CN210074037U - Composite pole piece and lithium ion battery - Google Patents
Composite pole piece and lithium ion battery Download PDFInfo
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- CN210074037U CN210074037U CN201920827341.4U CN201920827341U CN210074037U CN 210074037 U CN210074037 U CN 210074037U CN 201920827341 U CN201920827341 U CN 201920827341U CN 210074037 U CN210074037 U CN 210074037U
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- 239000002131 composite material Substances 0.000 title claims abstract description 67
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 42
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 165
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 136
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 87
- 239000002086 nanomaterial Substances 0.000 claims abstract description 57
- 239000010410 layer Substances 0.000 claims abstract description 55
- 239000011241 protective layer Substances 0.000 claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 24
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- 238000003756 stirring Methods 0.000 description 6
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
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- 239000002238 carbon nanotube film Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
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- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The utility model discloses a compound pole piece and lithium ion battery. The composite pole piece comprises an electrode substrate, a protective layer arranged on the surface of the electrode substrate and a carbon nano material layer arranged on the surface of the protective layer. The manufacturing method of the composite electrode provided by the utility model has the advantages of simple manufacturing process, low cost and easy large-scale production; the protective layer in the composite pole piece can improve the rigidity of a solid electrolyte interface and inhibit the growth of lithium dendrites, and meanwhile, the carbon nano-skeleton structure outside the protective layer plays a good supporting role on lithium metal, so that the volume change in the deposition/dissolution process of the lithium metal can be slowed down, and the thickness change of a lithium metal cathode in the charging and discharging process is eliminated; meanwhile, the existence of the carbon nano-skeleton structure can also increase the specific surface area, reduce the local current density, inhibit the growth of lithium dendrites and prevent the short circuit of the battery.
Description
Technical Field
The utility model particularly relates to a compound pole piece and lithium ion battery belongs to lithium ion secondary battery technical field.
Background
Lithium ion batteries are widely used in the field of portable devices such as mobile phones, notebook computers and digital products, and with the vigorous popularization of electric automobiles, higher requirements are put forward on the energy density and the power density of the lithium ion batteries. The carbon nano material is mostly selected as the traditional lithium ion battery cathode material, although the carbon cathode material shows excellent safety performance and cycle stability, the theoretical reversible specific capacity is only 372mAh/g, the energy density of the battery is difficult to break through 300Wh/kg, and the requirement of the electric automobile on long endurance mileage cannot be met.
The lithium metal cathode has high theoretical specific capacity (3860mAh/g) and low density (0.534 g/cm)3) And the lowest electrochemical potential (-3.04V vs. standard hydrogen electrode), so that the lithium metal as the cathode material provides a new way for realizing the high-energy-density energy storage device. Different from the process that lithium ions are inserted into and separated from a graphite sheet layer during the charging and discharging of a graphite cathode, the lithium metal cathode can generate the chemical deposition and dissolution process of lithium during the charging and discharging, and can bring about considerable volume change and uneven deposition during the lithium deposition/separation process, so that the lithium dendrite continuously grows and finally punctures a diaphragm, and the serious safety problem is caused. The U.S. Stanford university high and high teaches that a novel lithium sulfide SEI with uniform and high ionic conductivity is successfully designed and manufactured for stabilizing a lithium metal negative electrode through a sulfur steam-lithium metal gas-solid interface reaction method. Under the battery cycling conditions of high cycling surface capacity and high current density (5 mAh/cm)2，2mA/cm2) The uniform lithium sulfide SEI protective film can still effectively inhibit the generation of lithium dendrites and realize stable full battery long cycle. However, the method is complicated in process and harsh in operation conditions, and is not favorable for realizing large-scale industrial production.
SUMMERY OF THE UTILITY MODEL
The main object of the utility model is to provide a lithium metal/carbon nanomaterial composite electrode and a manufacturing method thereof and a lithium ion battery, thereby overcoming the defects in the prior art.
For realizing the purpose of the utility model, the utility model discloses a technical scheme include:
the embodiment of the utility model provides a manufacturing method of composite pole piece, it includes: and forming a carbon nano material layer on the surface of the electrode substrate in a mechanical rolling way.
