CN114242943A - Graphene film and preparation method thereof, symmetrical battery and preparation method thereof, full battery and preparation method thereof - Google Patents
Graphene film and preparation method thereof, symmetrical battery and preparation method thereof, full battery and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 88
- 239000011230 binding agent Substances 0.000 claims abstract description 22
- 239000002121 nanofiber Substances 0.000 claims abstract description 19
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002033 PVDF binder Substances 0.000 claims abstract description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 11
- 238000001291 vacuum drying Methods 0.000 claims abstract description 11
- 238000005096 rolling process Methods 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 88
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 61
- 239000003792 electrolyte Substances 0.000 claims description 29
- 239000010409 thin film Substances 0.000 claims description 21
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 12
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 11
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 10
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 24
- 239000002184 metal Substances 0.000 abstract description 24
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- 239000005486 organic electrolyte Substances 0.000 abstract description 4
- 210000004027 cell Anatomy 0.000 description 50
- 238000000034 method Methods 0.000 description 17
- 239000011229 interlayer Substances 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 230000001351 cycling effect Effects 0.000 description 8
- 210000001787 dendrite Anatomy 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910010710 LiFePO Inorganic materials 0.000 description 5
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012923 LiCoO2In Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- -1 stirring uniformly Substances 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- H01M4/134—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a graphene film and a preparation method thereof, a symmetrical battery and a preparation method thereof, a full battery and a preparation method thereof, and belongs to the field of lithium metal batteries. Dispersing graphene in isopropanol, adding a nanofiber binder, performing vacuum filtration and vacuum drying, and transferring and rolling the obtained film from a substrate to obtain the graphene film; the nanofiber binder comprises polyvinylidene fluoride and N-methyl pyrrolidone; the concentration of polyvinylidene fluoride in the nanofiber binder is 0.02-0.03 g/mL. The graphene film provided by the invention is applied to the lithium metal battery cathode, has the purposes of regulating and controlling the interface of Li metal and organic electrolyte and inhibiting the growth of dendritic crystals, and can simply and effectively manufacture a safe and stable-circulating lithium metal cathode.
Description
The application is a divisional application of an invention patent with application date of 2019, 07, 12 and application number of 201910628769.0, and the invention name of application of a graphene film in a lithium metal battery cathode, a symmetrical battery, a full battery and a preparation method.
Technical Field
The invention relates to the technical field of lithium metal batteries, in particular to a graphene film and a preparation method thereof, a symmetrical battery and a preparation method thereof, and a full battery and a preparation method thereof.
Background
Lithium Ion Batteries (LIBs) are the most widely used energy storage devices, and have a great impact on our daily lives. However, the theoretical capacity of the graphite negative electrode is only 372mAh g-1This greatly limits the application of LIBs to high energy storage areas. The lithium metal negative electrode has ten times of theoretical capacity (3860mAh g) of the traditional graphite negative electrode-1) And the most negative potential (-3.045V), making Lithium Metal Batteries (LMBs) the most promising candidate for next generation energy storage devices. However, lithium metal negative electrodes cause serious safety problems and poor cycle performance during cyclic charge and discharge due to dendrite growth, high reactivity, and infinite volume change of lithium metal. These problems limit the commercial use of LMBs. Scientists have proposed a number of modification methods for this, including electrolyte additives, artificial SEI films, solid electrolytes, structured negative electrodes, etc., which inhibit dendritic growth to some extent, but still have the problem of dendritic growth.
Disclosure of Invention
In view of this, the present invention provides a method for preparing a graphene film. The graphene film obtained by the invention is applied to the lithium metal battery cathode, has the purposes of regulating and controlling the interface of Li metal and organic electrolyte and inhibiting the growth of dendritic crystals, and can simply and effectively manufacture a safe and stable-circulating lithium metal cathode.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a graphene film, which comprises the following steps: dispersing graphene in isopropanol, adding a nanofiber binder, performing vacuum filtration and vacuum drying, and transferring and rolling the obtained film from a substrate to obtain the graphene film;
the nanofiber binder comprises polyvinylidene fluoride and N-methyl pyrrolidone;
the concentration of polyvinylidene fluoride in the nanofiber binder is 0.02-0.03 g/mL.
