targets, the control non-lithium ingredient of different depth
Changes of contents.
The preparation method of a kind of negative electrode for lithium secondary battery of the present invention, by regulating and controlling in vapor deposition or sputtering process
Technological parameter prepares the gradient fractionation richness lithium alloy cathode of element different, solves serondary lithium battery in cyclic process
Li dendrite and the problem of volume change, and then promote the cycle characteristics of battery.
A kind of lithium secondary battery of the present invention, the lithium secondary battery include shell and the lithium that is placed in shell
Secondary battery cathode, anode, organic bath and isolation film, the negative electrode for lithium secondary battery include array of protrusions electricity
Pole skeleton, nanoscale alloy skeleton and excessive active metal lithium, the active metal lithium are filled in nanoscale alloy skeleton
Hole in, form rich lithium alloy, the rich lithium alloy is deposited in the hole of the array electrode skeleton.
A kind of lithium secondary battery of the present invention, the negative electrode for lithium secondary battery provided are gradient fractionation richness lithium alloy electricity
Pole reduces current density, promotes electric current being uniformly distributed in rich lithium alloy, effectively inhibits growth and the electricity of Li dendrite
Dramatic strong volume change, improves the cyclical stability of interface stability and electrode.It is steady with high power capacity and superior cycle
Qualitative energy.
Description of the drawings
Fig. 1 is a kind of structural schematic diagram of negative electrode for lithium secondary battery；
Fig. 2 is that the lithium electrode that specific implementation mode method four is prepared is cathode, and lithium piece is to be charged to electrode
1.5V, obtained voltage capacity curve；
Fig. 3 is that Li is prepared in specific implementation mode method five | LiFePO4The first charge-discharge capacity voltage of system battery
Curve；
Fig. 4 is that Li is prepared in specific implementation mode method five | LiFePO4The discharge capacity cycle-index of system battery
Cycle performance correlation curve；
Fig. 5 is that Li is prepared in specific implementation mode method six | the first charge-discharge capacity voltage of KB/S system batteries is bent
Line；
Fig. 6 is that Li is prepared in specific implementation mode method six | the discharge capacity cycle-index of KB/S system batteries is followed
Ring performance comparison curve.
Fig. 7 prepares commercial cathode for specific implementation mode method eight and obtains the cycle performance figure of lithium-air battery；
Fig. 8 is the cycle performance that specific implementation mode method eight prepares the lithium-air battery that negative electrode for lithium secondary battery obtains
Figure.
In figure：1 array of protrusions electrode skeleton, 2 active metal lithiums, 3 nanoscale alloy skeletons.
Specific implementation mode
Specific implementation mode one：
A kind of negative electrode for lithium secondary battery, the negative electrode for lithium secondary battery mainly by array of protrusions electrode skeleton 1,
Nanoscale alloy skeleton 3 and active metal lithium 2 are constituted, the material of the array of protrusions electrode skeleton of the large aperture be Cu, Al,
Any one in Sn, Fe, Co, Ni, Zn, In, the nanoscale alloy skeleton include elemental lithium and non-elemental lithium, described
Non- elemental lithium material includes at least one of Sn, Si, Cu, In, Al, Mg, Ge, Zn, Ni, and the active metal lithium, which is filled in, to be received
In the hole of meter level alloy skeleton, and the rich lithium alloy of composition is come into full contact with nanoscale alloy skeleton, the rich lithium alloy is heavy
Product is in the hole of the array of protrusions electrode skeleton.
A kind of negative electrode for lithium secondary battery described in present embodiment, the raised battle array in the array of protrusions electrode skeleton
The cross sectional shape of row is any one of circle, polygon, five-pointed star, fan-shaped weight, and the diameter of section of the array of protrusions is
0.1 μm~5 μm, the depth of section of array of protrusions is 1 μm~50 μm.
A kind of negative electrode for lithium secondary battery described in present embodiment, the rich lithium alloy of the nanoscale alloy skeleton structure
In non-lithium ingredient be gradient distribution.
