CN112670516A - Three-dimensional composite current collector and preparation method thereof - Google Patents
Three-dimensional composite current collector and preparation method thereof Download PDFInfo
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- CN112670516A CN112670516A CN201911120217.5A CN201911120217A CN112670516A CN 112670516 A CN112670516 A CN 112670516A CN 201911120217 A CN201911120217 A CN 201911120217A CN 112670516 A CN112670516 A CN 112670516A
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- 239000011165 3D composite Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 162
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 133
- 239000000463 material Substances 0.000 claims abstract description 73
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- 238000000576 coating method Methods 0.000 claims abstract description 54
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- 238000003756 stirring Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 29
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- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 14
- 239000002041 carbon nanotube Substances 0.000 claims description 14
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 14
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- 239000004917 carbon fiber Substances 0.000 claims description 4
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- 238000002156 mixing Methods 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 claims 1
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- 210000001787 dendrite Anatomy 0.000 abstract description 6
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- 238000006243 chemical reaction Methods 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 229910000398 iron phosphate Inorganic materials 0.000 description 8
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 8
- 239000007773 negative electrode material Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
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- 238000012360 testing method Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
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- OPUHLOIVOZBBNY-UHFFFAOYSA-M lithium carbonic acid fluoride Chemical compound C(O)(O)=O.[Li+].[F-] OPUHLOIVOZBBNY-UHFFFAOYSA-M 0.000 description 3
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- 229910010941 LiFSI Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 description 1
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- NYEGWRCMKSLUPG-UHFFFAOYSA-N [O-2].[Zn+2].C=CC=C.C=CC1=CC=CC=C1 Chemical compound [O-2].[Zn+2].C=CC=C.C=CC1=CC=CC=C1 NYEGWRCMKSLUPG-UHFFFAOYSA-N 0.000 description 1
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- 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 description 1
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Images
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 invention provides a three-dimensional composite current collector and a preparation method thereof. The three-dimensional composite current collector comprises a copper foil base layer and a lithium-philic material coating of a negative electrode of a lithium battery coated on the copper foil base layer; the lithium-philic material coating for the negative electrode of the lithium battery comprises a three-dimensional spherical structure with the size of a plurality of micrometers. The lithium-philic material for the negative electrode of the lithium battery consists of a carbon material, a lithium-philic metal oxide, a binder and a lithium salt. The preparation method comprises the steps of firstly preparing lithium battery negative electrode lithium-philic material slurry, then coating the slurry on a copper foil base layer to form a lithium battery negative electrode lithium-philic material coating, and preparing the lithium battery negative electrode three-dimensional composite current collector. The composite coating with the micron-sized three-dimensional spherical structure is formed by coating the lithium-philic material for the lithium battery cathode on the copper foil, so that the current density of the lithium metal cathode can be effectively reduced, the generation of lithium dendrites is effectively relieved and reduced, and the cycle performance and the safety performance of the lithium metal battery are improved.
Description
Technical Field
The invention relates to the field of battery materials, in particular to a three-dimensional current collector and a preparation method thereof.
Background
The lithium ion battery which is commercialized successfully at present has the characteristics of high working voltage, long cycle life, no memory effect and the like, and is widely applied to the fields of electric automobiles, mobile electronic equipment and the like. However, with the economic development and the technological progress, higher requirements are increasingly made on the energy density of the lithium ion battery. Graphite and the like are mostly adopted as negative electrode materials of the traditional lithium ion battery, the theoretical capacity of the traditional lithium ion battery is limited, and the current commercial lithium ion battery is closer to the theoretical specific capacity of the traditional lithium ion battery. Therefore, there is a need to search for and develop a lithium battery with higher energy density. The theoretical energy density of the metal lithium negative electrode material can be about ten times that of a graphite negative electrode, and the metal lithium negative electrode material has higher specific capacity and lower potential than graphite, and becomes a hotspot of research in the field of lithium battery negative electrode materials.
Lithium-oxygen batteries and lithium-sulfur batteries with higher energy density both use lithium metal as the negative electrode. However, lithium metal as a battery negative electrode has three problems during charging and discharging: the lithium dendrite problem generated when lithium ions are reduced in the charging process of the lithium battery; the lithium metal and the organic solvent have extremely high chemical reaction activity to cause low coulombic efficiency; volume change caused by the dissolution process of the metallic lithium deposit. These problems limit the development of industrial applications of lithium metal batteries. The current solution to the problem of stability of the high specific energy lithium negative electrode mainly comprises: improving the electrolyte, constructing a metal lithium protective layer, designing a lithium compound negative electrode, constructing a three-dimensional structure current collector and the like.
