CN110071284A - The guard method of metal lithium electrode - Google Patents
The guard method of metal lithium electrode Download PDFInfo
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- CN110071284A CN110071284A CN201910155722.7A CN201910155722A CN110071284A CN 110071284 A CN110071284 A CN 110071284A CN 201910155722 A CN201910155722 A CN 201910155722A CN 110071284 A CN110071284 A CN 110071284A
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- lithium
- metal
- antimony trifluoride
- antimony
- piece
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of guard methods of metal lithium electrode, using a kind of simple alloyage, form one layer of artificial protective film on cathode of lithium surface using antimony trifluoride, can effectively reduce the polarization of cathode of lithium and the generation of dendrite inhibition.This method mainly utilizes antimony trifluoride to react with lithium and generates one layer of fine and close artificial protective film; first antimony trifluoride is dissolved in propene carbonate, uniform solution is made; pretreatment is carried out to lithium piece surface and removes the lithium that surface is oxidized; it is cut into disk; gained disk is immersed into the lithium electrode that obtains that treated of reaction in antimony trifluoride solution, is finally assembled into Symmetrical cells.The present invention is reacted for a long time by low concentration can be in the alloy-layer of lithium metal Surface Creation densification.The present invention sufficiently reduces the polarization of lithium an- ode, good cycling stability, and the generation of Li dendrite has obtained effective inhibition, obtain stable lithium an- ode, apply in lithium battery, lithium battery cycle performance and security performance can be improved, there is potential commercial applications value.
Description
Technical field
The present invention relates to a kind of preparation methods of lithium ion battery, more particularly to a kind of system of the electrode of lithium ion battery
Preparation Method and maintaining method are applied to technical field of lithium ion.
Background technique
In recent years, the continuous consumption of fossil energy and its derivative problem of environmental pollution are increasingly subject to the attention of people.For
The alleviation above problem, the renewable and clean energy resources such as the solar energy of the traditional energies such as Substitute coal, petroleum, natural gas and wind energy
Exploitation and effective use have become important research topic, and the growth momentum of New Energy Industry is also increasingly powerful.But solar energy
There are intermittent features with the new energy such as wind energy, and continual and steady energy supply can not be provided for power grid.Due to high energy
The advantages that metric density and stable cycle performance, in addition to being widely used in the fields such as mobile phone, laptop, electric car,
Lithium ion battery also has potential application prospect in terms of the intermittent new energy of storage solar energy and wind energy etc..
Along with gradually popularizing for hybrid vehicle in global range and electric car, charge-discharge type lithium battery is also gradually
It is deep into daily life.However, even if the energy density of lithium-ion battery systems has passed through modular battery
Each component such as electrode material, electrolyte, collector is optimized, and close to its theoretical value, but it is still unable to satisfy people
Demand to high-capacity lithium ion cell of new generation.One of the main reason for causing this embarrassment is that battery charging and discharging recycles
When single ion intercalation seriously limit the capacity of the anode containing lithium.The demand of the electric energy storage device of high-energy density makes
Researchers have turned one's attention to lithium an- ode.
Current commercialized negative electrode of lithium ion battery is graphitized carbon.Compared to traditional graphite cathode, lithium an- ode
Possess high energy density, 3800mAh/g, lower current potential, -3.045V.But lithium an- ode is fatal there is also one
The generation of problem-Li dendrite, lithium ion are easy during cathode of lithium surface is precipitated and deposits in cathode of lithium Surface Creation
The same dendrite of nano wire causes the short circuit of battery even to be exploded.How to inhibit the generation of Li dendrite, realizes to lithium an- ode
Effective protection, be one of key technology.Principal investigators mainly pass through the optimization of electrolyte and improvement, gold both at home and abroad at present
Belong to the means such as the surface modification of cathode of lithium to realize the protection of lithium an- ode.The optimization of electrolyte mainly enters in terms of additive
Hand, the use of additive greatly optimize the uniformity and stability of lithium anode SEI film, and additive mainly includes 2- first
Base furans, CO2、SO2And N2O gas molecule, VC and fluorochemical etc..The surface modification of lithium anode then relates generally to
Artificial SEI film and interface nano modification.Interface nano modification process is complicated, is only limitted to laboratory stage, does not industrialize
Basis.Linda F.Nazar discovery forms one layer of lithium fluoride and alloying substance, the production of Li dendrite on lithium surface using noble metal indium
Raw the phenomenon that being effectively suppressed, significantly improving for lithium battery stability, but higher cost may be implemented, it is not economical enough.Therefore,
Seeking safeguard measure more efficient to lithium an- ode, that process is simpler is particularly important, and becomes skill urgently to be resolved
Art problem.
