CN110190243A - A kind of preparation and application of the lithium an- ode with composite membrane - Google Patents
A kind of preparation and application of the lithium an- ode with composite membrane Download PDFInfo
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- CN110190243A CN110190243A CN201910459176.6A CN201910459176A CN110190243A CN 110190243 A CN110190243 A CN 110190243A CN 201910459176 A CN201910459176 A CN 201910459176A CN 110190243 A CN110190243 A CN 110190243A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention belongs to field of lithium, disclose the preparation and application of a kind of lithium an- ode with composite membrane, wherein preparation method is the following steps are included: organic component and inorganic lithium compound component are matched composite load on a current collector by the mass ratio of 1:1~98:1 by (1), in collection liquid surface formation composite membrane；(2) obtained surface is covered with the collector of composite membrane and lithium piece is assembled into battery and carries out electrochemical deposition, so that lithium metal is deposited on the surface and be covered on the collector of composite membrane, thus obtain the lithium an- ode material with composite membrane.The present invention is improved by the whole design to cathode material preparation method flow process, obtain the lithium an- ode material with composite membrane, it is able to solve the Li dendrite phenomenon that nonuniform deposition of the conventional lithium an- ode in cyclic process generates, and lithium an- ode reacts the phenomenon that dead lithium generated is to reduce cycle performance with electrolyte, it can be used as the cathode in lithium metal battery, improve lithium metal battery cycle life.
Description
Technical field
The invention belongs to field of lithium, a kind of preparation more particularly, to lithium an- ode with composite membrane and
Using.
Background technique
Lithium metal simple substance is due to minimum reduction potential (- 3.04V contrast standard hydrogen electrode) and most light metal
Density (0.53g/cm3), to have high theoretical specific capacity (3860mAh/g), it is accordingly regarded as next-generation high-energy-density
The negative electrode material of secondary cell.
But lithium metal, because of its active chemical property, there is following problems in use: (1) lithium metal
Nonuniform deposition can occur on a current collector in charge and discharge process, so that Li dendrite phenomenon is generated, the continuous growth of Li dendrite
Battery diaphragm may finally be pierced through, short circuit phenomenon is caused, or even causes battery explosion and catches fire；(2) lithium metal is in charge and discharge
Cheng Zhonghui and electrolyte react, and on the one hand lead to the irreversible consumption of electrolyte, on the other hand generate the lithium that reaction generates
Deposition causes dusting and dead lithium, so that cycle life be made to substantially reduce.
Therefore, in order to really realize the real large-scale production of lithium metal battery, developing one kind can make lithium uniformly sink
Product ever more important so that the lithium an- ode for inhibiting the generation of Li dendrite, and lithium and electrolyte capable of being prevented to react seems.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the purpose of the present invention is to provide a kind of with composite membrane
The preparation and application of lithium an- ode, wherein improved by the whole design to cathode material preparation method flow process,
The lithium an- ode material with composite membrane with specific structure and composition is obtained, conventional lithium an- ode is able to solve and is following
The Li dendrite phenomenon and lithium an- ode that nonuniform deposition during ring generates react the dead lithium of generation with electrolyte thus
The phenomenon that reducing cycle performance, can be used as the cathode in lithium metal battery, improve lithium metal battery cycle life.Utilize the present invention
The lithium an- ode of preparation can be used for next-generation lithium battery, the production including lithium-sulphur, lithium-air battery.
To achieve the above object, according to one aspect of the present invention, a kind of lithium an- ode with composite membrane is provided
The preparation method of material, which comprises the following steps:
(1) organic component and inorganic lithium compound component are matched into composite load in afflux by the mass ratio of 1:1~98:1
On body, to form composite membrane in the collection liquid surface；
(2) surface that the step (1) obtains is covered with the collector of composite membrane and lithium piece is assembled into battery and carries out electricity
Chemical deposition makes lithium metal be deposited on the surface and is covered on the collector of composite membrane, thus obtains the lithium metal with composite membrane
Negative electrode material.
