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CN107104227B - Lithium-ion battery cathode material and preparation method thereof - Google Patents

Lithium-ion battery cathode material and preparation method thereof Download PDF

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CN107104227B
CN107104227B CN201710391348.1A CN201710391348A CN107104227B CN 107104227 B CN107104227 B CN 107104227B CN 201710391348 A CN201710391348 A CN 201710391348A CN 107104227 B CN107104227 B CN 107104227B
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CN107104227A (en
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毛方会
杨玉洁
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Guangdong Canrd New Energy Technology Co ltd
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    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract

本发明属于储能研究领域，特别涉及一种锂离子电池正极材料，包括核结构和壳结构，所述核结构为二次颗粒结构，且其中包括具有多孔结构的主导电网络以及填充于所述多孔主导电网络孔结构中的纳米一次颗粒；所述纳米一次颗粒包括纳米钴酸锂、纳米锰酸锂、纳米磷酸铁锂、纳米镍钴锰、纳米镍钴铝、纳米镍酸锂、纳米锂钒氧化物、纳米富锂正极材料中的至少一种；所述主导网络结构之间存在较强的化学键和力作用；所述化学键将所述纳米一次颗粒紧密的锁定于所述主导电网络的孔结构中。从而确保该锂离子电池正极材料具有优良的电化学性能。The invention belongs to the field of energy storage research, and in particular relates to a positive electrode material for a lithium ion battery, comprising a core structure and a shell structure, wherein the core structure is a secondary particle structure, which includes a main conductive network with a porous structure and a Nano-primary particles in the pore structure of the porous main conductive network; the nano-primary particles include nano-lithium cobaltate, nano-lithium manganate, nano-lithium iron phosphate, nano-nickel-cobalt-manganese, nano-nickel-cobalt-aluminum, nano-lithium nickelate, nano-lithium At least one of vanadium oxide and nano-lithium-rich positive electrode material; there is a strong chemical bond and force between the dominant network structures; the chemical bond tightly locks the nano-primary particles in the main conductive network. in the pore structure. Thus, it is ensured that the positive electrode material of the lithium ion battery has excellent electrochemical performance.

Description

Lithium ion battery anode material and preparation method thereof
Technical Field
The invention belongs to the technical field of energy storage materials, and particularly relates to a lithium ion battery anode material and a preparation method thereof.
Background
Since birth, lithium ion batteries have revolutionary changes in the field of energy storage due to their advantages of rapid charging and discharging, good low-temperature performance, large specific energy, small self-discharge rate, small volume, light weight, and the like, and are widely used in various portable electronic devices and electric vehicles. However, with the improvement of living standard of people, higher user experience puts higher requirements on the lithium ion battery: longer standby time, faster charge and discharge speed, etc.; in order to solve the above problems, it is necessary to find a new electrode material having more excellent properties.
At present, the commercial lithium ion battery anode materials are basically semiconductors or insulators, the conductivity of material particles is very poor, in order to solve the problems, the prior art mainly comprises the steps of pelletizing the material particles after nano-crystallization to obtain a secondary particle structure, adding a conductive material with excellent conductivity in the primary particle pelletizing process and the like so as to improve the conductivity of the whole particles of the anode material; and meanwhile, the surface of the material is coated by adopting a coating technology, so that the conductivity of the surface of the material is increased.
However, primary particles with a nano structure are extremely easy to agglomerate and have high dispersion difficulty; the commonly used conductive agent materials are generally small in size (nanometer), large in specific surface area and difficult to disperse. However, in order to maximize the conductive effect of the conductive agent and to prepare a lithium ion battery anode secondary particle material with better performance, the uniform dispersion of the nano primary particles and the conductive agent must be ensured. Meanwhile, the contact area between the primary particles of the nano structure and the conductive agent is small, and the gap is large, so that the contact resistance is relatively large, and the internal resistance of the prepared anode material finished product is large, so that the electrochemical performance of the lithium ion battery taking the anode material as the anode material is influenced (mainly expressed as large resistance, large polarization and serious heating).
