CN108448065A - A kind of preparation method of the lithium anode of bend resistance - Google Patents
A kind of preparation method of the lithium anode of bend resistance Download PDFInfo
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- CN108448065A CN108448065A CN201810155074.0A CN201810155074A CN108448065A CN 108448065 A CN108448065 A CN 108448065A CN 201810155074 A CN201810155074 A CN 201810155074A CN 108448065 A CN108448065 A CN 108448065A
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- lithium
- graphene oxide
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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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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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
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Abstract
The present invention relates to a kind of preparation method of the lithium anode of bend resistance, 1) by being processed to graphene oxide dispersion, graphene oxide film is prepared, thickness is 1 μm~200 μm；2) graphene oxide membrane is dried, drying temperature is 30 DEG C~300 DEG C, and drying time is 1h~72h；3) lithium metal is heat-treated using heating equipment in an inert atmosphere, heating rate is 1~50 DEG C/min, and final temperature is 200~500 DEG C；4) after shaping to the graphene oxide membrane after drying, reduction, and the graphene oxide after reduction and molten metal lithium time of contact are 1~120s, obtain the composition metal cathode of lithium of bend resistance.The cathode is used as flexibility Li O2Battery and Li S battery cathode, capacity and cyclical stability of the battery under tradition and bending state are improved.
Description
Technical field
The present invention relates to a kind of preparation methods of the lithium anode of bend resistance, more particularly, to one kind with lithium metal
For the flexible metal technical field of lithium batteries of cathode.
Background technology
Flexible electronic devices are in practical application, needing to be provided simultaneously with high energy density and having bending deformability.
Each monomer can be chained up by split type design with stretchable material by people, be obtained whole with certain soft
The device of property.(A.Rogers, MRS Bull.2014,39,549) can make in addition, battery itself is allowed to have buckle resistance energy
Device is obtained directly to apply during bending.
The development for developing into electronic equipment, intelligent grid and electric vehicle of lithium ion battery is made that major contribution.
It develops to the current stage, energy density becomes the bottleneck for limiting its development.Since lithium metal has highest theoretical specific capacity
(3860mAh g-1) and minimum current potential (- 3.04V), become the key for preparing high-energy density lithium battery, such as Li-O2, Li-
The batteries such as S (P.G.Bruce, S.A.Freunberger, L.J.Hardwick, J.M.Tarascon, Nat.Mater.2012,
11,19).Therefore, the lithium battery for having both buckle resistance energy and high-energy density is prepared, it is necessary to consider lithium metal as cathode
When buckle resistance energy.Since lithium metal is in bending, it is easy that metallic lithium surface is caused to generate fold and protrusion due to deformation
Equal plastic deformations, these positions can become the nucleation site that lithium ion deposits in electrochemical process, influence lithium ion flow distribution, add
The growth of fast part dendrite.Bending can also destroy the SEI of metallic lithium surface, expose new lithium metal and reacted with electrolyte.It makes
It is reduced at coulombic efficiency, circulating battery bad stability, or even causes security risk.(Y.Y.Lu,Z.Y.Tu,L.A.Archer,
Nat.Mater.2014,13,961.)
To solve the above-mentioned problems, the lithium anode that bend resistance is prepared is crucial, and the present invention proposes a kind of bending resistance
The preparation method for rolling over lithium anode, solves the problems, such as lithium metal in flexible high-energy-density metal lithium battery applications.It should
Method is compound with redox graphene by lithium metal, obtains the composition metal cathode of lithium for having buckle resistance energy.By the cathode
As flexible Li-O2Battery and Li-S battery cathode, capacity and cyclical stability of the battery under tradition and bending state
It is improved.
Invention content
The object of the present invention is to by preparing, a kind of lithium anode of bend resistance is obtained.By the lithium anode application
In Li-O2And Li-S batteries, obtain the flexibility for having both good cycling stability under high-energy density, bend resistance and deformation state
Metal battery.
To achieve the above object, the technical solution that the present invention takes is：
1) by being processed to graphene oxide dispersion, it is prepared graphene oxide film, thickness is 1 μm~
200μm；
2) graphene oxide membrane is dried, drying temperature is 30 DEG C~300 DEG C, and drying time is 1h~72h；
3) lithium metal being heat-treated using heating equipment in an inert atmosphere, heating rate is 1~50 DEG C/min,
Final temperature is 200~500 DEG C；
4) after shaping to the graphene oxide membrane after drying, reduction, and the graphene oxide after reduction and melting gold
Category lithium time of contact is 1~120s, obtains the composition metal cathode of lithium of bend resistance.