The invention also provides the graphene film prepared by the preparation method in the technical scheme, and the thickness of the graphene film is 50 μm.
The invention also provides a symmetric battery, which sequentially comprises a negative battery shell, an elastic sheet, a gasket, a first lithium sheet, a first graphene film, a Celgard film, an electrolyte, a second graphene film, a second lithium sheet and a positive battery shell;
the first lithium sheet and the first graphene film have the same area, and the second lithium sheet and the second graphene film have the same area;
the first graphene film and the second graphene film are the graphene films in the technical scheme.
Preferably, the electrolyte comprises LiTFSI and an organic solvent, the organic solvent is a mixed solution of 1, 3-dioxolane and ethylene glycol dimethyl ether, and the concentration of the LiTFSI in the electrolyte is 1 mol/L.
The invention also provides a preparation method of the symmetrical battery in the technical scheme, which comprises the following steps:
and in the glove box, assembling a negative electrode battery shell, an elastic sheet, a gasket, a first lithium sheet, a first graphene film, a Celgard film, an electrolyte, a second graphene film, a second lithium sheet and a positive electrode battery shell in sequence to obtain the symmetrical battery.
The invention also provides a full battery, which sequentially comprises a negative battery shell, a lithium sheet, a graphene film, a diaphragm, an electrolyte, a positive electrode and a positive battery shell;
the graphene thin film is the graphene thin film according to the above claims.
Preferably, when the cathode is LiFePO4Electrode sheet or LiCoO2When the electrode plate is used, the diaphragm is a Celgard membrane; when the positive electrode is an air positive electrode, the diaphragm is a glass fiber film.
The invention also provides a preparation method of the full cell in the technical scheme, which comprises the following steps:
and in the glove box, assembling the negative electrode battery shell, the lithium sheet, the graphene film, the diaphragm, the electrolyte, the positive electrode and the positive electrode battery shell in sequence to obtain the full battery.
The invention provides a preparation method of a graphene film, which comprises the following steps: dispersing graphene in isopropanol, adding a nanofiber binder, performing vacuum filtration and vacuum drying, and transferring and rolling the obtained film from a substrate to obtain the graphene film; the nanofiber binder comprises polyvinylidene fluoride and N-methyl pyrrolidone; the concentration of polyvinylidene fluoride in the nanofiber binder is 0.02-0.03 g/mL. The graphene film obtained by the invention is introduced into the lithium battery cathode to be used as an interlayer so as to achieve the purposes of regulating and controlling the interface of Li metal and organic electrolyte and inhibiting the growth of dendritic crystals, the lithium metal cathode capable of safely and stably circulating is simply and effectively created, and the graphene film interlayer can regulate and control Li+Uniform deposition and nucleation, stable battery circulation and prolonged battery life. The data of the examples show that the lithium metal battery electrode provided by the invention can be at 1mA/cm2，1mAh/cm2The stable circulation time is more than 500h, the service life is far longer than that of a bare lithium electrode, even under the condition of large current (10 mA/cm)2) The method can realize long-life cycle, has smaller interface impedance before and after the cycle, has better interface stability and faster charge transfer rate, and has good performance in all batteries with the positive electrodes of lithium iron phosphate, lithium cobaltate and air electrodes.