In some more specific embodiments, the manufacturing method comprises: and arranging a carbon nano material on the surface of the electrode substrate, and forming the carbon nano material layer under the pressure condition of 1-10 MPa.
Further, the carbon nanomaterial includes any one or a combination of two or more of carbon foam, nanoporous carbon, carbon nanotube bundle, carbon paper, and carbon fiber, but is not limited thereto.
Preferably, the carbon nanotube bundle includes graphene.
Further, the morphology of the carbon nanomaterial includes any one or a combination of two or more of nanoparticles, nano single crystals, fibers, nano crystallites and nanocages, but is not limited thereto.
Further, the carbon nano material is a composite carbon nano material, and the composite carbon nano material comprises C-ZnO, C-Ag and C-Al2O3At least one of C-CuO and C-Au, or a combination of two or more thereof.
In some more specific embodiments, the manufacturing method further comprises: and manufacturing and forming a protective layer between the electrode substrate and the carbon nano material layer.
In some more specific embodiments, the manufacturing method specifically includes: placing the electrode substrate in a reaction solution for reaction treatment for 5-30s to form the protective layer; the solute of the reaction solution comprises one or a combination of more than two of polyvinylidene fluoride, zinc chloride, zinc fluoride, magnesium nitride, styrene butadiene rubber, carboxymethyl cellulose, Arabic gum and polyimide, but is not limited to the above; the solvent of the reaction solution includes one or a combination of two or more of N-methylpyrrolidone, N-dimethylformamide, dimethyl carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, ethylene carbonate, and tetrahydrofuran, but is not limited thereto.
Furthermore, the material of the electrode substrate comprises metal lithium.
The embodiment of the utility model provides a compound pole piece is still provided, including electrode base member, setting at the protective layer on electrode base member surface and set up the carbon nanometer material layer on protective layer surface.
Furthermore, the material of the electrode substrate comprises metal lithium.
Further, the material of the protective layer includes any one or a combination of two or more of an alloy, a metal oxide, a halide, a polymer, a sulfide, and a nitride, but is not limited thereto.
Further, the thickness of the protective layer is 0.1-10 μm.
Further, the carbon nano material layer has a three-dimensional porous skeleton structure.
Further, the material of the carbon nanomaterial layer is a carbon nanomaterial, and the carbon nanomaterial includes any one or a combination of two or more of carbon foam, nanoporous carbon, carbon nanotube bundle, carbon paper, and carbon fiber, but is not limited thereto.
Preferably, the carbon nanotube bundle is graphene.
Further, the morphology of the carbon nanomaterial includes any one or a combination of two or more of nanoparticles, nano single crystals, fibers, nano crystallites and nanocages, but is not limited thereto.
Furthermore, the carbon nano material layer is made of a composite carbon nano material which comprises C-ZnO, C-Ag and C-Al2O3At least one of C-CuO and C-Au, or a combination of two or more thereof.
Further, the thickness of the carbon nano material layer is 50-500 μm.
Further, the mass of the carbon nano material layer accounts for 20% -50% of the total mass of the dry materials in the composite electrode.
The embodiment of the utility model provides a lithium ion battery is still provided, include compound pole piece.
Compared with the prior art, the manufacturing method of the composite electrode provided by the utility model has the advantages of simple manufacturing process, low cost and easy large-scale production; the protective layer in the composite electrode can improve the rigidity of the solid electrolyte interface and inhibit the growth of lithium dendrites, and the carbon nano-skeleton structure outside the protective layer plays a good supporting role on lithium metal, so that the volume change in the deposition/dissolution process of the lithium metal can be slowed down, and the thickness change of a lithium metal cathode in the charging and discharging process can be eliminated; meanwhile, the existence of the carbon nano-skeleton structure can also increase the specific surface area, reduce the local current density, inhibit the growth of lithium dendrites and prevent the short circuit of the battery; and, the utility model provides a lithium metal/carbon nano-material composite negative plate can improve the security performance and the cycle performance of battery, applicable in different battery systems, battery model, and the range of application is wide.
