CN114512729B - Nanomaterial, negative electrode protection slurry, lithium negative electrode and lithium battery - Google Patents
Nanomaterial, negative electrode protection slurry, lithium negative electrode and lithium battery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M10/00—Secondary cells; Manufacture thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The application discloses a nanomaterial 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, and a cavity is formed between the inner core and the carbon layer shell; the inner core is a transition metal carbide nanoparticle or a transition metal sulfide nanoparticle, and is in a hollow spherical structure. The nano material can form a protective layer on the surface of the lithium negative electrode in situ, can improve the lithium affinity through the synergistic effect between the inner core and the carbon layer outer shell, and ensures that lithium deposition is more uniform, thereby effectively stabilizing the lithium negative electrode, reducing side reaction, relieving the generation of lithium dendrite and improving the coulombic efficiency and the cycle life of a lithium battery.
Description
Technical Field
The application relates generally to the technical field of batteries, and in particular relates to a nanomaterial for a negative electrode protection layer, negative electrode protection slurry, a lithium negative electrode and a lithium battery.
Background
Batteries using metallic lithium as the negative electrode have a considerably high energy density compared to conventional lithium ion batteries, and thus are of great interest. But it has the following problems in use: 1) The metal lithium cathode is easy to cause short circuit of the battery due to the generation of lithium dendrite in the cyclic charge and discharge process; 2) Dead lithium is generated due to the generation of the SEI film, resulting in low coulombic efficiency.
At present, the above problems are solved by arranging a protective layer on a lithium anode, wherein the material for forming the protective layer is carbon nano tube or carbon nano fiber, and the following defects exist in the adoption of the material: 1) The carbon material has high specific surface area, and side reactions occurring on the carbon material are increased, so that the coulomb efficiency of the battery is reduced; 2) The above carbon materials are not effective in directing the transfer of lithium ions and providing sites for lithium deposition; 3) If the active sites deposited by lithium 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 a lithium-philic element is doped into the carbon material, the lithium-philicity of the carbon material 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 foregoing drawbacks 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, the present application provides a nanomaterial for a negative electrode protective layer.
Preferably, the nanomaterial includes:
the inner core and the carbon layer shell are coated on the surface of the inner core, and a cavity is formed between the inner core and the carbon layer shell;
the inner core is a transition metal carbide nanoparticle or a transition metal sulfide nanoparticle, and is in a hollow spherical structure.
Preferably, the inner 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 core is 20 to 70nm, preferably 40 to 60nm.
Preferably, the inner diameter of the inner core is 5 to 10nm.
Preferably, the thickness of the carbon layer shell is 2-4 nm.
Preferably, the carbon layer shell is loaded with nitrogen atoms, and the loading amount of the nitrogen atoms is 1-10wt% based on the mass of the carbon layer shell.
As a second aspect of the present application, the present application provides a lithium anode protection paste.
Preferably, the lithium anode protection paste includes the nanomaterial for anode protection of the first aspect.
As a third aspect of the present application, the present application provides a lithium anode.
Preferably, the lithium anode includes:
a lithium negative electrode substrate and a protective layer formed on one or both side surfaces of the lithium negative electrode substrate, the protective layer being formed of 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, the present application provides 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 effects of this application:
the nano material can form a protective layer on the surface of the lithium negative electrode in situ, can improve the lithium philicity of the lithium negative electrode through the synergistic effect between the inner core and the carbon layer outer shell, and ensures that lithium deposition is more uniform, thereby effectively stabilizing the lithium negative electrode, reducing side reaction and relieving the generation of lithium dendrite, and improving the coulombic efficiency and the cycle life of a lithium battery.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the detailed description of non-limiting embodiments, made with reference to the following 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 iron carbide nanoparticles as the core.
Detailed Description
The present application is described in further detail below with reference to the drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention.
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present application will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
It should be noted that endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and that such range or value should be understood to include values approaching such range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to 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 implicitly indicating the number of technical features indicated.
Unless otherwise specified, all materials used in the present application are commercially available materials.
