CN104617259A - Method for protective treatment of lithium cathodes in lithium secondary batteries - Google Patents

Method for protective treatment of lithium cathodes in lithium secondary batteries Download PDF

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Publication number
CN104617259A
CN104617259A CN201510005152.5A CN201510005152A CN104617259A CN 104617259 A CN104617259 A CN 104617259A CN 201510005152 A CN201510005152 A CN 201510005152A CN 104617259 A CN104617259 A CN 104617259A
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lithium
protective layer
sio
situ
electrolyte
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CN104617259B (en
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郭玉国
李念武
殷雅侠
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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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
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • 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 method for in-situ protective treatment of lithium cathodes. The metallic lithium for the in-situ protective treatment of lithium cathodes can be applied to high-performance lithium secondary batteries. The method for in-situ protective treatment of lithium cathodes comprises a method for in-situ generation of silicon dioxide on the surfaces of the lithium cathodes. At a certain temperature, the treating fluid reacts with a passivation layer on the surface of the metallic lithium to obtain a silicon dioxide-containing protective layer. The method for preparing the in-situ protective treatment of lithium cathodes is simple, easy to control and high in practical degree. By applying the metallic lithium for in-situ protection to the lithium secondary batteries, the energy density and cycle performance of the batteries at present can be greatly improved and high practical value is provided.

Description

The conservation treatment of cathode of lithium in lithium secondary battery
Technical field
The present invention relates to the method for cathode of lithium conservation treatment in lithium secondary battery.
Background technology
Lithium secondary battery and lithium ion battery occupy critical role in energy storage equipment.Lithium is the metal that in all simple substance, the minimum and current potential of quality is minimum, and its theoretical specific capacity reaches 3860mA h/g, and the lithium battery be made up of lithium has that operating voltage is high, specific discharge capacity is high and the feature such as specific energy is large.But simple lithium can produce Li dendrite and safety problem as the lithium battery of negative pole.Early 1990s, Japanese Sony company using can the graphite of removal lithium embedded as negative pole, successfully prepare the better lithium ion battery of security performance.Development lithium ion battery through 30 years achieves huge business achievement.But the specific capacity of graphite only has 372mAh/g, can the positive electrode specific capacity of removal lithium embedded also be difficult to more than 200mA h/g.Therefore, at present commercial lithium ion battery is difficult to more than 200W h/Kg, is difficult to meet the development of new energy technology to the requirement of high-performance secondary cell.So the lithium secondary battery with high-energy-density receives increasing concern, the focus of lithium-sulfur cell and lithium-air battery current secondary cell area research especially.
The business-like biggest obstacle of lithium secondary battery is still the safety issue of Li dendrite and lithium.Because secondary lithium metal lithium anode surface in cyclic process may be formed " Li dendrite ", along with the increase " Li dendrite " of cycle-index sharply grows and wears out electrolyte and positive contact, cause internal short-circuit of battery and battery ultimate failure; Meanwhile, form " dead lithium " because lithium metal surface " Li dendrite " is soluble in electrolyte, contact with electron loss and cannot carry out electrochemical reaction.The generation of " dead lithium " makes the cycle efficieny of lithium metal reduce on the one hand, and highly active " dead lithium " delay easily and between electrolyte some side reactions occurs in the electrolytic solution on the other hand, is formed threaten the fail safe of battery.
Associating Eveready Bettery company of PolyPlus company and Sheldahl company adopt the method for plated film protection cathode of lithium to develop comparatively ripe lithium-sulfur cell.PolyPlus company way is: the negative pole of battery for substrate, adopts vapour deposition process with copper or polymer by lithium metal plated film in substrate, then wrap up one deck can the phosphate coating of conducting lithium ions.This method preparation cost of PolyPlus company is higher, is unsuitable for large-scale production.The people such as Zhang (Nature communication 2014,5:3015) utilize carbon-coating to protect metal lithium sheet to improve lithium-sulfur cell performance.Graphite, conductive carbon, binding agent PVDF are mixed into slurry by them, then are coated on stainless (steel) wire, are then pressed in metal lithium sheet by the stainless (steel) wire with graphite, and result of study shows that this Measures compare restrained effectively the growth of Li dendrite.But this method is not growth in situ coating layer on lithium sheet, suppression Li dendrite effect has certain discount, and preparation method is relatively complicated.