Drawings
Fig. 1 is a schematic structural diagram of a lithium metal/carbon nanomaterial composite anode according to an exemplary embodiment of the present invention;
fig. 2 is an electrical diagram of a full cell assembled with a composite negative electrode prepared in example 1 of the present invention;
fig. 3 is an electrical diagram of a composite anode assembled full cell prepared in example 4 of the present invention;
fig. 4 is an electrical performance diagram of a full cell assembled with a lithium metal negative electrode prepared in comparative example 1;
fig. 5 is an electrical property diagram of a full cell assembled with a lithium metal negative electrode prepared in comparative example 2.
Detailed Description
In view of the deficiencies in the prior art, the inventor of the present invention has made extensive studies and practices to provide the technical solution of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
The embodiment of the utility model mainly provides a lithium metal/carbon nano-material composite negative plate and preparation method and lithium ion battery thereof. The preparation method mainly comprises the following steps: a protective layer is constructed on the outer surface of the polished lithium metal in advance (the protective layer is mainly used for increasing the stability of a solid electrolyte interface layer), and a carbon nano material layer is arranged outside the protective layer in a mechanical rolling mode, has a framework structure and has a good supporting effect on the lithium metal, so that the volume change of the lithium metal in the deposition/dissolution process can be slowed down, and the thickness change of a lithium metal negative plate in the charging and discharging process is eliminated; meanwhile, the framework structure of the carbon nano material layer can increase the specific surface area, reduce the local current density, effectively inhibit the growth of lithium dendrites, improve the safety performance of the battery and prolong the cycle life of the lithium metal battery.
In the following, the technical solutions of the present invention will be described in further detail with reference to several preferred embodiments and the accompanying drawings, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative efforts belong to the protection scope of the present invention. In the following examples, the reagents used are all preferably analytically pure.
Referring to fig. 1, a lithium metal/carbon nanomaterial composite negative electrode includes an electrode substrate 1, a protective layer 11 disposed on the surface of the electrode substrate 1, and carbon nanomaterial layers 2 and 3 disposed on the surface of the protective layer; the electrode substrate 1 is a metal lithium plate, the protective layer is mainly formed by laminating any one or more than two layers of an alloy layer, a metal oxide layer, a halide layer, a polymer layer, a sulfide layer and a nitride layer, and the thickness of the protective layer 11 is 0.1-10 mu m. The protective layer 11 is coated on the surface of the electrode substrate 1; the carbon nanometer material layers 2 and 3 can be integrally arranged, and the carbon nanometer material layers 2 and 3 are coated on the surface of the protective layer 11; or the carbon nanometer material layer 2 and the carbon nanometer material layer 3 are respectively arranged on the two opposite surfaces of the electrode substrate 1, so that the electrode substrate 1 is arranged between the carbon nanometer material layer 2 and the carbon nanometer material layer 3; the carbon nano material layers 2 and 3 both have a three-dimensional porous skeleton structure, the carbon nano material layer is made of carbon nano materials, and the carbon nano materials comprise any one or a combination of more than two of carbon foam, nano porous carbon, carbon nanotube bundles, carbon paper and carbon fibers, but are not limited to the above; the thickness of the carbon nano material layer is 50-500 mu m; wherein, the mass of the carbon nano material covered on the lithium metal surface accounts for 20-50% of the total mass of the dry materials in the composite electrode.
Example 1:
a preparation method of a lithium metal/carbon nano material composite negative plate comprises the following steps:
1) dissolving 50mg of SBR in NMP solvent (0.5 wt%), and magnetically stirring (300 rpm/min) at 25 ℃ for 30min to uniformly disperse the SBR to obtain reaction liquid;
2) polishing a lithium metal sheet with the size of 8.0cm by 6.5cm by using a polishing block with 1000 meshes, immersing the lithium metal sheet in the reaction solution, reacting for 10s, taking out the lithium metal sheet, and standing for 10s in a clean surface dish;
3) immersing the lithium metal sheet treated in the step 2) in graphene powder to enable the outer surface of the lithium metal sheet to be completely covered by black graphene and a lithium metal luster-free surface to be exposed, then applying pressure on the lithium metal/graphene by using a roller until a compact graphene layer is formed on the surface of the lithium metal sheet and no powder falls off, and finally obtaining the lithium metal/graphene composite negative electrode sheet.