According to a first aspect of the present application, please refer to fig. 1, which shows a nanomaterial for a negative electrode protection layer according to a preferred embodiment of the present application, including a core 2 and a carbon layer shell 1 coated on a surface of the core, wherein a cavity 3 is provided between the core 2 and the carbon layer shell 1; 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 of the present application has a core @ void @ shell structure, i.e., a shell non-contact cladding core, which includes a single core, and the interior of the core 2 has a cavity, so that it has a hollow structure.
The carbon layer shell 1 is formed by a carbon-based material, and transition metal carbide nano particles or transition metal sulfide nano particles 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-philicity is improved, wherein the lithium-philicity group of the carbon-based material can be used as an active site for depositing metal lithium, and lithium ions can be induced to be uniformly deposited in the charge and discharge 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 carbon layer shell 1 and the inner core 2; 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 the optimal level;
the inner core 2 growing in the carbon layer shell 1 can prevent the nano material from falling off in the process of charging and discharging, the space (namely the hollow structure) in the inner core 2 can buffer the volume effect in the process of inserting/extracting lithium, provide a buffer space for the volume expansion of the inner core in the circulating process, inhibit the inner core crushing phenomenon caused by the volume expansion in the charging and discharging process, effectively protect the inner core in the high-current and long-circulating process, facilitate the stability of the whole nano material structure, and play a role in inhibiting lithium dendrite;
the transition metal carbide nano particles can construct a good conductive network, accelerate electron transmission and lithium ion diffusion, and have excellent electrochemical performance; the transition metal sulfide nano particles have higher conductivity, can accelerate the transmission rate of electrons and ions, are beneficial to alleviating polarization phenomenon, improve the rate capability of the battery and improve the capacity and stability of the battery;
by adopting the unique structure, the nano material has higher lithium affinity, rate capability and stable cycle performance, can ensure uniform lithium deposition, relieves the generation of lithium dendrites, and improves the coulomb efficiency, cycle performance and safety of the lithium battery.
Further, in some preferred embodiments of the present application, the carbon layer shell 1 has a spherical structure, so 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 higher specific surface area, is beneficial to reducing local current density, and further ensures 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, preferably the inner core is an iron carbide nanoparticle.
The SEI film can be reversibly generated and decomposed, and the SEI film can be embedded into the carbon layer shell, so that the problems of cell expansion and the like caused by mass generation of the SEI film can be reduced, the incidence rate of side reactions on the carbon layer shell 1 is reduced, and the coulomb efficiency and the cycle stability of the battery are improved.
Further, in some preferred embodiments of the present application, the outer diameter of the inner core 2 is 20-70 nm, which is related to the specific surface area of the inner core 2, and the size of the outer diameter affects the performance thereof.
Further, the outer diameter of the core 2 is preferably 40 to 60nm.
Further, in some preferred embodiments of the present application, the inner diameter of the core 2 is 5 to 10nm.
In the mode, when the inner diameter of the inner core 2, namely the diameter of the cavity inside the inner core, is 5-10 nm, on one hand, the inner core 2 can have a stable structure, collapse or breakage caused by the action of expansion force in the battery circulation process is prevented, the failure of the nano material structure is caused, and on the other hand, enough buffer space can be provided for the volume expansion of the inner core 2 in the lithium intercalation/deintercalation process.
Further, in some preferred embodiments of the present application, the thickness of the carbon layer casing 1 is 2 to 4nm.
The thickness of the carbon layer shell 1 can influence the effect of the inner core and can 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 act due to the excessive coating of the carbon layer shell 1 on the inner core 2 can be avoided, and on the other hand, the instability of the chemical and structure of the inner core 2 due to the imprecise 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 nano fibers and carbon nano tubes, so that the ion and electron transmission rate can be improved, and the reversible capacity of a battery can not be reduced.
Wherein the carbon layer shell 1 with the thickness of 2-4 nm can be formed by 1-5 single-layer carbon layers with the single-layer thickness of 0.5-2.5 nm, and preferably is formed by 1-2 single-layer carbon layers with the single-layer thickness of 1-2 nm; wherein the single-layer carbon layer may be an amorphous carbon layer (i.e., loose amorphous carbon structure) or a graphitized carbon layer (i.e., high graphitization degree crystalline carbon structure).