Furthermore, the battery containing the graphene film is easy to prepare and can be applied to large-scale electronic device equipment.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a schematic diagram of the principal structure of a symmetrical battery of the present invention;
FIG. 2 is a schematic view of the main structure of the full cell according to the present invention;
FIG. 3 shows the Li-GF symmetric cell and the bare Li-metal symmetric cell fabricated in example 1 at 1mAh/cm2At a low current density of 1mA/cm under the limit of capacity2Voltage change curve of;
FIG. 4 shows bare Li metal symmetric cells and Li-GF symmetric cells at 10mA/cm for example 12Current density of 5mAh/cm2Voltage change curve of;
FIG. 5 is a graph of EIS before cycling at 1C current density for the LFP/Li-metal full cell and the LFP/Li-GF full cell of example 1;
FIG. 6 is an EIS plot of the LFP/Li-metal full cell and the LFP/Li-GF full cell of example 1 after 5 cycles at a current density of 1C;
FIG. 7 is a scanned image of bare Li electrodes and Li-GF composite electrodes of example 1, where (a) is the bare Li metal surface prior to cycling; (b) bare Li metal surface after 50 cycles; (c) the surface of Li metal in the Li-GF composite electrode is obtained after 50 cycles;
FIG. 8 is a graph comparing coulombic efficiencies for LCO/Li-GF full cells and LCO/Li Metal full cells of example 2;
FIG. 9 is the 50 th cycle charge-discharge curve for the LCO/Li-GF full cell and the LCO/Li Metal full cell of example 2;
fig. 10 is a graph comparing constant current cycle charge and discharge curves of the lithium-oxygen battery and the pure Li metal battery manufactured in example 3, wherein (a) is the 2 nd cycle and (b) is the 40 th cycle.
Detailed Description
The invention provides an application of a graphene film in a lithium metal battery cathode, wherein the graphene film is introduced between a lithium cathode and a diaphragm as an interlayer. The invention introduces the graphene film as the interlayer to achieve the purposes of regulating and controlling the interface of Li metal and organic electrolyte and inhibiting the growth of dendritic crystals, and the method is simple and effectiveA lithium metal cathode capable of safely and stably circulating is formed, and Li can be regulated and controlled by a graphene film interlayer+Uniform deposition and nucleation, stable battery circulation and prolonged battery life.
The invention also provides a symmetric battery, which sequentially comprises a negative electrode battery shell, an elastic sheet, a gasket, a first lithium sheet, a first graphene film, a Celgard film, an electrolyte, a second graphene film, a second lithium sheet and a positive electrode battery shell, wherein the first lithium sheet and the first graphene film have the same area, and the second lithium sheet and the second graphene film have the same area.
In the invention, the thicknesses of the first graphene thin film and the second graphene thin film are preferably 47-53 μm independently, and more preferably 50 μm independently. The source of the graphene thin film is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In an embodiment of the present invention, the graphene thin film is preferably obtained by a method including the following steps: and dispersing graphene in isopropanol, adding a nanofiber binder, performing vacuum filtration and vacuum drying, and then transferring and rolling the obtained film from a substrate to obtain the graphene film.
In the invention, the concentration of the suspension obtained by dispersing graphene in isopropanol is preferably 0.4-0.6 mg/mL. In the present invention, the dispersion is preferably ultrasonic dispersion, and the specific operation of the ultrasonic dispersion is not particularly limited in the present invention, and may be performed in a manner well known to those skilled in the art.
In the present invention, the nanofiber binder is preferably obtained by a process comprising the steps of: PVDF (polyvinylidene fluoride) was dissolved in NMP (N-methylpyrrolidone). In the invention, the concentration of the nanofiber binder is preferably 0.02-0.03 g/mL.
In the invention, the nanofiber binder is preferably slowly dropped with 2-3 drops by using a disposable pasteur dropper in the magnetic stirring process. The process of the magnetic stirring is not specially limited, and the raw materials can be uniformly mixed. The dosage of the nanofiber binder is not specially limited, and the graphene film can be obtained.
The specific modes of vacuum filtration, vacuum drying, transfer from the substrate and rolling are not specially limited, and the graphene film can be obtained. In the embodiment of the present invention, the rolling is preferably performed until the surface is uniformly flat.
In the invention, the graphene film is preferably in a shape of a disc, and the diameter of the disc-shaped graphene film is preferably 15.5-16 mm. In the present invention, the mass of the wafer-shaped graphene thin film having a diameter of 16mm is preferably 43 to 50 mg. In the present invention, the graphene thin film is preferably cut into a circular sheet with a diameter of 16mm by a slicer, and then cleaned with clear water and dried in vacuum for use. In the present invention, when the graphene thin film is preferably in a disk shape, it is preferably used for preparing a button-shaped lithium metal battery.
In the present invention, the first lithium sheet and the second lithium sheet are preferably also cut into circular disks having a diameter of 16 mm. In an embodiment of the present invention, the first lithium sheet and the second lithium sheet are each preferably a lithium foil.