The present invention creatively adopts the method growing silicon dioxide in-situ conservation layer on lithium metal to suppress the growth of Li dendrite, by controlling the thickness of the effective Control protection layer such as consumption of reaction time, reactant.The protective layer of growth in situ effectively can suppress the growth of Li dendrite, thus improves the cycle performance of lithium secondary battery.The method of this growth in situ protective layer can be widely used in lithium secondary battery (lithium-sulfur cell, lithium-air battery etc.).
Summary of the invention
The object of this invention is to provide preparation method and the application of lithium secondary battery cathode material lithium metal in-situ conservation layer.
The preparation method of metal lithium sheet in-situ conservation layer provided by the invention; comprise the steps: lithium sheet to be placed in treatment fluid a period of time or treatment fluid to be coated in lithium sheet surface, after reaction certain hour, take out lithium sheet; wipe the treatment fluid of excess surface, obtain containing SiO 2the lithium sheet of protective layer.
In above-mentioned preparation method, described treatment fluid comprises and variously reacts the ester class, one or several in silanes that generate silicon dioxide with lithium hydroxide.Ester class comprises tetraethoxysilane, methyl silicate etc., and silanes comprises trim,ethylchlorosilane, dimethylchlorosilane, methyl trichlorosilane, tri isopropyl chlorosilane, methyldiphenyl base chlorosilane, tert-butyl diphenyl chlorosilane, dodecyl dimethyl chlorosilane and siloxanes etc.
In above-mentioned preparation method, the described state of lithium sheet in treatment fluid comprises lithium sheet part and immerses in treatment fluid and immerse completely in treatment fluid.
In above-mentioned preparation method, the soak time of lithium sheet in treatment fluid is 10s-10h, can be preferably 30s-90s.
In above-mentioned preparation method, described reaction temperature is-20-50 DEG C, can be preferably 5-35 DEG C.
Application provided by the present invention is the application of lithium metal as lithium secondary battery cathode material of band matcoveredn, particularly as the application of lithium-sulfur cell.
Compared with prior art; preparation method's advantage of lithium metal conservation treatment provided by the invention is that lithium metal generates protective layer by reaction in-situ, is regulated and controled component and the thickness of in-situ conservation layer by regulation and control lithium metal and the kind of reaction liquid and reaction time etc.Lithium metal after treatment effectively can control the growth of Li dendrite, its for lithium secondary battery particularly lithium-sulfur rechargeable battery time can significantly improve its cycle performance.The preparation method of this lithium metal in-situ conservation layer is simple, raw material is easy to get, is suitable for large-scale production.
In the present invention, lithium metal is protective layer used when lithium secondary battery; positive electrode adopts carbon/sulphur composite material, and wherein material with carbon element is one or several in microporous carbon, activated carbon, mesoporous carbon, macropore carbon, mesoporous microporous carbon, macropore microporous carbon, macropore mesoporous carbon, the mesoporous microporous carbon of macropore.Positive electrode also can adopt the positive electrode that current lithium ion battery is conventional in addition, as cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, cobalt nickel ion doped etc.
In the present invention, lithium metal is protective layer used when lithium secondary battery, and conductive additive adopts expanded graphite, hot soarfing from one or several in Graphene, carbon nano-tube, Ketjen black, carbon black and Super P.
In the present invention, lithium metal is protective layer used when lithium secondary battery, and binding agent adopts one or more in Kynoar (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), sodium cellulose glycolate (CMC), butadiene-styrene rubber (SBR), gelatin and cyclodextrin.
In the present invention, lithium metal is protective layer used when lithium secondary battery, and electrolyte adopts ester class electrolyte or ethers electrolyte, and the concentration of lithium salts is 0.1-5M, can be preferably 0.5-2.5M.