The prepared lithium metal/graphene composite negative plate, a nickel-cobalt-manganese positive plate and a diaphragm are laminated, and are matched with a carbonate electrolyte to assemble a lithium ion battery, and the current density of the formed lithium ion battery is 1mA/cm2The electrical properties under the conditions were tested, and the results are shown in fig. 2, and the lithium ion battery obtained by assembling the lithium metal/graphene composite negative electrode sheet manufactured in this example can stably cycle 40 cycles with a capacity retention rate of 90% or more, and the coulombic efficiency of 95% or more.
Example 2
A preparation method of a lithium metal/carbon nano material composite negative plate comprises the following steps:
1) firstly, 50mg of SBR is dissolved in a DMF solvent (1.0wt percent) and is magnetically stirred (300 rpm/min) for 60min at 25 ℃ to be uniformly dispersed to obtain a reaction solution;
2) polishing a lithium metal sheet with the size of 8.0cm by 6.5cm by using a polishing block with 1000 meshes, immersing the lithium metal sheet in the reaction solution, reacting for 20s, taking out, and standing for 15 s;
3) immersing the lithium metal sheet treated in the step 2) in the carbon nano tube powder to enable the outer surface of the lithium metal sheet to be completely covered by the carbon nano tube and the non-lithium metal luster surface to be exposed, then applying pressure on the lithium metal/carbon nano tube sheet by using a roller until a compact carbon nano tube layer is formed on the surface of the lithium metal sheet and no powder falls off, and finally obtaining the lithium metal/carbon nano tube composite negative plate.
The prepared lithium metal/carbon nano tube composite negative plate, the nickel-cobalt-manganese positive plate and the diaphragm are laminated, and are matched with carbonate electrolyte to assemble the lithium ion battery, and the current density of the formed lithium ion battery is 1mA/cm2The electrical properties under the conditions were tested, and the results were substantially identical to those of example 1
Example 3:
a preparation method of a lithium metal/carbon nano material composite negative plate comprises the following steps:
1) firstly, 100mg of zinc fluoride is dissolved in THF solvent (1.0 wt%), and is stirred by magnetic force (300 rpm/min) for 40min at 25 ℃ to be dispersed evenly to obtain reaction liquid;
2) polishing a lithium metal sheet with the size of 8.0cm by 6.5cm by using a polishing block with 1000 meshes, immersing the lithium metal sheet in the reaction solution, reacting for 30s, taking out, and standing for 10 s;
3) placing a piece of carbon paper (8.0cm by 6.5cm) with the same size on the upper surface and the lower surface of the lithium metal sheet treated in the step 2), placing the whole lithium metal sheet into a roller press, adjusting the pressure to be 5MPa, and enabling the surface of the lithium metal to be tightly combined with the carbon paper, thereby finally obtaining the lithium metal/carbon paper composite negative plate.
The prepared lithium metal/carbon paper composite negative plate, the nickel-cobalt-manganese positive plate and the diaphragm are laminated, and are matched with carbonate electrolyte to assemble the lithium ion battery, and the current density of the formed lithium ion battery is 1mA/cm2The electrical properties under the conditions were tested and the results were substantially identical to those of example 1.
Example 4:
a preparation method of a lithium metal/carbon nano material composite negative plate comprises the following steps:
1) dissolving 100mg of CMC in DMF (1.0 wt%), and magnetically stirring at 25 deg.C (300 rpm/min) for 30min to disperse uniformly to obtain reaction solution;
2) polishing a lithium metal sheet with the size of 8.0cm by 6.5cm by using a polishing block with 1000 meshes, immersing the lithium metal sheet in the reaction solution, reacting for 10s, taking out, and standing for 5 s;
3) uniformly covering two pieces of carbon paper (8.0cm by 6.5cm) with the same size on the upper surface and the lower surface of the lithium metal sheet treated in the step 2), wherein no obvious air bubbles are generated, and then applying pressure on the lithium metal/carbon paper sheet by using a roller until a compact carbon paper film is formed on the surface of the lithium metal sheet, thereby finally obtaining the lithium metal/carbon paper composite negative electrode sheet.
The prepared lithium metal/carbon paper composite negative plate, the nickel-cobalt-manganese positive plate and the diaphragm are laminated, and are matched with carbonate electrolyte to assemble the lithium ion battery, and the current density of the formed lithium ion battery is 1mA/cm2The electrical properties under the conditions were tested, and the results are shown in fig. 3, and the lithium ion battery obtained by assembling the lithium metal/carbon paper composite negative electrode sheet manufactured in this example can stably circulate for 60 cycles with a capacity retention rate of 90% or more, and the coulombic efficiency is maintained at 99% or more.
