CN102642024A - Lithium ion battery and anode strip thereof and stabilization lithium metal powder - Google Patents
Lithium ion battery and anode strip thereof and stabilization lithium metal powder Download PDFInfo
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Abstract
The invention belongs to the technical field of a lithium ion battery, and particularly relates to stabilization lithium metal powder. The stabilization lithium metal powder has a core shell structure; and the core layer is formed by lithium metal and is a composition consisting of an electron good conductor and a lithium ion good conductor. Compared with the prior art, the stabilization lithium metal powder provided by the invention has the advantages that: in the process of performing pre-lithiation of the anode-active material by use of the stabilization lithium metal powder, no limitation is imposed on the pressure of the cold pressing process, the 'dead lithium' disabling lithiation reaction is not produced, and the lithiation efficiency of the lithium metal powder is improved; and moreover, since the shell layer left on the electrode surface has good electron and lithium ion conductivity after the pre-lithiation, the electron and ion conductivity of the anode can be effectively improved so as to improve the electrochemical performance of the battery. In addition, the invention also discloses an anode strip performing pre-lithiation by use of the stabilization lithium metal powder, and a lithium ion battery comprising the anode strip.
Description
Technical field
The invention belongs to technical field of lithium ion, relate in particular to and a kind ofly have the stabilized lithium metal of composite conducting shell and adopt this stabilized lithium metal to carry out anode strip that preparatory lithiumation handles and the lithium ion battery that comprises this anode strip.
Background technology
The present stage extensive use of lithium ion battery is had higher requirement to the energy density of lithium ion battery.In lithium-ion battery system, first charge-discharge efficiency is mainly by the decision of efficient first of anode, and the efficient first that therefore improves anode can effectively improve the efficient first and the amplification capacity of battery, thereby realizes the lifting of energy content of battery density.
At present existingly mend lithium in advance through anode and improve the anode report of efficient first, patent application CN101790806, CN1830110, CN101522343 and US2009/0035663 disclose stabilized lithium metal and the application of benefit lithium in lithium battery.Stable lithium metal powder surface crust is the insulating barrier of electronics or lithium ion in the above-mentioned technology; This insulating barrier has avoided the lithium metal to contact with the direct of air; But electrode active material is being carried out to apply a pressure to it in the preparatory lithiumation process; After the shell on surface crushed the lithium metal of kernel is contacted with active material, could realize the preparatory lithiumation of active material.In actual application; On the one hand because the particle diameter heterogeneity of stabilized lithium metal; Can not guarantee that in cold pressure procedure all lithium metal powder shells are all crushed; The inner lithium of the lithium metallic particles of failing to crush can't participate in the lithiumation process of active material, has caused the existence of " dead lithium ", has reduced the efficient of preparatory lithiumation; The electronics or the ion insulation crust that remain on the anode strip after the lithiumation in advance on the other hand can hinder electronics and the transmission of lithium ion in pole piece, can produce certain influence to the chemical property of battery.
In view of this, necessaryly provide a kind of and have the stabilized lithium metal of composite conducting shell and adopt this stabilized lithium metal to carry out anode strip that preparatory lithiumation handles and the lithium ion battery that comprises this anode strip.
Summary of the invention
One of the object of the invention is: to the deficiency of prior art, and a kind of stabilized lithium metal with composite conducting shell is provided, with electronics and the ionic conductivity of improving anode effectively, thereby improves the chemical property of battery.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of stabilized lithium metal, said stabilized lithium metal has nucleocapsid structure, and said stratum nucleare is the lithium metal, and said shell is the compound that electronics good conductor and lithium ion good conductor are formed.Because the shell of stabilized lithium metal is by electronics good conductor and the compound composite conducting shell that constitutes of lithium ion good conductor; Thereby can avoid inner lithium metal powder to contact with extraneous atmosphere; Guarantee the chemical stability of lithium metal powder effectively, even electronics fast that exists in the shell simultaneously and lithium ion passage have guaranteed that it also can let the exchange of carrying out lithium between lithium metal and active material in the shell under the not impaired situation of shell.
As a kind of improvement of stabilized lithium metal of the present invention, said electronics good conductor is at least a in carbon-based material and the conducting polymer.
