CN107799736A - A kind of lithium metal composite negative pole of three-dimensional self-supporting parent lithium carrier encapsulation and preparation method thereof - Google Patents
A kind of lithium metal composite negative pole of three-dimensional self-supporting parent lithium carrier encapsulation and preparation method thereof Download PDFInfo
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- CN107799736A CN107799736A CN201710864608.2A CN201710864608A CN107799736A CN 107799736 A CN107799736 A CN 107799736A CN 201710864608 A CN201710864608 A CN 201710864608A CN 107799736 A CN107799736 A CN 107799736A
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- H—ELECTRICITY
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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Abstract
The invention discloses a kind of lithium metal composite negative pole of three-dimensional self-supporting parent lithium carrier encapsulation and preparation method thereof, comprise the following steps 1）Melamine foam obtains the close lithium three-dimensional self-supporting carrier of rich nitrogen in inert atmosphere through carbonization treatment；2）Lithium metal is encapsulated in the hole of three-dimensional self-supporting carrier, obtains lithium metal composite negative pole.Carrier of the carbon sponge obtained using melamine foam through being carbonized as lithium metal, there is guiding lithium metal uniform deposition, avoid acting on caused by dendrite.Qin Li functional groups are evenly distributed with the carrier, and deposit close lithium coating in the aperture surface of carrier, improve the close lithium performance of carrier, Volume Changes of the metal lithium electrode in cyclic process are effectively buffered, and the avtive spot that equally distributed Qin Li functional groups deposit as lithium metal on three-dimensional carrier, forming core overpotential is reduced, can effectively regulate and control the homogeneous nucleation of lithium metal, so as to avoid the generation of dendrite.
Description
Technical field
The present invention relates to the preparation of battery electrode material, and in particular to a kind of gold of three-dimensional self-supporting parent lithium carrier encapsulation
Belong to lithium composite negative pole and preparation method thereof.
Background technology
In recent years, with the rapid development of electric automobile and high-end portable formula electronic equipment, to high energy density cells
Demand is more and more urgent.Lithium metal is up to 3860mAhg-1Superelevation specific capacity and minimum electrochemical potential (relative standard's hydrogen electricity
Extremely -3.04V) become the ultimate negative pole of high-energy-density lithium battery.In addition, at this stage with lithium-sulfur cell and lithium air electricity
The lithium metal battery that Chi Wei is represented is considered as most promising energy storage system of future generation.However, although lithium anode
With great advantage, the commercialization that its safety problem and low circulation coulombic efficiency but hinder lithium metal battery significantly should
With.Lithium metal can produce Li dendrite in cyclic process, and dendrite, which constantly grows to pierce through barrier film and reach positive pole, causes short circuit and can
Safety problem (such as on fire, blast etc.) can further be triggered.In addition, different from traditional graphite electrode, lithium metal is being circulated throughout
Unlimited relative volume change occurs for Cheng Zhonghui, and the SEI films of metallic lithium surface can rupture under mechanically deform, expose
The fresh metal lithium come may proceed to react with electrolyte, and continuous rupture/reparations of SEI films causes lithium metal and electrolyte
Constantly consumption, therefore reduce circulation coulombic efficiency and the life-span of metal lithium electrode.
Many methods are attempted for solving the problems, such as that metal Li dendrite and coulombic efficiency are low, these methods be broadly divided into
Under several aspects：Optimize electrolyte by changing the method for solvent and addition electrolysis additive, strengthen SEI films to reach
Purpose, so as to limit the growth of Li dendrite；Before lithium metal circulation, artificial protective layer is constructed in metallic lithium surface, this
The artificial protective layer of layer has a homogeneous structure of compacting, high mechanical strength, can completely cut off the adverse reaction of lithium metal and electrolyte simultaneously
The growth of dendrite inhibition；The alloying of lithium metal, such as lithium boron alloy, lithium-aluminium alloy, the reactivity of alloy reduce, it is suppressed that branch
The growth of brilliant lithium；In addition, it also can effectively suppress the growth of metal Li dendrite using the solid electrolyte with high-modulus.These sides
Method improves the performance of lithium metal to a certain extent, improves its security, but do not change lithium metal fundamentally
Depositing behavior, and without solving the Volume Changes that occur in cyclic process of lithium metal, therefore these guard methods can not
Persistently effectively protect lithium metal.