As present invention further optimization, the step (1) is specifically first by organic component and inorganic lithium compound group
Divide and be dissolved in solvent, forms slurry, then on a current collector by slurry coating, it after the solvent is volatilized, can be in the collector
Surface forms composite membrane；
Wherein, the solvent is water, N-Methyl pyrrolidone, tetrahydrofuran, n,N-Dimethylformamide, dimethyl Asia
One or more of sulfone, thionyl chloride, chloroform, toluene.
As present invention further optimization, in the step (1), the composite membrane with a thickness of 5 μm~100 μm, it is excellent
It is selected as 20~50 μm；
In the step (2), current density size used in the electrochemical deposition is 0.1~5mA/cm2, preferably
1mA/cm2；The time of the electrochemical deposition is 0.5~500 hour, preferably 10 hours；Deposit the thickness of obtained lithium metal
Degree is 5~500 μm, preferably 20~100 μm；The face amount for depositing obtained lithium metal is 0.5~100mAh/cm2, preferably
10mAh/cm2。
As present invention further optimization, in the step (1), the organic component is silicon carbide/polypropylene nitrile, polyamides
Amine, carbonization amino acid, polyaniline, polyacrylamide, polyacrylic acid, nitrogen-doped graphene, melamine, gathers polyethylene glycol oxide
One or more of pyrroles；
The inorganic lithium compound component is lithium nitrate, lithium nitrite, lithium sulfide, lithium nitride, lithia, lithium fluoride, chlorine
Change one or more of lithium, lithium bromide, lithium iodide, lithium carbonate, lithium hydroxide, lithium metasilicate, lithium sulfate.
It further include adhesive component in the composite membrane in the step (1) as present invention further optimization, institute
Stating adhesive component is polyacrylic acid, butadiene-styrene rubber, carboxymethyl cellulose, acrylonitrile copolymer, Kynoar, polytetrafluoroethyl-ne
One or more of alkene；
Also, in the composite membrane, the mass ratio of organic component, inorganic lithium compound component and adhesive component three
Meet 1:1:1~98:1:1, preferably 8:1:1.
As present invention further optimization, in the step (1), the organic component is silicon carbide/polypropylene nitrile, described
Inorganic lithium compound component is lithium nitrate, and the adhesive component is acrylonitrile copolymer.
As present invention further optimization, in the step (1), the collector is copper foil, copper mesh, copper foam frame
One or more of frame, carbon paper, carbon fiber frame, goldleaf, silver foil.
It is another aspect of this invention to provide that the present invention provides what is be prepared using above-mentioned preparation method to have composite membrane
Lithium an- ode material as the cathode in lithium metal battery improve lithium metal battery cycle life in application.
Another aspect according to the invention, the present invention provides a kind of lithium metal secondary cells, including positive electrode, cathode
Material, diaphragm and electrolyte, which is characterized in that the negative electrode material is to be prepared using above-mentioned preparation method with compound
The lithium an- ode material of film.
As present invention further optimization, the positive electrode is LiFePO4, cobalt acid lithium, lithium titanate, nickel cobalt manganese three
One of first material, nickel cobalt aluminium ternary material, sulphur simple substance positive electrode, sulfide polymer positive electrode, air cathode material
Or it is several；
The diaphragm is selected from PP diaphragm, PE diaphragm, PP/PE/PP diaphragm, Al2O3Coated separator, fibreglass diaphragm, PVDF
Diaphragm, PET/Al2O3One or more of diaphragm, cellulosic separator, aramid fiber diaphragm；
The electrolyte be selected from ethers electrolyte, esters electrolyte, ether-ether mixed electrolytic solution, ionic liquid class electrolyte,
One or more of gel electrolyte, solid electrolyte.