Further, in some preferred embodiments of the present application, the carbon layer casing 1 is loaded with nitrogen atoms, and the loading amount of the nitrogen atoms is 1 to 10wt% based on the mass of the carbon layer casing.
The nitrogen atoms have higher lithium-philicity, and on one hand, the lithium-philicity of the nano material can be further improved 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 high-current charge and discharge capacity of the battery is further ensured. The nitrogen atom may be derived from N-containing species such as NH 3 One 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 core is as follows:
(1) preparing an iron-containing precursor:
FeCl is added 3 ·6H 2 O and terephthalic acid are dissolved in Dimethylformamide (DMF) to form a mixed solution, feCl 3 ·6H 2 The 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 at the temperature for 10-15 hours, and drying to obtain a crude product;
washing the crude product with ethanol, dispersing in ethanol, maintaining at 60-80 ℃ for 2-5 hours, and drying to obtain an iron-containing precursor, namely iron carbide nano particles;
(2) dissolving graphene and an iron-containing precursor which are well dispersed by ultrasonic into deionized water, stirring and reacting for 20-25 hours, and removing a solvent by rotary evaporation to obtain powder; wherein the mass ratio of the graphene to the iron-containing precursor is 1-2:1;
(3) adding the powder collected in the step (2) into Dimethylformamide (DMF) again for secondary hydrothermal reaction for 4-6 hours at 70-90 ℃, and collecting the product after drying;
(4) etching the collected product in hydrochloric acid for 20-25 hours, washing the product for multiple times by deionized water, and drying the product to obtain a final product, wherein the final product is the nano material of which the inner core is the iron carbide nano particles.
Referring to fig. 2, the final product had characteristic diffraction peaks at 2θ=26°, and characteristic diffraction peaks of iron carbide appeared near 2θ=45° and 2θ=48°.
The precursor is prepared from the nano material taking tungsten carbide nano particles, cobalt sulfide nano particles or molybdenum sulfide nano particles as cores and the salt of corresponding transition metal as raw materials.
According to a second aspect of the present application, there is provided a negative electrode protection paste including the nanomaterial as described above, by which a negative electrode is pretreated, a protective layer can be formed on the surface of the negative electrode to enhance the stability of the negative electrode.
Wherein, the content of the nano material is 5-10% based on the total mass of the slurry.
Further, in some preferred embodiments, the slurry further includes a polymer and an organic solvent to further improve the dispersion and coating properties of the negative electrode protection slurry of the present application and to help improve the mechanical properties of the protective layer formed therefrom. Wherein the polymer acts as a film former and a binder to aid in the formation of a protective layer of the paste on the negative electrode sheet, 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 polymer is preferably present in an amount of 1 to 5% based on the total mass of the paste. Among them, the organic solvent helps to enhance the solubility of the nano-materials and polymers to obtain a slurry with uniform texture, and is preferably a common volatile organic solvent which does not react with lithium metal, including ethylene glycol dimethyl ether, tetrahydrofuran, 1, 3-dioxolane, etc.
According to a third aspect of the present application, there is provided a lithium anode comprising: the lithium anode comprises a lithium anode substrate and a protective layer formed on one side or two side surfaces of the lithium anode substrate, wherein the protective layer is formed by the lithium anode protective slurry.
The lithium negative electrode matrix comprises a lithium foil made of at least one of metal lithium, lithium silicon alloy, lithium aluminum alloy, lithium tin alloy and lithium indium alloy, or the lithium negative electrode matrix is a copper foil or pure copper foil loaded with at least one of metal lithium, lithium silicon alloy, lithium aluminum alloy, lithium tin alloy and 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 the negative electrode protective slurry, wherein the coating mode comprises at least one of brushing, roller coating, spraying, knife coating, dip coating and spin coating. The protective layer can be used as a barrier layer to isolate electrolyte from directly contacting with the lithium negative electrode, reduce side reaction and improve coulomb efficiency of the lithium negative electrode; on the other hand, the protective layer contains the nano material, so that the flow of lithium ions can be homogenized, the deposition/dissolution of lithium ions of a lithium negative electrode can be effectively stabilized, and the growth of lithium dendrites can be inhibited, thereby improving the coulomb efficiency and the safety of a lithium battery.
