CN114512729A - Nanomaterial for negative electrode protection layer, negative electrode protection slurry, lithium negative electrode and lithium battery - Google Patents
Nanomaterial for negative electrode protection layer, negative electrode protection slurry, lithium negative electrode and lithium battery Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
The application discloses a nano material for a negative electrode protection layer, negative electrode protection slurry, a lithium negative electrode and a lithium battery. The nano material comprises an inner core and a carbon layer shell coated on the surface of the inner core, wherein a cavity is formed between the inner core and the carbon layer shell; the core is transition metal carbide nanoparticles or transition metal sulfide nanoparticles, and the core is in a hollow spherical structure. The nano material can form a protective layer on the surface of the lithium negative electrode in situ, and the lithium affinity can be improved through the synergistic effect between the inner core and the carbon layer shell, so that the lithium deposition is more uniform, the lithium negative electrode is effectively stabilized, the side reaction is reduced, the generation of lithium dendrites is relieved, and the coulombic efficiency and the cycle life of the lithium battery are improved.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a nano material for a negative electrode protection layer, negative electrode protection slurry, a lithium negative electrode and a lithium battery.
Background
Batteries using metallic lithium as a negative electrode have considerably higher energy density than conventional lithium ion batteries, and thus are receiving much attention. However, the following problems exist in the use of the utility model: 1) the lithium metal negative electrode is easy to cause short circuit of the battery due to the generation of lithium dendrite in the cyclic charge and discharge process; 2) due to the generation of the SEI film, dead lithium is generated, resulting in low coulombic efficiency.
At present, the problems are mostly solved by arranging a protective layer on a lithium negative electrode, wherein the material for forming the protective layer comprises carbon nanotubes or carbon nanofibers, and the adoption of the material has the following defects: 1) the carbon material has a high specific surface area, and side reactions occurring thereon are increased, thereby reducing the coulombic efficiency of the battery; 2) the above carbon materials are not effective in guiding the transfer of lithium ions and providing sites for lithium deposition; 3) if the active sites for lithium deposition are artificially introduced into the carbon material, for example, the end points of the carbon nanofibers are used as the active sites of lithium, or lithium-philic elements are doped into the carbon material, the lithium-philic property cannot be greatly improved, and the number of the active sites is limited, so that the deposition behavior of lithium cannot be effectively guided.
Disclosure of Invention
In view of the above-mentioned defects or shortcomings in the prior art, it is desirable to provide a nanomaterial for a negative electrode protection layer, a negative electrode protection slurry, a lithium negative electrode, and a lithium battery, so as to solve the problem of uneven lithium deposition of the existing lithium negative electrode by improving the lithium affinity of the negative electrode, thereby effectively stabilizing the lithium negative electrode.
As a first aspect of the present application, there is provided a nanomaterial for an anode protective layer.
Preferably, the nanomaterial comprises:
the core and the carbon layer shell are coated on the surface of the core, and a cavity is formed between the core and the carbon layer shell;
the core is transition metal carbide nanoparticles or transition metal sulfide nanoparticles, and the core is in a hollow spherical structure.
Preferably, the core is an iron carbide nanoparticle, a tungsten carbide nanoparticle, a cobalt sulfide nanoparticle, or a molybdenum sulfide nanoparticle.
Preferably, the outer diameter of the inner core is 20-70 nm, and preferably 40-60 nm.
Preferably, the inner diameter of the inner core is 5-10 nm.
Preferably, the thickness of the carbon layer shell is 2-4 nm.
Preferably, the carbon layer outer shell is loaded with nitrogen atoms, and the loading amount of the nitrogen atoms is 1 to 10 wt% based on the mass of the carbon layer outer shell.
As a second aspect of the present application, the present application provides a lithium anode protection paste.
Preferably, the lithium negative electrode protection paste includes the nanomaterial for a negative electrode protection layer described in the first aspect.
As a third aspect of the present application, the present application provides a lithium negative electrode.
Preferably, the lithium negative electrode includes:
a lithium negative electrode substrate and a protective layer formed on one or both surfaces of the lithium negative electrode substrate, the protective layer being formed from the negative electrode protective slurry according to the second aspect.
Preferably, the thickness of the protective layer is 10 to 50 μm.
As a fourth aspect of the present application, there is provided a lithium battery.
Preferably, the lithium battery comprises a positive electrode sheet, a negative electrode sheet, a separator and an electrolyte, wherein the negative electrode sheet comprises the lithium negative electrode of the third aspect.
The beneficial effect of this application:
the nano material can form a protective layer on the surface of the lithium negative electrode in situ, and the lithium affinity of the lithium negative electrode can be improved through the synergistic effect between the inner core and the carbon layer shell, so that the lithium deposition is more uniform, the lithium negative electrode is effectively stabilized, the side reaction is reduced, the generation of lithium dendrites is relieved, and the coulombic efficiency and the cycle life of the lithium battery are improved.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the following detailed description of non-limiting embodiments thereof, made with reference to the accompanying drawings in which:
FIG. 1 is a schematic structural diagram of a nanomaterial according to an embodiment of the present application;
fig. 2 is an X-ray diffraction pattern of a nanomaterial with an iron carbide nanoparticle as the core.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments with reference to the attached drawings.
