CN113328057A - Composite metal lithium cathode and preparation method thereof - Google Patents
Composite metal lithium cathode and preparation method thereof Download PDFInfo
- Publication number
- CN113328057A CN113328057A CN202010127640.4A CN202010127640A CN113328057A CN 113328057 A CN113328057 A CN 113328057A CN 202010127640 A CN202010127640 A CN 202010127640A CN 113328057 A CN113328057 A CN 113328057A
- Authority
- CN
- China
- Prior art keywords
- carbon material
- lithium
- film layer
- layer
- material film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 138
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 71
- 239000002184 metal Substances 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 85
- 239000011888 foil Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000013329 compounding Methods 0.000 claims abstract description 22
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 15
- 239000004917 carbon fiber Substances 0.000 claims description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 15
- 239000002041 carbon nanotube Substances 0.000 claims description 12
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000007731 hot pressing Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- 239000002923 metal particle Substances 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 5
- 230000003321 amplification Effects 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 104
- 239000002238 carbon nanotube film Substances 0.000 description 18
- 239000000758 substrate Substances 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000011889 copper foil Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 238000010586 diagram Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000002077 nanosphere Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N NMP Substances CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
-
- 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
- H01M4/134—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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a composite metal lithium cathode and a preparation method thereof, wherein the preparation method comprises the following steps: s1, adding a carbon material and other additive materials into a solvent, and stirring to prepare slurry; s2, preparing the slurry into a carbon material film layer blank; s3, sintering the carbon material film layer blank in an inert atmosphere to obtain a carbon material film layer; and S4, transferring the carbon material film layer to a lithium metal foil in a pressure compounding manner to prepare the composite lithium metal negative electrode. The preparation method is simple and convenient in preparation process, less in chemical solvent usage, capable of using the existing lithium battery production equipment, easy for industrial amplification, adjustable in process parameters and capable of stably protecting the lithium metal.
Description
Technical Field
The invention relates to the technical field of new energy materials, in particular to a composite metal lithium cathode formed by pressure compounding of a carbon material film and a preparation method thereof.
Background
With the update of products in the fields of new energy automobiles, unmanned planes and the like, higher requirements are put forward on the energy density of lithium ion batteries. The graphite negative electrode can not meet the pursuit of high energy density of the battery, and the metallic lithium negative electrode is regarded as an ideal negative electrode material of the next generation battery as a new research hotspot, has the lowest potential and larger specific capacity.
However, the dendrite and volume expansion problems of the lithium metal negative electrode lead to rapid attenuation of the battery capacity or short circuit of the battery, which causes safety problems and seriously affects the practical application of the lithium metal negative electrode.
At present, many measures are taken for protecting the metallic lithium negative electrode, for example, a chemical solvent is used for carrying out surface modification on the metallic lithium, a polymer material is coated on the surface of the metallic lithium, surface carbon coating is carried out on lithium powder, and the like, so that the service life is prolonged, wherein the manner of protecting the metallic lithium by the carbon material has a good effect, the carbon material and the lithium have good compatibility and are suitable for lithium deposition, abundant microscopic porous shapes can inhibit the volume expansion of the lithium negative electrode, and the carbon material protection method is simple to operate, low in pollution, low in risk and easy to industrialize.