The conventional double-salt LiTFSI/LiFSI system for improving the electrolyte is improved to a certain extent, but the process is not completely stable, the surface of a lithium cathode also becomes black in the long-time large-current charge and discharge process, the SEI on the surface is broken, and the performance is deteriorated. Most of the existing literature reports that a protective layer is directly grown on the surface of metallic lithium in situ for constructing the protective layer of metallic lithium, but the metallic lithium has strong reactivity, so that the in situ growth is difficult, the requirements on reaction conditions are strict, and the practical use of the method is limited. The preparation of the lithium-carbon composite electrode generally adopts a method of uniformly coating lithium powder on a carbon electrode, and the method introduces great potential safety hazard due to high reaction activity of the lithium powder and is difficult to industrialize.
The surface structure and material components of the current collector have important influence on the performance of the lithium ion battery, the current negative copper foil current collector used at present has low surface roughness and low bonding strength with active negative slurry, and the electrochemical performance of the lithium battery is limited to a great extent. The current collector with the three-dimensional structure is constructed, so that the actual current density of the electrode can be effectively reduced, the electric field on the surface of the electrode is uniformly distributed, the uniform deposition of metal lithium is induced, the volume expansion is relieved, and the growth of lithium dendrites can be effectively inhibited. However, most of the current collectors with the three-dimensional lithium-philic property reported in the prior art require complicated preparation process flows or expensive raw materials, and the bonding force of the surface modification layer is often weak.
The invention patent with the application number of CN201910524383.5 discloses a three-dimensional current collector for a secondary lithium ion battery negative electrode and a preparation method thereof. The method mainly comprises the step of putting the copper foil subjected to heat treatment into an electrolytic cell of a sodium sulfate solution for surface treatment to obtain the three-dimensional current collector for the negative electrode of the secondary lithium ion battery. The method can efficiently prepare a large number of three-dimensional current collectors, but has the defects of complex process, higher cost and heavier unit weight because the three-dimensional current collectors are directly processed on the copper foil, and is not beneficial to tab welding and large-scale production for manufacturing the electric core.
The invention patent with the application number of CN201711449563.9 discloses application of iron phosphate and an iron phosphate composite material as a negative electrode in a dual-ion battery. The structure of the iron phosphate and the iron phosphate doped material disclosed by the method is a porous sphere with a micro-nano structure; and uniformly mixing the iron phosphate and iron phosphate composite material with carbon black and a binder, then coating the mixture on a current collector, and carrying out vacuum drying and slicing to obtain the iron phosphate and iron phosphate composite material negative electrode. The composite material has the advantages of high potential and no generation of dendrite in the repeated charge and discharge process, but the method has the defects that the connection performance of the composite material and the metal lithium is not improved, so that the metal lithium on a negative electrode is easy to fall off.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a lithium-philic material for a lithium battery negative electrode, a three-dimensional composite current collector and a preparation method thereof. The three-dimensional composite current collector can obviously improve the cycle performance of the lithium metal battery, and the manufacturing method is simple to operate and can meet the requirements of industrial mass production and use.
In order to achieve the purpose, the invention provides a three-dimensional composite current collector which comprises a copper foil base layer and a lithium-philic material coating coated on the copper foil base layer; the lithium-philic material coating for the negative electrode of the lithium battery comprises a three-dimensional spherical structure with the size of a plurality of micrometers.
Preferably, the lithium-philic material coating of the negative electrode of the lithium battery consists of a carbon material, a lithium-philic metal oxide, a binder and a lithium salt;
the mass ratio of the carbon material, the lithium-philic metal oxide, the binder and the lithium salt is 5-35% by mass: 75% -45%: 15% -5%: 5 to 15 percent. .
In order to achieve the above object, the present invention further provides a method for preparing the three-dimensional composite current collector, comprising the following steps:
s1, weighing a predetermined amount of carbon material, lithium-philic metal oxide and lithium salt, and mixing and stirring for 0.5-4 h; adding a solvent, and stirring for 0.5-2 hours until the solvent is completely dissolved; then adding a predetermined amount of binder, and stirring for 4-10 hours to prepare lithium-philic material slurry of the negative electrode of the lithium battery;
s2, selecting a copper foil with the thickness of 6-20 microns as a base layer, coating the slurry obtained in the step S1 on the copper foil at the coating speed of 10-30 m/min, drying for 4-8 h in a forced air drying oven at 70-80 ℃, and drying for 8-12 h in a vacuum oven at 110-130 ℃ to obtain the three-dimensional composite current collector.
Preferably, the lithium-philic metal oxide comprises, but is not limited to, one or more of cobaltosic oxide, zinc oxide, and copper oxide.
Preferably, the carbon material includes, but is not limited to, one of carbon nanotube, carbon fiber, acetylene black, and graphene.
Preferably, the lithium salt includes, but is not limited to, one of lithium carbonate, lithium fluoride, lithium nitride, and lithium nitrate.
Preferably, the binder is one of styrene butadiene rubber, acrylic resin, acrylonitrile and polyvinylidene fluoride.
Preferably, the solvent is one of water and N-methyl pyrrolidone.