By the way that lithium metal is encapsulated in the hole of porous, electrically conductive carrier, can be occurred with buffer electrode in cyclic process
Volume Changes, so as to improve the complete homogeneity of SEI films, and these carriers have very big specific surface area, therefore substantially reduce
Effective current density, so as to slowing down the growth of metal Li dendrite.However, the carrier material disclosed in the prior art often has
Very big deadweight (such as porous copper foil, copper nano-wire etc.) needs extra collector, this considerably increases the weight of electrode,
So as to greatly reduce the specific capacity of whole electrode, therefore weaken advantage of the lithium metal as height ratio capacity electrode material.This
Outside, there is the three-dimensional carrier of labyrinth to generally require especially complex preparation process and technique for these, and preparation cost is very high, no
Beneficial to large-scale production.Importantly, except the specific surface area of three-dimensional conductive structure, the surface chemistry of lithium metal deposition vehicle
Important influence can be produced to the depositing behavior of lithium metal, decisive role is played to final electrode pattern, has close lithium special
Property carrier there is relatively low lithium metal deposition overpotential, can effectively guide lithium metal homogeneous nucleation, then lithium metal meeting
Homoepitaxial, so as to avoid the generation of Li dendrite, improve the security and circulation coulombic efficiency of electrode.And existing carrier
Material is often not concerned with this point.
In summary, in lithium anode present in prior art easily there is deposition dendrite behavior in lithium metal, and
The problem of change of volume, easily occurs in cyclic process for lithium metal, still lacks and is effectively protected method.
The content of the invention
In order to solve technical problem present in prior art, it is an object of the invention to provide a kind of three-dimensional self-supporting parent
Lithium metal composite negative pole of lithium carrier encapsulation and preparation method and application, lithium anode prepared by the preparation method are following
During ring can dendrite inhibition generation, there is very high circulation coulombic efficiency and cyclical stability, and there is high specific volume
Amount.Moreover, the preparation method of the lithium anode is simple, cost is low, it is easy to accomplish industrialization.
In order to solve the above technical problems, the technical scheme is that：
A kind of preparation method of the lithium metal composite negative pole of three-dimensional self-supporting parent lithium carrier encapsulation, comprises the following steps：
1) melamine foam obtains the close lithium three-dimensional self-supporting carrier of rich nitrogen in inert atmosphere through carbonization treatment；
2) lithium metal is encapsulated in the hole of three-dimensional self-supporting carrier, obtains lithium metal composite negative pole.
Melamine foam, also known as melamine foamed plastic, it is to be sent out by alkaline melamine resin by special process microwave
The flexible thermosetting foamed plastics for the nanoscale three-dimensional cross-linked network being brewed to.
Carrier of the rich nitrogen carbon sponge obtained using melamine foam through being carbonized as lithium metal, the nitrogen of high content is mainly with pyrrole
Cough up nitrogen, the form of pyridine nitrogen is uniformly distributed in carrier, the nitrogen-containing functional group of these close lithiums, the activity as lithium metal deposition
Site, forming core overpotential is reduced, can effectively guide lithium metal homogeneous nucleation, so as to avoid the generation of dendrite.
Preferably, in step 1), melamine foam is needed before carbonization through over cleaning, and the process of cleaning is successively third
It is cleaned by ultrasonic in ketone, deionized water and ethanol.It is easy to thoroughly remove the impurity in melamine foam.
Preferably, in step 1), the inert atmosphere is nitrogen atmosphere, helium atmosphere, neon atmosphere, argon atmosphere, excellent
Elect nitrogen atmosphere as.
Preferably, in step 1), during carbonization treatment, 850-950 DEG C is warming up to 2-5 DEG C of programming rate, is incubated 0.8-
2h, carry out carbonization treatment.