In view of the above, there is a need for a lithium ion battery cathode material and a preparation method thereof, which can uniformly disperse two materials (nano primary particles and conductive agent) with high dispersion difficulty, and ensure that the two materials are tightly connected together, thereby preparing a lithium ion battery cathode material with excellent performance.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the provided lithium ion battery cathode material comprises a core structure and a shell structure, wherein the core structure is a secondary particle structure and comprises a main electric conducting network with a porous structure and nano primary particles filled in the porous structure of the main electric conducting network; the nano primary particles comprise at least one of nano lithium cobaltate, nano lithium manganate, nano lithium iron phosphate, nano nickel cobalt manganese, nano nickel cobalt aluminum, nano lithium nickelate, nano lithium vanadium oxide and nano lithium-rich cathode material; strong chemical bonds and force action exist among the dominant network structures; the chemical bond tightly locks the nano-sized primary particles in the pore structure of the main conducting network. Thereby ensuring that the lithium ion battery anode material has excellent electrochemical performance. The invention is applicable to all materials which need primary particle pelletizing to obtain a secondary particle structure in the field of energy storage research, and specifically comprises lithium ion anode materials, lithium ion cathode materials (such as graphite, silicon carbon, lithium iron phosphate, alloy cathodes and the like) and other battery capacitor materials (such as lithium air batteries, fuel batteries, sodium ion batteries, zinc ion batteries and the like).
In order to achieve the purpose, the invention adopts the following technical scheme:
a lithium ion battery cathode material comprises a core structure and a shell structure, wherein the core structure is a secondary particle structure and comprises a main conducting network with a porous structure and nano primary particles filled in the porous structure of the main conducting network; the nano primary particles comprise at least one of nano lithium cobaltate, nano lithium manganate, nano lithium iron phosphate, nano nickel cobalt manganese, nano nickel cobalt aluminum, nano lithium nickelate, nano lithium vanadium oxide and nano lithium-rich cathode material; strong chemical bonds and force action exist among the dominant network structures; the chemical bond tightly locks the nano-sized primary particles in the pore structure of the main conducting network. The shell structure is a coating layer commonly used for cathode materials and is mainly obtained by coating and carbonizing materials such as asphalt and the like, so that the invention is not explained in detail.
As an improvement of the lithium ion battery anode material, the bond type providing the strong bonding force is a hydrogen bond or/and a chemical bond; the mass of the oxygen-containing functional groups forming the hydrogen bonds or/and the chemical bonds accounts for 1-40% of the mass of the whole main electric network structure.
As an improvement of the lithium ion battery anode material, the main electric conducting network has flexibility, and the inside of the main electric conducting network contains functional groups; the hydrogen bonds or/and chemical bonds result from the reaction of oxygen-containing functional groups within the main conducting network.
As an improvement of the lithium ion battery cathode material, the main conducting network structure is at least one of an open graphene structure, an open expanded graphite structure and a vermicular graphene structure; the primary particles comprise nano lithium ion battery anode particles; an auxiliary electric conduction network can be distributed between the main electric conduction network and the primary particles and tightly connects the main electric conduction network and the nano primary particles together.
As an improvement of the lithium ion battery anode material, the auxiliary conducting network is obtained by carbonizing a high polymer material; the high polymer material is obtained by in-situ polymerization of a high polymer monomer; the auxiliary conducting network further comprises at least one of conductive carbon black, super conductive carbon, Ketjen black, carbon nanotubes, graphene and acetylene black.
The invention also comprises a preparation method of the lithium ion battery anode material, which is characterized by mainly comprising the following steps:
step 1, precursor preparation: uniformly dispersing the primary particles in a solvent to obtain a precursor;
step 2, preparing a modified main power guide network structure: placing the main conducting network structure with the porous structure in an oxidation environment, and grafting a functional group to obtain a modified main conducting network structure;
step 3, filling: filling the precursor prepared in the step 1 into a modified main power transmission network structure;
step 4, closing the opening: placing the porous main electric network structure in a reducing atmosphere to promote functional groups grafted on the main electric network structure to react to generate strong bonding force, and sealing or partially sealing the pore structure in the porous main electric network structure;
and 5, coating and carbonizing the product obtained in the step 4 to obtain the finished product of the lithium ion battery anode material.
As an improvement of the preparation method of the lithium ion battery anode material, the surface of the primary particles in the step 1 is modified into functionalized primary particles, and the functional groups are carboxyl or/and hydroxyl; the grafted functional group in the step 2 comprises at least one of carboxyl, hydroxyl, epoxy, carbonyl, nitro and amino; and 4, adding a reducing agent or/and performing direct hydrothermal reduction on the reducing environment.
As an improvement of the preparation method of the lithium ion battery anode material, polymer monomers can be added in the step 1, namely, the primary particles and the polymer monomers are mixed and kneaded to obtain a precursor in which the polymer monomers are uniformly dispersed on the surfaces of the primary nanoparticles; in this case, it is necessary to perform a polymerization reaction after step 3, in which the product of step 3 is placed in an environment where an initiator is present to promote polymerization of the polymer monomer dispersed on the surface of the primary particles, thereby obtaining a high molecular polymer.