Contemplated above technical scheme through the invention will have good lithium ion to pass first compared with prior art
The collector and lithium metal of the organic/inorganic composite film of defeated property and excellent film forming are assembled into such as half-cell, then utilize electricity
Lithium metal is transferred to collector side by chemical deposition, and the lithium metal taking-up with composite protection film is finally used for lithium metal
The assembling of battery, the cathode that can be used as in lithium metal battery improve lithium metal battery cycle life.It is obtained in the present invention to have
The lithium an- ode of composite membrane (in compound film component, and includes simultaneously organic component and inorganic containing compound film component simultaneously
Lithium compound component, and can further preferably include adhesive component) and lithium metal ingredient, it can be used as lithium metal secondary battery cathode
Pole material is applied, and is especially applicable to lithium-LiFePO4, lithium-nickel-cobalt-manganese ternary, lithium-nickel cobalt aluminium ternary, the secondary electricity of lithium-sulphur
Chi Zhong.
Since current lithium an- ode still has the characteristics of dendritic growth, poor circulation, lithium metal battery be also difficult into
Row large-scale production.Therefore the present invention provides a kind of effectively with the lithium an- ode preparation method of composite protection film.Benefit
The lithium an- ode with organic/inorganic composite film prepared with method of the invention, on the one hand, the organic principle in composite membrane
It can make lithium ion uniform deposition, to reduce the growth of Li dendrite, the inorganic constituents in another aspect composite membrane can discharge
It reacts in the process with lithium metal and generates firm protective layer, reduce the consumption of lithium, to reduce the generation of dead lithium, Jin Eryan
The cycle life of long lithium metal.Experiment shows that the lithium an- ode prepared with the method for the invention can be in 1mA/cm2Electricity
Under current density, stabilization charge and discharge cycles more than 100 times are still able to maintain efficient coulombic efficiency；Have with prepared by the method
The lithium an- ode of composite protection film can be stablized applied to lithium-LiFePO4 circulates beyond 400 circles；The tool prepared with the method
There is the lithium an- ode of composite protection film to be applied to stabilization in lithium-sulphur full battery and circulates beyond 400 circles.Most of all, described
Method and process is simple, low in cost, can be realized heavy industrialization generation, has high commercial value.
The present invention makes it contain organic component and inorganic lithiumation simultaneously particularly by the composition of composite membrane on control collector
Polymer component, and the two mass ratio control be 1:1~98:1, using in composite membrane organic principle and inorganic constituents it is whole
Body cooperation, can make lithium ion uniform deposition, to reduce the growth of Li dendrite, and can be golden with lithium during after discharge
Category, which reacts, generates firm protective layer, reduces the consumption of lithium, to reduce the generation of dead lithium, and then extends following for lithium metal
The ring service life.The thickness control of composite membrane is further preferably 5 μm~100 μm (more preferably 20~50 μm) by the present invention, subsequent electrification
The thickness for learning the lithium metal deposited in deposition is preferably controlled to 5~500 μm (more preferably 20~100 μm), can further really
The lithium an- ode material obtained with composite membrane is protected as lithium metal battery cathode to follow in application, rising and improving lithium metal battery
The effect in ring service life.The thickness of suitable composite membrane and lithium metal plays an important role to the deposition of lithium, further by preferred
Different composite film thickness, and in conjunction with different current densities, it can be achieved that different coulombic efficiencies；Such as when the obtained gold of deposition
Belong to lithium thickness remain 50 μm it is constant when, by controlling current density for 2mA/cm2, it can be achieved that the composite layer of 50 μ m-thicks exists
Current density is 2mA/cm2, capacity 1mAh/cm2Under, coulombic efficiency highest, up to 99.7%；When composite bed thickness remains
50 μm it is constant when, by being 100 μm by the control of the deposition thickness of lithium metal, the lithium lithium Symmetrical cells accordingly obtained stablize the time most
Long.