Further, the graphene oxide preparation method can be classical Hummer ' s methods, can also be other sides
Method.
Further, the graphene oxide membrane can also pass through solvent flashing mode by vacuum filtration mode
Or spontaneous thin film-forming method obtains；It is required that the film has preferable homogeneity and intensity.
Further, the graphene oxide dispersion can be dispersed in water, ethyl alcohol, ethylene glycol, glycerine, N- methyl pyrroles
The combination of one or more of pyrrolidone, n,N-Dimethylformamide.
Further, the concentration of the graphene oxide dispersion can be 0.1mg/ml~10mg/ml；Further, institute
State when graphene oxide membrane is dried, drying mode can be forced air drying or vacuum drying.Further, described
Atmosphere of inert gases refer generally to argon atmosphere；Water content is less than 2ppm, and oxygen content is less than 2ppm.
Further, it can also be Muffle furnace that the heating equipment, which can be electric boiling plate,；Heating stepses need to ensure metal
Lithium is ultimately at molten condition.
Further, can carry out electronation using hydrazine hydrate to the reduction of graphene oxide membrane, can also be that heat is gone back
It is former.
Compound material further is carried out with lithium metal, can be redox graphene, can also be other any tools
Standby carbon-based material flexible.
Further, the time that the redox graphene film is contacted with molten metal lithium is 1s~120s；When contact
Between control, it is ensured that distribution of the lithium metal in redox graphene is more uniform.
Further, the composition metal cathode of lithium of bend resistance, can be directly used for the assembling of lithium metal full battery；Or to bend resistance
Composition metal cathode of lithium be processed setting after be used for lithium metal full battery assembling.
Further, the high-energy density full battery being prepared using the bend resistance lithium anode, including soft-package battery,
Wind cylinder battery and hull cell.
It is using this method that lithium metal is compound with redox graphene, obtain the composite metal lithium for having buckle resistance energy
Cathode.The cathode is used as flexibility Li-O2Battery and Li-S battery cathode, capacity of the battery under tradition and bending state with
And cyclical stability is improved.
Description of the drawings
Fig. 1 is the XRD characterization data of composition metal cathode of lithium prepared by embodiment 1.
Fig. 2 is the specific capacity curve of composition metal cathode of lithium prepared by embodiment 1.
Fig. 3 is that composition metal cathode of lithium prepared by embodiment 1 is used for Li-S full battery bending state performance comparisons.
Fig. 4 is that composition metal cathode of lithium prepared by embodiment 1 is used for Li-O2Full battery bending state performance comparison.
Specific implementation mode
It is further illustrated the present invention with reference to embodiment, but the scope of protection of present invention is not limited to implement
The range of example statement.
Embodiment 1
1) pass through Hummer ' s methods and 2mg/ml graphene oxide water solution dispersion liquids are prepared, utilize vacuum filtration mode
Graphene oxide film is obtained, thickness is 1 μm；
2) graphene oxide membrane is dried, drying temperature is 60 DEG C, drying time 12h；
3) lithium metal being heat-treated in argon inert atmosphere using heating equipment, heating rate is 1 DEG C/min,
Final temperature is 400 DEG C；
4) after shaping to the graphene oxide membrane after drying, graphene oxide using thermal reduction, and after restoring with
Molten metal lithium time of contact is 10s, obtains composition metal cathode of lithium.Its XRD characterization is as shown in Figure 1, it was demonstrated that lithium metal and carbon
Success is compound.Its specific discharge capacity is as shown in Figure 2.
5) the composition metal cathode of lithium is directly used in high-energy density Li-S and Li-O flexible2The group of full battery
Dress.
6) by assembled battery, the charge-discharge test under different current densities is carried out on blue electric tester, investigates Li-
S and Li-O2The charging and discharging capacity and cyclical stability of full battery.As it can be seen that under bending state, it is compound using bend resistance
The Li-S circulating batteries 100 of cathode assembling enclose, and capacity is maintained at 600mAh/g, and common lithium bears the Li-S circulating batteries 38 of assembling
Occurs short circuit after circle, specific capacity drastically reduces, as shown in Figure 3；Under bending state, the compound cathode of lithium assembling of bend resistance is utilized
Li-O2Circulating battery 50 encloses, and discharge voltage remains at 2.5V or more, and the Li-O of common cathode of lithium assembling2Battery, cycle 34
After circle, there is short-circuit, discharge voltage rapid drawdown, as shown in Figure 4.