It is noted that the endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and that such ranges or values are understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the description of the present application, the terms "first", "second", and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated.
Unless otherwise specified, all raw materials referred to in the present application are commercially available raw materials.
According to a first aspect of the present application, please refer to fig. 1, which illustrates a nanomaterial for a negative protective layer according to a preferred embodiment of the present application, comprising an inner core 2 and a carbon layer outer shell 1 coated on the surface of the inner core, wherein a cavity 3 is formed between the inner core 2 and the carbon layer outer shell 1; wherein the inner core 2 is a transition metal carbide nanoparticle or a transition metal sulfide nanoparticle, and the inner core 2 is in a hollow spherical structure.
Specifically, the nanomaterial disclosed by the application has a core @ gap @ shell structure, namely, a shell non-contact coating core, and comprises a single inner core, wherein the inner core 2 is internally provided with a cavity, so that the inner core is in a hollow structure.
The carbon layer shell 1 is formed by a carbon-based material, and transition metal carbide nanoparticles or transition metal sulfide nanoparticles in the carbon layer shell 1 can effectively change the electron distribution state around a carbon skeleton, increase active sites and effectively adjust the electrochemical behavior of the carbon-based material, so that the electronegativity of the carbon layer shell 1 is enhanced, and the lithium affinity is improved, wherein the lithium affinity groups of the carbon-based material can be used as the active sites for depositing metal lithium, and lithium ions can be induced to be uniformly deposited in the charging and discharging process;
the existence of the cavity 3 between the carbon layer shell 1 and the inner core 2 ensures that the carbon layer shell 1 and the inner core 2 are not in close contact and no chemical bond is formed between the two; because the electronegativity of the two materials is different, the electron cloud density is mutually influenced to generate a synergistic effect, so that the lithium affinity of the nano material reaches an optimal level;
the inner core 2 growing in the carbon layer shell 1 can prevent the structure of the nano material from falling off in the charging and discharging process, the space (namely, a hollow structure) in the inner core 2 can buffer the volume effect in the lithium embedding/removing process, a buffer space is provided for the volume expansion of the inner core in the circulating process, and the crushing phenomenon of the inner core caused by the volume expansion in the charging and discharging process is inhibited, so that the inner core is effectively protected in large-current and long-circulating processes, the stability of the whole nano material structure is facilitated, and the effect of inhibiting lithium dendrite is achieved;
the transition metal carbide nanoparticles can construct a good conductive network, accelerate electron transmission and lithium ion diffusion, and have excellent electrochemical properties; the transition metal sulfide nanoparticles have higher conductivity, can accelerate the transmission rate of electrons and ions, are beneficial to reducing the polarization phenomenon, improve the multiplying power performance of the battery and improve the capacity and the stability of the battery;
by adopting the unique structure, the nano material of the embodiment has higher lithium affinity, rate capability and stable cycle performance, can ensure uniform lithium deposition and relieve the generation of lithium dendrites, thereby improving the coulombic efficiency, cycle performance and safety of the lithium battery.
Further, in some preferred embodiments of the present application, the carbon layer outer shell 1 has a spherical structure, such that the nanomaterial of the present application has a yolk-eggshell structure with a hollow spherical inner core; the spherical carbon layer shell 1 has a high specific surface area, which is beneficial to reducing local current density and further ensuring the uniform deposition of lithium.
Further, in some preferred embodiments of the present application, the inner core 2 is an iron carbide nanoparticle, a tungsten carbide nanoparticle, a cobalt sulfide nanoparticle, or a molybdenum sulfide nanoparticle, and preferably, the inner core is an iron carbide nanoparticle.
Wherein, the iron carbide nanoparticle can make the reversible generation and the decomposition of SEI membrane, and this application can reduce because the battery core inflation scheduling problem that the SEI membrane produced in a large number of times through embedding iron carbide nanoparticle in the carbon layer shell for the side reaction incidence on the carbon layer shell 1 reduces, thereby improves the circulation stability of coulomb efficiency and battery.
Further, in some preferred embodiments of the present application, the outer diameter of the core 2 is 20 to 70nm, which is related to the specific surface area of the core 2, and the size of the outer diameter affects the performance.
Further, the outer diameter of the core 2 is preferably 40 to 60 nm.
Further, in some preferred embodiments of the present application, the inner diameter of the inner core 2 is 5 to 10 nm.
In the mode, when the inner diameter of the inner core 2 is 5-10 nm, the inner core 2 has a stable structure, the inner core is prevented from collapsing or breaking due to the action of expansion force in the battery cycle process, and the failure of the nanometer material structure is avoided, and on the other hand, a sufficient buffer space can be provided for the volume expansion of the inner core 2 in the lithium insertion/removal process.
Further, in some preferred embodiments of the present application, the thickness of the carbon layer outer shell 1 is 2 to 4 nm.