Example 5:
a preparation method of a lithium metal/carbon nano material composite negative plate comprises the following steps:
1) dissolving 50mg of zinc chloride in NMP solvent (0.5 wt%), and magnetically stirring at 25 ℃ (300 rpm/min) for 30min to disperse uniformly to obtain reaction solution;
2) polishing a lithium metal sheet with the size of 8.0cm by 6.5cm by using a polishing block with 1000 meshes, immersing the lithium metal sheet in the reaction solution, reacting for 10s, taking out, and standing for 5 s;
3) immersing the lithium metal sheet processed in the step 2) in graphene powder to enable the outer surface of the lithium metal sheet to be completely covered by black graphene and a lithium metal luster-free surface to be exposed, then putting the lithium metal/graphene sheet into a roller press, and adjusting the pressure to be 3MPa to enable a layer of compact graphene film to be formed on the upper surface and the lower surface of the lithium metal sheet, so as to finally obtain the lithium metal/graphene composite negative plate.
The prepared lithium metal/graphene composite negative plate, a nickel-cobalt-manganese positive plate and a diaphragm are laminated, and are matched with a carbonate electrolyte to assemble a lithium ion battery, and the current density of the formed lithium ion battery is 1mA/cm2The electrical properties under the conditions were tested, and the results were combined with the test in example 4The fruit is basically consistent.
Example 6:
a preparation method of a lithium metal/carbon nano material composite negative plate comprises the following steps:
1) dissolving 50mg of PI in a DMC solvent (0.5 wt%), and uniformly dispersing the solution by magnetic stirring (300 rpm/min) at 25 ℃ for 30min to obtain a reaction solution;
2) polishing a lithium metal sheet with the size of 8.0cm by 6.5cm by using a polishing block with 1000 meshes, immersing the lithium metal sheet in the reaction solution, reacting for 10s, taking out, and standing for 5 s;
3) immersing the lithium metal sheet treated in the step 2) in the C-ZnO powder to enable the outer surface of the lithium metal sheet to be completely covered by the C-ZnO and the non-lithium metal luster surface to be exposed, then putting the lithium metal/C-ZnO sheet into a rolling machine, and adjusting the pressure to be 4MPa to enable a layer of compact C-ZnO film to be formed on the upper surface and the lower surface of the lithium metal sheet, thereby finally obtaining the lithium metal/C-ZnO composite negative plate.
The prepared lithium metal/C-ZnO composite negative plate, a nickel-cobalt-manganese positive plate and a diaphragm are laminated by a lamination process and are matched with a carbonate electrolyte to assemble a lithium ion battery, and the current density of the formed lithium ion battery is 1mA/cm2The electrical properties under the conditions were tested and the results were substantially identical to those of example 4.
Example 7:
a preparation method of a lithium metal/carbon nano material composite negative plate comprises the following steps:
1) dissolving 100mg of magnesium chloride in a THF (tetrahydrofuran) solvent (1.0 wt%), and uniformly dispersing the magnesium chloride by magnetic stirring (300 rpm/min) at 25 ℃ for 60min to obtain a reaction solution;
2) polishing a lithium metal sheet with the size of 8.0cm by 6.5cm by using a polishing block with the size of 1000 meshes, immersing the lithium metal sheet in the reaction solution, standing for 30s, taking out the lithium metal sheet, and standing for 5 s;
3) immersing the lithium metal sheet treated in the step 2) in the C-CuO powder, then putting the lithium metal/C-CuO into a roller press, and adjusting the pressure to be 3MPa, so that a layer of compact C-CuO film is formed on the upper surface and the lower surface of the lithium metal sheet, and finally obtaining the lithium metal/C-CuO composite negative plate.
The prepared lithium metal/C-CuO composite negative plate, a nickel-cobalt-manganese positive plate and a diaphragm adopt a lamination process, a carbonate electrolyte is matched to assemble a lithium ion full battery, and the current density of the formed lithium ion battery is 1mA/cm2The electrical properties under the conditions were tested and the results were substantially identical to those of example 4.