Preferably, in step S1, the mass ratio of the carbon material, the lithium-philic metal oxide, the binder, and the lithium salt is 5% to 35%: 75% -45%: 15% -5%: 5 to 15 percent.
Compared with the prior art, the invention has the beneficial effects that:
1. the lithium-philic material for the negative electrode of the lithium battery provided by the invention forms a micron-sized three-dimensional spherical structure on the surface of the copper foil base layer, so that a composite current collector with a three-dimensional interconnected spherical structure is constructed, the specific surface area of the composite current collector is higher, the actual current density can be effectively reduced, and more Li can be provided+De-intercalation sites, thereby achieving uniform deposition; the three-dimensional structure can also buffer the volume change caused by the deposition of the metal lithium, relieve the volume expansion in the charging and discharging process and be beneficial to buffering the polarization reaction of the electrode, thereby improving the electrochemical performance of the electrode. In addition, the three-dimensional interconnected spherical structure provides a network which can be easily penetrated by electrolyte during charging and discharging, provides shorter transportation distance for lithium ions and electrons, and shortens Li+The lithium ion battery cathode lithium-philic material has more stable electrochemical performance and rate capability due to the diffusion path.
2. According to the lithium-philic material for the negative electrode of the lithium battery, provided by the invention, a carbon material, a lithium-philic metal oxide and a lithium salt are mixed together to prepare a lithium-philic transition metal oxide/carbon material/lithium ion composite material. 1) The carbon material functions as: the coating of the carbon material can relieve the volume expansion of the lithium-philic metal oxide; the conductivity of the alloy is enhanced; the structure of the composite material can be more stable. 2) The lithium-philic metal oxide functions as: on one hand, the defect of low specific capacity of the carbon material can be made up; on the other hand, the lithium-philic metal oxide can react with the lithium metal to anchor the lithium on the copper foil, and then the lithium metal can be firmly contacted with the copper foil through the combined action of chemical bonding force and external pressure, so that the contact impedance is reduced. 3) The lithium salt functions as: the lithium salt with a small proportion mainly plays a role in stabilizing the metal lithium, when the metal lithium is completely consumed, becomes lithium powder or is out of control thermally, the lithium salt can stabilize the safety performance of the battery, particularly the decomposition of lithium carbonate and lithium nitride, the side reaction of lithium fluoride and the like, and the generated gas can disconnect the connection of the active substance and the current collector. In addition, most of the lithium salt is non-conductive material, and the active reaction of lithium can be delayed to a certain extent in the charging and discharging process, so that the lithium salt plays a role in stabilizing the lithium metal cathode. Therefore, the lithium-philic metal oxide, the carbon material and the lithium salt are mixed to play a role, so that the electrochemical performance of the lithium-philic material of the negative electrode of the lithium battery is improved, and the roles of anchoring the lithium metal, increasing the conductivity and stabilizing the lithium metal are realized. And the three materials are mixed under the action of a binder and only used as a coating between the copper foil and the lithium metal, and the mixed material of the three materials can not be used as a negative electrode of a lithium battery when being used alone. Therefore, one of the three is not enough, otherwise, the performance of the lithium metal is lost.
3. In the three-dimensional composite current collector provided by the invention, a micron-sized three-dimensional spherical structure formed by coating a lithium-philic material of a negative electrode of a lithium battery on a copper foil is formed by the following mechanism: tubular or fibrous carbon material is high speed stirred and wound, and is agglomerated into micro spheres, added with lithium-philic metal oxide, filled with the lithium-philic metal oxide under stirring, and then coated and dried to form micron size spheres.
4. In the three-dimensional composite current collector provided by the invention, the micron-sized three-dimensional spherical structure formed by coating the lithium-philic material of the lithium battery negative electrode on the copper foil can effectively reduce the current density of the lithium metal negative electrode, thereby effectively relieving and reducing the generation of lithium dendrites and improving the cycle performance and safety performance of the lithium metal battery. Meanwhile, the micro-nano three-dimensional structure can provide space for the expansion of the metal lithium cathode, and the fracture of an SEI (solid electrolyte interphase) film on the surface of the lithium metal cathode is relieved, so that the coulomb efficiency of the lithium metal battery is improved to a certain extent.
5. In the three-dimensional negative electrode current collector provided by the invention, Gibbs free energy delta G of the lithium-philic metal oxide and the metallic lithium is less than 0, which shows that the lithium-philic metal oxide can react with the metallic lithium spontaneously, so that a lithium-philic material of a negative electrode of a lithium battery on a copper foil is tightly connected with the metallic lithium, the binding force of the copper foil and a lithium band is improved, and the probability of falling of the metallic lithium is reduced.
6. The three-dimensional negative current collector provided by the invention obviously improves the cycle performance of the lithium metal battery, has a simple manufacturing process, can meet the requirement of industrial batch production and use, and has excellent development prospect in the field of lithium battery application.