The thickness of the carbon layer shell 1 can influence the function of the inner core and influence the synergistic effect between the shell and the inner core 2, when the thickness of the carbon layer shell 1 is 2-4 nm, on one hand, the phenomenon that the inner core 2 cannot normally play a role due to the excessive coating of the carbon layer shell 1 on the inner core 2 can be avoided, on the other hand, the instability of the chemistry and the structure of the inner core 2 due to the incomplete or incomplete coating of the carbon layer shell 1 on the inner core 2 can be avoided, and the thickness is thinner than that of common carbon nanofiber and carbon nanotube, so that the ion and electron transmission rate can be improved, and the reversible capacity of the battery can not be reduced.
Wherein the carbon layer shell 1 with the thickness of 2-4 nm can be composed of 1-5 single carbon layers with the thickness of 0.5-2.5 nm, preferably 1-2 single carbon layers with the thickness of 1-2 nm; the single-layer carbon layer may be an amorphous carbon layer (i.e., a loose amorphous carbon structure) or a graphitized carbon layer (i.e., a high-graphitization crystalline carbon structure).
Further, in some preferred embodiments of the present application, nitrogen atoms are loaded in the carbon layer outer shell 1, and the loading amount of the nitrogen atoms is 1 to 10 wt% based on the mass of the carbon layer outer shell.
The nitrogen atoms have high lithium affinity, and the lithium affinity of the nano material can be further improved on the one hand by doping a certain amount of nitrogen atoms in the carbon layer shell; on the other hand, the conductivity of the nano material can be further improved, so that the internal resistance of the battery is reduced, and the large-current charge and discharge capacity of the battery is further ensured. The nitrogen atom may be derived from a N-containing species such as NH3One or more of acetonitrile, aniline or butylamine.
Wherein, the preparation process of a preferred embodiment of the nano material with the iron carbide nano particles as the inner core is as follows:
preparing an iron-containing precursor:
FeCl3·6H2Dissolving O and terephthalic acid in dimethyl formamide (DMF) to form a mixed solution, FeCl3·6H2The mass ratio of O to terephthalic acid is 1: 2-3, wherein the dimethylformamide contains a certain amount of sodium hydroxide;
heating the mixed solution to 90-110 ℃ at a heating rate of 3-10 ℃/min, reacting for 10-15 hours at the temperature, and drying to obtain a crude product;
cleaning the crude product with ethanol, dispersing the crude product in the ethanol, maintaining the crude product at the temperature of 60-80 ℃ for 2-5 hours, and drying to obtain an iron-containing precursor, namely iron carbide nanoparticles;
dissolving the graphene and the iron-containing precursor which are subjected to ultrasonic dispersion in deionized water, stirring and reacting for 20-25 hours, and performing rotary evaporation to remove the solvent to obtain powder; wherein the mass ratio of the graphene to the iron-containing precursor is 1-2: 1;
thirdly, adding the powder collected in the second step into Dimethylformamide (DMF) again for secondary hydrothermal reaction for 4-6 hours at the temperature of 70-90 ℃, and drying to collect a product;
etching the collected product in hydrochloric acid for 20-25 hours, washing the product for many times by deionized water, and drying the product to obtain a final product, wherein the core of the final product is a nano material of iron carbide nano particles.
Referring to fig. 2, the final product has a characteristic diffraction peak at 26 ° 2 θ, and characteristic diffraction peaks of iron carbide appear near 45 ° 2 θ and 48 ° 2 θ.
The preparation method comprises the following steps of preparing a precursor from a nano material taking tungsten carbide nano particles, cobalt sulfide nano particles or molybdenum sulfide nano particles as cores and corresponding transition metal salt as a raw material.
According to a second aspect of the present application, there is provided a negative electrode protection slurry, wherein the negative electrode protection slurry includes the nanomaterial described above, and a protective layer can be formed on the surface of the negative electrode by pretreating the negative electrode with the protection slurry, so as to enhance the stability of the negative electrode.
Wherein the content of the nano material is 5-10% by taking the total mass of the slurry as a reference.
Further, in some preferred embodiments, the slurry further includes a polymer and an organic solvent to further improve the dispersion property and coating property of the negative electrode protection slurry of the present application and to contribute to the improvement of the mechanical properties of the protective layer formed therefrom. The polymer plays a role of a film forming agent and a binding agent and is helpful for forming a protective layer on the negative electrode sheet by the slurry, and exemplary polymers include but are not limited to polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride, polydimethylsiloxane, polyvinyl alcohol, polyethylene terephthalate, polyvinyl chloride, polycarbonate and the like, wherein the content of the polymer is preferably 1-5% based on the total mass of the slurry. Wherein the organic solvent is helpful for enhancing the solubility of the nano-materials and the polymer so as to obtain a uniform slurry, and the organic solvent is preferably a common volatile organic solvent which does not react with metallic lithium and comprises ethylene glycol dimethyl ether, tetrahydrofuran, 1, 3-dioxolane and the like.
According to a third aspect of the present application, there is provided a lithium anode comprising: a lithium negative electrode substrate and a protective layer formed on one or both surfaces of the lithium negative electrode substrate, the protective layer being formed of the lithium negative electrode protective slurry as described above.