As an improvement of the preparation method of the lithium ion battery anode material, a high molecular polymer, a carbon source component, a conductive agent component and a solvent component are also added during kneading reaction; in step 1, the kneading process is as follows: kneading the nano primary particles, the surfactant 1, the polymer monomer and the solvent 1 to obtain a mixture 1; kneading the conductive agent component, the surfactant 2 and the solvent 2 to obtain a mixture 2; and then blending the mixture 1 and the mixture 2, and uniformly dispersing to obtain precursor slurry.
As an improvement of the preparation method of the lithium ion battery anode material, the filling process in the step 3 is as follows:
pretreating the porous main conducting network structure material, wherein the pretreatment comprises surface activation or/and surfactant addition;
before filling, placing the porous main conducting network structure material in a vacuum environment, vacuumizing, removing air in a pore structure, vacating a space for filling a precursor, and then placing the porous main conducting network structure material in precursor slurry to start filling;
in the filling process, pressure is applied to extrude the precursor into the hole; the temperature is increased, and the viscosity of the precursor is reduced; and (5) adding mechanical disturbance and opening the hole opening.
As an improvement of the preparation method of the lithium ion battery anode material of the present invention, the polymer monomer in step 1 includes acrylates, methacrylates, styrene, acrylonitrile, methacrylonitrile, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, divinylbenzene, trimethylolpropane trimethacrylate, methyl methacrylate, N-dimethylacrylamide, N-acryloylmorpholine, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl N-acrylate, cyclohexyl 2-acrylate, dodecyl acrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, 1, 6-hexanediol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, ethylene, At least one of ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol acrylate, bis-trihydroxypropane tetraacrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, propoxylated glycerol triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate; and 4, at least one of initiator cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.
As an improvement of the preparation method of the lithium ion battery anode material, a high molecular polymer, a carbon source component, a conductive agent component or/and a solvent component can be added during kneading reaction, wherein the high molecular polymer comprises at least one of polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), Styrene Butadiene Rubber (SBR), sodium carboxymethyl cellulose (CMC) and polyacrylonitrile, and the carbon source component comprises glucose, sucrose, soluble starch, cyclodextrin, furfural, sucrose, glucose, corn starch, tapioca starch, wheat starch, cellulose, polyvinyl alcohol, polyethylene glycol, polyethylene wax, phenolic resin, vinyl pyrrolidone, epoxy resin, polyvinyl chloride, polyalditol, furan resin, urea-formaldehyde resin, polymethyl methacrylate, polyvinylidene fluoride or polyacrylonitrile, petroleum coke, oil-based needle coke, and/or solvent component, The conductive agent component comprises at least one of conductive carbon black, super conductive carbon, Ketjen black, carbon nano tubes, graphene and acetylene black, and at least one of water, alcohols, ketones, alkanes, esters, aromatics, N-methylpyrrolidone, dimethylformamide, diethylformamide, dimethyl sulfoxide and tetrahydrofuran.
As an improvement of the preparation method of the lithium ion battery anode material, the preparation process of the main power conducting network structure in the step 2 comprises the following steps: preparing an open graphene structure, an open expanded graphite structure and a vermicular graphene structure: the preparation method comprises the following steps of taking crystalline flake graphite or microcrystalline graphite (vermicular graphene can be prepared, graphene lamella are connected together tightly, developed gap structures are distributed among the lamellae, and primary particles can be conveniently filled, meanwhile, the particle size of the microcrystalline graphene is small, the particle size of the prepared vermicular graphene is about 10 mu m and is matched with the diameter of the final finished product lithium ion battery anode particles), controlling the degree of oxidation intercalation (mainly moderate in degree of oxidation, too low in degree of oxidation, and incapable of forming a porous structure), completely stripping the graphite lamellae in the reduction process, and incapable of forming a connected porous structure), and then performing heat treatment and expansion to obtain the porous structure with openings between the lamellae and the connected lamellae among the same graphite; then, functional groups are grafted in an oxidizing environment to obtain the modified main conducting network structure
As an improvement of the preparation method of the lithium ion battery anode material, the surfactant 1 comprises at least one of a wetting agent, a dispersing agent, a penetrating agent, a solubilizer, a cosolvent and a latent solvent; the solvent 1 is at least one of water, alcohols, ketones, alkanes, esters, aromatics, N-methylpyrrolidone, dimethylformamide, diethylformamide, dimethyl sulfoxide and tetrahydrofuran. The surfactant 2 comprises at least one of a wetting agent, a dispersing agent, a penetrating agent, a solubilizer, a cosolvent and a cosolvent; the solvent 2 is at least one of water, alcohols, ketones, alkanes, esters, aromatics, N-methylpyrrolidone, dimethylformamide, diethylformamide, dimethyl sulfoxide and tetrahydrofuran.