The present invention using cladding process rather than uses the directly method of addition in the electrolytic solution, greatly in R&D process
Improve the performance of lithium an- ode.For example, traditional lithium nitrate is commonly used in ethers electrolyte as additive, but
Since it does not dissolve in esters and some other special electrolyte, cannot be used directly as additive.And use this
The method of invention can overcome the problems, such as this or similar completely, and one side cladding process can will be most of insoluble or indissoluble
Substance is added in entire battery system, on the other hand can be played by the collector that cladding process is modified in deposited metal lithium
Lithium deposition morphology is adjusted, lithium is made to be uniformly distributed effect on a current collector.Therefore the present invention provides one kind to be generally applicable in
Method in various electrolyte systems, all kinds of battery systems, and play pretty good effect.
Detailed description of the invention
Fig. 1 is stereoscan photograph of the embodiment 1 using the lithium an- ode prepared by the present invention with composite membrane.
Fig. 2 is coulombic efficiency test chart of the embodiment 2 using the lithium an- ode prepared by the present invention with composite membrane.
Fig. 3 is the full electricity of the lithium an- ode and lithium iron phosphate positive material composition with composite membrane prepared by embodiment 6
Pond test circulation volume figure (figure be directed to composite membrane lithium an- ode composition lithium-LiFePO4 full battery, multiplying power:
0.5C)。
Fig. 4 is the full battery test of the lithium an- ode and sulphur positive electrode composition with composite membrane prepared by embodiment 9
Circulation volume figure (figure be directed to Li-S full battery, multiplying power: 0.5C).
Fig. 5 is the coulomb effect with different-thickness composite membrane under different current density test conditions prepared by embodiment 10
Rate.
Fig. 6 is the lithium lithium Symmetrical cells test with lithium deposition thickness prepared by embodiment 11.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Embodiment 1
By silicon carbide/polypropylene nitrile, lithium nitrate, acrylonitrile copolymer with the mass ratio of 8:1:1, take water as a solvent uniformly mixed
Slurry is made in conjunction, is coated in copper foil current collector, and coating layer thickness is 10 μm.After the solvent is volatilized, by copper foil punching at diameter 16mm
Pole piece.By pole piece, diaphragm, lithium metal is assembled into button cell in the glove box that argon gas is protected, and adding concentration is 1M six
The ethylene carbonate and diethyl carbonate (volume ratio 1:1) electrolyte of lithium fluophosphate.
By the button cell assembled in aforementioned manners in 0.5mA/cm2Current density under discharge 20h, make collection liquid surface
Deposit 10mAh/cm2Lithium metal.After discharge off, above-mentioned button cell is dismantled, takes out the collector that deposited lithium metal,
As shown in Figure 1, for using the stereoscan photograph of the lithium an- ode prepared by the present invention with composite membrane, it can be found that lithium energy
It enough uniformly deposits and surface does not have dead lithium, illustrate the multifunctionality of the composite membrane.
Embodiment 2
By silicon carbide/polypropylene nitrile, lithium nitrate, acrylonitrile copolymer with the mass ratio of 8:1:1, take water as a solvent uniformly mixed
Slurry is made in conjunction, is coated in copper foil current collector, and coating layer thickness is 10 μm.After the solvent is volatilized, by copper foil punching at diameter 16mm
Pole piece.By pole piece, diaphragm, lithium metal is assembled into button cell in the glove box that argon gas is protected, and adding concentration is 1M six
The ethylene carbonate and diethyl carbonate (volume ratio 1:1) electrolyte of lithium fluophosphate.
By the button cell assembled in aforementioned manners in 1mA/cm2Current density under carry out coulombic efficiency test, make lithium
The deposition removing repeatedly on the copper foil for cover composite membrane obtains coulombic efficiency by the deposition overburden amount of every circle lithium, as shown in Fig. 2,
For using the coulombic efficiency test chart of the lithium an- ode prepared by the present invention with composite membrane, it can be found that with more than 100
Secondary stabilization charge and discharge cycles.