The sources of the negative electrode battery case, the spring plate, the gasket, the Celgard membrane, the electrolyte and the positive electrode battery case are not particularly limited in the present invention, and commercially available products well known to those skilled in the art can be used.
In the present invention, the electrolyte preferably includes LiTFSI (lithium bistrifluoromethylsulfonylamide) and an organic solvent, which is preferably a mixed solution of 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME). In the present invention, the concentration of LiTFSI in the electrolyte is preferably 1 mol/L.
The invention also provides a preparation method of the symmetrical battery in the technical scheme, which comprises the following steps:
and in the glove box, assembling a negative electrode battery shell, an elastic sheet, a gasket, a first lithium sheet, a first graphene film, a Celgard film, an electrolyte, a second graphene film, a second lithium sheet and a positive electrode battery shell in sequence to obtain the symmetrical battery.
The method of assembling the present invention is not particularly limited, and the assembling method known to those skilled in the art may be used.
In bookIn the invention, O in the glove box2Preferably in an amount of<0.01ppm，H2The content of O is preferably<0.01ppm。
The invention also provides a full battery which sequentially comprises a negative battery shell, a lithium sheet, a graphene film, a diaphragm, an electrolyte, a positive electrode and a positive battery shell.
In the present invention, the thickness of the graphene thin film is preferably 43 to 57 μm, and more preferably 50 μm. In the present invention, there is no particular limitation on the source of the graphene thin film, and a commercially available product known to those skilled in the art may be adopted, and in the embodiment of the present invention, the graphene thin film is preferably consistent with the preparation method in the above scheme, and is not described herein again.
In the invention, the graphene film is preferably in a shape of a disc, and the diameter of the disc-shaped graphene film is preferably 15.5-16 mm. In the present invention, the mass of the wafer-shaped graphene thin film having a diameter of 16mm is preferably 43 to 50 mg. In the present invention, the graphene thin film is preferably cut into a circular sheet with a diameter of 16mm by a slicer, and then cleaned with clear water and dried in vacuum for use. In the present invention, when the graphene thin film is preferably in a disk shape, it is preferably used for preparing a button-shaped lithium metal battery.
In the present invention, the thickness of the lithium sheet is preferably 0.45 mm.
In the present invention, the positive electrode is preferably LiFePO4Electrode sheet or LiCoO2When the electrode plate is used, the diaphragm is a Celgard membrane; when the positive electrode is preferably an air positive electrode, the separator is a glass fiber film.
The invention is used for the cathode battery shell, the graphene film, the lithium sheet, the Celgard film, the glass fiber film, the electrolyte and the LiFePO4Electrode sheet and LiCoO2The source of the electrode plate and the positive electrode battery case is not particularly limited, and commercially available products known to those skilled in the art can be adopted, specifically, lithium foil is purchased from shenzhen, kyozhi technologies ltd, and the CR2032 battery case is adopted for assembling the battery.
In the present invention, the positive electrode is preferably LiFePO4Electrode sheet or LiCoO2In the case of electrode sheets, the electrolyte preferably includes LiPF6And an organic solvent, preferably a mixed solution of Ethylene Carbonate (EC) and dimethyl carbonate (DMC), in which LiPF is present6The concentration of (B) is preferably 1 mol/L. In the present invention, the mass ratio of ethylene carbonate to dimethyl carbonate in the mixed solution is preferably 1: 1.
In the present invention, the LiFePO4LiFePO in electrode slice4The content of (b) is preferably 7-12 mg/cm2More preferably 10.5 to 11.5mg/cm2。
The invention is to the LiFePO4The preparation method of the electrode sheet is not particularly limited, and the preparation method known to those skilled in the art can be adopted, specifically, for example, the LiFePO with the mass ratio of 8:1:14Mixing the powder, conductive carbon black (SuperP), a binder polyvinylidene fluoride (PVDF) and N-methylpyrrolidone (NMP) to obtain a mixed material, coating the mixed material on an aluminum sheet, and drying in vacuum at 110 ℃ for 12 hours to obtain LiFePO4An electrode sheet. The invention has no special limit on the dosage and the coating amount of the N-methylpyrrolidone, and can ensure LiFePO4LiFePO in electrode slice4The content of (b) may be within the above-mentioned range.