The lithium negative electrode matrix comprises a lithium foil made of at least one of metal lithium, a lithium silicon alloy, a lithium aluminum alloy, a lithium tin alloy and a lithium indium alloy, or the lithium negative electrode matrix is a copper foil or a pure copper foil loaded with at least one of metal lithium, a lithium silicon alloy, a lithium aluminum alloy, a lithium tin alloy and a lithium indium alloy with certain capacity, and the thickness of the copper foil can be 5-12 mu m;
the protective layer is formed by coating the negative electrode protective slurry on the lithium negative electrode substrate and drying, and the coating mode comprises at least one of brush coating, roller coating, spray coating, blade coating, dip coating and spin coating. On one hand, the protective layer can be used as a barrier layer to isolate the direct contact of the electrolyte and the lithium cathode, so that side reactions are reduced, and the coulomb efficiency of the lithium cathode is improved; on the other hand, the protective layer contains the nano material, so that the lithium ion flow can be homogenized, the deposition/dissolution of lithium ions of the lithium negative electrode can be effectively stabilized, and the growth of lithium dendrites can be inhibited, thereby improving the coulombic efficiency and the safety of the lithium battery.
When pure copper foil is used as a lithium negative electrode matrix, at least one of lithium metal, lithium silicon alloy, lithium aluminum alloy, lithium tin alloy and lithium indium alloy with certain capacity is loaded on the protective layer after the protective layer is coated to form the lithium negative electrode, and the capacity of lithium has no special requirement.
Preferably, the thickness of the protective layer is 10 to 50 μm.
The appropriate thickness of the protective layer can maintain long-term stable circulation, and can not cause larger interface impedance to block lithium ion transmission.
As a fourth aspect of the present application, there is provided a lithium battery.
Preferably, the lithium battery comprises a positive electrode sheet, a negative electrode sheet, a separator and an electrolyte, wherein the negative electrode sheet comprises the lithium negative electrode of the third aspect.
For example, the negative electrode sheet may be directly served by the lithium negative electrode having the protective layer as described above, or may be a lithium negative electrode including a current collector and a protective layer disposed on the current collector. The current collector may be a conventional negative current collector such as copper foil, carbon-coated copper foil, or the like. The lithium battery provided by the embodiment of the application adopts the lithium negative electrode with the protective layer, so that the lithium battery has high cycle performance and high safety.
Illustratively, the positive electrode sheet includes a positive electrode current collector and a positive electrode sheet containing a positive electrode active material disposed on the positive electrode current collector. Illustratively, the positive electrode current collector may be, but is not limited to, a metal foil or the like (e.g., aluminum foil or the like), and the positive electrode active material is selected from LiFexMnyMzPO4(x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z is 1, wherein M is at least one of Al, Mg, Ga, Ti, Cr, Cu, Zn and Mo), Li3V2(PO4)3、Li3V3(PO4)3、LiNi0.5-xMn1.5-yMx+ yO4X is more than or equal to 0.1 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 1.5, M is at least one of Li, Co, Fe, Al, Mg, Ca, Ti, Mo, Cr, Cu and Zn), and LiVPO4F、Li1+xL1－y－zMyNzO2(L, M, N is at least one of Li, Co, Mn, Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B-0.1-0.2 x, 0-1 y, 0-1 z, 0-1 + z 1.0), Li2CuO2、Li5FeO4One ofOr a plurality thereof; preferably, the positive active material is selected from LiAl0.05Co0.15Ni0.80O2、LiNi0.80Co0.10Mn0.10O2、LiNi0.60Co0.20Mn0.20O2、LiCoO2、LiMn2O4、LiFePO4、LiMnPO4、LiNiPO4、LiCoPO4、LiNi0.5Mn1.5O4、Li3V3(PO4)3One or more of the following; more preferably, the positive active material is selected from sulfur, lithium sulfide, V2O5、MnO2、TiS2、FeS2One or more of (a).
Illustratively, the electrolyte comprises a solvent and a lithium salt, wherein the solvent has one or more of the following groups: ether groups, nitrile groups, cyanide groups, fluorine ester groups, tetrazolyl groups, fluorosulfonyl groups, chlorosulfonyl groups, nitro groups, carbonate groups, dicarbonate groups, nitrate groups, fluoroamide groups, diketone groups, azole groups, and triazine groups; the lithium salt is LiPF6、LiAsF6、LiClO4、LiBF6、LiN(CF3SO3)2、LiCF3SO3、LiC(CF3SO3)2And LiN (C)4F9SO2)(CF3SO3) One or more of (a).
Illustratively, the separator may be selected from polyethylene, polypropylene, polyvinylidene fluoride, and multilayer composite films of polyethylene, polypropylene, polyvinylidene fluoride.
The outside of the lithium battery is also provided with a package, which can be an aluminum plastic film, a stainless steel cylinder, a square aluminum shell, and the like.
The lithium battery can be a button battery or a laminated battery, a full battery or a half battery; the specific method for preparing the lithium battery is not particularly limited, and is a method for preparing a lithium battery which is conventional in the art.