In Fig. 2, the lithium copper battery that blank group uses the copper foil current collector for not carrying out any modification to be assembled, other
Part is identical as experimental group.
Embodiment 3
Selected inorganic matter is lithium fluoride.Remaining is same as Example 1.
Embodiment 4
Selected organic matter is melamine.Remaining is same as Example 1.
Embodiment 5
Selected organic matter is polyacrylamide.Remaining is same as Example 1.
Embodiment 6
By silicon carbide/polypropylene nitrile, lithium nitrate, acrylonitrile copolymer with the mass ratio of 8:1:1, take water as a solvent uniformly mixed
Slurry is made in conjunction, is coated in copper foil current collector, and coating layer thickness is 10 μm.After the solvent is volatilized, by copper foil punching at diameter 16mm
Pole piece.By pole piece, diaphragm, lithium metal is assembled into button cell in the glove box that argon gas is protected, and adding concentration is 1M six
The ethylene carbonate and diethyl carbonate (volume ratio 1:1) electrolyte of lithium fluophosphate.
By the button cell assembled in aforementioned manners in 0.5mA/cm2Current density under discharge 20h, make collection liquid surface
Deposit 10mAh/cm2Lithium metal.After discharge off, above-mentioned button cell is dismantled, takes out the collector that deposited lithium metal.
Selection positive electrode is LiFePO4, and the lithium an- ode with composite membrane that cathode is assembles and helps electricity
Pond, and add ethylene carbonate and diethyl carbonate (volume ratio 1:1) electrolyte that concentration is 1M lithium hexafluoro phosphate.
The lithium metal full battery of above-mentioned assembling is subjected to loop test, charge-discharge magnification 0.5C is illustrated in figure 3 full electricity
Pond test circulation volume figure, can stable circulation be more than 400 times and keep high capacity retention ratio, illustrate that it can be protected
Hold long cycle life.
Embodiment 7
Selected positive electrode is cobalt acid lithium.Remaining is same as Example 6.
Embodiment 8
Selected positive electrode is nickel-cobalt-manganese ternary material.Remaining is same as Example 6.
Embodiment 9
By silicon carbide/polypropylene nitrile, lithium nitrate, acrylonitrile copolymer with the mass ratio of 8:1:1, take water as a solvent uniformly mixed
Slurry is made in conjunction, is coated in copper foil current collector, and coating layer thickness is 10 μm.After the solvent is volatilized, by copper foil punching at diameter 16mm
Pole piece.By pole piece, diaphragm, lithium metal is assembled into button cell in the glove box that argon gas is protected, and adding concentration is 1M six
The ethylene carbonate and diethyl carbonate (volume ratio 1:1) electrolyte of lithium fluophosphate.
By the button cell assembled in aforementioned manners in 0.5mA/cm2Current density under discharge 20h, make collection liquid surface
Deposit 10mAh/cm2Lithium metal.After discharge off, above-mentioned button cell is dismantled, takes out the collector that deposited lithium metal.
Selecting positive electrode is sulphur anode, and the lithium an- ode with composite membrane that cathode is is assembled into full battery,
And add ethylene carbonate and diethyl carbonate (volume ratio 1:1) electrolyte that concentration is 1M lithium hexafluoro phosphate.
The lithium metal full battery of above-mentioned assembling is subjected to loop test, charge-discharge magnification 0.5C is illustrated in figure 4 full electricity
Pond test circulation volume figure, can stable circulation be more than 400 times and keep high capacity retention ratio, illustrate that it can be protected
Hold long cycle life.
In Fig. 4, blank group uses the copper foil current collector for not carrying out any modification to deposit what same amount of lithium was assembled
Lithium-sulfur cell, other conditions are identical as experimental group.