The invention is directed to the LiCoO2The preparation method of the electrode sheet is not particularly limited, and may be a preparation method well known to those skilled in the art, specifically, the electrode sheet contains 90% of LiCoO by mass2The powder, 5% acetylene black and 5% PVDF (polyvinylidene fluoride) are dissolved in NMP (N-methyl pyrrolidone) solvent and uniformly stirred, the stirred slurry is uniformly coated on aluminum foil by a coating machine, vacuum drying is carried out for 12h at the temperature of 110 ℃, and the aluminum foil is cut into round pieces with the diameter of 16mm for later use. In the present invention, the LiCoO2The active substance content of the electrode slice is preferably 12mg/cm2。
In an embodiment of the present invention, the air positive electrode is preferably provided by suzhou wingong sandisk energy science and technology limited, and the specific preparation method is preferably as follows: carbon powder and a binder are uniformly mixed and then coated on carbon paper to prepare the air anode, and the loading capacity of the carbon powder is preferably 0.5mg/cm2。
In the present invention, when the cathode is preferably an air cathode, the electrolyte preferably includes LiTFSI and tetraglyme, and the concentration of LiTFSI in the electrolyte is preferably 1 mol/L.
The invention also provides a preparation method of the full cell in the technical scheme, which comprises the following steps:
and in the glove box, assembling the negative electrode battery shell, the lithium sheet, the graphene film, the diaphragm, the electrolyte, the positive electrode and the positive electrode battery shell in sequence to obtain the full battery.
In the present invention, the atmosphere in the glove box is preferably identical to the above-described protocol, and will not be described herein.
The method of assembling the present invention is not particularly limited, and the assembling method known to those skilled in the art may be used.
The application of the graphene film in the negative electrode of the lithium metal battery, the symmetric battery, the full battery and the preparation method provided by the invention are described in detail with reference to the following examples, but the application of the graphene film in the negative electrode of the lithium metal battery, the symmetric battery, the full battery and the preparation method are not to be construed as limiting the scope of the invention.
In this example, the lithium foil was purchased from Shenzhen, Korozhida technology, Inc., and the battery was assembled using a CR2032 battery case.
Example 1
Graphene interlayer: dispersing graphene in an isopropanol solvent for ultrasonic dispersion to obtain a suspension liquid with the concentration of 0.4mg/mL, uniformly dispersing, then stirring at a high speed by using a magnetic stirrer, slowly pouring a nanofiber binder for stirring for 6 hours in the stirring process, slowly dropwise adding 2 drops by using a disposable pasteur dropper in the magnetic stirring process, then carrying out vacuum filtration and vacuum drying, and then transferring and rolling a graphene film from a substrate until the surface is uniform and flat, thereby obtaining a graphene interlayer with the thickness of 50 micrometers. The preparation method of the nanofiber binder comprises the following steps: PVDF was dissolved in NMP to give a concentration of 0.02 g/mL.
Li-GF composite electrode: the graphene film is cut into a wafer with the diameter of 16mm by a slicer, washed by clean water and then dried in vacuum, and the weight of the graphene film is 43mg, and the thickness of the graphene film is 50 mu m. The lithium foil was also cut into circular disks with a diameter of 16 mm.
LiFePO4(LFP) electrode pad: LiFePO with the mass ratio of 8:1:14Pouring SuperP (Ketjen black) and PVDF (polyvinylidene fluoride) into NMP (N-methyl pyrrolidone) solvent, stirring uniformly, coating the stirred slurry on aluminum foil uniformly by using a coating machine, and vacuum drying at 110 ℃ for 12 h. Cutting into 16mm diameter wafer, LiFePO4The active substance mass of the electrode slice is 7mg/cm2。
Battery system
The battery assembly was performed using a CR2032 battery case. Battery Assembly Process in glove Box (O)2<0.01ppm，H2O<0.01ppm) was completed. And the graphene film is placed on the upper surface of the lithium sheet.