In described ester class electrolyte, solvent is one or more in ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC) and propene carbonate (PC), and lithium hexafluoro phosphate (LiPF elected as by lithium salts 6), lithium perchlorate (LiClO 4), di-oxalate lithium borate (LiBOB), LiBF4 (LiBF 4), one or more in two (fluoroform sulphonyl) imine lithium (LiTFSI).
In described ethers electrolyte, solvent is one or more in TRIGLYME (TEGDME), 1,3 dioxolanes (DOL) and glycol dimethyl ether (DME).Lithium hexafluoro phosphate (LiPF elected as by lithium salts 6), lithium perchlorate (LiClO 4), (LiBOB), LiBF4 (LiBF in two oxalic acid boric acid 4) and two (fluoroform sulphonyl) imine lithium (LiTFSI) in one or more.
In the present invention, secondary lithium batteries barrier film is the one in PE film, PP film, PP/PE film, PP/PE/PP film and glass fibre element film (Whatman).
Accompanying drawing explanation
Fig. 1 is SiO in embodiment 1 2the SEM picture of protective layer and corresponding Mapping picture.
Fig. 2 is with SiO in embodiment 1 2the SEM picture of lithium sheet after 100 circulations of protective layer.
Fig. 3 is the SEM picture of embodiment 11 lithium sheet after 100 circulations.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Raw materials in following embodiment, if no special instructions, all can obtain from commercial channels.
The preparation of embodiment 1, lithium metal in-situ conservation layer
Under high-purity argon atmosphere, immersed in tetraethoxysilane by lithium sheet and react 90s, reaction temperature is 35 DEG C, wipes the tetraethoxysilane liquid of excess surface, can obtain SiO provided by the invention after being taken out by lithium sheet 2protective layer.
SiO is observed by cold field emission scanning electron microscopy (SEM) 2the appearance structure of protective layer, as shown in Figure 1, illustration is the Mapping picture of corresponding silicon and oxygen element.As can be seen from the figure element silicon and oxygen element are evenly distributed on protective layer.In addition, SiO can be found out from the sectional view of SEM 2the thickness of protective layer is 150nm.。
This with SiO 2the deposition of the lithium sheet of protective layer and peel off current potential and impedance test results lists in table 1.Test result when it does lithium-sulfur cell negative pole lists in table 2.
The preparation of embodiment 2, lithium metal in-situ conservation layer
Under high-pure helium atmosphere, tetraethoxysilane fluid drips is added in lithium sheet surface, reaction temperature is 40 DEG C, and reaction 300s, wipes the tetraethoxysilane liquid of excess surface, can obtain SiO provided by the invention 2protective layer.
Compared with embodiment 1, inert atmosphere changes helium into, tetraethoxysilane use amount significantly reduces, and change into and dripping on lithium sheet surface, the reaction time changes 300s into.
SiO is observed by cold field emission scanning electron microscopy (SEM) 2the appearance structure of protective layer, lamellar structure grows equably on lithium surface, and element is configured to silicon and oxygen element, and its thickness is 100nm.
This with SiO 2the deposition of the lithium sheet of protective layer and peel off current potential and impedance test results lists in table 1.Test result when it does lithium-sulfur cell negative pole lists in table 2.
The preparation of embodiment 3, lithium metal in-situ conservation layer
Under high-purity argon atmosphere, immersed in trim,ethylchlorosilane by lithium sheet and react 200s, reaction temperature is 40 DEG C, wipes the trim,ethylchlorosilane liquid of excess surface, can obtain SiO provided by the invention after being taken out by lithium sheet 2protective layer.
SiO is observed by cold field emission scanning electron microscopy (SEM) 2appearance structure, it is made up of multilayer chip structure, and component is silicon, oxygen and a small amount of chlorine element.In addition, SiO can be found out from the sectional view of SEM 2the thickness of protective layer is about 120nm.
This with SiO 2the deposition of the lithium sheet of protective layer and peel off current potential and impedance test results lists in table 1.Test result when it does lithium-sulfur cell negative pole lists in table 2.