Summary of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
The guard method of metal lithium electrode is able to achieve the protection of simply and effectively lithium an- ode, passes through lithium metal and antimony trifluoride
(SbF3) reaction method utilize cheap metal pentafluoride in a kind of alloy of lithium an- ode Surface Creation and lithium fluoride
Object antimony trifluoride prevents the generation of cathode of lithium dendrite, it is possible to reduce polarization brought by cathode of lithium, present invention process process letter
Single, effect is obvious, low in cost, it is easy to accomplish industrialization is expected to realize the practical application of cathode of lithium.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of guard method of metal lithium electrode, with the antimony trifluoride solution of low concentration and the gold on metal lithium electrode surface layer
Belong to lithium reaction, generate lithium antimony alloy and lithium fluoride, to form one layer of fine and close lithium antimony alloy and fluorine on metal lithium electrode surface
Change the composite protection layer of lithium, wherein the concentration of the antimony trifluoride in antimony trifluoride solution is 0.05~0.2 mole every liter.
As currently preferred technical solution, the guard method of metal lithium electrode includes the following steps:
A. the antimony trifluoride for weighing 53.6-107.2 milligrams is poured into 20 milliliters of vials with cover, and is added with liquid-transfering gun
3-6 milliliters of propene carbonate dissolves antimony trifluoride sufficiently in propene carbonate, obtains antimony trifluoride as solvent, stirring
Solution, it is spare；
B. disc-shaped lithium piece is prepared, control lithium piece diameter is not more than 12 millimeters, and lithium piece thickness is spare not higher than 0.2 millimeter；
C. the lithium piece in the b is pressed in stainless steel gasket, makes lithium piece and the abundant adhesion of stainless steel gasket and be bonded；
D. the lithium piece handled well in the c is placed in vial used in the step a together with stainless steel gasket
In, in the antimony trifluoride solution that is immersed in lithium piece in vial, carrying out 3~6 points of surface modification reaction of lithium anode
Zhong Hou, then lithium piece is taken out from antimony trifluoride solution, then lithium piece solution remained on surface is cleaned out with blotting paper, from
And obtain the metal lithium electrode with the composite protection layer of lithium antimony alloy and lithium fluoride.
As currently preferred technical solution, use the concentration of antimony trifluoride molten for 0.1 mole every liter of antimony trifluoride
Liquid carries out the surface modification reaction of lithium anode with the lithium metal on metal lithium electrode surface layer as reaction solution.
As currently preferred technical solution, selects at least one lithium salts to be dissolved in organic solvent, match preparing lithium ion
Electrolyte is assembled into lithium metal using the metal lithium electrode with lithium antimony alloy and the composite protection layer of lithium fluoride as cathode
The assembling process of Symmetrical cells, battery carries out under ar gas environment, and controls water < 0.01ppm in argon ambient atmosphere environment,
Oxygen < 0.01ppm.
As currently preferred technical solution, in lithium-ion electrolyte process for preparation, the lithium salts of selection is two (trifluoros
Sulfonyloxy methyl) imine lithium (LiTFSI) or lithium hexafluoro phosphate (LiPF6), the lithium concentration of electrolyte is not less than 1.0 moles
Every liter.
As currently preferred technical solution, in lithium-ion electrolyte process for preparation, the lithium in lithium-ion electrolyte
Lithium nitrate is continuously added on the basis of salt, makes the nitric acid lithium concentration of lithium-ion electrolyte not less than 0.01 mole every liter.
As currently preferred technical solution, in lithium-ion electrolyte process for preparation, organic mixed solvent is volume
Than the 1,3-dioxolane (DOL) and glycol dimethyl ether (DME) mixed solution for 1:1, or the carbonic acid for being 1:1 for volume ratio
The mixed solution of vinyl acetate (EC) and diethyl carbonate (DEC).
As currently preferred technical solution, in lithium metal Symmetrical cells assembling process, using film empty more than polypropylene
For diaphragm.
As currently preferred technical solution, the overall process for implementing the guard method of metal lithium electrode is all filled in argon gas
Glove box in carry out.