The invention has the advantages that:
1. the modified main electric conduction network structure and the modified primary particles (or the modified main electric conduction network contains polar functional groups, and the metal oxide has polarity, so that the metal oxide is relatively easy to mix uniformly and fill), and the modified main electric conduction network structure has similar functional groups, so that a precursor formed by the primary particles can enter the pore structure of the main electric conduction network; the full filling of the pore structure is realized, and the specific gravity of the primary particles in the lithium iron phosphate composite material is improved;
2. the strong bonding acting force between the inner sheet layers of the main power transmission network structure can effectively seal primary particles in the main power transmission network structure, and the stability of the primary particles in a finished product secondary particle structure is ensured; meanwhile, after the main power conducting network structure is sealed, the contact between the electrolyte and the primary particles can be effectively blocked, and the occurrence of gas generation side reactions in the charging and discharging process is reduced or even eliminated, so that the cycle performance of the battery is improved;
3. the auxiliary conducting network structure tightly connects the main conducting network structure and the primary particles, so that the contact area between the primary particles and the main conducting network is increased, the contact resistance is reduced, and the prepared battery assembled by the lithium ion battery anode material has lower impedance;
4. in the preparation process, the polymer monomer with low viscosity and the primary nano-particles are kneaded and dispersed, so that the uniform dispersion of the primary nano-particles can be ensured, and the polymer monomer is uniformly distributed on the surfaces of the primary nano-particles;
5. the precursor with lower viscosity (because the viscosity of the polymer monomer is low) is easier to fill into the pore structure of the main conducting network, and the pores of the porous structure of the main conducting network are all filled with the primary nanoparticles.
Detailed Description
The present invention and its advantageous effects will be described in detail below with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
Comparative example, a lithium iron phosphate secondary particle material having a particle diameter of 10 μm was prepared;
step 1, mixing: lithium iron phosphate with the particle size of 100nm, conductive carbon black, sodium dodecyl sulfate, polyvinylpyrrolidone and NMP (solid content of 0.5%) in a mass ratio of 94:4.9:1:0.1 are mixed and stirred for 10 hours to obtain slurry.
Step 2, preparing secondary particles: adjusting the spray drying condition to prepare lithium iron phosphate secondary particles with the particle diameter of 10 mu m; and then coating and carbonizing to obtain the finished product of the lithium ion battery anode material.
Example 1 is different from the comparative example in that the present example includes the following steps:
step 1, precursor preparation: mixing lithium iron phosphate with the particle size of 100nm, methyl methacrylate, sodium dodecyl sulfate (the mass ratio of the lithium iron phosphate to the methyl methacrylate to the sodium dodecyl sulfate is 95:4:1) and NMP, kneading the mixture (the solid content is 10%), revolving the mixture at 30 revolutions per minute and rotating the mixture at 300 revolutions per minute; kneading for 4h to obtain a uniformly dispersed precursor;
step 2, preparing a main conducting network structure of the modified vermicular graphene: selecting microcrystalline graphite as a raw material, adding concentrated sulfuric acid and potassium permanganate to perform oxidation intercalation to obtain graphite oxide, and performing heat treatment to obtain vermicular graphene; putting the vermicular graphene into a mixture of concentrated sulfuric acid, potassium permanganate and sodium nitrate to modify the vermicular graphene to obtain modified vermicular graphene grafted with 1% of functional groups for later use;
step 3, filling: vacuumizing the modified vermicular graphene obtained in the step 2, then placing the modified vermicular graphene in the precursor obtained in the step 1, applying pressure to the precursor, simultaneously performing ultrasonic oscillation to enable the precursor to be filled into the pore structure of the vermicular graphene, and separating to obtain the modified vermicular graphene filled with the precursor;
step 4, polymerization reaction: dissolving tert-butyl peroxybenzoate in NMP to obtain a solution, spraying the solution onto the surface of the modified vermicular graphene filled with the precursor obtained in the step (3), and heating to promote the polymerization of methyl methacrylate dispersed on the surface of the lithium iron phosphate particles, so that the lithium iron phosphate particles and the modified vermicular graphene sheet layer are tightly bonded together;
step 5, closing the opening: carrying out solvothermal reaction on the product obtained in the step (4), promoting functional groups grafted on vermicular graphene sheet layers (between adjacent sheet layers) to react, generating new chemical bonds, and sealing the openings of the vermicular graphene sheet layers;
and 6, coating and carbonizing the product obtained in the step 5 (and carbonizing the coating layer and the polymer at the same time) to obtain the finished product of the lithium ion battery anode material.