When the pure copper foil is used as a lithium negative electrode matrix, after the protective layer is coated, at least one of metal lithium, lithium silicon alloy, lithium aluminum alloy, lithium tin alloy and lithium indium alloy with certain capacity is loaded on the protective layer to form a lithium negative electrode, and the capacity of lithium is not particularly required.
Preferably, the thickness of the protective layer is 10 to 50 μm.
The thickness of the protective layer is suitable for maintaining long-term stable circulation, and can not cause larger interface impedance to prevent lithium ion transmission.
As a fourth aspect of the present application, the present application provides 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 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 having the protective layer including a current collector and disposed on the current collector. The current collector may be a conventional negative electrode current collector such as copper foil, carbon coated copper foil, or the like. The lithium battery provided by the embodiment of the application has high cycle performance and high safety due to the adoption of the lithium anode with the protective layer.
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. The positive electrode current collector may be exemplified by, but 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 LiFe x Mn y MzPO 4 (0.ltoreq.x.ltoreq.1, 0.ltoreq.y.ltoreq.1, 0.ltoreq.z.ltoreq.1, x+y+z=1, wherein M is at least one of Al, mg, ga, ti, cr, cu, zn, mo), li 3 V 2 (PO 4 ) 3 、Li 3 V 3 (PO 4 ) 3 、LiNi 0.5-x Mn 1.5-y M x+ y O 4 (-0.1.ltoreq.x.ltoreq.0.5, 0.ltoreq.y.ltoreq.1.5, M is at least one of Li, co, fe, al, mg, ca, ti, mo, cr, cu, zn), liVPO 4 F、Li 1+x L 1－y－z M y N z O 2 (L, M, N is at least one of Li, co, mn, ni, fe, al, mg, ga, ti, cr, cu, zn, mo, F, I, S, B, -0.1.ltoreq.x.ltoreq.0.2, 0.ltoreq.y.ltoreq.1, 0.ltoreq.z.ltoreq.1, 0.ltoreq.y+z.ltoreq.1.0), li 2 CuO 2 、Li 5 FeO 4 One or more of the following; preferably, the positive electrode active material is selected from LiAl 0.05 Co 0.15 Ni 0.80 O 2 、LiNi 0.80 Co 0.10 Mn 0.10 O 2 、LiNi 0.60 Co 0.20 Mn 0.20 O 2 、LiCoO 2 、LiMn 2 O 4 、LiFePO 4 、LiMnPO 4 、LiNiPO 4 、LiCoPO 4 、LiNi 0.5 Mn 1.5 O 4 、Li 3 V 3 (PO 4 ) 3 One or more of, etc.; more preferablyThe positive electrode active material is selected from sulfur, lithium sulfide, V 2 O 5 、MnO 2 、TiS 2 、FeS 2 One or more of the following.
Illustratively, the electrolyte comprises a solvent and a lithium salt, wherein the solvent has one or more of the following groups: ether, nitrile, cyano, fluoro, tetrazolyl, fluorosulfonyl, chlorosulfonyl, nitro, carbonate, dicarbonate, nitrate, fluoroamide, diketo, oxazolyl, and triazinyl; the lithium salt is LiPF 6 、LiAsF 6 、LiClO 4 、LiBF 6 、LiN(CF 3 SO 3 ) 2 、LiCF 3 SO 3 、LiC(CF 3 SO 3 ) 2 And LiN (C) 4 F 9 SO 2 )(CF 3 SO 3 ) One or more of the following.
Illustratively, the separator may be selected from a multi-layer composite film of polyethylene, polypropylene, polyvinylidene fluoride, and polyethylene, polypropylene, polyvinylidene fluoride.
The lithium battery is also provided with a package, such as 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, can be a full battery or a half battery; the specific preparation method of the lithium battery is not particularly limited, and is a conventional preparation method of a lithium battery in the art.