A kind of improvement as stabilized lithium metal of the present invention; Said carbon-based material is at least a in carbon black, acetylene black, conductive carbon fibre, CNT and the Graphene, and said conducting polymer is polyaniline, polypyrrole, polythiophene, polyacetylene and gathers at least a in two alkynes.
As a kind of improvement of stabilized lithium metal of the present invention, said lithium ion good conductor is Li
2CO
3, Li
4SiO
4, LiF, Li
3PO
3, TiO
2, Li
2TiO
3, Li
4Ti
5O
12, SiO
2, SnO
2, SiC, LiAlO
2, β-Al
2O
3, NiS, CuS, FeS, MnS, Ag
2S and TiS
2In at least a.
A kind of improvement as stabilized lithium metal of the present invention; The electronic conductivity of said electronics good conductor is higher than 10S/cm; The lithium ion conducting rate of said ion good conductor is higher than 0.1mS/cm, even to guarantee that stabilized lithium metal also can let the exchange of carrying out lithium between lithium metal and active material in the shell under the not impaired situation of shell.
As a kind of improvement of stabilized lithium metal of the present invention, the particle diameter of said stratum nucleare is 30～100um.The particle diameter of stratum nucleare lithium metal powder is too little, and then the activity of lithium is too big, is difficult for carrying out surface treatment, and if the particle diameter of stratum nucleare lithium metal powder is too big, then can cause surface treatment inhomogeneous, and by in the process of pressing, causes certain fire hazard easily.
As a kind of improvement of stabilized lithium metal of the present invention, the mass percent that said stratum nucleare accounts for the stabilized lithium metal gross mass is 90%～98%, if the shared mass fraction of stratum nucleare is too little, the efficient of mending lithium with this stabilized lithium metal in advance is not high.
A kind of improvement as stabilized lithium metal of the present invention; The thickness of said shell is 30～300nm; If the thickness of shell is too little, then its protective effect to stratum nucleare is not enough, if the thickness of shell is too big; The passage that need pass through when carrying out the lithium exchange between lithium metal in the shell and active material is oversize, and it is lower to cause mending lithium efficient.
With respect to prior art, the present invention has the advantage of following two aspects at least:
On the one hand; Adopting this stabilized lithium metal antianode active material to carry out in the preparatory lithiumation process; Pressure for cold pressing process has not had any restriction, can not produce to carry out lithiation " dead lithium ", has improved the lithiumation efficient of this lithium metal powder;
On the other hand, possess good electron and lithium ion conductivity simultaneously, can improve the electronics and the ionic conductivity of anode effectively, thereby improve the chemical property of battery owing to remain in the shell of electrode surface after lithiumation is accomplished in advance.
Another object of the present invention is to provide a kind of lithium ion battery anode strip; Comprise anode collector and be coated in the anode active material layer on the said anode collector that said anode active material layer adopts the described stabilized lithium metal of above-mentioned paragraph to carry out preparatory lithiumation and handles.
With respect to prior art; Lithium ion battery anode strip of the present invention is owing to adopted stabilized lithium metal to carry out preparatory lithiumation processing; Therefore can improve the efficient first of anode, thereby effectively raise the efficient first and the amplification capacity of battery, realize the lifting of energy content of battery density.
A further object of the invention is to provide a kind of lithium ion battery; Comprise cathode sheets, anode strip, be interval in the barrier film between said cathode sheets and the anode strip; And electrolyte; Said anode strip comprises anode collector and is coated in the anode active material layer on the said anode collector that said anode strip is above-mentioned lithium ion battery anode strip.
With respect to prior art, therefore lithium ion battery of the present invention has bigger efficient first and energy density because its anode has carried out preparatory lithiumation handles, and electric property preferably.
Description of drawings
Fig. 1 is the first charge-discharge curve of the button half-cell of embodiment 5 and Comparative Examples 3;
Fig. 2 is the first charge-discharge curve of the button half-cell of embodiment 10 and Comparative Examples 4;
Fig. 3 is the change curve of the enclosed pasture efficient of the full battery of button among Comparative Examples 3, Comparative Examples 4 and the embodiment 9 with cycle-index.
The specific embodiment
Below in conjunction with the specific embodiment and Figure of description the stabilized lithium metal that proposes among the present invention and the application in lithium ion battery thereof are described further, but method of the present invention is not limited to following examples.