It is further preferred that during carbonization treatment, 900 DEG C are warming up to 3 DEG C of programming rate, 1h is incubated, carries out at carbonization
Reason.
Using the Carbonization Conditions, be advantageous to form equally distributed Qin Li functional groups in the carbon sponge of preparation, these parents
Lithium functional group is nitrogen-containing functional group, oxygen-containing functional group etc., and nitrogen-containing functional group is most of to be existed in the form of pyrroles's nitrogen, pyridine nitrogen,
And lithium metal has higher combination energy.
Preferably, in step 2), method lithium metal being deposited in the hole of three-dimensional self-supporting carrier is using electrification
Sedimentation is learned to deposit to lithium metal in the hole of carrier, lithium metal is circulated into carrier hole using molten metal lithium perfusion
In, using roll-in method lithium metal is expressed in the hole of carrier or will directly made after the simply stacking of carrier and metallic lithium foil
With so that lithium metal is in hole of the redistribution to carrier during follow-up be on active service.
Preferably, method lithium metal being deposited in the hole of three-dimensional self-supporting carrier is will using electrochemical deposition method
Lithium metal is deposited in the hole of carrier.
Preferably, in step 2), the amount of the lithium metal of deposition is 1-5mAhcm-2。
The lithium metal composite negative pole that above-mentioned preparation method is prepared, its specific capacity are 1000~3500mA h g-1。
Preferably, the lithium metal in lithium metal composite negative pole is one or both of elemental metals lithium, lithium metal alloy
Combination above.
Preferably, before lithium metal is encapsulated in self-supporting carrier by step (2), it is additionally included in self-supporting carrier surface
The step of preparing close lithium coating.So as to further improve its close lithium.
It is further preferred that the close lithium coating includes simple substance coating or one kind in compound coat or two or more
Combination.
Still more preferably, the simple substance coating is the group of one kind in Si, Ge, Al, Ni, Mg or two kinds and the above
Close, the compound coat is ZnO, Al2O3、SiO、SiO2、GeO2In one kind or two kinds and the above combination.
Still more preferably, the thickness of described close lithium coating is 1nm~10 μm.The preparation method of close lithium coating includes
In magnetron sputtering, ald, electrochemical deposition, vacuum thermal evaporation, physical vapour deposition (PVD), chemical vapor deposition, ion plating
One kind or two or more combinations.
A kind of electrode material, including the lithium metal composite negative pole and the protective layer for being covered in its surface.
A kind of electrochemical energy storage device, including described electrode material.
The present invention advantageous effects be：
By being packaged in lithium metal in the three-dimensional self-supporting carrier for being evenly distributed with Qin Li functional groups, effectively buffer
Volume Changes of the metal lithium electrode in cyclic process, equally distributed Qin Li functional groups sink as lithium metal on three-dimensional carrier
The avtive spot of product forming core, reduces forming core overpotential, can effectively regulate and control lithium metal homogeneous nucleation, so as to avoid dendrite
Produce.
The three-dimensional self-supporting carrier being prepared is very smooth in microcosmic upper surface, without raised and tip, avoid by
Electrons/ions skewness caused by " point effect ", be advantageous to lithium metal and equably deposit/dissolve, thus the electrode exists
There is good cyclical stability and high coulombic efficiency, safe, long lifespan in cyclic process.
Because the three-dimensional self-supporting carrier has ultralight characteristic and avoids additionally weight increase caused by addition collector,
Therefore the lithium metal composite negative pole being prepared has the ratio energy of superelevation, has fully demonstrated the advantage of lithium metal height ratio capacity.
Brief description of the drawings
The Figure of description for forming the part of the application is used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its illustrate be used for explain the application, do not form the improper restriction to the application.
Fig. 1 be the SEM pictures (a) of three-dimensional self-supporting parent lithium richness nitrogen carbon sponge that the embodiment of the present invention 1 is prepared and
Its partial enlarged drawing (b).
Fig. 2 is that lithium metal forming core on copper foil (a) and rich nitrogen carbon sponge (b) deposits schematic diagram.