Example 8:
a preparation method of a lithium metal/carbon nano material composite negative plate comprises the following steps:
1) 50mg of CMC is firstly dissolved in DMF solvent (0.5wt percent) and is magnetically stirred (300 rpm/min) for 30min at 25 ℃ to be uniformly dispersed to obtain reaction liquid;
2) polishing a lithium metal sheet with the size of 8.0cm by 6.5cm by using a polishing block with 1000 meshes, immersing the lithium metal sheet in the reaction solution, standing for 20s, taking out the lithium metal sheet, and standing for 10 s;
3) immersing the lithium metal sheet treated in the step 2) in C-Al2O3In the powder, and then applying pressure to the lithium metal/C-Al by using a roller2O3Forming a layer of compact C-Al on the lithium sheet until the surface of the lithium sheet2O3Film to finally obtain lithium metal/C-Al2O3And compounding the negative plate.
The obtained lithium metal/C-Al2O3The composite negative plate, the nickel-cobalt-manganese positive plate and the diaphragm adopt a lamination process, are matched with carbonate electrolyte to assemble the lithium ion battery, and the current density of the formed lithium ion battery is 1mA/cm2The electrical properties under the conditions were tested and the results were substantially identical to those of example 4.
Example 9:
a preparation method of a lithium metal/carbon nano material composite negative plate comprises the following steps:
1) dissolving zinc fluoride and CMC in THF solvent (1.8:1), and magnetically stirring at 25 deg.C (300 rpm/min) for 30min to obtain reaction solution;
2) polishing and grinding the lithium metal sheet with the size of 8.0cm by 6.5cm by using a 1000-mesh grinding block, immersing the lithium metal sheet in the reaction solution, reacting for 20s, taking out, and standing for 10 s;
3) immersing the lithium metal sheet processed in the step 2) in graphene powder to enable the outer surface of the lithium metal sheet to be completely covered by black graphene and a lithium metal luster-free surface to be exposed, then putting the lithium metal/graphene sheet into a roller press, adjusting the pressure to be 3MPa to enable a layer of compact graphene carbon film to be formed on the upper surface and the lower surface of the lithium metal sheet, and finally obtaining the lithium metal/graphene composite negative plate.
The prepared lithium metal/graphene composite negative plate, a nickel-cobalt-manganese positive plate and a diaphragm are laminated by a lamination process and are matched with a carbonate electrolyte to assemble a lithium ion battery, and the current density of the formed lithium ion battery is 1mA/cm2The electrical properties under the conditions were tested and the results were substantially identical to those of example 4.
Example 10:
a preparation method of a lithium metal/carbon nano material composite negative plate comprises the following steps:
1) dissolving zinc chloride and SBR in a DMF solvent (1.8:1), and magnetically stirring (300 rpm/min) at 25 ℃ for 30min to uniformly disperse the zinc chloride and SBR to obtain a reaction solution;
2) polishing a lithium metal sheet with the size of 8.0cm by 6.5cm by using a polishing block with 1000 meshes, immersing the lithium metal sheet in the reaction solution, reacting for 20s, taking out and standing for 10 s;
3) immersing the lithium metal sheet treated in the step 2) in the carbon nanotube powder to enable the outer surface of the lithium metal sheet to be completely covered by the carbon nanotubes and no lithium metal luster surface to be exposed, then putting the lithium metal/carbon nanotube sheet into a roller press, adjusting the pressure to be 3MPa to enable the upper surface and the lower surface of the lithium metal sheet to form a layer of compact carbon nanotube film, and finally obtaining the lithium metal/carbon nanotube composite negative plate.
The prepared lithium metal/carbon nano tube composite negative plate, the nickel-cobalt-manganese positive plate and the diaphragm are assembled into the lithium ion battery by adopting a lamination process and matching with the carbonate electrolyte, and the current density of the formed lithium ion battery is 1mA/cm2The electrical properties under the conditions were tested and the results were substantially identical to those of example 4.