Comparative Examples 1
The preparation of stabilized lithium metal
The lithium metal 100g that battery is pure cuts into the small pieces of 1 * 1cm, under the Ar protective atmosphere, joins in the stainless steel reactor with high-speed stirred function, and this reactor head and bottom all are equipped with heating jacket.In this reactor, add 400g and have high boiling hydrocarbon ils (boiling point is greater than 250 ℃); Under 300～800rpm mixing speed, be warming up to 200 ℃; Remain the circulation of Ar air-flow in this process, treat to descend 8000rpm to stir 3min at a high speed in this mixture after all lithium fusions.3.0g oleic acid is added in this reactor, continue high-speed stirred 5min, then add 1.5g CO
2Remove heating jacket, mixing speed is reduced to 300rpm, and room temperature to be reduced to adds 5g polyethylene glycol oxide (PEO) dry powder in reactor.Further be heated to 80 ℃ and keep 15min, then be warming up to 175 ℃ and keep 1h again, in this process, remain the stir speed (S.S.) of 300rpm with the heating rate of 5 ℃/min.Treat that sample is cooled to room temperature; Under argon shield; This dispersion is filtered in the sintered glass funnel of sealing, and with hexane wash 3 times, to remove residual hydrocarbon ils; Use dry Ar air-flow to blow over and leach thing, sealing in the powder transfer that obtains to the holding bottle is preserved to remove residual volatile organic matter.
Preparatory lithiumation anode strip and comprise the preparation of the battery of this anode strip
Adopt graphite as anode active material, adopt the aforementioned stable lithium metal powder graphite anode sheet to be mended lithium: in drying shed, the lithium powder to be dispersed in the organic dispersing agent through following mode; This dispersion is sprayed on through (unit are guarantees certain lithium powder quantity for spray) on the vacuum drying pole piece; Vacuumize and remove organic solvent, after colding pressing pole piece is washed into disk, lithium sheet and the cobalt acid lithium electrode sheet of arranging in pairs or groups respectively; Barrier film adopts polypropylene, and electrolyte is 1M LPF
6(3: 7, V/V), assembling obtained CR2430 button half-cell and full battery to/ethylene carbonate (EC)+dimethyl carbonate (DMC) respectively.
Comparative Examples 2
Different with Comparative Examples 1 is: the anode active material that adopts in the lithiumation anode strip in advance is a silicon alloy.
All the other repeat no more with Comparative Examples 1 here.
Comparative Examples 3
Different with Comparative Examples 1 is: the anode strip of anode strip for not handling through the preparatory lithiumation of lithium powder.
All the other repeat no more with Comparative Examples 1 here.
Comparative Examples 4
Different with Comparative Examples 2 is: the anode strip of anode strip for not handling through the preparatory lithiumation of lithium powder.
All the other repeat no more with Comparative Examples 2 here.
The preparation of lithium metal powder
Under argon shield atmosphere, the lithium metal 30g of LITHIUM BATTERY purity is cut into the small pieces of 1 * 1cm, it is joined in the stainless steel reactor with high-speed stirred function, this reactor bottom and top all have heating jacket.In this reactor, add 120g higher boiling hydrocarbon ils, be warming up to 200 ℃ under the 500rpm mixing speed, remain the circulation of Ar gas in this process.Treat behind all lithium metal meltings this mixture to be stirred 3min under 8000rpm, 1.0g oleic acid is joined in the reactor, continue high-speed stirred 5min; Mixing speed is reduced to 300rpm, and temperature is reduced to 150 ℃, in reactor, adds the 0.45g conductive carbon fibre; This conductive carbon fibre adopts acid to carry out the surface sensitizing processing in advance; To improve the adhesion between itself and lithium metal core, after high speed 8000rpm stirred 5min, 300rpm stirred 1h; Then the heating rate with 20 ℃/min is warming up to 200 ℃, feeds 0.45g CO under the high speed 8000rpm condition
2Remove heating jacket, mixing speed is reduced to 300rpm, treats that temperature reduces to room temperature; Under argon shield; This dispersion is filtered in the sintered glass funnel of sealing, and with hexane wash 3 times, to remove residual hydrocarbon ils; Use dry Ar air-flow to blow over and leach thing, sealing in the powder transfer that obtains to the holding bottle is preserved to remove residual volatile organic matter.