Drawings
Fig. 1 is a real object diagram of a three-dimensional composite current collector prepared in example 1 of the present invention.
Fig. 2 is an electron microscope image of a three-dimensional spherical structure of the three-dimensional composite current collector prepared in example 1 of the present invention, with a ruler of 5 μm.
Fig. 3 is an electron microscope image of a three-dimensional spherical structure of the three-dimensional composite current collector prepared in example 1 of the present invention, with a scale of 20 μm.
Fig. 4 is a schematic diagram illustrating the formation of a three-dimensional spherical structure in the three-dimensional composite current collector provided by the present invention.
Fig. 5 is a schematic structural view of a three-dimensional composite current collector prepared in example 1 of the present invention.
Fig. 6 is a graph showing charge and discharge cycles and specific capacities of the three-dimensional composite current collectors prepared in example 1 of the present invention and comparative example 1.
Fig. 7 is a charge and discharge graph of the three-dimensional composite current collectors prepared in example 1 and comparative example 3 of the present invention.
FIG. 8 is a peel test chart of example 2 of the present invention and comparative example 5.
Fig. 9 is a graph of cycle retention of lithium and a coating of lithium-philic material of a negative electrode of a charging and discharging lithium battery of the three-dimensional composite current collector prepared in example 3 of the present invention.
Reference numerals:
1. a lithium metal layer; 2. coating a lithium-philic material of a negative electrode of the lithium battery; 3. a copper foil base layer.
Detailed Description
The technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood 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 of the present invention without any inventive step, are within the scope of the present invention.
The invention provides a preparation method of a three-dimensional composite current collector, which comprises the following steps:
s1, weighing a predetermined amount of carbon material, lithium-philic metal oxide and lithium salt, and mixing and stirring for 0.5-4 h; adding a solvent, and stirring for 0.5-2 hours until the solvent is completely dissolved; then adding a predetermined amount of binder, and stirring for 4-10 hours to prepare lithium-philic material slurry of the negative electrode of the lithium battery;
s2, selecting a copper foil with the thickness of 6-20 microns as a base layer, coating the slurry on the copper foil at the coating speed of 10-30 m/min, drying for 4-8 h in a forced air drying oven at 70-80 ℃, and drying for 8-12 h in a vacuum oven at 110-130 ℃ to obtain the three-dimensional composite current collector.
Further, the solvent is one of water and N-methyl pyrrolidone.
Further, in step S1, the mass ratio of the carbon material, the lithium-philic metal oxide, the binder, and the lithium salt is 5% to 35%: 75% -45%: 15% -5%: 5 to 15 percent.
Further, the lithium-philic metal oxide includes, but is not limited to, one or more of cobaltosic oxide, zinc oxide, and copper oxide.
Further, the carbon material includes, but is not limited to, one of carbon nanotube, carbon fiber, acetylene black, graphene.
Further, the lithium salt includes, but is not limited to, one of lithium carbonate, lithium fluoride, lithium nitride, and lithium nitrate.
Further, the binder is one of styrene butadiene rubber, acrylic resin, acrylonitrile and polyvinylidene fluoride.
The following describes in further detail the method for preparing the three-dimensional composite current collector provided by the present invention through examples 1 to 17 and comparative examples 1 to 5 with reference to the accompanying drawings 1 to 9.
Example 1
The preparation method of the three-dimensional composite current collector comprises the following steps:
s1, weighing 30g of carbon nano tube and 55g of copper oxide particles, and placing the carbon nano tube and the copper oxide particles in a stirring tank to stir for 2 hours; then adding 10g of lithium carbonate into the stirring tank, stirring for 2 hours, then adding a proper amount of N-methyl pyrrolidone, and stirring for 2 hours until the lithium carbonate is completely dissolved; then adding 5g of polyvinylidene fluoride into a stirring tank, and stirring for 10 hours to prepare lithium-philic material slurry for the negative electrode of the lithium battery;
s2, selecting a copper foil with the thickness of 8 microns and without impurities on the surface as a base layer, coating the slurry on the copper foil, coating the copper foil by using a coating machine at the coating speed of 10m/min, then baking the copper foil for 4 hours in a forced air drying oven at the temperature of 75 ℃, and finally baking the copper foil for 12 hours in a vacuum oven at the temperature of 120 ℃ to prepare the three-dimensional composite current collector.
The three-dimensional composite current collector prepared in example 1 will be described with reference to fig. 1 to 5. As shown in fig. 1, the three-dimensional composite current collector prepared in example 1 of the present invention exhibited a black color.