Comparative example 1:
a preparation method of a lithium metal negative plate comprises the following steps:
1) dissolving 50mg of SBR in NMP solvent (0.5 wt%), and magnetically stirring (300 rpm/min) at 25 ℃ for 30min to uniformly disperse the SBR to obtain reaction liquid;
2) and (3) polishing the lithium metal sheet with the size of 8.0cm by 6.5cm by using a 1000-mesh polishing block, immersing the lithium metal sheet in the reaction solution for reaction for 5s, taking out the lithium metal sheet for standing for 10s, and applying pressure to the lithium metal sheet by using a roller to finally obtain the lithium metal negative electrode sheet.
3) The lithium metal sheet treated in the step 2), the nickel-cobalt-manganese positive plate and the diaphragm are assembled into the lithium ion battery by adopting a lamination process and matching with a carbonate electrolyte, and the current density of the formed lithium ion battery is 1mA/cm2The results of the tests on the cycle performance under the conditions are shown in fig. 4, the capacity retention rate of the battery obtained by the comparative example can only cycle twenty-few circles at 80%, and the capacity fading is obvious.
Comparative example 2
A preparation method of a lithium metal negative plate comprises the following steps:
1) and (2) polishing a lithium metal sheet with the size of 8.0cm by 6.5cm by using a 1000-mesh polishing block, immersing the lithium metal sheet into carbon nanotube powder to enable the outer surface of the lithium metal sheet to be completely covered by the carbon nanotubes and a lithium metal luster-free surface to be exposed, putting the lithium metal/carbon nanotube sheet into a roller press, adjusting the pressure to be 4MPa to enable a layer of compact carbon nanotube film to be formed on the upper surface and the lower surface of the lithium metal sheet, and finally obtaining the lithium metal/carbon nanotube composite negative electrode sheet.
2) The lithium metal sheet treated in the step 1), a nickel-cobalt-manganese positive plate and a diaphragm are assembled into a lithium ion battery by adopting a lamination process and a carbonate electrolyte, and the current density of the formed lithium ion battery is 1mA/cm2The cycling performance under the conditions is tested, the result is shown in fig. 5, the battery capacity retention rate obtained by the comparative example can only stably cycle thirty or more circles at 80%, and the capacity attenuation is slow, which indicates that the existence of the porous carbon nano skeleton can play a certain supporting and protecting role on lithium relative to pure lithium metalThe application is as follows.
Comparative example 3
A preparation method of a lithium metal negative plate comprises the following steps:
1) the lithium is heated to a melting point of 180 ℃ or higher to melt it.
2) And covering a layer of array template on the graphene oxide film, and removing the template after the flash etching to obtain the graphene net with array cavities. Molten lithium is poured into the interlayer of the graphene oxide by utilizing the capillary effect, the graphene oxide is immediately reduced after contacting the molten lithium and generates gas, the volume of the film expands to facilitate pouring of the molten lithium, and finally the lithium/graphene negative electrode is obtained.
3) The lithium metal sheet obtained in the step 2), a nickel-cobalt-manganese positive plate and a diaphragm are assembled into a lithium ion battery by adopting a lamination process and matching with a carbonate electrolyte, and the current density of the formed lithium ion battery is 1mA/cm2The cycle performance under the condition is tested, and the result is shown in fig. 5, the battery capacity retention rate of 80% obtained by the comparative example can stably cycle for fifty or more circles, but the process is complex, the required graphene oxide sheet cannot be continuously produced, the molten liquid lithium can only be operated under the protection of argon, and the significance and the value of the practical application are not large.
The batteries obtained in example 1 and comparative examples 1 to 3 were tested, and the test results are shown in table 1, and it is demonstrated by combining the examples and comparative examples that the lithium metal/carbon nanomaterial composite negative electrode sheet obtained by mechanical rolling can effectively inhibit the growth of lithium dendrites, improve the safety performance of the battery, and can obtain good cycling stability and significantly improve the cycle life of the lithium metal battery when applied to the lithium ion battery.
Table 1: comparison of results of Electrical Performance test of the batteries in example 1 and comparative examples 1 to 3
In addition, the present inventors have also conducted experiments using other materials and conditions listed in this specification, etc., in the manner of examples 1 to 10, and have also succeeded in producing a lithium metal/carbon nanomaterial composite negative electrode sheet having stable cycle properties and excellent electrochemical properties and safety properties.
It should be noted that, in the present context, an element defined by the phrase "comprising … …" does not exclude the presence of other identical elements in steps, processes, methods or experimental facilities including the element.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and to implement the present invention, and therefore, the protection scope of the present invention should not be limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered by the protection scope of the present invention.