Adopt graphite as anode active material, adopt the lithium metal powder of method for preparing gained the graphite anode sheet to be mended lithium: in drying shed, the lithium powder to be dispersed in the organic dispersing agent through following mode; This dispersion is sprayed on through (unit are guarantees certain lithium powder quantity for spray) on the vacuum drying pole piece; Vacuumize and remove organic solvent, after colding pressing pole piece is washed into disk, lithium sheet and the cobalt acid lithium electrode sheet of arranging in pairs or groups respectively; Barrier film adopts polypropylene, and electrolyte is 1M LiPF
6(3: 7, V/V), assembling obtained CR2430 button half-cell and full battery to/EC+EMC respectively.
Different with embodiment 1 is the preparation of lithium metal powder:
Under argon shield atmosphere, the lithium metal 30g of LITHIUM BATTERY purity is cut into the small pieces of 1 * 1cm, it is joined in the stainless steel reactor with high-speed stirred function, this reactor bottom and top all have heating jacket.In this reactor, add 120g higher boiling hydrocarbon ils, be warming up to 200 ℃ under the 500rpm mixing speed, remain the circulation of Ar gas in this process.Treat behind all lithium metal meltings this mixture to be stirred 3min under 8000rpm; 1.0g oleic acid is joined in the reactor, continue high-speed stirred 5min, mixing speed is reduced to 300rpm; Temperature is reduced to 150 ℃, in reactor, adds 0.45g conductive carbon fibres peacekeeping 0.3g nano-TiO
2Mixed powder end, this mixed-powder is through the ball mill mixing gained, and conductive carbon fibre adopts acid to carry out the surface sensitizing processing earlier before mixing, to improve itself and TiO
2Adhesion between particle, lithium metal core, after high speed 8000rpm stirred 5min, 300rpm stirred 1h, and then the heating rate with 20 ℃/min is warming up to 200 ℃, feeds 0.15g CO under the high speed 8000rpm condition
2Remove heating jacket, mixing speed is reduced to 300rpm, treats that temperature reduces to room temperature; Under argon shield; This dispersion is filtered in the sintered glass funnel of sealing, and with hexane wash 3 times, to remove residual hydrocarbon ils; Use dry Ar air-flow to blow over and leach thing, sealing in the powder transfer that obtains to the holding bottle is preserved to remove residual volatile organic matter.
All the other repeat no more with embodiment 1 here.
Different with embodiment 1 is the preparation of lithium metal powder:
Under argon shield atmosphere, the lithium metal 30g of LITHIUM BATTERY purity is cut into the small pieces of 1 * 1cm, it is joined in the stainless steel reactor with high-speed stirred function, this reactor bottom and top all have heating jacket.In this reactor, add 120g higher boiling hydrocarbon ils, be warming up to 200 ℃ under the 500rpm mixing speed, remain the circulation of Ar gas in this process.Treat behind all lithium metal meltings this mixture to be stirred 3min under 8000rpm, 1.0g oleic acid is joined in the reactor, continue high-speed stirred 5min; Mixing speed is reduced to 300rpm, and temperature is reduced to 150 ℃, in reactor, adds the mixed powder end of 0.45g CNT and 0.3g nano-silicon oxide; This mixed-powder is through the ball mill mixing gained, and CNT adopts acid to carry out the surface sensitizing processing before mixing earlier, to improve the adhesion between itself and silicon oxide particles, lithium metal core; After high speed 8000rpm stirs 5min; 300rpm stirs 1h, and then the heating rate with 20 ℃/min is warming up to 200 ℃, feeds 0.15g CO under the high speed 8000rpm condition
2Remove heating jacket, mixing speed is reduced to 300rpm, treats that temperature reduces to room temperature; Under argon shield; This dispersion is filtered in the sintered glass funnel of sealing, and with hexane wash 3 times, to remove residual hydrocarbon ils; Use dry Ar air-flow to blow over and leach thing, sealing in the powder transfer that obtains to the holding bottle is preserved to remove residual volatile organic matter.
All the other repeat no more with embodiment 1 here.