The guard method of lithium an- ode of the present invention forms protective layer on lithium an- ode surface.Weigh a certain amount of trifluoro
Change antimony, pour into vial with cover, a certain amount of propene carbonate is added, stirring dissolves antimony trifluoride sufficiently.Take 15.6 millimeters
The lithium piece of diameter is pressed into the sheet that thickness is about 0.2 mm of thickness, is cut into the disk that diameter is 12 millimeters.It will treated lithium
Piece is gently pressed in stainless steel gasket, makes lithium piece and the abundant adhesion of stainless steel gasket.Will treated lithium piece together with stainless steel pad
Piece is gently put into vial, in the antimony trifluoride solution for being immersed in lithium piece in vial, is taken after reacting a period of time
Out, with blotting paper that the processing of its surface solution is clean.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage:
1. the method for the present invention, which is reacted using antimony trifluoride with lithium metal, generates one layer of fine and close lithium antimony alloy and layer of lithium fluoride
It is placed in cathode of lithium surface, facilitates the uniform abjection and deposition of lithium ion, the generation of Li dendrite is prevented, to improve lithium battery
With stability and security performance；
2. the method for the present invention utilizes a kind of cheap metal fluoride antimony trifluoride (SbF3) prevent cathode of lithium branch
Brilliant generation, the experimentation is simple, and effect is obvious, it is possible to reduce polarization brought by cathode of lithium is expected to realize cathode of lithium
Practical application；
3. the method for the present invention also improves the bulk life time and quality of battery while improving the battery electrode service life；
4. the key of the method for the present invention is to react to cause at one layer of lithium metal Surface Creation for a long time by low concentration
Close lithium antimony alloy and layer of lithium fluoride.By electro-chemical test it is found that the method for the present invention can sufficiently reduce lithium an- ode
Polarization, is reduced to 50 millivolts in the charge and discharge every square centimeter after-polarization in 1 hour of 1 milliampere hour, good cycling stability shows Li dendrite
Generation obtained effective inhibition, obtain stable lithium an- ode, apply in lithium battery, the circulation of lithium battery can be improved
Performance and security performance have potential commercial applications value.
Detailed description of the invention
Fig. 1 is the lithium piece that uses of the present invention and treated lithium piece and the symmetrical button cell comparison diagram that finally assembles,
In figure a be lithium piece, figure b is the obtained lithium piece after the processing of the surface modification reaction of lithium anode, and figure c is final assembling
Symmetrical button cell.
Fig. 2 is the compound of the lithium antimony alloy for preparing and lithium fluoride after the lithium piece of the embodiment of the present invention one is reacted with antimony trifluoride
The x-ray diffractogram of powder of protective layer.
Fig. 3 is the chemical property curve for the lithium metal Symmetrical cells that the embodiment of the present invention one assembles.
Fig. 4 is the chemical property curve for the lithium metal Symmetrical cells that the embodiment of the present invention two assembles.
Fig. 5 is the chemical property curve for the lithium metal Symmetrical cells that the embodiment of the present invention three assembles.
Fig. 6 is the chemical property curve for the lithium metal Symmetrical cells that the embodiment of the present invention four assembles.
Fig. 7 is the chemical property curve for the lithium metal Symmetrical cells that the embodiment of the present invention five assembles.
Specific embodiment
Above scheme is described further below in conjunction with specific implementation example, the preferred embodiment of the present invention is described in detail such as
Under:
Embodiment one:
In the present embodiment, referring to FIG. 1 to FIG. 3, a kind of guard method of metal lithium electrode includes the following steps:
A. the antimony trifluoride for weighing 53.6 milligrams pours into 20 milliliters of vials with cover, and is added 3 milliliters with liquid-transfering gun
As solvent, stirring dissolves antimony trifluoride sufficiently in propene carbonate, obtains antimony trifluoride solution propene carbonate, standby
With；
B. the lithium piece for taking 15.6 mm dias is pressed into smooth cylinder with a thickness of the sheet of 0.2 mm of thickness, then
It is cut into the disk that diameter is 12 millimeters with mold, it is spare；
C. the lithium piece in the b is pressed in stainless steel gasket, makes lithium piece and the abundant adhesion of stainless steel gasket and be bonded；
D. the lithium piece handled well in the c is placed in vial used in the step a together with stainless steel gasket
In, in the antimony trifluoride solution that is immersed in lithium piece in vial, carrying out surface modification reaction 5 minutes of lithium anode
Afterwards, then by lithium piece it takes out from antimony trifluoride solution, is then cleaned out lithium piece solution remained on surface with blotting paper, thus
Obtain the metal lithium electrode with the composite protection layer of lithium antimony alloy and lithium fluoride；
E. the metal lithium electrode prepared in the d is put into CR2032 battery case, the more empty films of selection polypropylene are
Diaphragm, two (trimethyl fluoride sulfonyl) imine lithiums (LiTFSI) of 1 mole every liter of electrolyte selection are dissolved in 1 that volume ratio is 1:1,
In 3- dioxolanes (DOL)/glycol dimethyl ether (DME) mixed solution, while lithium nitrate is added, makes prepared lithium-ion electric
The nitric acid lithium concentration for solving liquid is 0.01 mole every liter.The present embodiment selects lithium salts to be dissolved in organic solvent, prepares lithium-ion electric