Fig. 3 is the XPS spectrum for the three-dimensional self-supporting parent lithium richness nitrogen carbon sponge that the embodiment of the present invention 1 is prepared, and is shown
The nitrogen-containing functional group of wherein close lithium.
Fig. 4 Li atomic adsorptions are in a) pure carbon-coating, (b) pyridine N, c) pyrroles N and d) in graphite mould N structures optimize structure side
View and top view.(rhodo chromosphere:Li atoms；Basketball:N atoms；Grey ball:C atoms).
Fig. 5 is the SEM of the lithium anode for the three-dimensional self-supporting parent lithium carrier encapsulation that the embodiment of the present invention 1 is prepared
Picture.
Fig. 6 is following for the lithium anode for the three-dimensional self-supporting parent lithium carrier encapsulation that the embodiment of the present invention 1 is prepared
Ring coulombic efficiency figure.
Fig. 7 be the lithium anode (b) of three-dimensional self-supporting parent lithium carrier encapsulation that is prepared of the embodiment of the present invention 1 with
It is deposited on the pattern contrast after the cathode of lithium (a) on copper foil circulates 140 weeks.
Fig. 8 is the lithium anode for the three-dimensional self-supporting parent lithium carrier encapsulation that the embodiment of the present invention 1 is prepared with sinking
Cathode of lithium of the product on copper foil is in the front and rear impedance contrast of circulation.
Fig. 9 is the SEM of the lithium anode for the three-dimensional self-supporting parent lithium carrier encapsulation that the embodiment of the present invention 2 is prepared
Picture (a) is the SEM pictures of the lithium anode for the three-dimensional self-supporting parent lithium carrier encapsulation being prepared, and (b) is to be deposited on
The SEM pictures of the lithium anode of copper foil surface.
Figure 10 is the lithium anode for the three-dimensional self-supporting parent lithium carrier encapsulation that the embodiment of the present invention 3 is prepared
SEM pictures.
Figure 11 is the lithium anode composition for the three-dimensional self-supporting parent lithium carrier encapsulation that the embodiment of the present invention 3 is prepared
Symmetrical cells and metallic lithium foil Symmetrical cells and the negative pole composition being deposited on copper foil Symmetrical cells constant current charge-discharge it is bent
Line contrasts, and it is 0.5mAh cm often to enclose deposition/dissoluble capacity-2, current density is 0.5mA cm-2。
Embodiment
It is noted that described further below is all exemplary, it is intended to provides further instruction to the application.It is unless another
Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in this manual using term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
Embodiment 1
(1) a kind of preparation of three-dimensional self-supporting parent lithium carrier
Commercialization melamine foam is cleaned by ultrasonic in acetone, deionized water and ethanol successively, then in high pure nitrogen atmosphere
In with 3 DEG C of min-1Heating rate be warming up to 900 DEG C and carry out lithium at carbonization, be incubated 1h, obtain three-dimensional self-supporting richness nitrogen carbon sponge,
High nitrogen content is most of in the carrier exists in the form of pyrroles's nitrogen, pyridine nitrogen, and these nitrogen-containing functional groups have higher with lithium
Combination energy, there is close lithium characteristic.
(2) preparation of the lithium anode of three-dimensional self-supporting parent lithium carrier encapsulation
Using shape needed for above-mentioned three-dimensional self-supporting richness nitrogen carbon sponge carrier is cut into as working electrode, using metallic lithium foil as pair
Electrode and reference electrode are assembled into button cell, by 1mA h cm-2Lithium metal with 1mA cm-2Current density constant current electrification
Learn depositing encapsulation and lithium metal composite negative pole is formed in the hole of carrier.
In the SEM pictures such as Fig. 1 of the three-dimensional self-supporting parent lithium richness nitrogen carbon sponge being prepared shown in (a), the SEM figures
Partial enlarged drawing is such as shown in (b).As seen from Figure 1, the three-dimensional self-supporting carrier of preparation is very smooth in microcosmic upper surface, not convex
Rise and tip, avoid the electrons/ions skewness as caused by " point effect ", be advantageous to lithium metal equably deposit/
Dissolving, the electrode that can to prepare have good cyclical stability and high coulombic efficiency, security in cyclic process
High, long lifespan.