Embodiment 2 is different from embodiment 1 in that this embodiment includes the following steps:
step 2, preparing a main conducting network structure of the modified vermicular graphene: selecting microcrystalline graphite as a raw material, adding concentrated sulfuric acid and potassium permanganate to perform oxidation intercalation to obtain graphite oxide, and performing heat treatment to obtain vermicular graphene; putting the vermicular graphene into a mixture of concentrated sulfuric acid, potassium permanganate and sodium nitrate to modify the vermicular graphene to obtain modified vermicular graphene grafted with 5% of functional groups for later use;
the rest is the same as the embodiment 1, and the description is omitted.
Embodiment 3 is different from embodiment 1 in that this embodiment includes the following steps:
step 2, preparing a main conducting network structure of the modified vermicular graphene: selecting microcrystalline graphite as a raw material, adding concentrated sulfuric acid and potassium permanganate to perform oxidation intercalation to obtain graphite oxide, and performing heat treatment to obtain vermicular graphene; putting the vermicular graphene into a mixture of concentrated sulfuric acid, potassium permanganate and sodium nitrate to modify the vermicular graphene to obtain modified vermicular graphene grafted with 15% of functional groups for later use;
the rest is the same as the embodiment 1, and the description is omitted.
Embodiment 4 is different from embodiment 1 in that this embodiment includes the following steps:
step 2, preparing a main conducting network structure of the modified vermicular graphene: selecting microcrystalline graphite as a raw material, adding concentrated sulfuric acid and potassium permanganate to perform oxidation intercalation to obtain graphite oxide, and performing heat treatment to obtain vermicular graphene; putting the vermicular graphene into a mixture of concentrated sulfuric acid, potassium permanganate and sodium nitrate to modify the vermicular graphene to obtain modified vermicular graphene grafted with 20% of functional groups for later use;
the rest is the same as the embodiment 1, and the description is omitted.
Embodiment 5 differs from embodiment 1 in that this embodiment includes the following steps:
step 2, preparing a main conducting network structure of the modified vermicular graphene: selecting microcrystalline graphite as a raw material, adding concentrated sulfuric acid and potassium permanganate to perform oxidation intercalation to obtain graphite oxide, and performing heat treatment to obtain vermicular graphene; putting the vermicular graphene into a mixture of concentrated sulfuric acid, potassium permanganate and sodium nitrate to modify the vermicular graphene to obtain modified vermicular graphene grafted with 25% of functional groups for later use;
the rest is the same as the embodiment 1, and the description is omitted.
Embodiment 6 differs from embodiment 1 in that this embodiment includes the following steps:
step 2, preparing a main conducting network structure of the modified vermicular graphene: selecting microcrystalline graphite as a raw material, adding concentrated sulfuric acid and potassium permanganate to perform oxidation intercalation to obtain graphite oxide, and performing heat treatment to obtain vermicular graphene; putting the vermicular graphene into a mixture of concentrated sulfuric acid, potassium permanganate and sodium nitrate to modify the vermicular graphene to obtain modified vermicular graphene grafted with 40% of functional groups for later use;
the rest is the same as the embodiment 1, and the description is omitted.