It solves liquid and is assembled into lithium metal pair using the metal lithium electrode with lithium antimony alloy and the composite protection layer of lithium fluoride as cathode
Claim battery, the assembling process of battery carries out under ar gas environment, and controls water < 0.01ppm in argon ambient atmosphere environment, oxygen
<0.01ppm。
Experimental test and analysis:
The lithium piece use to the present embodiment method and treated lithium piece and the symmetrical button cell finally assembled are referring to figure
1, figure a therein are lithium piece, and figure b is the lithium piece obtained after the processing of the surface modification reaction of lithium anode, and figure c is final
The symmetrical button cell of assembling.The lithium antimony alloy and lithium fluoride prepared after being reacted with antimony trifluoride the lithium piece of the present embodiment method
Composite protection layer powder carry out x-ray diffraction experiment analysis contain respectively in artificial protective film as shown in Figure 2 referring to fig. 2
LiF and Li3Sb.Electrochemical property test is carried out to the lithium metal Symmetrical cells of the present embodiment method assembling, obtains lithium metal pair
Claim the chemical property curve of battery, test condition is selected with 1mA/cm-2Current density charge and discharge 1 hour, referring to Fig. 3, by Fig. 3
Know electricity during recycling after-polarization in 600 hours still less than 100mV and being can be found that by illustration in constant current charge-discharge
Pressure is constantly in steady state, shows that the generation of Li dendrite has obtained effective inhibition in charge and discharge process.The present embodiment utilizes
The antimony trifluoride solution of low concentration is reacted with the lithium metal on metal lithium electrode surface layer, generates lithium antimony alloy and lithium fluoride, thus
Metal lithium electrode surface forms the composite protection layer of one layer of fine and close lithium antimony alloy and lithium fluoride.The present embodiment is simple using one kind
Alloyage, utilize antimony trifluoride (SbF3) on cathode of lithium surface a kind of alloy and lithium fluoride substance are formed, it can be effectively reduced
The polarization of cathode of lithium and the generation of dendrite inhibition.The present embodiment method mainly utilizes antimony trifluoride to react one layer of cause of generation with lithium
Close alloy and lithium fluoride protective layer, main method are as follows: antimony trifluoride is dissolved in propene carbonate is made uniform molten first
Liquid.Pretreatment is carried out to lithium piece surface and removes the lithium that surface is oxidized, 12 millimeters of diameter of disk is cut into, gained disk is immersed
The reaction lithium electrode that obtains that treated, is finally assembled into Symmetrical cells in antimony trifluoride solution.The key of this method is by low
Concentration is reacted for a long time can be in one layer of lithium metal Surface Creation fine and close alloy and layer of lithium fluoride.It can by electro-chemical test
Know, this method can sufficiently reduce the polarization of lithium an- ode, drop in the charge and discharge every square centimeter after-polarization in 1 hour of 1 milliampere hour
Down to 50 millivolts, good cycling stability shows that the generation of Li dendrite has obtained effective inhibition, obtains stable lithium an- ode,
Apply in lithium battery, the cycle performance and security performance of lithium battery can be improved, there is potential commercial applications value.
Embodiment two:
The present embodiment is basically the same as the first embodiment, and is particular in that:
In the present embodiment, referring to fig. 4, a kind of guard method of metal lithium electrode, includes the following steps:
A. the antimony trifluoride for weighing 107.2 milligrams pours into 20 milliliters of vials with cover, and is added 6 milliliters with liquid-transfering gun
Propene carbonate as solvent, stirring dissolves antimony trifluoride sufficiently in propene carbonate, obtains antimony trifluoride solution, standby
With；
B. the lithium piece for taking 15.6 mm dias is pressed into smooth cylinder with a thickness of the sheet of 0.2 mm of thickness, then
It is cut into the disk that diameter is 12 millimeters with mold, it is spare；
C. the lithium piece in the b is pressed in stainless steel gasket, makes lithium piece and the abundant adhesion of stainless steel gasket and be bonded；
D. the lithium piece handled well in the c is placed in vial used in the step a together with stainless steel gasket
In, in the antimony trifluoride solution that is immersed in lithium piece in vial, carrying out surface modification reaction 5 minutes of lithium anode
Afterwards, then by lithium piece it takes out from antimony trifluoride solution, is then cleaned out lithium piece solution remained on surface with blotting paper, thus
Obtain the metal lithium electrode with the composite protection layer of lithium antimony alloy and lithium fluoride；
E. the metal lithium electrode prepared in the d is put into CR2032 battery case, the more empty films of selection polypropylene are
Diaphragm, two (trimethyl fluoride sulfonyl) imine lithiums (LiTFSI) that electrolyte selection concentration is 1 mole every liter are dissolved in volume ratio and are
In the 1,3- dioxolanes (DOL) of 1:1/glycol dimethyl ether (DME) mixed solution.It is organic that the present embodiment selects lithium salts to be dissolved in
In solvent, prepare lithium-ion electrolyte, using the metal lithium electrode with lithium antimony alloy and the composite protection layer of lithium fluoride as bear
Pole is assembled into lithium metal Symmetrical cells, and the assembling process of battery carries out under ar gas environment, and controls argon ambient atmosphere ring
Water < 0.01ppm in border, oxygen < 0.01ppm.