The XPS spectrum for the three-dimensional self-supporting parent lithium richness nitrogen carbon sponge being prepared is as shown in Figure 3, it is seen that, it is prepared
The surface of three-dimensional self-supporting carrier be evenly distributed with the nitrogen-containing functional group of close lithium.Fig. 4 is to be obtained based on first-principles calculations
The lithium atom arrived adsorbs the change of the structure after different nitrogen-containing functional groups, as shown in Fig. 4 (a), without the pure carbon of nitrogen-containing functional group
Layer is not disturbed by lithium atom, remains perfect planar structure, and with most long Li-C distances (0.22nm) and most
Small combination energy -0.029Hartree, and certain change all occurs for all nitrogen-containing functional groups structure after lithium is adsorbed shaped like torsion
Bent or local crowning, and big combination energy is showed, there is stronger combination between this explanation N and Li, and this is advantageous to
Li absorption and the uniform redistribution in electrode surface, so as to guiding lithium metal homogeneous nucleation deposition, avoid dendrite from producing
Effect.
The SEM pictures of the lithium anode for the three-dimensional self-supporting parent lithium carrier encapsulation being prepared, as shown in figure 5, receiving
The lithium metal particle of metrical scale is evenly distributed in carrier framework surface, illustrates that lithium metal can uniformly sink in the carrier surface
Product, so as to avoid the generation of dendrite.
Forming core deposition schematic diagram is as shown in Figure 2 in copper foil and on rich nitrogen carbon sponge for lithium metal.
The lithium anode (NGCS) for the three-dimensional self-supporting parent lithium carrier encapsulation being prepared in copper foil surface with depositing
Obtained lithium anode circulation coulomb efficiency comparative's figure, as shown in fig. 6, the coulombic efficiency of NGCS electrodes is apparently higher than in copper foil
Surface deposits obtained lithium anode, and cyclical stability greatly improves, circulation 140 circle after NGCS electrodes coulombic efficiency still
So it is maintained at more than 97.5%.
The lithium anode (b) for the three-dimensional self-supporting parent lithium carrier encapsulation being prepared is born with the lithium being deposited on copper foil
Pattern after pole (a) is circulated 140 weeks contrasts, as shown in fig. 7, the cathode of lithium being deposited on copper foil presentation after the circle of circulation 140 is high
Spend development pine-tree structure, dendrite be sub-micron to micro-meter scale, structure is very loose, on the contrary, NGCS electrode cycles 140 enclose
The surface topography of uniform ground is still presented afterwards, lithium metal tight is on carrier framework surface, it was demonstrated that NGCS electrodes can
Suppress the generation of dendrite in cyclic process.
The lithium anode for the three-dimensional self-supporting parent lithium carrier encapsulation being prepared and the cathode of lithium being deposited on copper foil
In the front and rear electrochemical impedance spectroscopy of circulation, subtract significantly as shown in figure 8, circulating NGCS electrodes after the preceding and circle of circulation 140 and all having
Small interface impedance, this explanation NGCS polarization of electrode reduce.
Embodiment 2
(1) a kind of preparation of three-dimensional self-supporting carrier
Commercialization melamine foam is cleaned by ultrasonic in acetone, deionized water and ethanol successively, then in high pure nitrogen atmosphere
In with 5 DEG C of min-1Heating rate be warming up to 950 DEG C and carry out lithium at carbonization, be incubated 1h, obtain three-dimensional self-supporting richness nitrogen carbon sponge,
High nitrogen content is most of in the carrier exists in the form of pyrroles's nitrogen, pyridine nitrogen, and these nitrogen-containing functional groups have higher with lithium
Combination energy, there is close lithium characteristic.
(2) preparation of the lithium anode of three-dimensional self-supporting parent lithium carrier encapsulation
Using shape needed for above-mentioned three-dimensional self-supporting richness nitrogen carbon sponge carrier is cut into as working electrode, using metallic lithium foil as pair
Electrode and reference electrode are assembled into button cell, by 2mA h cm-2Lithium metal with 0.5mA cm-2Current density Constant Electric Current
Chemical deposition is encapsulated in formation lithium metal composite negative pole in the hole of carrier.