Example 1
Preparation of (I) nano material
Preparing an iron-containing precursor:
116mg FeCl3·6H2o and 270mg of terephthalic acid were added to 5mL of Dimethylformamide (DMF) containing 0.8moL of sodium hydroxide to form a mixed solution;
transferring the mixed solution into a reaction kettle, heating to 100 ℃ at the heating rate of 5 ℃/min, keeping the temperature for reaction for 12 hours, and then carrying out vacuum drying to obtain a crude product;
washing the crude product with ethanol for several times, then dispersing the crude product in ethanol, maintaining at 70 ℃ for 3 hours, and performing vacuum drying to obtain a crude product, namely an iron-containing precursor;
adding 1.5g of ultrasonically dispersed graphene and 1.5g of prepared precursor into 30mL of deionized water, stirring for reacting for 24 hours, and then performing rotary evaporation to remove the solvent to obtain powder;
thirdly, adding the powder obtained in the second step into dimethyl formamide (DMF) again for secondary hydrothermal reaction, reacting for 6 hours at 80 ℃, and then drying in vacuum to collect a product;
and fourthly, etching the collected powder in 1M hydrochloric acid for 24 hours, then washing the powder for many times by using deionized water, drying the powder in vacuum, and collecting a final product, wherein the final product is a nano material with an inner core made of iron carbide nano particles, and the thickness of the outer shell of the carbon layer is 2.2nm, the outer diameter of the inner core is 45nm, and the inner diameter of the inner core is 5.4nm through identification.
Preparation of (di) lithium negative electrode
Adding the prepared nano material into a certain amount of polyethylene oxide (PEO) and ethylene glycol dimethyl ether (DME), and uniformly mixing to form negative electrode protection slurry, wherein the content of the nano material in the slurry is 10%, and the content of the polyethylene oxide is 5%;
coating the obtained lithium negative electrode protection slurry on a copper foil, and drying in a 60 ℃ oven to obtain the copper foil with a protection layer, wherein the thickness of the protection layer is 10 microns; then 1mA/cm was used on the copper foil with the protective layer-2The current density of (2) was adjusted to perform lithium metal deposition, and a lithium negative electrode having a protective layer was obtained.
(III) preparation of Li vs Cu button lithium battery
The negative plate adopts the lithium negative electrode, the positive plate adopts lithium foil, then the PE diaphragms are added into the negative plate and the positive plate, the negative plate and the positive plate are tightly pressed by applying pressure of 0.1-1 Mpa, and the negative plate and the positive plate are packaged in a button cell shell and injected with electrolyte to prepare the Li vs Cu button cell. The electrolyte is prepared as follows: mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) according to the mass ratio of EC to DEC to EMC of 3:2:5 to obtain an organic solvent; adding lithium salt LiPF to the organic solvent6To LiPF6The molar concentration of (A) is 1.1 mol/L; and then adding fluoroethylene carbonate which accounts for 3 percent of the total mass of the electrolyte into the organic solvent to obtain the electrolyte.
Example 2
A lithium battery was fabricated according to the method of example 1, except that the nanomaterial was fabricated in a different process such that the nanomaterial was different in the thickness of the carbon shell, the size of the outer diameter of the core, and the size of the inner diameter of the core.
The preparation of the nanomaterial of this example is as follows:
preparing an iron-containing precursor:
120mg FeCl3·6H2o and 250mg of terephthalic acid were added to 5mL of Dimethylformamide (DMF) containing 0.8moL of sodium hydroxide to form a mixed solution;
transferring the mixed solution into a reaction kettle, heating to 100 ℃ at the heating rate of 5 ℃/min, keeping the temperature for reaction for 12 hours, and then carrying out vacuum drying to obtain a crude product;
washing the crude product with ethanol for several times, then dispersing the crude product in ethanol, maintaining at 70 ℃ for 3 hours, and performing vacuum drying to obtain a crude product, namely an iron-containing precursor;
adding 2.5g of ultrasonically dispersed graphene and 2.0g of prepared precursor into 30mL of deionized water, stirring for reacting for 24 hours, and then performing rotary evaporation to remove the solvent to obtain powder;
thirdly, adding the powder obtained in the second step into dimethyl formamide (DMF) again for secondary hydrothermal reaction, reacting for 6 hours at 90 ℃, and then drying in vacuum to collect a product;
and fourthly, etching the collected powder in 1M hydrochloric acid for 24 hours, then washing the powder for many times by using deionized water, drying the powder in vacuum, and collecting a final product, wherein the final product is a nano material with an inner core made of iron carbide nano particles, and the thickness of the outer shell of the carbon layer is 4nm, the outer diameter of the inner core is 58nm, and the inner diameter of the inner core is 9.8nm through identification.