Experimental test and analysis:
Electrochemical property test is carried out to the lithium metal Symmetrical cells of the present embodiment method assembling, it is symmetrically electric to obtain lithium metal
The chemical property curve in pond, test condition are selected with 1mA/cm-2Current density charge and discharge 1 hour, referring to fig. 4, as shown in Figure 4
The voltage one during recycling after-polarization in 140 hours still less than 100mV and being can be found that by illustration in constant current charge-discharge
It is directly in steady state, shows that the generation of Li dendrite has obtained effective inhibition in charge and discharge process.The present embodiment utilizes low dense
The antimony trifluoride solution of degree is reacted with the lithium metal on metal lithium electrode surface layer, generates lithium antimony alloy and lithium fluoride, thus in lithium gold
Belong to electrode surface and forms one layer of fine and close lithium antimony and lithium fluoride protective layer.The present embodiment utilizes a kind of simple solvent reaction method,
Utilize antimony trifluoride (SbF3) in cathode of lithium surface formation alloy and lithium fluoride, the polarization and suppression of cathode of lithium can be effectively reduced
The generation of dendrite processed.The present embodiment method mainly utilizes antimony trifluoride to react with lithium and generates one layer of fine and close alloy protecting layer, main
Want method are as follows: antimony trifluoride is dissolved in propene carbonate uniform solution is made first.Pretreatment is carried out to lithium piece surface to remove
The lithium that surface is oxidized is removed, 12 millimeters of diameter of disk is cut into, gained disk is immersed and reacts everywhere in antimony trifluoride solution
Lithium electrode after reason, is finally assembled into Symmetrical cells.The key of this method is that reacted for a long time by low concentration can be in lithium
Metal surface generates one layer of fine and close alloy-layer.By electro-chemical test it is found that this method can sufficiently reduce lithium an- ode
Polarization, be reduced to 50 millivolts in the charge and discharge every square centimeter after-polarization in 1 hour of 1 milliampere hour, good cycling stability shows lithium branch
Brilliant generation has obtained effective inhibition, obtains stable lithium an- ode, applies in lithium battery, following for lithium battery can be improved
Ring performance and security performance have potential commercial applications value.
Embodiment three:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, referring to Fig. 5, a kind of guard method of metal lithium electrode includes the following steps:
A. the antimony trifluoride for weighing 53.6 milligrams pours into 20 milliliters of vials with cover, and is added 3 milliliters with liquid-transfering gun
As solvent, stirring dissolves antimony trifluoride sufficiently in propene carbonate, obtains antimony trifluoride solution propene carbonate, standby
With；
B. the lithium piece for taking 15.6 mm dias is pressed into smooth cylinder with a thickness of the sheet of 0.2 mm of thickness, then
It is cut into the disk that diameter is 12 millimeters with mold, it is spare；
C. the lithium piece in the b is pressed in stainless steel gasket, makes lithium piece and the abundant adhesion of stainless steel gasket and be bonded；
D. the lithium piece handled well in the c is placed in vial used in the step a together with stainless steel gasket
In, in the antimony trifluoride solution that is immersed in lithium piece in vial, carrying out surface modification reaction 5 minutes of lithium anode
Afterwards, then by lithium piece it takes out from antimony trifluoride solution, is then cleaned out lithium piece solution remained on surface with blotting paper, thus
Obtain the metal lithium electrode with the composite protection layer of lithium antimony alloy and lithium fluoride；
E. the metal lithium electrode prepared in the d is put into CR2032 battery case, the more empty films of selection polypropylene are
Diaphragm, two (trimethyl fluoride sulfonyl) imine lithiums (LiTFSI) that electrolyte selection concentration is 1 mole every liter are dissolved in volume ratio and are
In the 1,3-dioxolane (DOL) of 1:1/glycol dimethyl ether (DME) mixed solution, while lithium nitrate is added, makes prepared
The nitric acid lithium concentration of lithium-ion electrolyte is 0.01 mole every liter.The present embodiment selects lithium salts to be dissolved in organic solvent, prepares
Lithium-ion electrolyte is assembled into using the metal lithium electrode with lithium antimony alloy and the composite protection layer of lithium fluoride as cathode
The assembling process of lithium metal Symmetrical cells, battery carries out under ar gas environment, and control the water in argon ambient atmosphere environment <
0.01ppm, oxygen < 0.01ppm.