The symmetric battery (Li-GF symmetric battery) is assembled according to the sequence of a negative battery shell, an elastic sheet, a gasket, a first lithium sheet, a first graphene film, Celgard film, electrolyte (1M LiTFSI in DOL/DME), a second graphene film, a second lithium sheet and a positive battery shell. The main structural schematic diagram of the resulting symmetrical cell is shown in fig. 1.
The full cell (LFP/Li-GF full cell) is based on negative cell shell-lithium sheet-graphene film-Celgard film-electrolyte (1.0M LiPF6 in EC:DMC＝1:1wt％)-LiFePO4And sequentially assembling the electrode plate and the positive electrode battery shell. The main structural schematic diagram of the full cell is shown in fig. 2.
Electrochemical testing
Symmetrical batteries: respectively at a low current density of 1mA/cm2Low capacity of 1mAh/cm2(ii) a High current density 10mA/cm2High capacity of 5mAh/cm2Under the conditions of (1) constant current charge-discharge cycle.
FIG. 3 shows the Li-GF symmetric cell and the bare Li-metal symmetric cell at 1mAh/cm obtained in example 12At a low current density of 1mA/cm under the limit of capacity2The voltage change curve shows the cycling stability and electrochemical deposition/stripping performance of bare Li metal and Li-GF. As can be seen from FIG. 3, the voltage of the bare Li metal symmetric battery suddenly drops to-0.20V in the first discharge process, which is 4 times that of the Li-GF symmetric battery. The voltage of the Li-GF symmetric cell gradually stabilized, about-0.07V, as the cycling proceeded. Li + is deposited on the graphene interlayer in the circulation process, and a stable SEI film is formed on the surface of the graphene interlayer, so that Li + can be uniformly deposited. However, the voltage of the bare Li metal symmetrical battery is gradually reduced, the voltage is reduced to-0.40V after about 250 hours, the polarization is serious, and on the contrary, the Li-GF symmetrical battery has lower polarization after 500 hours (250 cycles) of circulation and is more stable in circulation.
FIG. 4 shows Li-GF symmetric cells at high capacity limit of 5mAh/cm2At a high current density of 10mA/cm2The voltage change curve shows the cycle stability and electrochemical deposition/stripping performance of the bare Li metal and Li-GF symmetrical battery under the conditions of high capacity and large current. As can be seen from fig. 4, even after 100 cycles (100h), the overpotential of the symmetric cell with the Li-GF composite electrode was still below 0.07V, and the overpotential fluctuated, but still was less than 0.1V. While the symmetric cell with bare Li electrode showed an overpotential of 0.4V and random fluctuations early in the beginning of the cycling. In contrast, the symmetric cell with the Li-GF composite electrode exhibited superior cycling stability.
EIS: and testing the full battery after different cycle times at room temperature. The test frequency is 0.01 Hz-100 kHz, and the amplitude is 5 mV.
The interface resistance and the negative electrode surface charge transfer resistance are related to the high-frequency region semicircle. FIGS. 5 and 6 show the bare Li electrode and Li-GF composite electrode as the negative electrode and LiFePO as the positive electrode, respectively4The full cells constructed, respectively corresponding to the EIS results of the LFP/Li-metal full cell and the LFP/Li-GF full cell before and after the 1C current density cycle, had a large interface impedance of 375ohm before the cycle of the bare Li metal full cell, because a passivation film was formed on the surface of the electrode. After 5 cycles, the interfacial resistance dropped to 222ohm, since the passivation film decomposed and lithium dendrite formation caused an increase in surface area. The interface impedance before the LFP/Li-GF full battery is circulated is only 103ohm, and the interface impedance after the LFP/Li-GF full battery is circulated for 10 times is 85ohm, which shows that the Li-GF electrode is favorable for the oxidation-reduction reaction and accelerates the charge transmission process. This also explains well why Li-GF symmetric cells have lower voltage poles than bare Li metal symmetric cellsAnd (4) transforming.