As shown in fig. 2, the three-dimensional composite current collector prepared in this embodiment has a micron-sized three-dimensional spherical structure, and is formed by interconnecting micro-nano particles, and the surfaces of the spherical particles have a dense porous structure. The three-dimensional porous spherical structure can relieve the volume expansion problem of the lithium-philic material of the lithium battery cathode in circulation to a certain extent, can also store the infiltration of electrolyte, shortens the back-and-forth path of lithium ions, and improves the rate capability and long-term circulation stability of the lithium-philic material of the lithium battery cathode. The mesoporous structure generated by the micron-sized spheres provides a network which can be easily penetrated by electrolyte, and the porosity of the mesoporous structure is combined with the micro-nano-sized structural units to remarkably improve the electrochemical performance.
In addition, in the lithium-philic material coating of the negative electrode of the lithium battery, the carbon nano tube is successfully coated outside the copper oxide. The carbon material of the outer layer can not only enhance the conductivity of the lithium-philic metal oxide, but also serve as a protective layer, so that the mechanical property of the lithium-philic metal oxide is improved, and the cycle performance and the service life of the lithium-philic metal oxide are prolonged.
As shown in fig. 4, the formation process of the three-dimensional spherical structure in the three-dimensional composite current collector mainly includes: tubular or fibrous carbon material is high speed stirred and wound, and is agglomerated into micro spheres, added with lithium-philic metal oxide, filled with the lithium-philic metal oxide under stirring, and then coated and dried to form micron size spheres.
As shown in fig. 5, in the three-dimensional composite current collector provided by the present invention, a lithium-philic material for a negative electrode of a lithium battery is coated on a copper foil base layer to construct a micro-nano-sized three-dimensional spherical composite current collector. The Gibbs free energy delta G of the lithium-philic metal oxide in the lithium-philic material of the negative electrode of the lithium battery and the metallic lithium is less than 0, which shows that the lithium-philic metal oxide can react with the metallic lithium spontaneously, so that the lithium-philic material film of the negative electrode of the lithium battery compounded on the copper foil is tightly connected with the metallic lithium layer, the binding force between the copper foil and a lithium band is improved, and the probability of falling of the metallic lithium is reduced.
Therefore, the lithium-philic metal oxide, the carbon material and the lithium salt are mixed to play a role, so that the electrochemical performance of the lithium-philic material of the negative electrode of the lithium battery is improved, and the effects of anchoring the metal lithium, conducting and stabilizing the metal lithium are realized. And the three materials are mixed under the action of the binder and only used as a coating between the copper foil and the lithium metal, and the mixed material of the three materials is singly used and is not used as a negative electrode of the lithium battery. Therefore, one of the three is not enough, otherwise, the performance of the lithium metal is lost.
Comparative example 1
The difference from example 1 is that: the lithium-philic material for the negative electrode of the lithium battery is not coated on the copper foil base layer, and the battery with the negative electrode being a pure lithium sheet is prepared.
Referring to fig. 6, it was experimentally found that the capacity retention rate of the lithium battery using the three-dimensional composite current collector prepared in example 1 was 97% @350 cycles as the number of cycles increased, while the capacity retention rate of the battery using the pure lithium sheet prepared in comparative example 1 was gradually decreased as the number of cycles increased. Therefore, the battery cycle performance of the lithium battery with the three-dimensional composite current collector prepared in the embodiment 1 of the invention is far better than that of the pure lithium sheet battery prepared in the comparative example 1, which shows that the cycle performance of the lithium metal battery can be remarkably improved by coating the lithium-philic material of the negative electrode of the lithium battery.
Comparative example 2
The difference from example 1 is that: in the preparation of the lithium-philic material slurry for the negative electrode of the lithium battery, a carbon material (carbon nano tube) is not added to prepare a composite current collector.
Through the charge and discharge cycle test, the battery assembled by adopting the composite current collector prepared in the comparative example 2 as the negative electrode current collector of the lithium battery has inferior battery cycle performance and stability performance to those of the battery in the example 1. This is mainly due to: although the specific capacity of the lithium-philic metal oxide negative electrode material is higher than that of the carbon material, the lithium-philic metal oxide negative electrode material is inferior to the carbon material in the aspect of cycle stability and has low rate capability. The lithium-philic metal oxide copper oxide which is not coated by the carbon material can repeatedly react with the lithium metal to cause large volume change, so that the cathode material is easy to pulverize, the current collector and the active material gradually lose point contact, the electrochemical energy storage reaction capacity is gradually lost, and the capacity attenuation is fast.
Compared with the comparative example 2, the comparison also shows that the lithium battery assembled by the three-dimensional negative electrode current collector prepared in the example 1 can inhibit the volume expansion of copper oxide and enhance the conductivity during the charging and discharging processes; on the other hand, the three-dimensional spherical structure formed by the carbon material and the lithium-philic metal oxide improves the specific surface area of the negative electrode current collector, the excellent specific surface area increases the utilization rate of the negative electrode material, more surface area is exposed to the electrolyte, and the load on lithium ions is improved to a great extent, so that the lithium battery prepared in the embodiment 1 has excellent electrochemical performance and battery cycle performance.