Experimental test and analysis:
Electrochemical property test is carried out to the lithium metal Symmetrical cells of the present embodiment method assembling, it is symmetrically electric to obtain lithium metal
The chemical property curve in pond, test condition are selected with 0.25mA/cm-2、0.5mA/cm-2、0.75mA/cm-2、1mA/cm-2、
1.5mA/cm-2Each charge and discharge of current density 1 hour test chemical property, referring to Fig. 5, as shown in Figure 5 in different current densities
Treated down, and lithium piece shows stability.Antimony trifluoride solution and metal lithium electrode surface layer of the present embodiment using low concentration
Lithium metal reaction, lithium antimony alloy and lithium fluoride are generated, to form one layer of fine and close lithium antimony alloy on metal lithium electrode surface
With the composite protection layer of lithium fluoride.The present embodiment utilizes a kind of simple solvent reaction method, utilizes antimony trifluoride (SbF3) in lithium
Negative terminal surface forms lithium antimony alloy and lithium fluoride, and the polarization of cathode of lithium and the generation of dendrite inhibition can be effectively reduced.This reality
Applying a method mainly utilizes antimony trifluoride to react one layer of fine and close alloy of generation and lithium fluoride protective layer, main method with lithium are as follows:
Antimony trifluoride is dissolved in propene carbonate first, uniform solution is made.Pretreatment is carried out to lithium piece surface and removes surface by oxygen
The lithium of change is cut into 12 millimeters of diameter of disk, and gained disk is immersed the lithium electricity that obtains that treated of reaction in antimony trifluoride solution
Pole is finally assembled into Symmetrical cells.The key of this method is to react to give birth on lithium metal surface for a long time by low concentration
At one layer of fine and close alloy and layer of lithium fluoride.By electro-chemical test it is found that this method can sufficiently reduce lithium an- ode
Polarization, is reduced to 50 millivolts in the charge and discharge every square centimeter after-polarization in 1 hour of 1 milliampere hour, good cycling stability shows Li dendrite
Generation obtained effective inhibition, obtain stable lithium an- ode, apply in lithium battery, the circulation of lithium battery can be improved
Performance and security performance have potential commercial applications value.
Example IV:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, referring to Fig. 6, a kind of guard method of metal lithium electrode includes the following steps:
A. the antimony trifluoride for weighing 53.6 milligrams pours into 20 milliliters of vials with cover, and is added 3 milliliters with liquid-transfering gun
As solvent, stirring dissolves antimony trifluoride sufficiently in propene carbonate, obtains antimony trifluoride solution propene carbonate, standby
With；
B. the lithium piece for taking 15.6 mm dias is pressed into smooth cylinder with a thickness of the sheet of 0.2 mm of thickness, then
It is cut into the disk that diameter is 12 millimeters with mold, it is spare；
C. the lithium piece in the b is pressed in stainless steel gasket, makes lithium piece and the abundant adhesion of stainless steel gasket and be bonded；
D. the lithium piece handled well in the c is placed in vial used in the step a together with stainless steel gasket
In, in the antimony trifluoride solution that is immersed in lithium piece in vial, carrying out surface modification reaction 5 minutes of lithium anode
Afterwards, then by lithium piece it takes out from antimony trifluoride solution, is then cleaned out lithium piece solution remained on surface with blotting paper, thus
Obtain the metal lithium electrode with the composite protection layer of lithium antimony alloy and lithium fluoride；
E. the metal lithium electrode prepared in the d is put into CR2032 battery case, the more empty films of selection polypropylene are
Diaphragm, it is 1 mole every liter of lithium hexafluoro phosphate (LiPF that electrolyte, which selects concentration,6) it is dissolved in the ethylene carbonate that volume ratio is 1:1
In ester (EC), diethyl carbonate (DEC) mixed solution.The present embodiment selects lithium salts to be dissolved in organic solvent, matches preparing lithium ion
Electrolyte is assembled into lithium metal using the metal lithium electrode with lithium antimony alloy and the composite protection layer of lithium fluoride as cathode
The assembling process of Symmetrical cells, battery carries out under ar gas environment, and controls water < 0.01ppm in argon ambient atmosphere environment,
Oxygen < 0.01ppm.
Experimental test and analysis:
Electrochemical property test is carried out to the lithium metal Symmetrical cells of the present embodiment method assembling, it is symmetrically electric to obtain lithium metal
The chemical property curve in pond, test condition are selected with 0.5mA/cm-2Current density charge and discharge 0.5 hour, test electrochemistry
Can, referring to Fig. 6, as shown in Figure 6 in industrialized esters electrolyte, so there is lower polarization recycling 250 hours successors,
By illustration it can be seen that during constant current charge-discharge voltage maintain always steady state illustrate Li dendrite generation to
Effectively inhibit.The present embodiment is reacted using the antimony trifluoride solution of low concentration with the lithium metal on metal lithium electrode surface layer, and lithium is generated
Antimony alloy and lithium fluoride, to form the complex protection of one layer of fine and close lithium antimony alloy and lithium fluoride on metal lithium electrode surface
Layer.The present embodiment utilizes a kind of simple solvent reaction method, utilizes antimony trifluoride (SbF3) closed in cathode of lithium surface formation lithium antimony
The compound of gold and lithium fluoride, can be effectively reduced the polarization of cathode of lithium and the generation of dendrite inhibition.The present embodiment method master
It to be reacted using antimony trifluoride with lithium and generate one layer of fine and close lithium antimony alloy and lithium fluoride composite protection layer, main method are as follows: is first
First antimony trifluoride is dissolved in propene carbonate, uniform solution is made.Pretreatment removing surface is carried out to lithium piece surface to be oxidized
Lithium, be cut into 12 millimeters of diameter of disk, gained disk immersed into the lithium electrode that obtains that treated of reaction in antimony trifluoride solution,
Finally it is assembled into Symmetrical cells.The key of this method is that reacted for a long time by low concentration can be in lithium metal Surface Creation one
Layer fine and close lithium antimony alloy and layer of lithium fluoride.By electro-chemical test it is found that this method can sufficiently reduce lithium an- ode
Polarization, is reduced to 50 millivolts in the charge and discharge every square centimeter after-polarization in 1 hour of 1 milliampere hour, good cycling stability shows Li dendrite
Generation obtained effective inhibition, obtain stable lithium an- ode, apply in lithium battery, the circulation of lithium battery can be improved
Performance and security performance have potential commercial applications value.