Example 1
Preparation of (one) nanomaterials
(1) Preparing an iron-containing precursor:
116mg FeCl 3 ·6H 2 o and 270mg of terephthalic acid are 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, dispersing the crude product in ethanol, maintaining at 70 ℃ for 3 hours, and vacuum drying to obtain a crude product, namely an iron-containing precursor;
(2) adding 1.5g of graphene subjected to ultrasonic dispersion and 1.5g of prepared precursor into 30mL of deionized water, stirring and reacting for 24 hours, and then removing the solvent by rotary evaporation to obtain powder;
(3) adding the powder obtained in the step (2) into Dimethylformamide (DMF) again for secondary hydrothermal reaction at 80 ℃ for 6 hours, and then drying in vacuum to collect a product;
(4) etching the collected powder in 1M hydrochloric acid for 24 hours, then washing the powder with deionized water for multiple times, and collecting a final product after vacuum drying, wherein the final product is a nano material with an inner core of iron carbide nano particles, and the thickness of the carbon layer outer shell is identified to be 2.2nm, the outer diameter of the inner core is identified to be 45nm, and the inner diameter of the inner core is identified to be 5.4nm.
Preparation of 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 mu m; then 1mA/cm was applied to the copper foil with the protective layer -2 And (3) carrying out metal lithium deposition to obtain the lithium anode with the protective layer.
Preparation of Li vs Cu button lithium cell
The negative plate adopts the lithium negative electrode, the positive plate adopts the lithium foil, then PE diaphragms are added in the negative plate and the positive plate, the negative plate and the positive plate are pressed tightly 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. Wherein, the electrolyte is prepared as follows: mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and ethylmethyl carbonate (EMC) according to a mass ratio EC: DEC: emc=3:2:5 as an organic solvent; adding lithium salt LiPF to the organic solvent 6 To LiPF 6 The molar concentration of (2) is 1.1mol/L; and then to saidAdding fluoroethylene carbonate accounting 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 such that the carbon layer outer shell thickness, the inner core outer diameter size, and the inner core inner diameter size of the nanomaterial were different.
The nanomaterial of this example was prepared as follows:
(1) preparing an iron-containing precursor:
120mg FeCl 3 ·6H 2 o 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 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, dispersing the crude product in ethanol, maintaining at 70 ℃ for 3 hours, and vacuum drying to obtain a crude product, namely an iron-containing precursor;
(2) adding 2.5g of graphene subjected to ultrasonic dispersion and 2.0g of prepared precursor into 30mL of deionized water, stirring and reacting for 24 hours, and then removing the solvent by rotary evaporation to obtain powder;
(3) adding the powder obtained in the step (2) into Dimethylformamide (DMF) again for secondary hydrothermal reaction, and vacuum drying and collecting a product after reacting for 6 hours at 90 ℃;
(4) etching the collected powder in 1M hydrochloric acid for 24 hours, then washing the powder with deionized water for multiple times, and collecting a final product after vacuum drying, wherein the final product is a nano material with an inner core of iron carbide nano particles, and the thickness of the carbon layer outer shell is identified to be 4nm, the outer diameter of the inner core is identified to be 58nm, and the inner diameter of the inner core is identified to be 9.8nm.
Example 3
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 layer outer shell thickness of the nanomaterial was different:
the preparation of the nanomaterial is as follows:
similar to the preparation method of the nanomaterial in example 1, the amounts of graphene and iron-containing precursor in step (2) were set to 2.5g and 1.5g, and the final product was collected after the reaction, and it was identified that the carbon layer shell of the obtained nanomaterial consisted of 5 to 7 carbon layers, the thickness of the carbon layer shell was 12nm, the outer diameter of the core was 45nm, and the inner diameter of the core was 5.4nm.
Example 4
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 layer outer shell thickness of the nanomaterial was different:
the preparation of the nanomaterial is as follows:
similar to the preparation method of the nanomaterial in example 1, the amounts of graphene and iron-containing precursor in step (2) were set to 0.5g and 1.5g, and the final product was collected after the reaction, and it was identified that the carbon layer shell of the obtained nanomaterial consisted of 1-2 layers of carbon layer, the thickness of the carbon layer shell was 1.5nm, the outer diameter of the core was 45nm, and the inner diameter of the core was 5.4nm.