For example, in Interconnected hollow carbon nanospheres for stable lithium metal anodes (published as nature technology, published as 2014/27), a hollow carbon nanosphere film layer is constructed by a template method and transferred to the surface of metal lithium as a protective layer of a metal lithium negative electrode, the hollow gap is used for relieving volume expansion, and the carbon nanosphere film layer is used for inhibiting lithium dendrite growth. However, the template method is adopted to prepare the carbon sphere film layer, more chemical reagents are used, specifically, the polystyrene nano-microspheres adopted by the template method can be prepared by evaporating the aqueous solvent, and in the step of filling the binder PVDF, the solvent NMP needs to be removed by heating; the copper foil needs to be etched in the transfer of the carbon sphere film layer, a (NH4)2S2O8 solvent needs to be used, the waste is serious, the steps are complicated, and the large-scale production is difficult. For example, CN108365202A cinnanwu and the like use carbon powder or fluffy carbon material, and the lithium-carbon composite material is prepared by spraying carbon powder on the surface of a lithium sheet and pressing and compounding, the carbon powder is difficult to control, is not beneficial to production operation, and has great pollution and certain danger. For example, patent CN110190257A wangzhong 28635and the like disclose a preparation method of graphene-coated protected metal lithium microspheres, wherein an inert solvent is required for both a metal lithium microsphere dispersion liquid and a graphene dispersion liquid, the usage amount of a chemical solvent is large, the operation is complex, and the operation is performed by using a metal lithium dispersion and a carbon material powdery substance, so that the risk is high, and the requirement on the operation environment is high.
In summary, the lithium negative electrode has the problems of dendritic crystal growth, volume expansion and the like, most of the existing solutions use more chemical reagents, adopt powdery materials, are inconvenient to operate, have high pollution and danger, have complex processing steps, and are difficult to industrialize.
Disclosure of Invention
The invention aims to provide a preparation method of a composite metal lithium negative electrode, which is used for solving the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a composite metal lithium negative electrode comprises the following steps:
s1, adding a carbon material and other additive materials into a solvent, and stirring to prepare slurry;
s2, preparing the slurry into a carbon material film layer blank;
s3, sintering the carbon material film layer blank in an inert atmosphere to obtain a carbon material film layer;
and S4, transferring the carbon material film layer to a metal lithium foil in a pressure compounding manner to prepare the composite metal lithium negative electrode.
Preferably, the preparation method of the carbon material film layer blank in S2 includes: uniformly attaching the slurry to a release layer to form; the carbon material film layer in S3 includes a release layer and a carbon material layer attached to the surface of the release layer, and the composite lithium metal negative electrode in S4 is formed by combining the carbon material layer and the lithium metal foil.
Further, the preparation method of the lithium composite metal negative electrode in S4 specifically includes: transferring the carbon material film layer to a metal lithium foil in a pressure compounding mode; or coating a metal lithium foil between the two carbon material film layers, and preparing the sandwich-type metal lithium composite cathode in a pressure compounding manner.
Further, the method for preparing the lithium composite metal anode in S4 more specifically includes: positioning the release layer of the carbon material film layer on the outer surface of the carbon material film layer, bonding the other surface of the carbon material film layer with the outer surface of the metal lithium foil in a pressure compounding manner, and peeling the release layer from the carbon material layer so as to bond the carbon material layer on the metal lithium foil; or the metal lithium foil is coated between the two carbon material film layers in a pressure compounding mode, so that the carbon material layer of each carbon material film layer is tightly combined with the metal lithium foil, and then the release layer on the outer surface of each carbon material film layer is stripped from the corresponding carbon material layer, so that the metal lithium composite negative electrode in the sandwich form is prepared.
Preferably, the pressure compounding method includes rolling and hot pressing.
Preferably, the sintering temperature in S3 is more than 200 ℃, and the sintering time is more than 1 hour.
Preferably, the inert atmosphere in S3 is a nitrogen atmosphere or an argon atmosphere.
Preferably, the carbon material in S1 includes one or more of hard carbon, soft carbon, graphite, graphene, carbon fiber, carbon nanotube, and the like.
Preferably, the other additive materials described in S1 include one or more of polymers, inorganic nanoparticles, and metal particles.
The invention also provides a composite metal lithium cathode of the lithium ion battery, which is prepared by the method. The composite lithium metal cathode comprises a metal lithium foil, wherein one surface of the metal lithium foil is covered with an even carbon material layer to form a composite lithium metal cathode with a carbon material protective layer on the outer surface, or the two surfaces of the metal lithium foil are both covered with even carbon material layers to form a composite lithium metal cathode with a sandwich structure.
The invention also provides a lithium ion battery, and the negative electrode of the lithium ion battery adopts the composite metal lithium negative electrode.