Comparative example 3
The difference from example 1 is that: in the preparation of the lithium-philic material slurry of the negative electrode of the lithium battery, no lithium salt (lithium carbonate) is added to prepare a composite current collector.
As shown in fig. 7, the electrochemical performance of the battery assembled by using the composite current collector prepared in comparative example 3 as a negative electrode current collector of a lithium battery was inferior to that of example 1 through the charge-discharge cycle test. This is mainly due to: the metallic lithium has the lowest reduction potential and is relatively active, the charge-discharge curve of the battery on the lithium salt-free coating is unstable, and the current can be more stable due to the non-conductivity of the dispersed lithium salt, so that the charge-discharge curve of the embodiment 1 is more stable.
In the lithium-philic material for the negative electrode of the lithium battery, a small proportion of lithium salt mainly plays a role in stabilizing metal lithium, and when the metal lithium is completely consumed and becomes lithium powder or is out of control thermally, the lithium salt can stabilize the safety performance of the battery, particularly the decomposition of lithium carbonate and lithium nitride, the side reaction of lithium fluoride and the like, and the generated gas can break the connection between an active substance and a current collector. In addition, most of the lithium salt is non-conductive material, and the active reaction of lithium can be delayed to a certain extent in the charging and discharging process, so that the lithium salt plays a role in stabilizing the lithium metal cathode.
Comparative example 4
The difference from example 1 is that: in the preparation of the lithium-philic material slurry of the negative electrode of the lithium battery, the composite current collector is prepared without adding lithium-philic metal oxide (copper oxide).
Through the charge-discharge cycle test, the battery assembled by adopting the composite current collector prepared in the comparative example 4 as the negative electrode current collector of the lithium battery has inferior battery cycle performance and specific capacity to those of the battery in the example 1. This is mainly due to: as a negative electrode material, a carbon material has a low potential, forms an interface film with an electrolyte, and is liable to cause lithium deposition; the ion migration speed is low, so the charge-discharge rate is low, and the electrochemical performance of the lithium battery is influenced. Furthermore, carbon materials suffer irreversible capacity loss due to side reactions during the first charge and discharge. Compared with the comparative example 4, the lithium battery assembled by the three-dimensional negative electrode current collector prepared in the example 1 is also shown, and the defect of low specific capacity of the carbon material can be compensated by adding the lithium-philic metal oxide in the charging and discharging processes.
Meanwhile, the reaction delta G of the lithium-philic metal oxide and the metallic lithium in the lithium-philic material coating of the negative electrode of the lithium battery prepared in the embodiment is less than 0, and belongs to a spontaneous reaction, so that the lithium-philic metal oxide can react with the metallic lithium to anchor the lithium on the copper foil. Then, the metal lithium can be firmly contacted with the copper foil through the combined action of chemical binding force and external pressure, and the contact resistance is reduced.
Example 2
The preparation method of the three-dimensional composite current collector comprises the following steps:
s1, weighing 30g of carbon nano tube and 55g of zinc oxide particles, and placing the carbon nano tube and the zinc oxide particles in a stirring tank to stir for 2 hours; then adding 10g of lithium carbonate into the stirring tank, stirring for 2 hours, then adding a proper amount of N-methyl pyrrolidone, and stirring for 2 hours until the lithium carbonate is completely dissolved; then adding 5g of polyacrylonitrile LA133 into a stirring tank, and stirring for 10 hours to prepare lithium-philic material slurry of the negative electrode of the lithium battery;
s2, selecting a copper foil with the thickness of 8 microns and without impurities on the surface as a base layer, coating the slurry on the copper foil, coating the copper foil by using a coating machine at the coating speed of 10m/min, then baking the copper foil for 4 hours in a forced air drying oven at the temperature of 75 ℃, and finally baking the copper foil for 12 hours in a vacuum oven at the temperature of 120 ℃ to prepare the three-dimensional composite current collector.
Comparative example 5
The difference from example 2 is that: graphite is coated on a copper foil current collector to prepare the traditional graphite cathode.
FIG. 8 is a peel test chart of example 2 of the present invention and comparative example 5. As shown in fig. 7, the peel strength of the three-dimensional composite current collector negative electrode of the LA133/ZnO system prepared in example 2 is equivalent to that of the conventional graphite negative electrode, which indicates that the three-dimensional composite current collector prepared in this embodiment improves the bonding force between the copper foil and the lithium tape, reduces the probability of lithium metal falling, and further improves the electrochemical performance of the lithium battery to a certain extent.