The preparation of embodiment 4, lithium metal in-situ conservation layer
Under high-purity argon atmosphere, immersed by lithium sheet in the mixing material of tetraethoxysilane and trim,ethylchlorosilane and react 90s, reaction temperature is 35 DEG C, wipes the liquid of excess surface, can obtain SiO provided by the invention after being taken out by lithium sheet 2protective layer.
SiO is observed by cold field emission scanning electron microscopy (SEM) 2appearance structure, it is made up of multilayer chip structure, and component is silicon, oxygen and a small amount of chlorine element.Protective layer can cover the surface of lithium equably.In addition, SiO can be found out from the sectional view of SEM 2the thickness of protective layer is about 120nm.
This with SiO 2the deposition of the lithium sheet of protective layer and peel off current potential and impedance test results lists in table 1.Test result when it does lithium-sulfur cell negative pole lists in table 2.
The preparation of embodiment 5, lithium metal in-situ conservation layer
Under high-purity argon atmosphere, lithium sheet is immersed in the mixing material of methyl silicate, dimethylchlorosilane, methyl trichlorosilane and react 120s, wipe the liquid of excess surface after being taken out by lithium sheet, SiO provided by the invention can be obtained 2protective layer.
SiO is observed by cold field emission scanning electron microscopy (SEM) 2appearance structure, it is made up of multilayer chip structure, and component is silicon, oxygen and a small amount of chlorine element.Protective layer can cover the surface of lithium equably.In addition, SiO can be found out from the sectional view of SEM 2the thickness of protective layer is about 50-150nm.
This with SiO 2the deposition of the lithium sheet of protective layer and peel off current potential and impedance test results lists in table 1.Test result when it does lithium-sulfur cell negative pole lists in table 2.
The preparation of embodiment 6, lithium metal in-situ conservation layer
Other conditions are identical with embodiment 4, and difference is that reaction temperature is 50 DEG C.Obtain SiO provided by the invention 2protective layer.This with SiO 2the deposition of the lithium sheet of protective layer and peel off current potential and impedance test results lists in table 1.Test result when it does lithium-sulfur cell negative pole lists in table 2.
The preparation of embodiment 7, lithium metal in-situ conservation layer
Other conditions are identical with embodiment 4, and difference is that reaction temperature is 0 DEG C.Obtain SiO provided by the invention 2protective layer.This with SiO 2the deposition of the lithium sheet of protective layer and peel off current potential and impedance test results lists in table 1.Test result when it does lithium-sulfur cell negative pole lists in table 2.
The preparation of embodiment 8, lithium metal in-situ conservation layer
Other conditions are identical with embodiment 4, and difference is that reaction temperature is 5 DEG C.Obtain SiO provided by the invention 2protective layer.This with SiO 2the deposition of the lithium sheet of protective layer and peel off current potential and impedance test results lists in table 1.Test result when it does lithium-sulfur cell negative pole lists in table 2.
The preparation of embodiment 9, lithium metal in-situ conservation layer
Under high-purity argon atmosphere, immersed in tetraethoxysilane by lithium sheet and react 10s, reaction temperature is 35 DEG C, wipes the tetraethoxysilane liquid of excess surface, can obtain SiO provided by the invention after being taken out by lithium sheet 2protective layer.
SiO is observed by cold field emission scanning electron microscopy (SEM) 2appearance structure, it is made up of lamellar structure, and component is silicon, oxygen element.In addition, SiO can be found out from the sectional view of SEM 2the thickness of protective layer is about 50nm.
This with SiO 2the deposition of the lithium sheet of protective layer and peel off current potential and impedance test results lists in table 1.Test result when it does lithium-sulfur cell negative pole lists in table 2.
The preparation of embodiment 10, lithium metal in-situ conservation layer
Under high-purity argon atmosphere, immersed in tetraethoxysilane by lithium sheet and react 600s, reaction temperature is 35 DEG C, wipes the tetraethoxysilane liquid of excess surface, can obtain SiO provided by the invention after being taken out by lithium sheet 2protective layer.