Compared with the prior art, the invention has the beneficial effects that:
1. the method provided by the invention only uses the solvent in the first slurry preparation process, so that the consumption of the chemical solvent is small, and the environmental pollution can be reduced; meanwhile, as the preparation of the slurry is an inherent step of lithium battery production, the existing lithium battery production equipment can be adopted, and other equipment is not needed;
2. the metal lithium foil and the carbon material film layer are adopted for pressure compounding, so that the environment requirement is low, the foil compounding is adopted, the safety is higher, and the problems that harsher environment conditions and a large amount of chemical reagents are needed in the lithium powder treatment are solved;
3. compared with a three-dimensional framework (such as a carbon sphere membrane layer prepared by a template method) and polymer surface protection, the method disclosed by the invention is simple in preparation process and easier to operate, the three-dimensional membrane framework is formed, deposition of lithium is facilitated, lithium dendrites are accommodated, polymers (such as PVDF and polyimide polymers in the embodiment) are filled, the flexibility and elasticity of the membrane layer are ensured, the volume change in lithium de-intercalation cycle is adapted, and the membrane layer has excellent mechanical stability and electrochemical stability.
Drawings
FIG. 1 is a schematic diagram of a pressure recombination step of a lithium composite anode according to a first embodiment;
FIG. 2 is a schematic view showing a pressure recombination step of a lithium composite metal negative electrode in a sandwich form according to the second embodiment;
FIG. 3 is a scanning electron microscope image of a lithium metal composite negative electrode protected by a carbon material film layer;
FIG. 4 is a charge-discharge cycle diagram of a metallic lithium negative electrode (shown as a lithium negative electrode) and a metallic lithium composite negative electrode (shown as a composite negative electrode) protected by a carbon material layer of the present invention;
fig. 5 is a lithium-lithium symmetric cycle diagram of a lithium metal composite anode protected with a carbon material layer.
In fig. 1: 1-aluminum foil, 2-carbon material layer, 3-lithium layer, 4-copper foil, 5-carbon material film layer, 7-composite film layer and 8-composite metal lithium cathode; in fig. 2: 1-aluminum foil, 2-carbon layer, 3-lithium layer, 4-carbon layer, 5-copper foil, 6-carbon material film layer, 7-carbon material film layer, 8-composite film layer and 9-sandwich type composite metal lithium cathode.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the embodiment provides a preparation method of a composite metal lithium negative electrode, which comprises the following steps:
s1, weighing 100-300mg of carbon fiber and 30-100mg of dispersing agent, adding into the solvent, and preparing the stably dispersed slurry by means of ultrasound, stirring and the like;
s2, uniformly scraping and coating the slurry on an aluminum foil substrate serving as a release layer through a coating process, wherein the height of the scraper is set to be 5-200 microns, and a carbon fiber film layer blank is prepared and comprises the aluminum foil substrate and a carbon material slurry layer attached to the surface of the aluminum foil substrate;
s3, placing the prepared carbon fiber film layer blank in a tube furnace, and performing heat treatment at 200-500 ℃ for 2-6 hours in a nitrogen atmosphere or an argon atmosphere, wherein the lifting temperature rate is controlled at 50-150 ℃/h to prepare a carbon fiber film layer, and the carbon fiber film layer consists of a release layer and a carbon fiber layer attached to the release layer;
s4, overlapping and aligning the carbon fiber film layer and the metal lithium foil to enable the release layer to face outwards, enabling the carbon fiber layer to be opposite to the surface of the metal lithium foil, transferring the carbon fiber film layer to the surface of the metal lithium foil in a rolling or pressure thermal compounding mode, and then peeling the carbon fiber layer from the release layer to prepare the composite metal lithium cathode with the carbon fiber layer tightly combined with the surface of the metal lithium foil.
The solvent used in S1 includes water, ethanol, NMP, and the like.