Embodiment 2
1) pass through Hummer ' s methods and 10mg/ml graphene oxide water solution dispersion liquids are prepared, utilize vacuum filtration side
Formula obtains graphene oxide film, and thickness is 200 μm；
2) graphene oxide membrane is dried, drying temperature is 300 DEG C, drying time 72h；
3) lithium metal is heat-treated using heating equipment in an inert atmosphere, heating rate is 50 DEG C/min, most
Finishing temperature is 500 DEG C；
4) after shaping to the graphene oxide membrane after drying, it is made to be heat-treated with molten metal lithium Contact；
And the graphene oxide after restoring and molten metal lithium time of contact are 120s, obtain composition metal cathode of lithium.
5) the composition metal cathode of lithium is directly used in high-energy density Li-O flexible2The assembling of full battery.
Embodiment 3
1) pass through Hummer ' s methods and 2mg/ml graphene oxide alcohol-water mixed dispersion liquids be prepared, using it is spontaneous at
Film mode obtains graphene oxide film, and thickness is 100 μm；
2) graphene oxide membrane is dried, drying temperature is 30 DEG C, drying time 1h；
3) lithium metal is heat-treated using heating equipment in an inert atmosphere, heating rate is 25 DEG C/min, most
Finishing temperature is 200 DEG C；
4) graphene oxide membrane after drying restores it using hydrazine hydrate, and restore after graphene oxide with
Molten metal lithium time of contact is 60s, obtains composition metal cathode of lithium.
5) setting is processed to the composition metal cathode of lithium being prepared.
6) the composition metal cathode of lithium of the bend resistance is directly used in the assembling of high-energy density Li-S full batteries flexible.
Embodiment 4
1) pass through Hummer ' s methods and 1mg/ml graphene oxide water solution dispersion liquids are prepared, utilize vacuum filtration mode
It obtains, by being processed graphene oxide dispersion, graphene oxide film being prepared, thickness is 50 μm；
2) graphene oxide membrane is dried, drying temperature is 80 DEG C, and drying time is for 24 hours；
3) lithium metal is heat-treated using heating equipment in an inert atmosphere, heating rate is 10 DEG C/min, most
Finishing temperature is 350 DEG C；
4) graphene oxide membrane and molten metal lithium Contact are heat-treated, and the graphene oxide after restoring with it is molten
It is 30s to melt lithium metal time of contact, obtains composition metal cathode of lithium.
5) setting is processed to the composition metal cathode of lithium being prepared.
6) the composition metal cathode of lithium is directly used in high-energy density Li-O flexible2The assembling of full battery.
The present invention provides a kind of preparation method of the lithium anode of bend resistance.The present invention is by by lithium metal and oxygen reduction
Graphite alkene is compound, and by regulating and controlling graphene oxide, it is negative can to obtain the controllable composite metal lithium of thickness, size, shape, dimension
Pole.The composition metal cathode of lithium has excellent buckle resistance energy.After tested, for pure metal lithium, the bending resistance is used
The flexible Li-S and Li-O that folding composition metal cathode of lithium is assembled into2Electrochemistry of the full battery after bending and under bending state
Performance gets a promotion.In addition, being used in conjunction with solar cell using the Li-S soft-package batteries, bent energy stores system is constructed
System, has further opened up thinking to prepare the flexible energy storage system of high-energy density.
Claims (9)
1. a kind of preparation method of the lithium anode of bend resistance, it is characterised in that including steps are as follows：
1) by being processed to graphene oxide dispersion, graphene oxide film is prepared, thickness is 1 μm~200 μ
m；
2) graphene oxide membrane is dried, drying temperature is 30 DEG C~300 DEG C, and drying time is 1h~72h；
3) lithium metal is heat-treated using heating equipment in an inert atmosphere, heating rate is 1~50 DEG C/min, finally
Temperature is 200~500 DEG C；
4) after shaping to the graphene oxide membrane after drying, reduction, and the graphene oxide after reduction and molten metal lithium
Time of contact is 1~120s, obtains the composition metal cathode of lithium of bend resistance.