Embodiment 7 is different from embodiment 1 in that this embodiment includes the following steps:
step 1, precursor preparation: mixing modified lithium iron phosphate (surface activated), carbon nanotubes and NMP with the particle size of 100nm (solid content is 10%) and kneading, wherein the revolution is 30 revolutions per minute and the rotation is 300 revolutions per minute; kneading for 4h to obtain uniformly dispersed precursor slurry;
step 2, preparing a main conducting network structure of the modified vermicular graphene: selecting microcrystalline graphite as a raw material, adding concentrated sulfuric acid and potassium permanganate to perform oxidation intercalation to obtain graphite oxide, and performing heat treatment to obtain vermicular graphene; putting the vermicular graphene into a mixture of concentrated sulfuric acid, potassium permanganate and sodium nitrate to modify the vermicular graphene to obtain modified vermicular graphene grafted with 20% of functional groups for later use;
step 3, filling: vacuumizing the modified vermicular graphene obtained in the step 2, then placing the modified vermicular graphene in the precursor obtained in the step 1, applying pressure to the precursor, simultaneously performing ultrasonic oscillation to enable the precursor to be filled into a vermicular graphene pore structure, and separating to obtain the modified vermicular graphene filled with the precursor;
step 4, closing the opening: carrying out solvothermal reaction on the product obtained in the step (3) to promote functional groups grafted on the vermicular graphene sheet layers (between adjacent sheet layers) to react to generate new chemical bonds, and sealing the openings of the vermicular graphene sheet layers;
and 5, coating and carbonizing the product obtained in the step 4 (and carbonizing the coating layer and the polymer at the same time) to obtain the finished product of the lithium ion battery anode material.
The rest is the same as the embodiment 1, and the description is omitted.
Embodiment 8 differs from embodiment 1 in that this embodiment includes the following steps:
step 1, kneading: mixing lithium iron phosphate with a particle size of 100nm + lithium cobaltate (the mass ratio of the lithium iron phosphate to the lithium cobaltate is 9:1), trimethylolpropane trimethacrylate, hexadecyl dimethyl allyl ammonium chloride (the mass ratio of the lithium iron phosphate to the lithium cobaltate is 90:4:1), and ethanol (the solid content is 10%), kneading, wherein the revolution is 5 revolutions per minute, and the rotation is 10 revolutions per minute; kneading for 8h to obtain a mixture 1; mixing methyl vinyl dimethoxysilane, graphene, polyoxyethylene alkylphenol ether (mass ratio of methyl vinyl dimethoxysilane to graphene: polyoxyethylene alkylphenol ether is 5:4.9:0.1) and ethanol, kneading (solid content is 4%), revolving for 5 revolutions/min, and rotating for 10 revolutions/min; kneading for 8h to obtain a mixture 2; mixing the mixture 1 and the mixture 2 (the mass ratio of (lithium iron phosphate + lithium cobaltate) and the graphene is 90:4.9), kneading continuously, revolving for 5 revolutions per minute and rotating for 10 revolutions per minute; kneading for 6h to obtain a precursor in which the polymer monomer is uniformly coated on the surface of the primary particles (lithium iron phosphate and lithium cobaltate), the polymer monomer and the graphene are uniformly dispersed, and the graphene and the primary particles are uniformly dispersed;
step 2, preparing the main conducting network structure of the modified expanded graphite: flake graphite is selected as a raw material, then concentrated sulfuric acid and potassium permanganate are added for oxidation intercalation to obtain graphite oxide, and then heat treatment is carried out to obtain expanded graphite; placing the expanded graphite in a mixture of concentrated sulfuric acid, potassium permanganate and sodium nitrate to modify the expanded graphite to obtain a modified expanded graphite main power grid structure grafted with 20% of functional groups for later use;
step 3, filling: vacuumizing the main conductive network structure of the modified expanded graphite obtained in the step (2), then placing the vacuumized main conductive network structure of the modified expanded graphite in the precursor obtained in the step (1), applying pressure to the precursor, simultaneously performing ultrasonic oscillation to enable the precursor to be filled into the main conductive network structure of the modified expanded graphite, and separating to obtain the main conductive network structure of the modified expanded graphite filled with the precursor;
step 4, polymerization reaction: dissolving tert-butyl peroxybenzoate in NMP to obtain a solution, spraying the solution on the surface of the modified expanded graphite filled with the precursor obtained in the step (3), and heating to promote the polymerization of methyl methacrylate dispersed on the surface of the primary particles, so that the primary particles and the modified expanded graphite sheet are tightly bonded together;
step 5, closing the opening: adding a reducing agent into the product obtained in the step (4) to promote functional groups grafted on the modified expanded graphite sheet layers (between the adjacent sheet layers) to react to generate new chemical bonds, and sealing the openings of the modified expanded graphite sheet layers;
the rest is the same as the embodiment 1, and the description is omitted.