SiO is observed by cold field emission scanning electron microscopy (SEM) 2appearance structure, it is made up of lamellar structure, and component is silicon, oxygen element.In addition, SiO can be found out from the sectional view of SEM 2the thickness of protective layer is about 2 μm.
This with SiO 2the deposition of the lithium sheet of protective layer and peel off current potential and impedance test results lists in table 1.Test result when it does lithium-sulfur cell negative pole lists in table 2.
The test of comparison example 1, common lithium sheet
In order to compare lithium-sulfur cell test performance, common lithium sheet is listed in table 2 as test result during lithium-sulfur cell negative pole.
The common lithium sheet of application examples is used for lithium-sulfur cell test
Common lithium sheet is used for lithium-sulfur cell test, and its test result lists in table 2.
At inert atmosphere glove box (H 2o<0.1ppm, O 2<0.1ppm) in, with lithium sheet for negative pole, Ceglard2325 is barrier film, the lithium sheet of embodiment 1-10 is positive pole, and electrolyte lithium salt selects LiTFSI, and the mixed liquor of DOL/DME selected by solvent, assembling lithium battery, LAND2100 battery test system is tested.Test condition is: constant current charge-discharge under the current density of 0.1mA, and charge/discharge capacity controls at 1mAh, measures the deposition obtaining the lithium ion of embodiment 1-10 as shown in table 1 with stripping current potential.In addition, test its ac impedance spectroscopy with Auto Lab, draw corresponding resistance value by matching, be listed in table 1.
At inert atmosphere glove box (H 2o<0.1ppm, O 2<0.1ppm) in, lithium sheet prepared in embodiment 1-10 and common lithium sheet (comparison example 1) are negative pole, Ceglard 2325 is barrier film, carbon/sulfur compound is positive pole, and conductive carbon elects Ketjen black as, and PVDF elected as by binding agent, electrolyte lithium salt selects LiTFSI, the mixed liquor of DOL/DME selected by solvent, and assembling lithium battery, LAND2100 battery test system is tested.Measuring current density is 0.2C (1C=1675mA h/g).Test result lists in table 2.
In addition, the appearance structure after the lithium sheet with protective layer in embodiment 1 100 circulation as shown in Figure 2.Appearance structure in comparison example 1 after common lithium sheet 100 circulation as shown in Figure 3.
Deposition/stripping the current potential of table 1, lithium ion and resistance value
The capacity of lithium-sulfur cell and coulombic efficiency in table 2, application examples
As can be seen from the contrast of the protective layer thickness of embodiment 1-10, lithium ion sedimentation potential and resistance value; the kind, reaction temperature, time etc. of reactant liquor have a great impact protective layer thickness; conversion zone is thicker, and its lithium ion sedimentation potential is higher, and resistance value is larger.Compared to the reactant liquor of other kind, the protective layer resistance value that tetraethoxysilane produces is minimum.By Optimal Parameters, the thickness of reasonable adjusting protective layer and composition are the keys of lithium anode protection.
Because lithium-sulfur cell exists the problem of many sulphions dissolving, there is effect of shuttling back and forth in its charging process, cause it to occur low coulombic efficiency and poor cycle performance.The capability retentions that common lithium sheet is 95%, 100 circulations as the coulombic efficiency of negative pole are 63.6% (comparison example 1).
As can be seen from the lithium-sulfur cell the performance test results of embodiment 1-10 and comparison example 1, the lithium sheet with in-situ conservation layer is very large on the impact of lithium-sulfur cell performance.The kind of protective layer is very large on the impact of lithium-sulfur cell performance; wherein tetraethoxysilane, trim,ethylchlorosilane and their mixed liquor are that prepared by treatment fluid protective layer used shows good performance (as embodiment 1, embodiment 3, embodiment 4) in lithium-sulfur cell; wherein especially with the mixed liquor of tetraethoxysilane and trim,ethylchlorosilane for treatment fluid, the lithium-sulfur cell performance best (see embodiment 4 and embodiment 8) that the protective layer of preparation obtains at 5-35 DEG C.Too thick protective layer can reduce capacity and the coulombic efficiency of lithium-sulfur cell greatly, reduces its cycle performance (as embodiment 10); Although too thin protective layer can make lithium-sulfur cell play higher specific capacity, along with the carrying out of circulation, the protective layer likely destroyed coulombic efficiency that causes reduces (embodiment 9).Therefore the protective layer selecting suitable reactions liquid to generate suitable thickness is the key improving lithium-sulfur cell performance.