Example 5
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 inner diameter of the inner core of the nanomaterial was different in size:
the preparation of the nanomaterial is as follows:
similar to the preparation method of the nanomaterial in example 1, the reaction condition of the secondary hydrothermal reaction in the step (3) is set to be 100 ℃ for 6 hours, and the final product is collected after the reaction, and the thickness of the carbon layer outer shell is identified to be 2.2nm, the outer diameter of the core is identified to be 45nm, and the inner diameter of the core is identified to be 13nm.
Example 6
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 inner diameter of the inner core of the nanomaterial was different in size:
the preparation of the nanomaterial is as follows:
similar to the preparation method of the nanomaterial in example 1, the reaction condition of the secondary hydrothermal reaction in the step (3) is set to 40 ℃ for 6 hours, and the final product is collected after the reaction, and the thickness of the carbon layer outer shell is identified to be 2.2nm, the outer diameter of the core is identified to be 45nm, and the inner diameter of the core is identified to be 3nm.
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 anode, and the anode protective paste prepared in example 1 was used in this example, and the protective layer formed on the copper foil by the anode protective paste had a thickness of 50 μm.
Example 8
A lithium battery was fabricated according to the method of example 1, except that the lithium negative electrode and the lithium battery were fabricated differently.
The lithium negative electrode of this example was prepared as follows:
adding the nano material prepared in the step (one) 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 prepared from 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 adopts an aluminum foil coated with ternary materials, specifically, NCM811, a conductive agent Super-P and an adhesive PVDF are mixed according to the mass ratio of 95:2:3 and then dispersed in N-methylpyrrolidone (NMP), and the mixture is stirred and mixed uniformly to obtain positive electrode slurry; uniformly coating the anode slurry on an aluminum foil, drying, and carrying out cold pressing and slitting procedures to obtain an anode plate; preparing a bare cell from a positive plate, a negative plate and a diaphragm (PE film) through a lamination process, filling the cell into an aluminum plastic film packaging shell, and then injecting electrolyte to prepare a laminated lithium battery; wherein the electrolyte was the same as in example 1.
Example 9
A lithium battery was prepared according to the method of example 1, except that cobalt sulfide nanoparticles were used for the inner core of the nanomaterial, and the nanomaterial of this example was prepared as follows:
(1) preparing a precursor:
200mg CoCl 3 ·6H 2 o and 120mg thioacetamide (CH) 3 CSNH 2 ) Adding 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, dispersing the crude product in ethanol, maintaining at 60 ℃ for 8 hours, and vacuum drying to obtain a crude product, namely a precursor;
(2) adding 2.0g of graphene subjected to ultrasonic dispersion and 1.8g of prepared precursor into 30mL of deionized water, stirring and reacting for 24 hours, and then removing the solvent by rotary evaporation to obtain powder;
(3) adding the powder obtained in the step (2) into absolute ethyl alcohol again to carry out secondary hydrothermal reaction, and vacuum drying and collecting a product after reacting for 6 hours at 160 ℃;
(4) etching the collected powder in 1M hydrochloric acid for 24 hours, then washing the powder with deionized water for multiple times, and collecting a final product after vacuum drying, wherein the final product is a nano material with a cobalt sulfide nano particle as an inner core, and the thickness of the carbon layer outer shell is 3.4nm, the outer diameter of the inner core is 51nm, and the inner diameter of the inner core is 6.2nm.
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 layer shell of the nanomaterial was doped with N atoms.
The nanomaterial of this example was prepared as follows:
(1) preparing an iron-containing precursor:
116mg FeCl 3 ·6H 2 o and 270mg of terephthalic acid are 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, dispersing the crude product in ethanol, maintaining at 70 ℃ for 3 hours, and vacuum drying to obtain a crude product, namely an iron-containing precursor;
(2) adding 1.5g of graphene subjected to ultrasonic dispersion, 1.5g of prepared precursor and 0.15g of butylamine into 30mL of deionized water, stirring and reacting for 24 hours, and then removing the solvent by rotary evaporation to obtain powder;
(3) adding the powder obtained in the step (2) into Dimethylformamide (DMF) again for secondary hydrothermal reaction at 80 ℃ for 6 hours, and then drying in vacuum to collect a product;
(4) etching the collected powder in 1M hydrochloric acid for 24 hours, washing the powder with deionized water for multiple times, and collecting a final product after vacuum drying, wherein the final product is a nano material with an inner core of iron carbide nano particles, the thickness of the carbon layer outer shell is identified to be 2.2nm, the outer diameter of the inner core is identified to be 45nm, the inner diameter of the inner core is 5.4nm, and 10wt% of nitrogen atoms are loaded in the carbon layer outer shell.