Topography characterization
And opening the battery after the charge-discharge cycle in the glove box, and taking out the lithium sheet. And (3) putting the lithium sheets in the symmetrical battery into a DOL/DME solvent, putting the lithium sheets in the full battery into an EC/DMC solvent, carefully cleaning for three times, washing off redundant electrolyte and impurities on the surface, and then carrying out vacuum drying. The lithium sheet was then observed using a scanning electron microscope.
In order to observe the regulation and control effect of the graphene interlayer on the growth of lithium metal dendrites more visually, a lithium metal electrode before circulation and a lithium metal electrode at a current density of 1mA/cm are used2Cutoff capacity of 1mAh/cm2The bare lithium electrode and the Li-GF composite electrode after 50 cycles were observed under a scanning electron microscope, and the results obtained are shown in fig. 7.
The lithium metal surface before cycling was substantially flat with slight bumps and pits (fig. 7 a). After 50 times of constant current circulation, because the surface charge of the bare Li metal electrode is uneven, Li + is unevenly nucleated, and a large number of lithium dendrites appear on the surface of the bare Li metal electrode along with the increase of the deposition/stripping times and are connected into sheets (figure 7 b). In contrast, the lithium metal surface of the Li-GF composite electrode (fig. 7c), although also exhibiting lithium dendrite growth, is far less abundant than the bare Li metal electrode. The repeated growth and stripping of lithium dendrites forms a dead lithium layer, which causes the electrode to gradually lose effectiveness, affecting the battery life. Irregular lithium dendrite growth can also puncture the separator causing a battery short circuit, causing safety problems.
Example 2
LiCoO2(LCO) electrode sheet: 90% LiCoO2(LCO) powder, 5% acetylene black and 5% PVDF (polyvinylidene fluoride) are dissolved in NMP (N-methyl pyrrolidone) solvent and uniformly stirred, the stirred slurry is uniformly coated on an aluminum foil by a coating machine, and vacuum drying is carried out for 12 hours at the temperature of 110 ℃. Cutting into 16mm diameter circular slices, LiCoO2The active substance mass of the electrode slice is 12mg/cm2。
Battery system
The battery assembly was performed using a CR2032 battery case. Battery Assembly Process in glove Box (O)2<0.01ppm，H2O<0.01ppm) was completed. And the graphene film is placed on the upper surface of the lithium sheet.
LCO/Li-GF full cell is based on negative electrode cell shell-lithium sheet-graphene film-Celgard film-electrolyte (1.0M LiPF)6 in EC:DMC＝1:1wt％)-LiCoO2And sequentially assembling the electrode plate and the positive electrode battery shell.
LCO/Li Metal full cell based on negative cell shell-lithium sheet-Celgard membrane-electrolyte (1.0 MLiPF)6 in EC:DMC＝1:1wt％)-LiCoO2And sequentially assembling the electrode plate and the positive electrode battery shell.
Electrochemical testing
Circulating between 2.4V and 4.2V, and firstly circulating for two times at 0.1C current for activation and then carrying out charge-discharge cycle test at 1C current.
Fig. 8 is a coulombic efficiency comparison graph of an LCO/Li-GF full cell and an LCO/Li Metal full cell, and it can be seen from fig. 8 that the coulombic efficiency of the LCO full cell with a Li-GF composite electrode is in a stable state in 100 cycles, the coulombic efficiency is stabilized at about 100%, while the coulombic efficiency of the LCO full cell with a bare lithium electrode is unstable and is reduced to below 90% at the lowest, which indicates that the graphene interlayer can effectively improve the cycle stability of the LCO cell.
Fig. 9 shows the 50 th cycle charge-discharge curves of the LCO/Li-GF full cell and the LCO/Li Metal full cell, and it can be seen from fig. 9 that after 50 cycles, the LCO/Li-GF full cell with the composite electrode still maintains the specific capacity of 60mA · h/g, while the specific capacity of the LCO full cell with the bare lithium electrode is reduced to 24mA · h/g, and the overpotential is obviously increased. This should be due to the formation and growth of lithium dendrites and the increase of dead lithium layers during repeated charging and discharging. Therefore, the graphene interlayer can effectively reduce the capacity attenuation of the LCO full cell and reduce the polarization phenomenon.