Embodiment 9 is different from embodiment 4 in that this embodiment includes the following steps:
step 1, precursor preparation: mixing Nickel Cobalt Manganese (NCM) with the particle size of 100nm, methyl methacrylate, sodium dodecyl sulfate (the mass ratio of nickel cobalt manganese to methyl methacrylate: sodium dodecyl sulfate is 95:4:1) and NMP, kneading the mixture (the solid content is 10%), revolving the mixture at 30 revolutions/min and rotating the mixture at 300 revolutions/min; kneading for 4h to obtain a uniformly dispersed precursor;
step 2, preparing a main conducting network structure of the modified vermicular graphene: selecting microcrystalline graphite as a raw material, adding concentrated sulfuric acid and potassium permanganate to perform oxidation intercalation to obtain graphite oxide, and performing heat treatment to obtain vermicular graphene; putting the vermicular graphene into a mixture of concentrated sulfuric acid, potassium permanganate and sodium nitrate to modify the vermicular graphene to obtain modified vermicular graphene grafted with 20% of functional groups for later use;
the rest is the same as embodiment 4 and is not described again.
Assembling the battery: stirring the positive electrode materials prepared in the comparative examples and the examples with a conductive agent, a binder and a solvent to obtain electrode slurry, and then coating the electrode slurry on a current collector to form a positive electrode; assembling the positive electrode, the negative electrode (graphite is an active substance) and the isolating film to obtain a bare cell, and then bagging to perform top side sealing, drying, liquid injection, standing, formation, shaping and degassing to obtain a finished battery.
And (3) testing the material performance:
and (3) gram capacity test: the gram capacity test of the battery cores prepared from the silicon-carbon materials of the examples and the comparative examples is carried out in an environment at 25 ℃ according to the following flow: standing for 3 min; charging to 4.2V by a constant current of 0.2C and charging to 0.05C by a constant voltage of 4.2V; standing for 3 min; discharging to 3.0V at constant current of 0.2C to obtain discharge capacity D1; standing for 3 min; discharging to 3.85V at constant current of 0.2C; and (3) standing for 3min, then completing the capacity test, and dividing the weight of the silicon-carbon material in the negative electrode plate by D1 to obtain the gram capacity of the negative electrode, wherein the obtained result is shown in Table 1.
Testing internal resistance: the internal resistance of the cells prepared from the lithium iron phosphate materials in the examples and the comparative examples is tested in an environment at 25 ℃ according to the following procedures: standing for 3 min; charging to 3.85V at a constant current of 1C and charging to 0.1C at a constant voltage of 3.85V; standing for 3 min; and testing the DCR value of the battery cell by adopting an electrochemical workstation, wherein the obtained result is shown in table 1.
And (3) rate performance test: the rate performance of the battery cells prepared from the silicon-carbon materials of the examples and the comparative examples is tested in an environment at 25 ℃ according to the following procedures: standing for 3 min; charging to 4.2V by a constant current of 0.2C and charging to 0.05C by a constant voltage of 4.2V; standing for 3 min; discharging to 3.0V at constant current of 0.2C to obtain discharge capacity D1; standing for 3 min; charging to 4.2V by a constant current of 0.2C and charging to 0.05C by a constant voltage of 4.2V; standing for 3 min; discharging the 2C to 3.0V at constant current to obtain discharge capacity D21; standing for 3 min; rate performance testing was then completed and the cell rate performance was D2/D1 x 100% with the results shown in table 1.
And (3) cycle test, namely, performing cycle test on the battery cells prepared from the silicon-carbon materials of the examples and the comparative examples in an environment at 25 ℃ according to the following flow: standing for 3 min; charging to 4.2V by a constant current of 0.2C and charging to 0.05C by a constant voltage of 4.2V; standing for 3 min; discharging to 3.0V at constant current of 0.2C to obtain discharge capacity D1; standing for 3min, charging to 4.2V at constant current of 0.2C and charging to 0.05C at constant voltage of 4.2V; standing for 3 min; discharging to 3.0V at constant current of 0.2C to obtain discharge capacity Di; standing for 3min "and repeating 299 times to obtain D300, then completing the cycle test, and calculating the capacity retention rate to be D300/D1 × 100%, and obtaining the results shown in Table 1.
From table 1, the lithium ion battery cathode material with excellent performance can be prepared by the method, and the battery core assembled by taking the lithium ion battery cathode material as the cathode active substance has excellent electrochemical performance. Specifically, comparing the comparative example with examples 1 to 6, it can be seen that, as the oxygen-containing functional groups on the modified main conducting network structure sheet layer increase, the electrochemical performance of the battery cell becomes better first and then worse, because when the oxygen-containing functional groups are too small, the sealing effect is poor, and the battery cell cannot fully function; when the oxygen-containing functional group is too much, the seal is too tight, and ion diffusion during charge and discharge is hindered. The present invention is applicable to all materials requiring primary particle pelletizing to obtain a secondary particle structure in the field of energy storage research, and specifically includes lithium ion positive electrode materials, lithium ion negative electrode materials (such as graphite, silicon carbon, lithium iron phosphate, alloy negative electrode, etc.), and other battery capacitor materials (such as lithium air battery, fuel cell, sodium ion battery, zinc ion battery, etc.).