Example 3
The preparation method of the three-dimensional composite current collector comprises the following steps:
s1, weighing 30g of carbon nano tube and 55g of cobaltosic oxide particles, and placing the carbon nano tube and the cobaltosic oxide particles in a stirring tank to stir for 2 hours; then adding 10g of lithium carbonate into the stirring tank, stirring for 2 hours, then adding a proper amount of N-methyl pyrrolidone, and stirring for 2 hours until the lithium carbonate is completely dissolved; then adding 5g of styrene butadiene rubber into a stirring tank, and stirring for 10 hours to prepare lithium-philic material slurry for the negative electrode of the lithium battery;
s2, selecting a copper foil with the thickness of 8 microns and without impurities on the surface as a base layer, coating the slurry on the copper foil, coating the copper foil by using a coating machine at the coating speed of 10m/min, then baking the copper foil for 4 hours in a forced air drying oven at the temperature of 75 ℃, and finally baking the copper foil for 12 hours in a vacuum oven at the temperature of 120 ℃ to prepare the three-dimensional composite current collector.
As shown in fig. 9, with the increase of the number of charge and discharge cycles, the cycle retention rate of the lithium-philic material coating of the negative electrode of the lithium battery and lithium is kept to be more than 97% before the number of cycles is 500, and the lithium battery has excellent electrochemical performance; then, the retention rate showed a tendency of slowly decreasing with the increase of the number of charge-discharge cycles. It can be seen that the electrochemical performance of the lithium metal negative electrode is greatly improved by adopting the lithium-philic coating as the current collector in example 3.
Examples 4 to 10
The difference from example 1 is that: in the preparation of the lithium-philic material slurry for the negative electrode of the lithium battery, the types of the carbon material, the lithium-philic metal oxide, the binder and the lithium salt are different, and are shown in table 1, and the others are the same as those in example 1, and are not described again.
Table 1 shows the types of raw materials for the lithium-philic materials for the negative electrodes of lithium batteries in examples 1 and 4 to 10
| Examples | Carbon material | Lithium-philic metal oxides | Binder | Lithium salt |
| Example 1 | Carbon nanotube | Copper oxide | Polyvinylidene fluoride | Lithium carbonate |
| Example 4 | Graphene | Copper oxide | Styrene butadiene rubber | Lithium fluoride |
| Example 5 | Acetylene black | Cobaltosic oxide | Acrylonitrile | Lithium nitride |
| Example 6 | Carbon fiber | Cobaltosic oxide | Acrylic resin | Lithium nitrate |
| Example 7 | Carbon nanotube | Zinc oxide | Polyvinylidene fluoride | Lithium carbonate |
| Example 8 | Graphene | Zinc oxide | Styrene butadiene rubber | Lithium fluoride |
| Example 9 | Acetylene black | Copper oxide | Acrylonitrile | Lithium nitride |
| Example 10 | Carbon fiberVitamin C | Zinc oxide | Acrylic resin | Lithium nitrate |
As shown in table 1, in the present invention, the types of the carbon material, the lithium-philic metal oxide, the binder, and the lithium salt in the preparation of the lithium-philic material slurry for the negative electrode of the lithium battery are different, and all of them will have a certain influence on the three-dimensional spherical structure of the lithium-philic material for the negative electrode of the lithium battery on the composite current collector: the tubular carbon material provides a framework, the powdery carbon material and other materials are compositely stacked, and the size range of a three-dimensional structure formed by the layered carbon material is large. The lithium-philic material, the binder and the lithium salt stabilizer are filled and stacked in the lithium-philic material. The produced lithium salt can improve the stability of electrochemical performance and safety performance, and the lithium salt without producing gas can stabilize the electrochemical behavior of the battery.
In example 4, due to the layered structure of the graphene, part of the lithium-philic material coating of the negative electrode of the lithium battery forms an irregular three-dimensional structure sphere, and the other part forms a three-dimensional structure with other shapes.
In example 5, the acetylene black is in a powder form, so the lithium-philic material coating of the negative electrode of the lithium battery is basically in a three-dimensional random structure, and a small number of irregular three-dimensional structure spheres exist.
Examples 11 to 17
The difference from example 1 is that: in the preparation of the lithium-philic material slurry for the negative electrode of the lithium battery, the mass of the carbon material, the lithium-philic metal oxide, the binder and the lithium salt are different, and as shown in table 2, the rest is the same as that in example 1, and the details are not repeated herein.
Table 2 shows the mass settings of the raw materials in the lithium-philic materials for the negative electrodes of the lithium batteries in examples 1 and 11 to 17
| Examples | Carbon nanotube | Copper oxide | Polyvinylidene fluoride | Lithium carbonate |
| Example 1 | 30g | 55g | 5g | 10g |
| Example 11 | 25g | 60g | 5g | 10g |
| Example 12 | 20g | 60g | 5g | 15g |
| Example 13 | 15g | 65g | 10g | 10g |
| Example 14 | 10g | 70g | 10g | 10g |
| Example 15 | 5g | 75g | 5g | 15g |
| Example 16 | 15g | 75g | 5g | 5g |
| Example 17 | 35g | 45g | 15g | 5g |
As shown in table 2, in the present invention, the mass of the carbon material, the lithium-philic metal oxide, the binder, and the lithium salt in the preparation of the lithium-philic material slurry for the negative electrode of the lithium battery is different, and all of them will have a certain influence on the three-dimensional spherical structure of the lithium-philic material on the composite current collector. Wherein, the more the binder, the greater the adhesion between the lithium-philic coating and the copper foil, but the resistance of the film is increased, and the content of the binder is at least 5%.