Embodiment five:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, referring to Fig. 7, a kind of guard method of metal lithium electrode includes the following steps:
A. the antimony trifluoride for weighing 53.6 milligrams pours into 20 milliliters of vials with cover, and is added 3 milliliters with liquid-transfering gun
As solvent, stirring dissolves antimony trifluoride sufficiently in propene carbonate, obtains antimony trifluoride solution propene carbonate, standby
With；
B. the lithium piece for taking 15.6 mm dias is pressed into smooth cylinder with a thickness of the sheet of 0.2 mm of thickness, then
It is cut into the disk that diameter is 12 millimeters with mold, it is spare；
C. the lithium piece in the b is pressed in stainless steel gasket, makes lithium piece and the abundant adhesion of stainless steel gasket and be bonded；
D. the lithium piece handled well in the c is placed in vial used in the step a together with stainless steel gasket
In, in the antimony trifluoride solution that is immersed in lithium piece in vial, carrying out surface modification reaction 5 minutes of lithium anode
Afterwards, then by lithium piece it takes out from antimony trifluoride solution, is then cleaned out lithium piece solution remained on surface with blotting paper, thus
Obtain the metal lithium electrode with the composite protection layer of lithium antimony alloy and lithium fluoride；
E. the metal lithium electrode prepared in the d is put into CR2032 battery case, the more empty films of selection polypropylene are
Diaphragm, it is 1 mole every liter of lithium hexafluoro phosphate (LiPF that electrolyte, which selects concentration,6) it is dissolved in the ethylene carbonate that volume ratio is 1:1
In ester (EC), diethyl carbonate (DEC) mixed solution.The present embodiment selects lithium salts to be dissolved in organic solvent, matches preparing lithium ion
Electrolyte is assembled into lithium metal using the metal lithium electrode with lithium antimony alloy and the composite protection layer of lithium fluoride as cathode
The assembling process of Symmetrical cells, battery carries out under ar gas environment, and controls water < 0.01ppm in argon ambient atmosphere environment,
Oxygen < 0.01ppm.
Experimental test and analysis:
Electrochemical property test is carried out to the lithium metal Symmetrical cells of the present embodiment method assembling, it is symmetrically electric to obtain lithium metal
The chemical property curve in pond, test condition are selected with 0.25mA/cm-2Current density charge and discharge 1 hour, test electrochemistry
Can, referring to Fig. 7, polarizes during 230 hours or so charge and discharge cycles remain steady always as shown in Figure 7, it can by illustration
Effective inhibition has been arrived with find out voltage maintains steady state to illustrate Li dendrite always during constant current charge-discharge generation.
The present embodiment is reacted using the antimony trifluoride solution of low concentration with the lithium metal on metal lithium electrode surface layer, and lithium antimony alloy and fluorine are generated
Change lithium, to form the composite protection layer of one layer of fine and close lithium antimony alloy and lithium fluoride on metal lithium electrode surface.The present embodiment
Using a kind of simple solvent reaction method, antimony trifluoride (SbF is utilized3) in cathode of lithium surface formation lithium antimony alloy and lithium fluoride
Layer, can be effectively reduced the polarization of cathode of lithium and the generation of dendrite inhibition.The present embodiment method mainly utilize antimony trifluoride with
Lithium reaction generates one layer of fine and close lithium antimony alloy and lithium fluoride protective layer, main method are as follows: antimony trifluoride is dissolved in carbon first
Uniform solution is made in acid propylene ester.Pretreatment is carried out to lithium piece surface and removes the lithium that surface is oxidized, is cut into 12 millimeters of diameter
Disk, gained disk is immersed into the lithium electrode that obtains that treated of reaction in antimony trifluoride solution, is finally assembled into Symmetrical cells.