Claims (11)
1. A composite pole piece, comprising: the electrode comprises an electrode base body, a protective layer arranged on the surface of the electrode base body and a carbon nano material layer arranged on the surface of the protective layer.
2. The composite pole piece of claim 1, wherein: the electrode base includes a lithium substrate.
3. The composite pole piece of claim 1, wherein: the protective layer is coated on the surface of the electrode substrate, and the thickness of the protective layer is 0.1-10 mu m.
4. The composite pole piece of claim 3, wherein: the protective layer is mainly formed by stacking any one or more than two of an alloy layer, a metal oxide layer, a halide layer, a polymer layer, a sulfide layer and a nitride layer.
5. The composite pole piece of claim 1, wherein: the carbon nano material layer has a three-dimensional porous skeleton structure, and the protective layer is completely coated by the carbon nano material layer, or the electrode substrate is arranged between the two carbon nano material layers.
6. The composite pole piece of claim 5, wherein: the carbon nanomaterial layer is mainly composed of a carbon nanomaterial.
7. The composite pole piece of claim 6, wherein: the morphology of the carbon nano material comprises any one or the combination of more than two of nano particles, nano single crystals, fibers, nano microcrystals and nano cages.
8. The composite pole piece of claim 5, wherein: the carbon nano material layer is mainly composed of a composite carbon nano material.
9. The composite pole piece of claim 5, wherein: the thickness of the carbon nano material layer is 50-500 mu m.
10. The composite pole piece of claim 1, wherein: the mass of the carbon nano material layer accounts for 20-50% of the total mass of the dry materials in the composite electrode.
11. A lithium ion battery characterized by comprising the composite pole piece of any one of claims 1 to 10.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111987287A (en) * | 2020-08-26 | 2020-11-24 | 北京工业大学 | Lithium metal electrode and preparation method and application thereof |
| CN112103553A (en) * | 2020-10-21 | 2020-12-18 | 上海交通大学烟台信息技术研究院 | Novel lithium ion battery or lithium battery and preparation method thereof |
| CN112117438A (en) * | 2020-09-27 | 2020-12-22 | 蜂巢能源科技有限公司 | Negative plate, preparation method thereof and solid-state battery |
| CN113725392A (en) * | 2021-09-09 | 2021-11-30 | 郑州大学 | Interface modified metal zinc cathode and preparation method thereof |
| CN114388746A (en) * | 2020-10-21 | 2022-04-22 | 安徽盟维新能源科技有限公司 | Lithium metal negative electrode, lithium metal battery, preparation method of lithium metal negative electrode and lithium metal battery and method for inhibiting lithium dendrite |
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2019
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111987287A (en) * | 2020-08-26 | 2020-11-24 | 北京工业大学 | Lithium metal electrode and preparation method and application thereof |
| CN111987287B (en) * | 2020-08-26 | 2022-02-11 | 北京工业大学 | Lithium metal electrode and preparation method and application thereof |
| CN112117438A (en) * | 2020-09-27 | 2020-12-22 | 蜂巢能源科技有限公司 | Negative plate, preparation method thereof and solid-state battery |
| CN112103553A (en) * | 2020-10-21 | 2020-12-18 | 上海交通大学烟台信息技术研究院 | Novel lithium ion battery or lithium battery and preparation method thereof |
| CN114388746A (en) * | 2020-10-21 | 2022-04-22 | 安徽盟维新能源科技有限公司 | Lithium metal negative electrode, lithium metal battery, preparation method of lithium metal negative electrode and lithium metal battery and method for inhibiting lithium dendrite |
| CN114388746B (en) * | 2020-10-21 | 2024-01-23 | 安徽盟维新能源科技有限公司 | Lithium metal negative electrode, lithium metal battery, preparation method of lithium metal negative electrode and lithium dendrite inhibition method |
| CN113725392A (en) * | 2021-09-09 | 2021-11-30 | 郑州大学 | Interface modified metal zinc cathode and preparation method thereof |
| CN113725392B (en) * | 2021-09-09 | 2023-02-21 | 郑州大学 | Interface modified metal zinc cathode and preparation method thereof |
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