It should be noted that, in the lithium-philic material for the negative electrode of the lithium battery provided by the present invention, the lithium-philic metal oxide may also be other kinds of metal oxides, and the lithium salt may also be other kinds of lithium salts, as will be understood by those skilled in the art.
In summary, the invention provides a three-dimensional composite current collector and a preparation method thereof. The three-dimensional composite current collector comprises a copper foil base layer and a lithium-philic material coating of a negative electrode of a lithium battery coated on the copper foil base layer; the lithium-philic material coating for the negative electrode of the lithium battery comprises a three-dimensional spherical structure with the size of a plurality of micrometers. The lithium-philic material for the negative electrode of the lithium battery consists of a carbon material, a lithium-philic metal oxide, a binder and a lithium salt. The preparation method comprises the steps of firstly preparing lithium-philic material slurry of the negative electrode of the lithium battery, then coating the slurry on a copper foil base layer, and preparing the three-dimensional composite current collector of the negative electrode of the lithium battery. The composite coating with the micron-sized three-dimensional spherical structure is formed by coating the lithium-philic material for the lithium battery cathode on the copper foil, so that the current density of the lithium metal cathode can be effectively reduced, the generation of lithium dendrites is effectively relieved and reduced, and the cycle performance and the safety performance of the lithium metal battery are improved.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present invention.
Claims (9)
1. A three-dimensional composite current collector, characterized by: the three-dimensional composite current collector comprises a copper foil base layer and a lithium-philic material coating of a lithium battery negative electrode coated on the copper foil base layer; the lithium-philic material coating for the negative electrode of the lithium battery comprises a three-dimensional spherical structure with the size of a plurality of micrometers.
2. The three-dimensional composite current collector of claim 1, wherein: the lithium-philic material coating of the negative electrode of the lithium battery consists of a carbon material, a lithium-philic metal oxide, a binder and a lithium salt; the mass ratio of the carbon material, the lithium-philic metal oxide, the binder and the lithium salt is 5-35% by mass: 75% -45%: 15% -5%: 5 to 15 percent.
3. A method of preparing the three-dimensional composite current collector as claimed in any one of claims 1-2, wherein: the method comprises the following steps:
s1, weighing a predetermined amount of carbon material, lithium-philic metal oxide and lithium salt, and mixing and stirring for 0.5-4 h; adding a solvent and stirring until the solvent is completely dissolved; then adding a predetermined amount of binder, and stirring for 4-10 hours to prepare lithium-philic material slurry of the negative electrode of the lithium battery;
s2, selecting a copper foil with the thickness of 6-20 microns as a base layer, coating the lithium battery negative electrode lithium-philic material slurry obtained in the step S1 on the copper foil to form a lithium battery negative electrode lithium-philic material coating, wherein the coating speed is 10-30 m/min, drying for 4-8 h in a forced air drying oven at 70-80 ℃, and drying for 8-12 h in a vacuum oven at 110-130 ℃ to obtain the three-dimensional composite current collector.
4. The method for preparing a three-dimensional composite current collector according to claim 3, wherein: in step S1, the mass ratio of the carbon material, the lithium-philic metal oxide, the binder, and the lithium salt is 5% to 35%: 75% -45%: 15% -5%: 5 to 15 percent.
5. The method for preparing a three-dimensional composite current collector according to claim 3, wherein: the lithium-philic metal oxide includes but is not limited to one or more of cobaltosic oxide, zinc oxide and copper oxide.
6. The method for preparing a three-dimensional composite current collector according to claim 3, wherein: the carbon material includes but is not limited to one of carbon nanotube, carbon fiber, acetylene black and graphene.
7. The method for preparing a three-dimensional composite current collector according to claim 3, wherein: the lithium salt includes but is not limited to one of lithium carbonate, lithium fluoride, lithium nitride and lithium nitrate.
8. The method for preparing a three-dimensional composite current collector according to claim 3, wherein: the binder includes but is not limited to one of styrene butadiene rubber, acrylic resin, acrylonitrile and polyvinylidene fluoride.
9. The method for preparing a three-dimensional composite current collector according to claim 3, wherein: the solvent is one of water and N-methyl pyrrolidone.
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| CN115679122B (en) * | 2022-11-23 | 2024-03-15 | 陈畅 | Electrode with composite structure and manufacturing method and application thereof |
| CN117613283A (en) * | 2024-01-22 | 2024-02-27 | 中自环保科技股份有限公司 | Negative copper foil current collector and preparation process and application thereof |
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