As shown in fig. 1, the step of transferring the carbon fiber film layer to the surface of the lithium metal foil at S4 includes the following steps:
1. the aluminum foil substrate 1 of the carbon material film layer 5 is positioned on the outer surface of the carbon material film layer 5, and the other surface of the carbon material film layer 5, namely the outer surface of the carbon material layer 2, is combined with the surface of the metal lithium foil 3 in a rolling or hot-pressing and other pressure compounding mode to form a composite film layer 7;
2. the aluminum foil base 1 was peeled off the carbon material layer 2 to form a lithium composite anode 8.
The other surface of the lithium metal foil 3 is combined with the copper foil 4, and is not changed in the process of S4.
The release layer can also adopt copper foil.
The coating process can be replaced by a spraying process, and the carbon material slurry can be uniformly attached to the surface of the release layer.
Example 2:
the embodiment provides a preparation method of a composite metal lithium negative electrode, which comprises the following steps:
s1, weighing 100-300mg of carbon nano tube and 30-100mg of polymer Pvdf, adding into a solvent, and preparing stably dispersed slurry by means of ultrasound, stirring and the like;
s2, uniformly scraping and coating one part of slurry on an aluminum foil substrate serving as a first release layer through a coating process, uniformly scraping and coating the other part of slurry on a copper foil substrate serving as a second release layer, wherein the heights of scrapers are set to be 5-200 microns, and a first carbon nanotube film blank and a second carbon nanotube film blank are prepared, the first carbon nanotube film blank comprises the aluminum foil substrate and a carbon nanotube slurry layer attached to the surface of the aluminum foil substrate, and the second carbon nanotube film blank comprises a copper foil substrate and a carbon nanotube slurry layer attached to the surface of the copper foil substrate;
s3, placing the prepared first carbon nano tube film layer blank and the second carbon nano tube film layer blank in a tube furnace, and carrying out heat treatment at 200-500 ℃ for 2-6 hours in a nitrogen atmosphere or an argon atmosphere, wherein the lifting temperature rate is controlled to be 50-150 ℃/h, so as to prepare a first carbon nano tube film layer and a second carbon nano tube film layer;
s4, clamping the metal lithium foil between the first carbon nanotube film layer and the second carbon nanotube film layer, overlapping and aligning the three layers, and transferring the first carbon nanotube film layer and the second carbon nanotube film layer to two surfaces of the metal lithium foil in a rolling or pressure thermal compounding mode to prepare the lithium-carbon composite cathode material.
The solvent used in S1 includes water, ethanol, NMP, and the like.
As shown in fig. 2, S4 specifically includes the following steps:
1. respectively positioning the aluminum foil substrate 1 of the first carbon nanotube film layer 6 and the copper foil substrate 5 of the second carbon nanotube film layer 7 on the outer surface of the first carbon nanotube film layer 6 and the outer surface of the second carbon nanotube film layer 7, and respectively combining the other surface of the first carbon nanotube film layer 6, namely the outer surface of the carbon nanotube layer 2 and the other surface of the second carbon nanotube film layer 7, namely the carbon nanotube layer 4 with the upper and lower surfaces of the metal lithium foil 3 in a rolling or hot-pressing equal-pressure compounding manner to form a composite film layer 8;
2. and stripping the aluminum foil substrate 1 from the first carbon nanotube layer 2, and stripping the copper foil substrate 5 from the second carbon nanotube layer 4 to form the composite metal lithium cathode 9 in a sandwich form, wherein the first carbon nanotube layer 2 and the second carbon nanotube layer 4 are tightly combined on the upper surface and the lower surface of the metal lithium foil 3.
Example 3:
the present embodiment provides another preparation method of a composite lithium metal anode, which is similar to the preparation method of the second embodiment, and the difference is that 100-300mg of graphene is used as the carbon material in S1, and 30-100mg of polyimide is used as the additive.
Referring to fig. 3, which is a scanning electron microscope image of the lithium composite anode protected by the carbon material film prepared in any one of examples 1 to 3, fig. 3 shows that the composite lithium anode material is successfully prepared by successfully transferring the carbon material protection film onto the lithium metal anode.