Embodiment 10
Designed coating (coating the composite membrane of formation) is with a thickness of 10 μm, 50 μm and 100 μm, in 0.5mA/cm2's
Discharge 20h under current density, and collection liquid surface is made to deposit 10mAh/cm2Lithium metal, the lithium of corresponding deposition with a thickness of 50 μm,
Remaining test condition is same as Example 2.
Suitably the thickness of composite membrane and lithium metal plays the role of the deposition of lithium vital, as shown in figure 5, different
Composite film thickness under different current densities have different coulombic efficiencies, it is 50 μ m-thicks that wherein coulombic efficiency is highest
Composite layer is 2mA/cm in current density2, capacity 1mAh/cm299.7% corresponding to lower.
Embodiment 11
Designed coating (coating the composite membrane of formation) thickness is fixed as 50 μm, respectively to it in 0.5mA/cm2's
Discharge 20h, 40h and 80h under current density, and collection liquid surface deposition is made to correspond to 10mAh/cm2, 20mAh/cm2, 40mAh/cm2
Lithium metal, the lithium thickness of corresponding deposition is respectively 50 μm, 100 μm and 200 μm, and by pole piece, diaphragm, lithium metal is in argon gas guarantor
Lithium lithium Symmetrical cells (lithium piece that positive and negative anodes use same deposition condition) is assembled into the glove box of shield, and adding concentration is 1M six
The ethylene carbonate and diethyl carbonate (volume ratio 1:1) electrolyte of lithium fluophosphate.
Suitably the thickness of composite membrane and lithium metal plays the role of the deposition of lithium vital, as shown in fig. 6, different
Lithium deposition thickness in lithium lithium Symmetrical cells have the different stabilization time, it is that deposited 100 μm that wherein stability is highest
Thick lithium piece is stablized circulation and has been reached 400 hours.
Through the foregoing embodiment, it is not difficult to find out that, the lithium an- ode with composite membrane obtained, such as embodiment in the present invention
Shown in 1 Fig. 1, lithium is uniformly deposited on the surface of collector, it is seen then that the collector modified by cladding process is in deposited metal lithium
When can play the role of adjust lithium deposition morphology, be uniformly distributed lithium on a current collector.As shown in Fig. 2 of embodiment 2, with this
The lithium an- ode of invention the method preparation can be in 1mA/cm2Current density under, the stabilization charge and discharge more than 100 times follow
Ring is still able to maintain efficient coulombic efficiency.As shown in Fig. 3 of embodiment 6, with the lithium with composite protection film of the method preparation
Metal negative electrode can be stablized applied to lithium-LiFePO4 circulates beyond 400 circles.As shown in Fig. 4 of embodiment 9, with the method system
The standby lithium an- ode with composite protection film is applied to stabilization in lithium-sulphur full battery and circulates beyond 400 circles, and blank group exists
Just decaying rapidly after 50 circle of circulation.The film thickness of different composite film is of crucial importance final coulombic efficiency, and
The obtained coulombic efficiency of different current densities is also different；As shown in 10 Fig. 5 of embodiment, different film thicknesses is to final
Coulombic efficiency be of crucial importance, furthermore from the embodiment 10 as can be seen that different current density is obtained
Coulombic efficiency is also different.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the lithium an- ode material with composite membrane, which comprises the following steps:
(1) organic component and inorganic lithium compound component are matched into composite load on a current collector by the mass ratio of 1:1~98:1,
To form composite membrane in the collection liquid surface；
(2) surface that the step (1) obtains is covered with the collector of composite membrane and lithium piece is assembled into battery and carries out electrochemistry
Deposition, makes lithium metal be deposited on the surface and is covered on the collector of composite membrane, thus obtain the lithium an- ode with composite membrane
Material.