In addition, the original position SEM picture (Fig. 2) after circulation, silicon dioxide layer of protection effectively can suppress the growth of Li dendrite, thus makes surface very smooth.And there is no treated lithium sheet, circulate after 100 circles in lithium-sulfur cell, the surface of lithium is rugged and rough (Fig. 3), the growth phenomenon of Li dendrite very obvious.
In sum, the present invention reacts with the LiOH on metal lithium sheet surface with ester class, silanes etc., in-situ preparation SiO on lithium metal 2or the SiO of functionalization 2protective layer.The in-situ conservation layer prepared effectively can prevent the formation of Li dendrite, improves the cyclical stability of lithium secondary battery.The method preparation is simple, cheaper starting materials is easy to get, is suitable for large-scale production, has good application prospect.
Foregoing is only the preferred embodiments of the present invention; not for limiting embodiment of the present invention; those of ordinary skill in the art are according to central scope of the present invention and spirit; can carry out corresponding flexible or amendment very easily, therefore protection scope of the present invention should be as the criterion with the protection range required by claims.

Claims (10)

1. a preparation method for lithium metal in-situ preparation protective layer, is characterized in that the main component of protective layer is SiO 2.Its preparation method is as follows: under an inert atmosphere, is immersed in by lithium metal and is coated on lithium metal in treatment fluid or by treatment fluid, reaction a period of time, generates SiO 2or the SiO of functionalization 2protective layer.
2. method according to claim 1, treatment fluid comprises and variously reacts the ester class, one or several in silanes that generate silicon dioxide with metallic lithium surface passivation layer.Ester class comprises tetraethoxysilane, methyl silicate etc., and silanes comprises trim,ethylchlorosilane, dimethylchlorosilane, methyl trichlorosilane, tri isopropyl chlorosilane, methyldiphenyl base chlorosilane, tert-butyl diphenyl chlorosilane, dodecyl dimethyl chlorosilane and siloxanes etc.; Preferably, described treatment fluid is made up of tetraethoxysilane and trim,ethylchlorosilane.
3. method according to claim 1, inert gas comprises all kinds of gases do not reacted with lithium, comprises one or more in argon gas, helium, neon etc.
4. method according to claim 1, at the generated in-situ SiO of lithium metal 2the thickness of protective layer is 0.02-10 μm, and controllable condition is preferably 0.05-1 μm.
5. method according to claim 1, tetraethoxysilane used and the volume ratio of lithium metal are 0.1:1-50:1, can be preferably 1:1-20:1.
6. method according to claim 1, at metallic lithium surface in-situ preparation SiO 2the reaction time of protective layer is 5s-10h, can be preferably 30s-90s.
7. method according to claim 1, at metallic lithium surface in-situ preparation SiO 2the reaction temperature of protective layer is-20-50 DEG C, can be preferably 5-35 DEG C.
8. a lithium secondary battery, comprise negative material, barrier film, electrolyte and positive electrode to form, positive electrode is cobalt acid lithium, LiMn2O4, lithium nickelate, LiFePO4, ternary material and rich lithium material etc., and negative material is the lithium sheet that the method for one of claim 1-7 obtains being with matcoveredn; Barrier film comprises PP film, PE film, PP/PE film, PP/PE/PP film.
9. lithium secondary battery according to claim 8, electrolyte comprises ester class electrolyte, ethers electrolyte and ionic liquid class electrolyte.
10. an energy storage elements, is characterized in that: described energy storage elements contains the lithium secondary battery that according to any one of claim 8,9, method prepares.
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