Example 3
A lithium battery was fabricated according to the method of example 1, except that the nanomaterial fabrication process was varied to vary the carbon shell thickness of the nanomaterial:
the preparation of the nano material is as follows:
similar to the preparation method of the nanomaterial in the embodiment 1, the amount of the graphene and the iron-containing precursor in the step two is set to be 2.5g and 1.5g, the final product is collected after the reaction, and the carbon layer shell of the obtained nanomaterial is identified to be composed of 5-7 carbon layers, the thickness of the carbon layer shell is 12nm, the outer diameter of the inner core is 45nm, and the inner diameter of the inner core is 5.4 nm.
Example 4
A lithium battery was fabricated according to the method of example 1, except that the nanomaterial fabrication process was varied to vary the carbon shell thickness of the nanomaterial:
the preparation of the nano material is as follows:
similar to the preparation method of the nanomaterial in the embodiment 1, the amount of the graphene and the iron-containing precursor in the step (ii) is set to be 0.5g and 1.5g, the final product is collected after the reaction, and the carbon layer shell of the nanomaterial obtained is identified to be composed of 1-2 carbon layers, wherein the thickness of the carbon layer shell is 1.5nm, the outer diameter of the inner core is 45nm, and the inner diameter of the inner core is 5.4 nm.
Example 5
A lithium battery was fabricated according to the method of example 1, except that the nanomaterial fabrication process was varied such that the inner diameters of the cores of the nanomaterials were different in size:
the preparation of the nano material is as follows:
similar to the preparation method of the nano material in the embodiment 1, the reaction conditions of the secondary hydrothermal in the third step are set to be 100 ℃ for 6 hours, the final product is collected after the reaction, and the thickness of the carbon layer shell is 2.2nm, the outer diameter of the inner core is 45nm, and the inner diameter of the inner core is 13nm through identification.
Example 6
A lithium battery was fabricated according to the method of example 1, except that the nanomaterial fabrication process was varied such that the inner diameters of the cores of the nanomaterials were different in size:
the preparation of the nano material is as follows:
similar to the preparation method of the nano material in the embodiment 1, the reaction conditions of the secondary hydrothermal in the third step are set to be 40 ℃ for 6 hours, the final product is collected after the reaction, and the thickness of the carbon layer shell is 2.2nm, the outer diameter of the inner core is 45nm, and the inner diameter of the inner core is 3nm through identification.
Example 7
A lithium battery was fabricated according to the method of example 1, except that the thickness of the protective layer was varied during the fabrication of the lithium negative electrode, and the negative electrode protection paste fabricated in example 1 was used in this example, and the thickness of the protective layer formed on the copper foil by the negative electrode protection paste was 50 μm.
Example 8
A lithium battery was manufactured according to the method of example 1, except that a lithium negative electrode and a lithium battery were manufactured differently.
The lithium negative electrode of this example was prepared as follows:
adding the nano material prepared in the step (I) into a certain amount of polyethylene oxide (PEO) and ethylene glycol dimethyl ether (DME), and uniformly mixing to form negative electrode protection slurry, wherein the content of the nano material in the slurry is 5%, and the content of the polyethylene oxide is 1%;
the obtained negative electrode protection slurry was coated on a lithium foil made of metallic lithium, and dried in an oven at 60 ℃ to obtain a lithium negative electrode having a protective layer with a thickness of 10 μm.
The lithium battery of this example was prepared as follows:
the negative plate adopts the lithium negative electrode; the positive plate is made of aluminum foil coated with a ternary material, specifically, NCM811, a conductive agent Super-P and a binder PVDF are mixed according to a mass ratio of 95:2:3, dispersed in N-methyl pyrrolidone (NMP), and stirred and mixed uniformly to obtain positive slurry; uniformly coating the anode slurry on an aluminum foil, drying, and then performing cold pressing and slitting processes to obtain an anode plate; preparing a bare cell from a positive plate, a negative plate and a diaphragm (PE film) by a lamination process, filling the cell into an aluminum-plastic film packaging shell, and injecting electrolyte to prepare a laminated lithium battery; the electrolyte was the same as in example 1.
Example 9
A lithium battery was fabricated according to the method of example 1, except that cobalt sulfide nanoparticles were used as the core of the nanomaterial, and the nanomaterial of this example was fabricated as follows:
preparing a precursor:
200mg CoCl3·6H2o and 120mg of thioacetamide (CH)3CSNH2) Adding the mixture into 30mL of absolute ethyl alcohol to form a mixed solution;
transferring the mixed solution into a reaction kettle, heating to 160 ℃ at a heating rate of 10 ℃/min, keeping the temperature for reaction for 20 hours, and then carrying out vacuum drying to obtain a crude product;
washing the crude product with ethanol for several times, then dispersing the crude product in ethanol, maintaining the temperature at 60 ℃ for 8 hours, and performing vacuum drying to obtain a crude product, namely a precursor;
adding 2.0g of ultrasonically dispersed graphene and 1.8g of prepared precursor into 30mL of deionized water, stirring for reacting for 24 hours, and then performing rotary evaporation to remove the solvent to obtain powder;
thirdly, adding the powder obtained in the second step into absolute ethyl alcohol again for secondary hydrothermal reaction, reacting for 6 hours at 160 ℃, and then carrying out vacuum drying to collect a product;
etching the collected powder in 1M hydrochloric acid for 24 hours, then washing the powder for many times by using deionized water, drying the powder in vacuum, and collecting a final product, wherein the final product is a nano material of which the inner core is cobalt sulfide nano particles, the thickness of the outer shell of the carbon layer is 3.4nm, the outer diameter of the inner core is 51nm, and the inner diameter of the inner core is 6.2 nm.