Different with embodiment 1 is the preparation of lithium metal powder:
Under argon shield atmosphere, the lithium metal 30g of LITHIUM BATTERY purity is cut into the small pieces of 1 * 1cm, it is joined in the stainless steel reactor with high-speed stirred function, this reactor bottom and top all have heating jacket.In this reactor, add 120g higher boiling hydrocarbon ils, be warming up to 200 ℃ under the 500rpm mixing speed, remain the circulation of Ar gas in this process.Treat behind all lithium metal meltings this mixture to be stirred 3min under 8000rpm; 1.0g oleic acid is joined in the reactor, continue high-speed stirred 5min, mixing speed is reduced to 300rpm; Temperature is reduced to 120 ℃; In reactor, add with the ultrasonic mixed liquor that is dispersed with polypyrrole (10%) 1.0g and nano-silicon oxide (10%) 0.4g in N-methyl pyrrolidone (NMP), high speed 8000rpm stirred 3min after constant temperature stirred 20min, and then 300rpm stirs 30min to extract nmp solvent under the vacuum condition; Heating rate with 20 ℃/min is warming up to 200 ℃ again, feeds 0.4g CO under the high speed 8000rpm condition
2Remove heating jacket, mixing speed is reduced to 300rpm, treats that temperature reduces to room temperature; Under argon shield; This dispersion is filtered in the sintered glass funnel of sealing, and with hexane wash 3 times, to remove residual hydrocarbon ils; Use dry Ar air-flow to blow over and leach thing, sealing in the powder transfer that obtains to the holding bottle is preserved to remove residual volatile organic matter.
All the other repeat no more with embodiment 1 here.
Different with embodiment 1 is the preparation of lithium metal powder:
Under argon shield atmosphere, the lithium metal 30g of LITHIUM BATTERY purity is cut into the small pieces of 1 * 1cm, it is joined in the stainless steel reactor with high-speed stirred function, this reactor bottom and top all have heating jacket.In this reactor, add 120g higher boiling hydrocarbon ils, be warming up to 200 ℃ under the 500rpm mixing speed, remain the circulation of Ar gas in this process.Treat behind all lithium metal meltings this mixture to be stirred 3min under 8000rpm; 1.0g oleic acid is joined in the reactor, continue high-speed stirred 5min, mixing speed is reduced to 300rpm; Temperature is reduced to 120 ℃; In reactor, add with the ultrasonic mixed liquor that is dispersed with polypyrrole (10%) 1.0g and nano aluminium oxide (10%) 0.4g in N-methyl pyrrolidone (NMP), high speed 8000rpm stirred 3min after constant temperature stirred 20min, and then 300rpm stirs 30min to extract nmp solvent under the vacuum condition; Heating rate with 20 ℃/min is warming up to 200 ℃ again, feeds 0.4g CO under the high speed 8000rpm condition
2Remove heating jacket, mixing speed is reduced to 300rpm, treats that temperature reduces to room temperature; Under argon shield; This dispersion is filtered in the sintered glass funnel of sealing, and with hexane wash 3 times, to remove residual hydrocarbon ils; Use dry Ar air-flow to blow over and leach thing, sealing in the powder transfer that obtains to the holding bottle is preserved to remove residual volatile organic matter.
All the other repeat no more with embodiment 1 here.
Different with embodiment 1 is: anode active material is a silicon alloy.
All the other repeat no more with embodiment 1 here.
Embodiment 7
Different with embodiment 2 is: anode active material is a silicon alloy.
All the other repeat no more with embodiment 2 here.
Embodiment 8
Different with embodiment 3 is: anode active material is a silicon alloy.
All the other repeat no more with embodiment 3 here.
Embodiment 9
Different with embodiment 4 is: anode active material is a silicon alloy.
All the other repeat no more with embodiment 4 here.
Embodiment 10
Different with embodiment 5 is: anode active material is a silicon alloy.
All the other repeat no more with embodiment 5 here.
Stability test
In order to examine or check the stability of the stabilized lithium metal that proposes among the present invention; Adopt following method to assess: under argon shield atmosphere; With synthesize the lithium powder that obtains join in the test bag with the nmp solvent that contains 0.5% ultra-pure water; Sealing is placed in 60 ℃ of insulating boxs and kept 72 hours, then tests the lithium tenor in this sample.Obviously, residue lithium tenor is high more, and the composite conducting shell is effective more to the protective effect of lithium metal core.Can see that from table 1 lithium metal powder with composite conducting shell that the present invention proposes has the chemical stability close with Comparative Examples, the amount of residual lithium maintains more than 30%.