A kind of negative electrode for lithium secondary battery described in present embodiment, the content of non-elemental lithium accounts in the rich lithium alloy
The 10%~30% of rich lithium alloy total amount.
A kind of negative electrode for lithium secondary battery described in present embodiment, the array of protrusions electrode skeleton are with large aperture
The three-dimensional collector (array electrode or foam electrode) of structure prevents from receiving as the carrier of rich lithium alloy and the supporter of electrode
Structure destruction of the rice skeleton in long-term cyclic process causes caving in for electrode, improves the cyclical stability of electrode, and fully press down
The volume change of electrode processed；The rich lithium alloy of the Nanoalloy skeleton structure can sufficiently promote electric current in rich lithium alloy
Be uniformly distributed, effectively slow down violent volume change of non-lithium material during removal lithium embedded, improve the stability of electrode；Institute
The reactivity of interface cathode of lithium can effectively be reduced by stating the rich lithium alloy of gradient distribution, improve interface stability, further
Improve the chemical property of cathode of lithium.
Specific implementation mode two：
The preparation method of negative electrode for lithium secondary battery according to specific implementation mode one, includes the following steps：
Step a, template prepares array of protrusions electrode skeleton；
Step b, vacuum evaporation or magnetron sputtering prepare nanoscale alloy skeleton, filling active metal lithium.
The preparation method of negative electrode for lithium secondary battery described in present embodiment, in step a protrusions array electrode skeletons
The preparation of porous masterplate uses thickness for 20 μm of polycarbonate membrane, so that it injury mark is occurred by the bombardment of nuclear fission fragment,
Make trace corrosion at hole with chemical attack again, prepares porous masterplate.
The preparation method of negative electrode for lithium secondary battery described in present embodiment, in step b vacuum evaporation use more crucibles
Prepared by mode, using pure lithium and non-elemental lithium particle as evaporation source, substrate is array of protrusions electrode skeleton, the vacuum
Vacuum degree >=2 × 10 of room-2The output power of Pa, vacuum evaporation power supply are 50~150W, are added in evaporation source crucible non-
The content of elemental lithium is 10%~50%, and time of vacuum thermal evaporation is 15~30min, and substrate is away from evaporation source in vacuum evaporation room
The distance of crucible is 5~15cm.
The preparation method of negative electrode for lithium secondary battery described in present embodiment, magnetron sputtering uses more targets in step b
Prepared by mode, in vacuum sputtering cabin Du≤5 × 10 Zhen Kong-3Pa, magnetic control sputtering device output power of power supply are 15~30W, are sputtered
Argon gas flow in journey is 15~25L/min, and the vacuum sputtering time is 20~60min.
The preparation method of negative electrode for lithium secondary battery described in present embodiment, vacuum evaporation is with pure lithium and non-elemental lithium
For grain respectively as evaporation source, substrate is array collector, by adjusting deposited chamber vacuum degree, output power, evaporation source ratio, steaming
Plate time, the substrate parameters such as at a distance from evaporation source, the structure of regulation and control vapor deposition lithium alloy.When the present invention prepares gradient lithium alloy,
It is prepared using more crucible modes, there is the evaporation source of different element ratios in crucible, crucible is controlled by controlling different output power
Temperature, so that it is had a different evaporation rates, prepare the lithium alloy with non-elemental lithium concentration gradients.
The preparation method of negative electrode for lithium secondary battery described in present embodiment, magnetron sputtering use magnetic control sputtering device (type
Number be JCP-350M2), substrate surface deposit suitable thickness rich lithium alloy.Output power, gas stream are sputtered by adjusting
The parameters such as amount, vacuum degree, sedimentation time regulate and control the microstructure of rich lithium alloy electrode.When the present invention prepares gradient lithium alloy, adopt
With the mode of more targets, by controlling constituent content, sputtering power in different targets, the control non-lithium ingredient of different depth
Changes of contents.