As shown in figure 9, the lithium anode (a) for the three-dimensional self-supporting parent lithium carrier encapsulation being prepared is with being deposited on copper
The SEM pictures of the lithium anode (b) on paper tinsel surface, such as scheme shown in (a), lithium metal particle and bulk are uniformly wrapped in carrier framework
Surface, surface topography relative smooth and is produced without dendrite, and has obvious Li dendrite on the copper foil of equivalent capability.
Embodiment 3
(1) a kind of preparation of three-dimensional self-supporting carrier
Commercialization melamine foam is cleaned by ultrasonic in acetone, deionized water and ethanol successively, then in high pure nitrogen atmosphere
In with 3 DEG C of min-1Heating rate be warming up to 900 DEG C and carry out lithium at carbonization, be incubated 1h, obtain three-dimensional self-supporting richness nitrogen carbon sponge,
High nitrogen content is most of in the carrier exists in the form of pyrroles's nitrogen, pyridine nitrogen, and these nitrogen-containing functional groups have higher with lithium
Combination energy, there is close lithium characteristic.
(2) preparation of the lithium anode of three-dimensional self-supporting parent lithium carrier encapsulation
Using shape needed for above-mentioned three-dimensional self-supporting richness nitrogen carbon sponge carrier is cut into as working electrode, using metallic lithium foil as pair
Electrode and reference electrode are assembled into button cell, by 4mA h cm-2Lithium metal with 0.5mA cm-2Current density Constant Electric Current
Chemical deposition is encapsulated in formation lithium metal composite negative pole in the hole of carrier.
The SEM pictures of the lithium anode for the three-dimensional self-supporting parent lithium carrier encapsulation being prepared, as shown in Figure 10, gold
Category lithium is uniformly filled in the hole of carrier framework, and the smooth no dendrite of electrode surface produces.
The Symmetrical cells and lithium metal of the lithium anode composition for the three-dimensional self-supporting parent lithium carrier encapsulation being prepared
The constant current charge-discharge curve comparison of the Symmetrical cells of paper tinsel Symmetrical cells and the negative pole composition being deposited on copper foil, as shown in figure 11,
It is 0.5mAh cm often to enclose deposition/dissoluble capacity-2, current density is 0.5mA cm-2.As illustrated, it is made up of lithium paper tinsel symmetrical
Battery overpotential in cyclic process gradually increases, and this is probably because SEI films are constantly repaired/ruptured and cause in cyclic process
Battery impedance is continuously increased, and the Symmetrical cells situation being made up of the lithium anode being deposited on copper foil is even worse, close to 130h
After overpotential is continuously increased, voltage shows fluid bust phenomenon, can be inferred that the generation of Li dendrite causes
Inside battery micro-short circuit；And NGCS composition metals cathode of lithium composition Symmetrical cells shown in cyclic process it is excellent
Stability, this is the chemical property and the equably embodiment of lithium metal deposition/course of dissolution improved.
Embodiment 4
(1) a kind of preparation of three-dimensional self-supporting carrier
Commercialization melamine foam is cleaned by ultrasonic in acetone, deionized water and ethanol successively, then in high pure nitrogen atmosphere
In with 3 DEG C of min-1Heating rate be warming up to 900 DEG C and carry out lithium at carbonization, be incubated 1h, obtain three-dimensional self-supporting richness nitrogen carbon sponge.
(2) in three-dimensional self-supporting deposited on supports parent's lithium coating
The method being pyrolyzed using zinc acetate prepares layer of ZnO coating on three-dimensional self-supporting carrier surface, and specific method is
Dried after three-dimensional self-supporting carbon sponge is soaked into 10s in 0.02mol/L zinc acetate ethanol solution, repeatedly this operation six times,
Then it is heat-treated 20min at 450 DEG C and obtains ZnO thin layers.