Example 10
A lithium battery was fabricated according to the method of example 1, except that the nanomaterial was fabricated in a different process such that the carbon shell of the nanomaterial was doped with N atoms.
The preparation of the nanomaterial of this example is as follows:
preparing an iron-containing precursor:
116mg FeCl3·6H2o and 270mg of terephthalic acid were added to 5mL of Dimethylformamide (DMF) containing 0.8moL of sodium hydroxide to form a mixed solution;
transferring the mixed solution into a reaction kettle, heating to 100 ℃ at a heating rate of 5 ℃/min, keeping the temperature for reaction for 12 hours, and then carrying out vacuum drying to obtain a crude product;
washing the crude product with ethanol for several times, then dispersing the crude product in ethanol, maintaining at 70 ℃ for 3 hours, and performing vacuum drying to obtain a crude product, namely an iron-containing precursor;
adding 1.5g of ultrasonically dispersed graphene, 1.5g of prepared precursor and 0.15g of butylamine into 30mL of deionized water, stirring for reacting for 24 hours, and then performing rotary evaporation to remove the solvent to obtain powder;
thirdly, adding the powder obtained in the second step into dimethyl formamide (DMF) again for secondary hydrothermal reaction, reacting for 6 hours at 80 ℃, and then drying in vacuum to collect a product;
and fourthly, etching the collected powder in 1M hydrochloric acid for 24 hours, then washing the powder for many times by using deionized water, drying the powder in vacuum, and collecting a final product, wherein the final product is a nano material with an inner core being iron carbide nano particles, the thickness of a shell of a carbon layer is identified to be 2.2nm, the outer diameter of the inner core is 45nm, the inner diameter of the inner core is 5.4nm, and 10 wt% of nitrogen atoms are loaded in the shell of the carbon layer.
Comparative example 1
A lithium battery is prepared according to the method of the embodiment 1, and the core of the nano material is the iron carbide nano particles, except that the iron carbide nano particles are in a solid spherical structure, and a cavity is not arranged between the carbon layer shell and the core;
the preparation of the nano material is as follows:
similar to the preparation method of the nano material in the embodiment 1, the powder obtained by removing the solvent through rotary evaporation in the step (II) is directly collected to obtain the nano material.
Comparative example 2
A lithium battery was fabricated according to the method of example 1, with the core of the nanomaterial being iron carbide nanoparticles with a hollow spherical structure, except that no cavity was provided between the carbon shell and the core;
the preparation of the nano material is as follows:
similar to the preparation method of the nano material in the embodiment 1, the product obtained by the secondary hydrothermal and drying in the step III is directly collected to obtain the nano material.
Comparative example 3
A lithium battery was fabricated according to the method of example 1, in which the core of the nanomaterial was iron carbide nanoparticles, and a cavity was formed between the outer shell and the core of the carbon layer, except that the iron carbide nanoparticles had a solid spherical structure;
the preparation of the nano material is as follows:
similar to the preparation method of the nano material in the embodiment 1, the powder obtained by evaporating the solvent in the step two is directly collected without carrying out secondary hydrothermal treatment, and the powder is directly put into 1M hydrochloric acid for etching to obtain the nano material.
Comparative example 4
A lithium battery was fabricated according to the method of example 1, except that a protective layer was prepared by uniformly mixing 10% iron carbide nanoparticles, 5% polyethylene oxide, and ethylene glycol dimethyl ether (DME) to form a lithium negative electrode pre-treatment protective slurry;
the iron carbide nanoparticles were prepared as follows:
similar to the preparation method of the nano material in the embodiment 1, the crude product obtained in the step (r) is directly collected to obtain the nano material.
Comparative example 5
A lithium battery was fabricated in accordance with the method of example 1, except that a copper foil without a protective layer was used as the negative electrode sheet.
The lithium batteries prepared in examples 1 to 10 and comparative examples 1 to 5 were subjected to average coulombic efficiency and normal temperature cycle performance tests:
the normal temperature cycle performance test process is as follows:
at 25 ℃, charging the lithium ion battery to 4.5V by using a constant current of 1C, charging to a cut-off current of 0.05C by using a constant voltage of 4.5V, standing for 30min, and discharging the lithium ion battery to 2.7V by using a constant current of 1C, wherein the process is marked as a charge-discharge cycle process, and the discharge capacity of the time is the discharge capacity of the first cycle;
and (4) carrying out a cyclic charge-discharge test on the lithium ion battery according to the mode, and taking the discharge capacity of the nth cycle.
Capacity retention (%) of the lithium ion battery after n cycles is [ discharge capacity of the n-th cycle/discharge capacity of the first cycle ] × 100%; the number of cycles at which the capacity retention was 80% was recorded.