Table 1 lithium metal powder is through the amount of kish behind the stability test
| Sample | The shell composition | The amount of remaining lithium metal |
| Comparative Examples 1 | Li 2CO 3、PEO | 31.9 |
| Embodiment | ||
| 1 | Carbon fiber, Li 2CO 3 | 30.1 |
| Embodiment | ||
| 2 | Carbon fiber, TiO 2、Li 2CO 3 | 35.2 |
| Embodiment | ||
| 3 | CNT、SiO x、Li 2CO 3 | 34.6 |
| Embodiment | ||
| 4 | Polypyrrole, SiO x、Li 2CO 3 | 37.5 |
| Embodiment | ||
| 5 | Polypyrrole, aluminium oxide, Li 2CO 3 | 39.6％ |
The electric conductivity test
In order to examine or check the electric conductivity of the stabilized lithium metal that proposes among the present invention, in drying shed, adopt the powder resistivity appearance that the electrical conductivity of each synthetic lithium metal powder is tested.Can see that from table 2 than Comparative Examples, the lithium metal powder of embodiment of the invention gained has the electronic conductivity of obvious raising, the improvement that this helps the raising of preparatory lithiumation efficient and adopts the chemical property of preparatory lithiumation electrode battery.
The electronic conductivity of table 2 lithium metal powder
| Sample | The shell composition | Electronic conductivity (S/cm) |
| Comparative Examples 1 | Li 2CO 3、PEO | 2.78 |
| |
Carbon fiber, Li 2CO 3 | 258.6 |
| |
Carbon fiber, TiO 2、Li 2CO 3 | 212.8 |
| |
CNT、SiOx、Li 2CO 3 | 186.2 |
| |
Polypyrrole, SiOx, Li 2CO 3 | 38.1 |
| |
Polypyrrole, aluminium oxide, Li 2CO 3 | 40.3 |
Electrochemical property test
The first charge-discharge efficiency of the half-cell that table 3 makes respectively for embodiment of the invention 1-5.Can see that than Comparative Examples 3 (adopt not the graphite of lithiumation as active material of positive electrode) in advance and Comparative Examples 1, the tool of efficient first of employing embodiment of the invention 1-5 gained battery is significantly improved.
The first charge-discharge efficiency of table 3 embodiment 1-5 gained half-cell
| Sample | The shell composition | Efficient first |
| Comparative Examples 3 | - | 77.0％ |
| Comparative Examples 1 | Li 2CO 3、PEO | 82.6 |
| Embodiment | ||
| 1 | Carbon fiber, Li 2CO 3 | 86.0 |
| Embodiment | ||
| 2 | Carbon fiber, TiO 2、Li 2CO 3 | 86.8 |
| Embodiment | ||
| 3 | CNT、SiO x、Li 2CO 3 | 88.1 |
| Embodiment | ||
| 4 | Polypyrrole, SiO x、Li 2CO 3 | 88.6 |
| Embodiment | ||
| 5 | Polypyrrole, aluminium oxide, Li 2CO 3 | 89.4％ |
The first charge-discharge efficiency of the half-cell that table 4 makes respectively for embodiment of the invention 6-10.We find that in experimentation the half-cell that adopts embodiment 6-10 to make is respectively compared with Comparative Examples 4 with Comparative Examples 2 (adopting silicon alloy as active material of positive electrode), and the lifting of discharging efficiency is more obvious first.
The first charge-discharge efficiency of table 4 embodiment 6-10 gained half-cell
| Sample | The shell composition | Efficient first |
| Comparative Examples 4 | - | 48.7％ |
| Comparative Examples 2 | Li 2CO 3、PEO | 77.7 |
| Embodiment | ||
| 6 | Carbon fiber, Li 2CO 3 | 85.6％ |
| Embodiment 7 | Carbon fiber, TiO 2、Li 2CO 3 | 87.6％ |
| Embodiment 8 | CNT、SiO x、Li 2CO 3 | 88.9％ |
| Embodiment 9 | Polypyrrole, SiO x、Li 2CO 3 | 87.8％ |
| Embodiment 10 | Polypyrrole, aluminium oxide, Li 2CO 3 | 88.5％ |
Fig. 1 has provided the half-cell that the graphite pole piece assembling after adopting the preparatory lithiumation of embodiment 5 lithium metal powders to handle obtains and the first charge-discharge curve of Comparative Examples 3.Can see that from figure because the existence of lithiumation effect in advance, electrode embedding lithium capacity first reduces greatly, increases to some extent and take off the lithium capacity first, makes first charge-discharge efficiency obtain significant raising.