Example 3
The air positive electrode is provided by Suzhou wingong sanden energy science and technology, Inc. And uniformly mixing the carbon powder and the binder, and coating the mixture on carbon paper to prepare the air anode. The loading capacity of the carbon powder is 0.5mg/cm2。
Battery system
The battery assembly was performed using a CR2032 battery case. Battery packLoaded in a glove box (O)2<0.01ppm，H2O<0.01ppm) was completed. And the graphene film is placed on the upper surface of the lithium sheet.
All-cell (O)2The Li-GF full cell) is assembled according to the sequence of a negative cell shell, a lithium sheet, a graphene film, glass fiber, electrolyte (1M LiTFSI in TRAGLYME is 100 Vol%) -an air positive electrode and a positive electrode cell shell, and the lithium-oxygen cell is obtained.
Electrochemical testing
All-battery: at 100mA · g-1Current, 250 mA. h.g-1And carrying out constant current circulation test under the cut-off capacity, wherein the test voltage range is 2.2V-4.5V.
Fig. 10 is a comparison graph of constant current cycling charge and discharge curves of a lithium-oxygen battery and a pure Li metal battery, wherein (a) is the 2 nd cycle, and (b) is the 40 th cycle, and it can be seen from the comparison of the graphs in fig. 10(a) and (b), for the lithium-oxygen battery with a bare lithium negative electrode, the polarization phenomenon becomes more and more obvious as the cycle progresses, the polarization is severe after the 40 th cycle and the capacity rapidly decays, while the capacity of the lithium-oxygen battery with a Li-GF composite electrode does not decay and obviously polarize, the charge voltage is kept below 4.2V, and the discharge voltage is stabilized at about 2.6V.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The preparation method of the graphene film is characterized by comprising the following steps: dispersing graphene in isopropanol, adding a nanofiber binder, performing vacuum filtration and vacuum drying, and transferring and rolling the obtained film from a substrate to obtain the graphene film;
the nanofiber binder comprises polyvinylidene fluoride and N-methyl pyrrolidone;
the concentration of polyvinylidene fluoride in the nanofiber binder is 0.02-0.03 g/mL.
2. The graphene thin film prepared by the preparation method of claim 1, wherein the thickness of the graphene thin film is 50 μm.
3. A symmetric battery is characterized by sequentially comprising a negative battery shell, an elastic sheet, a gasket, a first lithium sheet, a first graphene film, a Celgard film, an electrolyte, a second graphene film, a second lithium sheet and a positive battery shell;
the first lithium sheet and the first graphene film have the same area, and the second lithium sheet and the second graphene film have the same area;
the first graphene thin film and the second graphene thin film are the graphene thin film according to claim 2.
4. The symmetric battery as claimed in claim 3, wherein the electrolyte comprises LiTFSI and an organic solvent, the organic solvent is a mixed solution of 1, 3-dioxolane and glycol dimethyl ether, and the concentration of LiTFSI in the electrolyte is 1 mol/L.
5. A method of manufacturing a symmetrical battery according to claim 3 or 4, comprising the steps of:
and in the glove box, assembling a negative electrode battery shell, an elastic sheet, a gasket, a first lithium sheet, a first graphene film, a Celgard film, an electrolyte, a second graphene film, a second lithium sheet and a positive electrode battery shell in sequence to obtain the symmetrical battery.
6. The full battery is characterized by sequentially comprising a negative battery shell, a lithium sheet, a graphene film, a diaphragm, an electrolyte, a positive electrode and a positive battery shell;
the graphene thin film according to claim 2.
7. Full cell according to claim 6, wherein when the positive electrode is LiFePO4Electrode sheet or LiCoO2When the electrode plate is used, the diaphragm is Celgard a film; when the positive electrode is an air positive electrode, the diaphragm is a glass fiber film.
8. The method for producing a full cell according to claim 6 or 7, characterized by comprising the steps of:
and in the glove box, assembling the negative electrode battery shell, the lithium sheet, the graphene film, the diaphragm, the electrolyte, the positive electrode and the positive electrode battery shell in sequence to obtain the full battery.
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