The test results are shown in the following table:
from the results given in the above table, compared with comparative examples 1 to 5, the normal temperature cycle performance of the lithium batteries of examples 1 to 2 and example 10 is significantly improved, and the average coulombic efficiency is also improved to a certain extent, which shows that the lithium negative electrode is pretreated by the lithium negative electrode pretreatment protection slurry containing the nanomaterial of the embodiment of the present application, so that the deposition/dissolution of lithium ions in the lithium negative electrode can be effectively stabilized, the growth of lithium dendrites can be inhibited, the coulombic efficiency and the cycle stability of the lithium battery can be improved, and the safety of the battery can be enhanced.
Specifically, as can be seen from comparison between example 1 and comparative examples 1 to 3, the yolk-eggshell structure nanomaterial with a hollow spherical inner core according to the present application shows a more excellent effect of stabilizing a lithium negative electrode than a nanomaterial with a solid spherical inner core coated with a carbon layer shell, a nanomaterial with a hollow spherical inner core coated with a carbon layer shell, and a nanomaterial with a solid spherical inner core coated with a carbon layer shell in a non-contact manner, which are derived from a synergistic effect between the carbon layer shell and the inner core and a volume buffer effect of the inner core, so that the nanomaterial has an effect of uniformly depositing lithium.
As can be seen from comparison between example 1 and comparative example 4, the nanomaterial of the present application has better cycling performance than iron carbide nanoparticles without shells, which indicates that the nanomaterial of the present application can significantly improve the lithium affinity of the negative electrode through the synergistic effect of the carbon shell and the iron carbide nanoparticles, and can make lithium deposition more uniform, thereby contributing to improving the cycling stability of the battery.
As can be seen from comparison of example 1 with comparative example 5, the lithium battery with the protective layer has a longer cycle life compared to the lithium battery without the protective layer, which indicates that the nanomaterial provided by the present application has excellent ability to stabilize the lithium negative electrode, and can be used as an additive for forming the protective layer of the lithium negative electrode to improve the cycle performance of the lithium battery.
As can be seen from the comparison between the embodiment 1 and the embodiments 3 and 4 and between the embodiment 1 and the embodiments 5 and 6, the thickness of the carbon layer shell and the inner diameter of the inner core can affect the lithium affinity and the lithium deposition performance of the nano material, and further affect the cycle stability of the battery, and the battery adopting the nano material with the carbon layer shell thickness of 2-4 nm and the inner diameter of the inner core of 5-10 nm shows excellent average coulombic efficiency and cycle performance.
It can be known from the comparison between example 1 and example 10 that the lithium affinity of the nanomaterial can be further improved by loading a certain amount of nitrogen atoms in the carbon layer shell, so that the battery using the nanomaterial has better cycle performance.
The batteries adopted in the embodiments and the comparative examples have relatively high average coulombic efficiency, so that the coulombic efficiency of the batteries can be further improved by only about 0.6% at most, and in the limited space, the average coulombic efficiency of the batteries of the embodiments 1 to 10 is improved by at least 0.07% compared with that of the batteries of the comparative examples 1 to 5, which shows that the nanomaterial for the negative electrode protective layer can produce relatively obvious improvement on the coulombic efficiency of the batteries even in the limited improved space by inducing the uniform deposition of lithium.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (10)
1. A nanomaterial for an anode protective layer, comprising:
the core and the carbon layer shell are coated on the surface of the core, and a cavity is formed between the core and the carbon layer shell;
the core is transition metal carbide nanoparticles or transition metal sulfide nanoparticles, and the core is in a hollow spherical structure.
2. The nanomaterial for an anode protective layer according to claim 1, wherein the core is an iron carbide nanoparticle, a tungsten carbide nanoparticle, a cobalt sulfide nanoparticle, or a molybdenum sulfide nanoparticle.
3. The nanomaterial for a negative electrode protective layer according to claim 1, wherein the outer diameter of the core is 20 to 70nm, preferably 40 to 60 nm.
4. The nanomaterial for a negative electrode protective layer according to claim 1, wherein the inner diameter of the core is 5 to 10 nm.
5. The nanomaterial for an anode protective layer according to claim 1, wherein the carbon layer shell has a thickness of 2 to 4 nm.
6. The nanomaterial for a negative electrode protective layer according to any one of claims 1 to 5, wherein the carbon layer shell carries nitrogen atoms in an amount of 1 to 10 wt% based on the mass of the carbon layer shell.
7. A negative electrode protection slurry comprising the nanomaterial for a negative electrode protection layer according to any one of claims 1 to 6.
8. A lithium negative electrode, characterized by comprising:
a lithium negative electrode substrate and a protective layer formed on one or both surfaces of the lithium negative electrode substrate, the protective layer being formed from the negative electrode protective slurry according to claim 7.
9. The lithium negative electrode according to claim 8, wherein the protective layer has a thickness of 10 to 50 μm.
10. A lithium battery comprising a positive electrode sheet, a negative electrode sheet, a separator and an electrolyte, wherein the negative electrode sheet comprises the lithium negative electrode according to claim 8 or 9.
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