Referring to fig. 4, which is a charge-discharge cycle diagram of a lithium metal negative electrode (shown as a lithium negative electrode) in the prior art and a composite lithium metal negative electrode (shown as a composite negative electrode) protected by a carbon material layer according to any one of embodiments 1 to 3 of the present invention, in the figure, a conventional lithium negative electrode is represented by a hollow circle, and a composite lithium metal negative electrode of the present invention is represented by a solid circle, and the figure shows that, under the same test conditions and a high surface capacity and a high current density, when a capacity retention rate is 80%, the lithium negative electrode cycles 76 circles, and the composite lithium metal negative electrode cycles 320 circles, and thus, the cycle performance of the composite lithium metal negative electrode is significantly improved.
FIG. 5 is a lithium symmetrical cycle diagram of a lithium composite metal lithium negative electrode protected with a carbon material layer according to any one of examples 1 to 3 of the present invention, wherein the lithium negative electrode is represented by a broken line and the lithium composite negative electrode is represented by a solid line. Fig. 5 illustrates that the interfacial stability of the composite lithium metal negative electrode is better than that of the lithium negative electrode: the longer the voltage stabilization time, the better the electrode performance, the dotted line represents the time voltage value of the lithium negative electrode, the solid line represents the time voltage value of the composite metal lithium negative electrode, and the comparison shows that the voltage of the composite metal lithium negative electrode is more stable than that of the lithium negative electrode, and the cycle performance is better.
According to the invention, carbon materials such as hard carbon, soft carbon, graphite, graphene, carbon fiber and carbon nano tube are used as the components of the protective layer of the metal lithium foil, the carbon materials have the characteristics of high stability and excellent conductivity, and are suitable for deposition and stripping of lithium ions, meanwhile, the porous form formed by the carbon materials is used for storing lithium, and relieving the volume expansion of lithium, and the added polymer material is used for binding the carbon materials, and provides certain elasticity and toughness, so that the integrity of the pole piece in the electrochemical process is ensured. Meanwhile, the method does not use lithium powder, is safer, adopts a film material for pressure compounding, has the advantages of simple preparation process and easy amplification, has the advantages of high thickness controllability and high stability, can realize industrialization by slightly changing the existing lithium ion battery production line, is used as a metal lithium composite cathode, obviously improves the cycle performance of the battery, and has very wide application prospect in the field of lithium ion batteries.
Example 4:
the embodiment provides a composite metal lithium negative electrode of a lithium ion battery, which is prepared by any one of the methods of embodiments 1 to 3, and comprises a metal lithium foil, wherein one surface of the metal lithium foil is covered with a uniform carbon material layer to form the composite metal lithium negative electrode with a carbon material protective layer on the outer surface, or two surfaces of the metal lithium foil are covered with uniform carbon material layers to form the composite metal lithium negative electrode with a sandwich structure.
Example 5:
this example provides a lithium ion battery, in which the negative electrode of the lithium composite metal negative electrode described in example 4 is used.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (11)
1. A preparation method of a composite metal lithium cathode is characterized by comprising the following steps: the method comprises the following steps:
s1, adding a carbon material and other additive materials into a solvent, and stirring to prepare slurry;
s2, preparing the slurry into a carbon material film layer blank;
s3, sintering the carbon material film layer blank in an inert atmosphere to obtain a carbon material film layer;
and S4, transferring the carbon material film layer to a metal lithium foil in a pressure compounding manner to prepare the composite metal lithium negative electrode.
2. The method of claim 1, wherein: the preparation method of the carbon material film layer blank in the S2 comprises the following steps: uniformly attaching the slurry to a release layer to form; the carbon material film layer in S3 includes a release layer and a carbon material layer attached to the surface of the release layer, and the composite lithium metal negative electrode in S4 is formed by combining the carbon material layer and the lithium metal foil.
3. The method of claim 2, wherein: the preparation method of the lithium composite metal negative electrode in S4 includes: transferring the carbon material film layer to a metal lithium foil in a pressure compounding mode; or coating a metal lithium foil between the two carbon material film layers, and preparing the sandwich-type metal lithium composite cathode in a pressure compounding manner.