Specific implementation mode three：
According to the lithium secondary battery described in specific implementation mode one, the lithium secondary battery includes shell and is placed in shell
Internal negative electrode for lithium secondary battery, anode, organic bath and isolation film, the negative electrode for lithium secondary battery include convex
Array electrode skeleton, nanoscale alloy skeleton and excessive active metal lithium are played, the active metal lithium is filled in nanoscale
In the hole of alloy skeleton, rich lithium alloy is formed, the rich lithium alloy is deposited in the hole of the array electrode skeleton.
According to the lithium secondary battery described in specific implementation mode one, the gradient fractionation richness lithium alloy secondary lithium batteries that provide
Cathode reduces current density, promotes electric current being uniformly distributed in rich lithium alloy, effectively inhibit the growth of Li dendrite with
The violent volume change of electrode, improves the cyclical stability of interface stability and electrode.With high power capacity and superior cycle
Stability
Specific implementation mode four：
Lithium secondary battery prepared by the negative electrode for lithium secondary battery according to specific implementation mode one, the lithium are secondary
Negative electrode battery is Electrode, and commercial metal lithium piece is to electrode, 1mol/L lithium hexafluoro phosphates (LiPF6)/ethylene carbonate
(EC) (volume ratio=1+dimethyl carbonate (DMC):2) it is electrolyte, polypropylene screen is diaphragm, assembles CR2025 button cells.
Battery is with 0.5mA/cm2Current density charging, blanking voltage 1.5V.Fig. 2 is the voltage-capacity curve of battery, such as Fig. 2 institutes
Show, the content of the active lithium of the negative electrode for lithium secondary battery is 3.8mAh/cm2, current lithium secondary battery body can be met
It is the theoretical capacity requirement of positive electrode.
Specific implementation mode five：
Lithium secondary battery prepared by the negative electrode for lithium secondary battery according to specific implementation mode one, the lithium are secondary
Negative electrode battery is Electrode；The iron phosphate lithium electrode of preparation is anode, and the preparation method of iron phosphate lithium electrode is as follows：With phosphorus
Sour iron lithium (LiFePO4) it is positive active material, in mass ratio=8 with conductive agent (Super-P), binder (PVDF):1:1 is mixed
It closes, appropriate n-methyl-2-pyrrolidone (NMP) solvent is added, be coated on collector Al foils after stirring evenly, it is true at 120 DEG C
Dry 10h, is washed into the disk of diameter 14mm in empty drying box；1mol/L lithium hexafluoro phosphates (LiPF6)/ethylene carbonate (EC)+
(volume ratio=1 dimethyl carbonate (DMC):2) it is electrolyte, polypropylene screen is diaphragm, assembles CR2025 button cells.Battery is first
It is first activated for 3 times with the rate charge-discharge of 0.1C (1C=170mAh/g), then with the circulation of 1C, the voltage of charge and discharge
Ranging from 2.5-4.2V.Its first charge-discharge curve and cycle performance curve difference are as shown in Figure 3, Figure 4, can from Fig. 3
Go out Li | LiFePO4Discharge capacity is 147.4mAh/g to system battery for the first time, it can be seen that Li from Fig. 4 | LiFePO4System battery
Capacity retention ratio is 86.36% after recycling 300 times, and commercial lithium piece recycles the apparent decaying of i.e. 150 appearance.
Specific implementation mode six：
Lithium secondary battery prepared by the negative electrode for lithium secondary battery according to specific implementation mode one, the lithium are secondary
Negative electrode battery is Electrode；The KB/S electrodes of preparation are anode, and the preparation method of KB/S electrodes is as follows：It is anode with KB/S
Active material, in mass ratio=8 with conductive agent (Super-P), binder (PVDF):1:1 mixing, is added appropriate N- methyl -2-
Pyrrolidones (NMP) solvent is coated in after stirring evenly on collector Al foils, dry 10h, punching in 120 DEG C of vacuum drying chambers
At the disk of diameter 14mm；The bis- trifluoromethanesulfonimide lithiums (LiTFSI) of 1mol/L/glycol dimethyl ether (DEM)+1,3- two
Oxygen defends ring (DOL) (volume ratio 1:1)+1%LiNO3For electrolyte, polypropylene screen is diaphragm, assembles CR2025 button cells.