2. the preparation method of the lithium an- ode material with composite membrane as described in claim 1, which is characterized in that the step
(1) it is specifically that first organic component and inorganic lithium compound component are dissolved in solvent, forms slurry, then the slurry is coated in
On collector, after the solvent is volatilized, composite membrane can be formed in the collection liquid surface；
Wherein, the solvent is water, N-Methyl pyrrolidone, tetrahydrofuran, n,N-Dimethylformamide, dimethyl sulfoxide, chlorine
Change one or more of sulfoxide, chloroform, toluene.
3. the preparation method of the lithium an- ode material with composite membrane as described in claim 1, which is characterized in that the step
(1) in, the composite membrane with a thickness of 5 μm~100 μm, preferably 20~50 μm；
In the step (2), current density size used in the electrochemical deposition is 0.1~5mA/cm2, preferably 1mA/
cm2；The time of the electrochemical deposition is 0.5~500 hour, preferably 10 hours；Deposit obtain lithium metal with a thickness of 5
~500 μm, preferably 20~100 μm；The face amount for depositing obtained lithium metal is 0.5~100mAh/cm2, preferably
10mAh/cm2。
4. the preparation method of the lithium an- ode material with composite membrane as described in claim 1, which is characterized in that the step
(1) in, the organic component is silicon carbide/polypropylene nitrile, polyamide, polyethylene glycol oxide, carbonization amino acid, polyaniline, polyacrylamide
One or more of amine, polyacrylic acid, nitrogen-doped graphene, melamine, polypyrrole；
The inorganic lithium compound component be lithium nitrate, lithium nitrite, lithium sulfide, lithium nitride, lithia, lithium fluoride, lithium chloride,
One or more of lithium bromide, lithium iodide, lithium carbonate, lithium hydroxide, lithium metasilicate, lithium sulfate.
5. the preparation method of the lithium an- ode material with composite membrane as described in claim 1, which is characterized in that the step
It (1) further include adhesive component in the composite membrane in, the adhesive component is polyacrylic acid, butadiene-styrene rubber, carboxymethyl fibre
Tie up one or more of element, acrylonitrile copolymer, Kynoar, polytetrafluoroethylene (PTFE)；
Also, in the composite membrane, the mass ratio of organic component, inorganic lithium compound component and adhesive component three meets
1:1:1~98:1:1, preferably 8:1:1.
6. the preparation method of the lithium an- ode material with composite membrane as claimed in claim 4, which is characterized in that the step
(1) in, the organic component is silicon carbide/polypropylene nitrile, and the inorganic lithium compound component is lithium nitrate, the adhesive component
For acrylonitrile copolymer.
7. the preparation method of the lithium an- ode material with composite membrane as described in claim 1, which is characterized in that the step
(1) in, the collector is one of copper foil, copper mesh, copper foam frame, carbon paper, carbon fiber frame, goldleaf, silver foil or several
Kind.
8. the lithium an- ode with composite membrane being prepared using the preparation method as described in claim 1-7 any one
Material is improving the application in lithium metal battery cycle life as the cathode in lithium metal battery.
9. a kind of lithium metal secondary cell, including positive electrode, negative electrode material, diaphragm and electrolyte, which is characterized in that described negative
Pole material is the lithium an- ode material with composite membrane being prepared using such as claim 1-7 any one preparation method
Material.
10. lithium metal secondary cell as claimed in claim 9, which is characterized in that the positive electrode is LiFePO4, cobalt acid
Lithium, lithium titanate, nickel-cobalt-manganese ternary material, nickel cobalt aluminium ternary material, sulphur simple substance positive electrode, sulfide polymer positive electrode, sky
One or more of gas positive electrode；
The diaphragm is selected from PP diaphragm, PE diaphragm, PP/PE/PP diaphragm, Al2O3Coated separator, fibreglass diaphragm, PVDF every
Film, PET/Al2O3One or more of diaphragm, cellulosic separator, aramid fiber diaphragm；
The electrolyte is selected from ethers electrolyte, esters electrolyte, ether-ether mixed electrolytic solution, ionic liquid class electrolyte, gel
One or more of electrolyte, solid electrolyte.
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