(3) preparation of the lithium anode of three-dimensional self-supporting parent lithium carrier encapsulation
Above-mentioned three-dimensional self-supporting richness nitrogen carbon sponge carrier is cut into certain shape, the method poured into using molten metal lithium
Lithium metal composite negative pole is prepared, specific preparation method is that heating lithium metal is at into molten condition to 250 DEG C, by carbon sponge
One end is immersed in the lithium metal of melting, and due to its close lithium characteristic, molten metal lithium can fill up the hole of carrier, obtain after cooling
Obtain lithium metal composite negative pole.
The preferred embodiment of the application is the foregoing is only, is not limited to the application, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (10)
- A kind of 1. preparation method of the lithium metal composite negative pole of three-dimensional self-supporting parent lithium carrier encapsulation, it is characterised in that：Including Following steps：1) melamine foam obtains the close lithium three-dimensional self-supporting carrier of rich nitrogen in inert atmosphere through carbonization treatment；2) lithium metal is encapsulated in the hole of three-dimensional self-supporting carrier, obtains lithium metal composite negative pole.
- 2. preparation method according to claim 1, it is characterised in that：In step 1), melamine foam needs before carbonization Through over cleaning, the process of cleaning is to be cleaned by ultrasonic successively in acetone, deionized water and ethanol.Being easy to will be miscellaneous in melamine foam Matter thoroughly removes.
- 3. preparation method according to claim 1, it is characterised in that：In step 1), the inert atmosphere be nitrogen atmosphere, Helium atmosphere, neon atmosphere, preferably argon atmosphere, nitrogen atmosphere.
- 4. preparation method according to claim 1, it is characterised in that：In step 1), during carbonization treatment, with 2-5 DEG C of liter Warm speed is warming up to 850-950 DEG C, is incubated 0.8-2h, carries out carbonization treatment；Preferably, during carbonization treatment, 900 DEG C is warming up to 3 DEG C of programming rate, is incubated 1h, carries out carbonization treatment.
- 5. preparation method according to claim 1, it is characterised in that：In step 2), lithium metal is deposited on three-dimensional from branch It is in the hole for deposit to lithium metal using electrochemical deposition method carrier, using molten metal to support the method in the hole of carrier Lithium metal is circulated into carrier hole, lithium metal is expressed in the hole of carrier or will carried using roll-in method by lithium perfusion Body after metallic lithium foil simply stacking with directly using so that the lithium metal hole of redistribution to carrier during follow-up be on active service In；Preferably, it is by metal using electrochemical deposition method that lithium metal is deposited on to method in the hole of three-dimensional self-supporting carrier Lithium is deposited in the hole of carrier；Preferably, in step 3), the amount of the lithium metal of deposition is 1-5mAhcm-2。
- 6. preparation method according to claim 1, it is characterised in that：Lithium metal is encapsulated in into self-supporting in step (2) to carry Before in body, the step of self-supporting carrier surface prepares close lithium coating is additionally included in；Preferably, the close lithium coating includes simple substance coating or one kind in compound coat or two or more combinations；Preferably, the simple substance coating is the combination of one kind in Si, Ge, Al, Ni, Mg or two kinds and the above, the chemical combination Thing coating is ZnO, Al2O3、SiO、SiO2、GeO2In one kind or two kinds and the above combination；Preferably, the thickness of described close lithium coating is 1nm-10 μm.The preparation method of close lithium coating includes magnetron sputtering, atom Layer deposition, electrochemical deposition, vacuum thermal evaporation, physical vapour deposition (PVD), chemical vapor deposition, one kind in ion plating or two kinds And the combination of the above.
- 7. the lithium metal composite negative pole that any preparation methods of claim 1-6 are prepared, its specific capacity is 1000~ 3500mA h g-1。
- 8. lithium metal composite negative pole according to claim 7, it is characterised in that：Lithium metal in lithium metal composite negative pole is Combination more than one or both of elemental metals lithium, lithium metal alloy.
- A kind of 9. electrode material, it is characterised in that：Including the lithium metal composite negative pole of claim 7 or 8 and it is covered in its table The protective layer in face.
- A kind of 10. electrochemical energy storage device, it is characterised in that：Including the electrode material described in claim 9.
Priority Applications (1)
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