4. The production method according to claim 3, characterized in that: the preparation method of the lithium composite metal anode described in S4 more specifically includes: positioning the release layer of the carbon material film layer on the outer surface of the carbon material film layer, bonding the other surface of the carbon material film layer with the outer surface of the metal lithium foil in a pressure compounding manner, and peeling the release layer from the carbon material layer so as to bond the carbon material layer on the metal lithium foil; or the metal lithium foil is coated between the two carbon material film layers in a pressure compounding mode, so that the carbon material layer of each carbon material film layer is tightly combined with the metal lithium foil, and then the release layer on the outer surface of each carbon material film layer is stripped from the corresponding carbon material layer, so that the metal lithium composite negative electrode in the sandwich form is prepared.
5. The production method according to any one of claims 1 to 4, characterized in that: the pressure compounding mode comprises rolling and hot pressing.
6. The method of claim 1, wherein: the sintering temperature in the S3 is more than 200 ℃, and the sintering time is more than 1 hour.
7. The production method according to claim 1 or 6, characterized in that: the inert atmosphere in the S3 is nitrogen atmosphere or argon atmosphere.
8. The method of claim 1, wherein: the carbon material in S1 includes one or more of hard carbon, soft carbon, graphite, graphene, carbon fiber, carbon nanotube, and the like.
9. The method of claim 1, wherein: the other additive materials in the S1 comprise one or more of polymers, inorganic nano particles and metal particles.
10. A composite lithium metal anode prepared by the method of any one of claims 1 to 9.
11. A lithium ion battery, wherein the negative electrode thereof is the lithium composite metal negative electrode according to claim 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010127640.4A CN113328057A (en) | 2020-02-28 | 2020-02-28 | Composite metal lithium cathode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010127640.4A CN113328057A (en) | 2020-02-28 | 2020-02-28 | Composite metal lithium cathode and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113328057A true CN113328057A (en) | 2021-08-31 |
Family
ID=77412598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010127640.4A Pending CN113328057A (en) | 2020-02-28 | 2020-02-28 | Composite metal lithium cathode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113328057A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114899351A (en) * | 2022-04-29 | 2022-08-12 | 蜂巢能源科技股份有限公司 | Composite lithium metal cathode, solid-state battery and preparation method of composite lithium metal cathode |
| FR3136117A1 (en) * | 2022-05-24 | 2023-12-01 | Saft | Negative electrode for lithium primary electrochemical element |
| CN118117044A (en) * | 2024-04-30 | 2024-05-31 | 济南中瑞泰新材料科技有限公司 | Preparation method and application of three-dimensional carbon material modified lithium metal |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110135810A1 (en) * | 2009-12-03 | 2011-06-09 | Marina Yakovleva | Finely deposited lithium metal powder |
| CN108346776A (en) * | 2018-02-08 | 2018-07-31 | 清华大学 | A kind of composition metal cathode of lithium of sandwich structure and preparation method thereof |
| CN108713267A (en) * | 2016-08-19 | 2018-10-26 | 株式会社Lg化学 | Including the cathode of multiple protective layer and the lithium secondary battery including the cathode |
| CN109686921A (en) * | 2018-11-21 | 2019-04-26 | 清华大学 | A kind of composition metal cathode of lithium and preparation method thereof with lithium carbon compound interface layer |
| CN109830656A (en) * | 2019-01-09 | 2019-05-31 | 清华大学 | A kind of preparation method of the lithium anode with solid-liquid compound interface layer |
-
2020
- 2020-02-28 CN CN202010127640.4A patent/CN113328057A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110135810A1 (en) * | 2009-12-03 | 2011-06-09 | Marina Yakovleva | Finely deposited lithium metal powder |
| CN108713267A (en) * | 2016-08-19 | 2018-10-26 | 株式会社Lg化学 | Including the cathode of multiple protective layer and the lithium secondary battery including the cathode |