Comparative example 1
The lithium battery was prepared according to the method of example 1, the inner core of the nanomaterial being iron carbide nanoparticles, except that the iron carbide nanoparticles were of solid spherical structure, and no cavity was provided between the carbon layer outer shell and the inner core;
the preparation of the nanomaterial is as follows:
similar to the preparation method of the nanomaterial in example 1, the powder obtained by rotary evaporation to remove the solvent in step (2) is directly collected.
Comparative example 2
A lithium battery was prepared according to the method of example 1, the inner core of the nanomaterial being iron carbide nanoparticles of hollow spherical structure, except that no cavity was provided between the carbon layer outer shell and the inner core;
the preparation of the nanomaterial is as follows:
and (3) similar to the preparation method of the nano material in the embodiment 1, the product obtained after the secondary hydrothermal treatment and drying in the step (3) is directly collected.
Comparative example 3
The lithium battery was prepared according to the method of example 1, the inner core of the nanomaterial being iron carbide nanoparticles, wherein a cavity was provided between the outer shell of the carbon layer and the inner core, except that the iron carbide nanoparticles were of solid spherical structure;
the preparation of the nanomaterial is as follows:
similar to the preparation method of the nanomaterial in example 1, the powder obtained by evaporating the solvent in step (2) is directly collected, and is directly put into 1M hydrochloric acid for etching without secondary hydrothermal treatment.
Comparative example 4
A lithium battery was fabricated according to the method of example 1, except that a protective layer was prepared using a pretreatment protective slurry for lithium negative electrode, which was formed by uniformly mixing 10% iron carbide nanoparticles, 5% polyethylene oxide, and ethylene glycol dimethyl ether (DME);
the preparation of the iron carbide nanoparticles was as follows:
and (3) directly collecting the crude product obtained in the step (1) similarly to the preparation method of the nano material in the embodiment 1.
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 a negative electrode sheet.
Average coulombic efficiency and normal temperature cycle performance tests were performed on the lithium batteries prepared in examples 1 to 10 and comparative examples 1 to 5:
the normal temperature cycle performance test process is as follows:
charging the lithium ion battery to 4.5V at 25 ℃ with 1C constant current, charging the lithium ion battery to 0.05C with 4.5V constant voltage, and discharging the lithium ion battery to 2.7V with 1C constant current after the lithium ion battery is placed for 30min, wherein the discharge capacity is the discharge capacity of the first cycle in a charge-discharge cycle process;
and (3) carrying out a cyclic charge and discharge test on the lithium ion battery according to the mode, and taking the discharge capacity of the nth cycle.
The capacity retention (%) = [ discharge capacity of nth cycle/discharge capacity of first cycle ] ×100% after n cycles of the lithium ion battery; the number of cycles with a capacity retention of 80% was recorded.
The test results are shown in the following table:
from the results shown in the table, compared with comparative examples 1 to 5, the normal temperature cycle performance of the lithium batteries of examples 1 to 2 and 10 is obviously improved, and the average coulombic efficiency is also improved to a certain extent, which indicates that the pretreatment of the lithium negative electrode by the lithium negative electrode pretreatment protection slurry containing the nanomaterial of the embodiment of the application can effectively stabilize the deposition/dissolution of lithium ions of the lithium negative electrode and inhibit the growth of lithium dendrites, thereby improving the coulombic efficiency and the cycle stability of the lithium battery and enhancing the safety of the battery.