2. the method as described in claim 1, it is characterized in that the restoring method of the step 4) is：To the graphite oxide after drying
Alkene film restores it using hydrazine hydrate.
3. the method as described in claim 1, it is characterized in that the restoring method of the step 4) is：Molten metal lithium Contact
It is heat-treated.
4. the method as described in claim 1, it is characterized in that the composition metal cathode of lithium of bend resistance, it is entirely electric to be directly used in lithium metal
The assembling in pond；Or the assembling that lithium metal full battery is used for after setting is processed to the composition metal cathode of lithium of bend resistance.
5. according to the method for claim 1, it is characterised in that：The graphene oxide membrane by vacuum filtration mode,
Or it is obtained by solvent flashing mode or spontaneous thin film-forming method.
6. according to the method for claim 1, it is characterised in that：The graphene oxide dispersion is water, ethyl alcohol, second two
The combination of one or more of alcohol, glycerine, N-Methyl pyrrolidone or n,N-Dimethylformamide；Graphene oxide point
The concentration of dispersion liquid is 0.1mg/ml~10mg/ml.
7. according to the method for claim 1, it is characterised in that：When graphene oxide membrane is dried, drying mode
It is forced air drying or vacuum drying.
8. method described in accordance with the claim 1, it is characterised in that：Atmosphere of inert gases refers to argon atmosphere, and water content is less than
2ppm, oxygen content are less than 2ppm.
9. according to the method for claim 1, it is characterised in that full battery includes soft-package battery, winding cylinder battery and thin
Film battery.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109378476A (en) * | 2018-09-27 | 2019-02-22 | 苏州大学 | Using the method for self assembly RGO film preparation lithium electrode protective layer |
| CN109755538A (en) * | 2019-02-01 | 2019-05-14 | 哈尔滨工程大学 | A kind of Li-Ti3C2- rGO composite film material and preparation method thereof |
| CN111261833A (en) * | 2020-01-19 | 2020-06-09 | 中南大学 | Self-supporting lithium metal cathode and preparation and application thereof |
| CN111933948A (en) * | 2020-08-18 | 2020-11-13 | 武汉先见科技有限公司 | Lithium-sulfur battery, lithium-sulfur battery positive electrode material, lithium-sulfur battery negative electrode material and preparation method of lithium-sulfur battery positive electrode material |
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| CN105789559A (en) * | 2016-04-21 | 2016-07-20 | 清华大学 | Flexible lithium metal cell negative pole and preparation method thereof |
| CN106450514A (en) * | 2016-11-11 | 2017-02-22 | 南开大学 | Quasi-solid Na-CO2 secondary battery and preparation method thereof |
| CN107611391A (en) * | 2017-09-05 | 2018-01-19 | 珠海格力电器股份有限公司 | Lithium metal secondary battery cathode and preparation method thereof |
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2018
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Patent Citations (4)
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| CN105374991A (en) * | 2014-08-13 | 2016-03-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Metal lithium-framework carbon composite material and preparation method thereof, negative electrode and secondary battery |
| CN105789559A (en) * | 2016-04-21 | 2016-07-20 | 清华大学 | Flexible lithium metal cell negative pole and preparation method thereof |
| CN106450514A (en) * | 2016-11-11 | 2017-02-22 | 南开大学 | Quasi-solid Na-CO2 secondary battery and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109378476A (en) * | 2018-09-27 | 2019-02-22 | 苏州大学 | Using the method for self assembly RGO film preparation lithium electrode protective layer |
| CN109378476B (en) * | 2018-09-27 | 2021-07-02 | 苏州大学 | Method for preparing lithium electrode protective layer by adopting self-assembled RGO film |
| CN109755538A (en) * | 2019-02-01 | 2019-05-14 | 哈尔滨工程大学 | A kind of Li-Ti3C2- rGO composite film material and preparation method thereof |
| CN111261833A (en) * | 2020-01-19 | 2020-06-09 | 中南大学 | Self-supporting lithium metal cathode and preparation and application thereof |
| CN111261833B (en) * | 2020-01-19 | 2021-06-22 | 中南大学 | Self-supporting lithium metal cathode and preparation and application thereof |
| CN111933948A (en) * | 2020-08-18 | 2020-11-13 | 武汉先见科技有限公司 | Lithium-sulfur battery, lithium-sulfur battery positive electrode material, lithium-sulfur battery negative electrode material and preparation method of lithium-sulfur battery positive electrode material |
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