| CN108346776A (en) * | 2018-02-08 | 2018-07-31 | 清华大学 | A kind of composition metal cathode of lithium of sandwich structure and preparation method thereof |
| CN109686921A (en) * | 2018-11-21 | 2019-04-26 | 清华大学 | A kind of composition metal cathode of lithium and preparation method thereof with lithium carbon compound interface layer |
| CN109830656A (en) * | 2019-01-09 | 2019-05-31 | 清华大学 | A kind of preparation method of the lithium anode with solid-liquid compound interface layer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114899351A (en) * | 2022-04-29 | 2022-08-12 | 蜂巢能源科技股份有限公司 | Composite lithium metal cathode, solid-state battery and preparation method of composite lithium metal cathode |
| FR3136117A1 (en) * | 2022-05-24 | 2023-12-01 | Saft | Negative electrode for lithium primary electrochemical element |
| CN118117044A (en) * | 2024-04-30 | 2024-05-31 | 济南中瑞泰新材料科技有限公司 | Preparation method and application of three-dimensional carbon material modified lithium metal |
| CN118117044B (en) * | 2024-04-30 | 2024-07-19 | 济南中瑞泰新材料科技有限公司 | Preparation method and application of three-dimensional carbon material modified lithium metal |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102201565B (en) | High-capacity metal lithium powder composite cathode and preparation method thereof, and multi-layer composite electrode | |
| CN112909234A (en) | Preparation method and application of lithium cathode or sodium cathode | |
| CN111430681B (en) | Negative electrode material, negative electrode sheet, preparation method of negative electrode sheet and all-solid-state lithium ion battery | |
| CN109037626B (en) | Alkali metal-based negative electrode and preparation method and application thereof | |
| CN113328057A (en) | Composite metal lithium cathode and preparation method thereof | |
| CN111261833B (en) | Self-supporting lithium metal cathode and preparation and application thereof | |
| CN108878893A (en) | A kind of fast charge negative electrode of lithium ion battery modified collector and preparation method thereof | |
| Xing et al. | Endowing Cu foil self-wettable in molten lithium: A roll-to-roll wet coating strategy to fabricate high-performance ultrathin lithium metal anodes | |
| CN101414679A (en) | Composite material and preparation method thereof, and cathode and lithium battery | |
| Li et al. | Lithiophilic interface guided transient infiltration of molten lithium for stable 3D composite lithium anodes | |
| CN112271272B (en) | Three-dimensional porous lithium cathode protected by organic modification layer on surface and preparation method and application thereof | |
| CN110993953B (en) | Positive plate, solid-state chemical power supply and preparation method | |
| CN117497723A (en) | Preparation method of MOF-derived carbon-coated silicon nanoparticle-limited MXene composite anode material of lithium ion battery | |
| CN115312776B (en) | Preparation method of high specific energy composite solid-state positive electrode | |
| CN113497217A (en) | Electrode, preparation method thereof and battery | |
| CN112750993A (en) | Silicon-carbon composite material, preparation method thereof, negative electrode and battery | |
| CN113745464B (en) | Preparation and application of liquid sodium-potassium alloy @ flexible hollow carbon paper electrode | |
| CN114373933B (en) | Solid-state battery positive plate, preparation method thereof and solid-state battery | |
| CN115084562A (en) | Carbon fluoride based metal lithium battery and manufacturing method thereof | |
| CN114824168A (en) | Lithium supplement agent and method for lithium ion battery anode, anode plate, lithium supplement slurry and battery | |
| CN106654226A (en) | High-capacity safe conductive high-polymer-coated elemental sulfur electrode material and manufacturing method thereof | |
| CN113506867A (en) | MoS for lithium ion battery2N/N doped composite material and preparation method thereof | |
| CN111646472A (en) | Method for in-situ preparation of porous silicon-carbon composite negative electrode material | |
| CN118073544B (en) | High-power graphite electrode and preparation method thereof | |
| CN112830465B (en) | Preparation method of modified LATP material and application of modified LATP material in inhibiting growth of lithium dendrites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210831 |