Specifically, as can be seen from comparison of example 1 and comparative examples 1 to 3, the nano material with the egg yolk-eggshell structure, in which the core is hollow sphere, shows a more excellent effect of stabilizing the lithium anode compared with the nano material with the carbon layer outer shell coating the solid sphere core, the nano material with the carbon layer outer shell coating the hollow sphere core, and the nano material with the carbon layer outer shell non-contact coating the solid sphere core, which results from the synergistic effect between the carbon layer outer shell and the core and the volume buffer effect of the core, so that the nano material has the effect of uniformly depositing lithium.
As can be seen from a comparison between example 1 and comparative example 4, the nanomaterial of the present application has better cycle performance than the iron carbide nanoparticle without the shell, 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 layer shell and the iron carbide nanoparticle, and can make the lithium deposition more uniform, thereby helping to improve the cycle stability of the battery.
As can be seen from a comparison of example 1 and comparative example 5, the lithium battery having the protective layer has a longer cycle life than the lithium battery having no protective layer, indicating that the nanomaterial provided in the present application has an excellent ability to stabilize a lithium anode, and can be used as an additive for forming a lithium anode protective layer to improve the cycle performance of the lithium battery.
As is apparent from comparison of examples 1 and 3 and 4 and examples 1 and 6, the thickness of the outer shell and the inner diameter of the inner core of the carbon layer affect the lithium-philicity and lithium deposition performance of the nanomaterial, and thus the cycling stability of the battery is affected, and the battery using the nanomaterial having the carbon layer with the outer shell thickness of 2 to 4nm and the inner diameter of the inner core of 5 to 10nm shows superior average coulombic efficiency and cycling performance.
As can be seen from a comparison of example 1 and example 10, loading a certain amount of nitrogen atoms in the carbon layer shell can further improve the lithium-philicity of the nanomaterial, so that the battery using the nanomaterial has better cycle performance.
Among them, the batteries used in examples and comparative examples herein have had relatively high average coulombic efficiency, resulting in a space in which the battery coulombic efficiency can be further improved by at most about 0.6%, and in this limited space, the average coulombic efficiency of the batteries of examples 1 to 10 is improved by at least 0.07% as compared to comparative examples 1 to 5, indicating that the nanomaterial for negative electrode protective layer of the present application can produce relatively significant improvement in the coulombic efficiency of the battery even in a limited lifting space by inducing uniform deposition of lithium.
The foregoing description is only of the preferred embodiments of the present application and is presented as a description of the principles of the technology being utilized. It will be appreciated by persons skilled in the art that the scope of the invention referred to in this application is not limited to the specific combinations of features described above, but it is intended to cover other embodiments in which any combination of features described above or equivalents thereof is possible without departing from the spirit of the invention. Such as the above-described features and technical features having similar functions (but not limited to) disclosed in the present application are replaced with each other.
Claims (9)
1. A nanomaterial for a negative electrode protective layer, comprising:
the inner core and the carbon layer shell are coated on the surface of the inner core, and a cavity is formed between the inner core and the carbon layer shell;
the inner core is iron carbide nano particles, tungsten carbide nano particles, cobalt sulfide nano particles or molybdenum sulfide nano particles, the outer diameter of the inner core is 20-70 nm, and the inner core is of a hollow spherical structure.
2. The nanomaterial for a negative electrode protection layer according to claim 1, characterized in that the outer diameter of the core is 40 to 60nm.
3. The nanomaterial for a negative electrode protection layer according to claim 1, characterized in that the inner diameter of the core is 5 to 10nm.
4. The nanomaterial for a negative electrode protection layer according to claim 1, characterized in that the thickness of the carbon layer shell is 2 to 4nm.
5. The nanomaterial for a negative electrode protective layer according to any one of claims 1 to 4, characterized in that nitrogen atoms are supported in the carbon layer outer shell in an amount of 1 to 10wt% based on the mass of the carbon layer outer shell.
6. A negative electrode protection paste comprising the nanomaterial for a negative electrode protection layer according to any one of claims 1 to 5.
7. A lithium anode, comprising:
a lithium negative electrode substrate and a protective layer formed on one or both side surfaces of the lithium negative electrode substrate, the protective layer being formed of the negative electrode protective slurry according to claim 6.
8. The lithium anode according to claim 7, wherein the thickness of the protective layer is 10 to 50 μm.
9. 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 of claim 7 or 8.
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