The key of this method be reacted for a long time by low concentration can in one layer of lithium metal Surface Creation fine and close lithium antimony alloy and
Layer of lithium fluoride.By electro-chemical test it is found that this method can sufficiently reduce the polarization of lithium an- ode, often put down in 1 milliampere hour
Square centimetre of charge and discharge after-polarization in 1 hour is reduced to 50 millivolts, and good cycling stability shows that the generation of Li dendrite has obtained effective suppression
System, obtains stable lithium an- ode, applies in lithium battery, the cycle performance and security performance of lithium battery can be improved, and has
There are potential commercial applications to be worth.
Combination attached drawing of the embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, substitution, combination or the simplification made, should be equivalent substitute mode, as long as meeting goal of the invention of the invention,
Without departing from the technical principle and inventive concept of the guard method of metal lithium electrode of the present invention, protection model of the invention is belonged to
It encloses.
Claims (9)
1. a kind of guard method of metal lithium electrode, which is characterized in that with antimony trifluoride solution and the lithium metal electricity of low concentration
The lithium metal on pole surface layer reacts, and generates lithium antimony alloy and lithium fluoride, to form one layer of fine and close lithium on metal lithium electrode surface
The composite protection layer of antimony alloy and lithium fluoride, wherein the concentration of the antimony trifluoride in antimony trifluoride solution is 0.05~0.2 mole
Every liter.
2. the guard method of metal lithium electrode according to claim 1, which comprises the steps of:
A. the antimony trifluoride for weighing 53.6-107.2 milligrams pours into 20 milliliters of vials with cover, and 3-6 milli is added with liquid-transfering gun
The propene carbonate risen dissolves antimony trifluoride sufficiently in propene carbonate, obtains antimony trifluoride solution as solvent, stirring,
It is spare；
B. disc-shaped lithium piece is prepared, control lithium piece diameter is not more than 12 millimeters, and lithium piece thickness is spare not higher than 0.2 millimeter；
C. the lithium piece in the b is pressed in stainless steel gasket, makes lithium piece and the abundant adhesion of stainless steel gasket and be bonded；
D. the lithium piece handled well in the c is placed in vial used in the step a together with stainless steel gasket, is made
Lithium piece is immersed in the antimony trifluoride solution in vial, after carrying out surface modification reaction 3~6 minutes of lithium anode,
Lithium piece is taken out from antimony trifluoride solution again, is then cleaned out lithium piece solution remained on surface with blotting paper, thus
To the metal lithium electrode with lithium antimony alloy and the composite protection layer of lithium fluoride.
3. the guard method of metal lithium electrode according to claim 2, it is characterised in that: use the concentration of antimony trifluoride for
0.1 mole every liter of antimony trifluoride solution carries out lithium anode as reaction solution, with the lithium metal on metal lithium electrode surface layer
Surface modification reaction.
4. the guard method of metal lithium electrode according to claim 2, it is characterised in that: at least one lithium salts is selected to be dissolved in
In organic solvent, lithium-ion electrolyte is prepared, to make with the metal lithium electrode of lithium antimony alloy and the composite protection layer of lithium fluoride
For cathode, lithium metal Symmetrical cells are assembled into, the assembling process of battery carries out under ar gas environment, and controls ar gas environment gas
Water < 0.01ppm in atmosphere environment, oxygen < 0.01ppm.
5. the guard method of metal lithium electrode according to claim 4, it is characterised in that: in lithium-ion electrolyte process for preparation
In, the lithium salts of selection is two (trimethyl fluoride sulfonyl) imine lithiums (LiTFSI) or lithium hexafluoro phosphate (LiPF6), the lithium of electrolyte from
Sub- concentration is not less than 1.0 moles every liter.
6. the guard method of metal lithium electrode according to claim 5, it is characterised in that: in lithium-ion electrolyte process for preparation
In, lithium nitrate is continuously added on the basis of lithium salts in lithium-ion electrolyte, keeps the nitric acid lithium concentration of lithium-ion electrolyte not low
In 0.01 mole every liter.
7. the guard method of metal lithium electrode according to claim 4, it is characterised in that: in lithium-ion electrolyte process for preparation
In, organic mixed solvent is the 1,3-dioxolane (DOL) that volume ratio is 1:1 and glycol dimethyl ether (DME) mixed solution, or
Person is the mixed solution of the ethylene carbonate (EC) that volume ratio is 1:1 and diethyl carbonate (DEC).
8. the guard method of metal lithium electrode according to claim 4, it is characterised in that: assembled in lithium metal Symmetrical cells
Cheng Zhong uses empty film more than polypropylene for diaphragm.
9. the guard method of metal lithium electrode described according to claim 1~any one of 8, it is characterised in that: implement lithium gold
The overall process for belonging to the guard method of electrode all carries out in the glove box of argon gas filling.
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