For battery with the circulation of 0.2C (1C=1675mA/g), the voltage range of charge and discharge is 1.7-2.6V.Its first charge-discharge is bent
Line and cycle performance are as shown in Figure 5, Figure 6, from Fig. 5 it can be seen that Li | KB/S system batteries occur in discharge process 2 it is flat
Platform corresponds to the 2 steps reaction of sulphur positive discharge process, i.e. Li respectively2SnAnd Li2The forming process of S, Li | KB/S systems battery is for the first time
Discharge capacity is 1019mAh/g, from Fig. 6 it can be seen that Li | capacity retention ratio is after KB/S systems circulating battery 100 times
55%, and capacity retention ratio only has 42% after commercial lithium piece recycles 100 times, cycle performance significantly improves.
Specific implementation mode seven：
Lithium secondary battery prepared by the negative electrode for lithium secondary battery according to specific implementation mode one, the lithium are secondary
Negative electrode battery is Electrode；The iron phosphate lithium electrode of preparation is anode, and the preparation method of iron phosphate lithium electrode is as follows：With phosphorus
Sour iron lithium (LiFePO4) it is positive active material, in mass ratio=8 with conductive agent (Super-P), binder (PVDF):1:1 is mixed
It closes, appropriate n-methyl-2-pyrrolidone (NMP) solvent is added, be coated on collector Al foils after stirring evenly, it is true at 120 DEG C
Dry 10h, is washed into the disk of diameter 14mm in empty drying box；Replace diaphragm and electrolyte, assembling using PEO base solid electrolytes
CR2025 button cells.Battery is activated for 2 times with the rate charge-discharge of 0.1C (1C=170mAh/g) first, then with 1C's
The voltage range of circulation, charge and discharge is 2.8-4.2V.The discharge capacity for the first time of battery reaches 127mAh/g, recycles 300 times
Later, discharge capacity still has 104mAh/g, and specific discharge capacity only has 96mAh/g after commercial pure lithium electrode recycles 300 times, recycles
Performance significantly improves.
Specific implementation mode eight：
Lithium secondary battery prepared by the negative electrode for lithium secondary battery according to specific implementation mode one, the lithium are secondary
Negative electrode battery is Electrode；The carbon material air electrode of preparation is anode, and the preparation method of air electrode is as follows：With
Super-P is positive active material, in mass ratio=9 with binder (PVDF):1 mixing, is added appropriate N- methyl -2- pyrrolidines
Ketone (NMP) solvent is coated in after stirring evenly in foamed nickel current collector, and the dry 10h in 120 DEG C of vacuum drying chambers is washed into straight
The disk of diameter 14mm；It is using the bis- trifluoromethanesulfonimide lithiums (LiTFSI) of 1mol/L/tetraethyleneglycol dimethyl ether (TEGDME)
Electrolyte, glass fibre assemble CR2025 button lithium-air batteries as diaphragm.Battery is carried out with the current density of 200mA/g
Cycle, limitation charge/discharge capacity are 500mAh/g, and cycle performance comparison is as shown in Figure 7, Figure 8, from the comparison of Fig. 7 and Fig. 8
, it can be seen that recycling 45 discharge platforms using the lithium-air battery of commercial lithium electrode apparent decaying occurs, and use the present invention
The lithium-air battery of middle lithium electrode is recycled to 54 times and apparent decaying just occurs, and cycle performance of battery significantly improves.
Several lithium secondary batteries provided by the invention, it includes the cathode of lithium pole pieces described in first aspect present invention, but not
It is limited to these types of battery.