Fig. 2 has provided the half-cell that the silicon alloy pole piece assembling after adopting the preparatory lithiumation of embodiment 10 lithium metal powders to handle obtains and the first charge-discharge curve of Comparative Examples 4.Can see among the figure that because the existence of lithiumation effect in advance, electrode embedding lithium capacity first decreases, and increases to some extent and take off the lithium capacity first, makes first charge-discharge efficiency obtain significant raising.
Fig. 3 has provided the silicon alloy that anode adopts the preparatory lithiumation of metallic lithium powder to handle, and negative electrode adopts cobalt acid lithium, and barrier film adopts polypropylene screen, and electrolyte adopts 1M LiPF
6/ EC+EMC (3: 7, full V/V) the button cell battery enclosed pasture efficient that obtains of assembling with the variation of circulation.From figure, can see; After the preparatory lithiumation processing of metallic lithium powder, the first charge-discharge efficiency of battery is improved significantly, and compares with Comparative Examples 4; Lithium metal powder with composite conducting shell has shown higher lithiumation efficient; And in cyclic process subsequently, its coulomb efficient remains on the level near 100%, has shown superior chemical property.
Above-mentioned lithium metal powder with composite conducting shell has shown good chemical stability and active electrochemical stability; Can mend lithium to the electrode of secondary lithium battery; Adopt the rechargeable lithium ion batteries of preparatory lithiumation electrode, can be applicable to electric automobile, hybrid vehicle, mobile electronic device and other electronic products.Above-mentioned lithium metal powder has lithiumation efficient efficiently, has guaranteed the efficiency for charge-discharge that battery is high and the energy density of raising.
According to the announcement and the instruction of above-mentioned specification, those skilled in the art in the invention can also change and revise above-mentioned embodiment.Therefore, the specific embodiment that discloses and describe above the present invention is not limited to also should fall in the protection domain of claim of the present invention modifications and changes more of the present invention.In addition, although used some specific terms in this specification, these terms are explanation for ease just, the present invention is not constituted any restriction.
Claims (10)
1. stabilized lithium metal, it is characterized in that: said stabilized lithium metal has nucleocapsid structure, and said stratum nucleare is the lithium metal, and said shell is the compound that electronics good conductor and lithium ion good conductor are formed.
2. stabilized lithium metal according to claim 1 is characterized in that: said electronics good conductor is at least a in carbon-based material and the conducting polymer.
3. stabilized lithium metal according to claim 2; It is characterized in that: said carbon-based material is at least a in carbon black, acetylene black, conductive carbon fibre, CNT and the Graphene, and said conducting polymer is polyaniline, polypyrrole, polythiophene, polyacetylene and gathers at least a in two alkynes.
4. stabilized lithium metal according to claim 1 is characterized in that: said lithium ion good conductor is Li
2CO
3, Li
4SiO
4, LiF, Li
3PO
3, TiO
2, Li
2TiO
3, Li
4Ti
5O
12, SiO
2, SnO
2, SiC, LiAlO
2, β-Al
2O
3, NiS, CuS, FeS, MnS, Ag
2S and TiS
2In at least a.
5. stabilized lithium metal according to claim 1 is characterized in that: the electronic conductivity of said electronics good conductor is higher than 10S/cm, and the lithium ion conducting rate of said ion good conductor is higher than 0.1mS/cm.
6. stabilized lithium metal according to claim 1 is characterized in that: the particle diameter of said stratum nucleare is 30～100um.
7. stabilized lithium metal according to claim 1 is characterized in that: the mass percent that said stratum nucleare accounts for said stabilized lithium metal is 90%～98%.
8. stabilized lithium metal according to claim 1 is characterized in that: the thickness of said shell is 30～300nm.
9. lithium ion battery anode strip; Comprise anode collector and be coated in the anode active material layer on the said anode collector, it is characterized in that: said anode active material layer adopts each described stabilized lithium metal of claim 1 to 8 to carry out preparatory lithiumation and handles.
10. lithium ion battery; Comprise cathode sheets, anode strip, be interval in the barrier film between said cathode sheets and the anode strip; And electrolyte; Said anode strip comprises anode collector and is coated in the anode active material layer on the said anode collector that it is characterized in that: said anode strip is the described lithium ion battery anode strip of claim 9.
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Cited By (46)
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