Claims (9)
1. a kind of negative electrode for lithium secondary battery, it is characterised in that：The negative electrode for lithium secondary battery is mainly by array of protrusions
Electrode skeleton, nanoscale alloy skeleton and active metal lithium are constituted, the material of the array of protrusions electrode skeleton of the large aperture
For any one in Cu, Al, Sn, Fe, Co, Ni, Zn, In, the nanoscale alloy skeleton includes elemental lithium and non-lithium member
Element, the non-elemental lithium material include at least one of Sn, Si, Cu, In, Al, Mg, Ge, Zn, Ni, the active metal
Lithium is filled in the hole of nanoscale alloy skeleton, and comes into full contact with the rich lithium alloy of composition with nanoscale alloy skeleton, described
Rich lithium alloy is deposited in the hole of the array of protrusions electrode skeleton.
2. a kind of negative electrode for lithium secondary battery according to claim 1, it is characterised in that：The array of protrusions electrode bone
The cross sectional shape of array of protrusions in frame is any one of circle, polygon, five-pointed star, fan-shaped weight, the array of protrusions
Diameter of section be 0.1 μm~5 μm, the depth of section of array of protrusions is 1 μm~50 μm.
3. a kind of negative electrode for lithium secondary battery according to claim 1, it is characterised in that：The nanoscale alloy skeleton knot
Non- lithium ingredient is distributed for gradient in the rich lithium alloy of structure.
4. a kind of negative electrode for lithium secondary battery according to claim 1, it is characterised in that：Non- lithium in the rich lithium alloy
The content of element accounts for the 10%~30% of rich lithium alloy total amount.
5. the preparation method of the negative electrode for lithium secondary battery described in a kind of one of claim 1-4, it is characterised in that：Including as follows
Step：
Step a, template prepares array of protrusions electrode skeleton；
Step b, vacuum evaporation or magnetron sputtering prepare nanoscale alloy skeleton, filling active metal lithium.
6. the preparation method of negative electrode for lithium secondary battery according to claim 5, it is characterised in that：Step a protrusions battle arrays
The preparation of porous masterplate uses thickness for 20 μm of polycarbonate membrane in row electrode skeleton, so that it is gone out by the bombardment of nuclear fission fragment
Existing injury mark, then make trace corrosion at hole with chemical attack, prepare porous masterplate.
7. the preparation method of negative electrode for lithium secondary battery according to claim 5, it is characterised in that：Vacuum is steamed in step b
Plating is prepared using more crucible modes, and using pure lithium and non-elemental lithium particle as evaporation source, substrate is array of protrusions electrode bone
Frame, vacuum degree >=2 × 10 of the vacuum chamber-2The output power of Pa, vacuum evaporation power supply are 50~150W, evaporation source earthenware
The content for the non-elemental lithium being added in crucible is 10%~50%, and time of vacuum thermal evaporation is 15~30min, in vacuum evaporation room
Distance of the substrate away from evaporation source crucible is 5~15cm.
8. the preparation method of negative electrode for lithium secondary battery according to claim 5, it is characterised in that：Magnetic control splashes in step b
It penetrates and is prepared using more target modes, in vacuum sputtering cabin Du≤5 × 10 Zhen Kong-3Pa, magnetic control sputtering device output power of power supply are 15
~30W, the argon gas flow in sputtering process are 15~25L/min, and the vacuum sputtering time is 20~60min.
9. the lithium secondary battery described in a kind of one of claim 1-9, it is characterised in that：The lithium secondary battery includes shell
And it is placed in negative electrode for lithium secondary battery, anode, organic bath and isolation film in shell, the secondary lithium batteries
Cathode includes array of protrusions electrode skeleton, nanoscale alloy skeleton and excessive active metal lithium, and the active metal lithium is filled out
It fills in the hole of nanoscale alloy skeleton, forms rich lithium alloy, the rich lithium alloy is deposited on the array electrode bone
In the hole of frame.
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