TABLE 1 cell performance table prepared from different lithium ion battery anode materials
Figure BDA0001307594530000121
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (8)

1. A lithium ion battery positive electrode material comprises a core structure and a shell structure, wherein the core structure is a secondary particle structure and comprises a main electric conduction network with a porous structure and nano primary particles filled in the pore structure of the main electric conduction network; the nano primary particles comprise at least one of nano lithium cobaltate, nano lithium manganate, nano lithium iron phosphate, nano nickel cobalt manganese, nano nickel cobalt aluminum, nano lithium nickelate, nano lithium vanadium oxide and nano lithium-rich cathode material; stronger bonding force action exists between the main power supply networks; and tightly locking the nano-sized primary particles in the pore structure of the main conducting network by the bonding force;
the category of bonds providing strong bonding forces are hydrogen bonds or/and chemical bonds; the mass of the oxygen-containing functional groups forming the hydrogen bonds or/and the chemical bonds accounts for 1-40% of the mass of the whole main electric network;
the preparation method mainly comprises the following steps:
step 1, precursor preparation: uniformly dispersing the primary particles in a solvent to obtain a precursor;
step 2, preparing a modified main power guide network structure: placing the main conducting network structure with the porous structure in an oxidation environment, and grafting a functional group to obtain a modified main conducting network structure;
step 3, filling: filling the precursor prepared in the step 1 into a modified main power transmission network structure;
step 4, closing the opening: placing the porous main electric network structure in a reducing atmosphere to promote functional groups grafted on the main electric network structure to react to generate strong bonding force, and sealing or partially sealing the pore structure in the porous main electric network structure;
and 5, coating and carbonizing the product obtained in the step 4 to obtain the finished product of the lithium ion battery anode material.
2. The lithium ion battery cathode material of claim 1, wherein the main conducting network has flexibility and contains functional groups inside; the hydrogen bonds or/and chemical bonds result from the reaction of oxygen-containing functional groups within the main conducting network.
3. The lithium ion battery cathode material of claim 1, wherein the main conductive network is at least one of an open graphene structure, an open expanded graphite structure, and a vermicular graphene structure; the nano primary particles comprise nano lithium ion battery anode particles; and an auxiliary electric conduction network is also distributed between the main electric conduction network and the primary particles and tightly connects the main electric conduction network and the nano primary particles together.
4. The lithium ion battery cathode material according to claim 3, wherein the auxiliary conducting network is obtained by carbonizing a high polymer material; the high polymer material is obtained by in-situ polymerization of a high polymer monomer; the auxiliary conducting network further comprises at least one of conductive carbon black, super conductive carbon, Ketjen black, carbon nanotubes, graphene and acetylene black.
5. The lithium ion battery cathode material of claim 1, wherein the surface of the primary particles in step 1 is modified into functionalized primary particles, and the functional groups are carboxyl groups or/and hydroxyl groups; the functional group grafted in the step 2 comprises at least one of carboxyl, hydroxyl, epoxy, carbonyl, nitro and amino; and 4, adding a reducing agent or/and performing direct hydrothermal reduction on the reducing atmosphere.
6. The lithium ion battery cathode material of claim 1, wherein a polymer monomer is further added in step 1, i.e., the primary particles and the polymer monomer are mixed and kneaded to obtain a precursor in which the polymer monomer is uniformly dispersed on the surface of the primary nanoparticles; in this case, it is necessary to perform a polymerization reaction after step 3, in which the product of step 3 is placed in an environment where an initiator is present to promote polymerization of the polymer monomer dispersed on the surface of the primary particles, thereby obtaining a high molecular polymer.
7. The lithium ion battery cathode material as claimed in claim 6, wherein a high molecular polymer, a carbon source component, a conductive agent component, and a solvent component are further added during kneading reaction; in step 1, the kneading process is as follows: kneading the nano primary particles, the surfactant 1, the polymer monomer and the solvent 1 to obtain a mixture 1; kneading the conductive agent component, the surfactant 2 and the solvent 2 to obtain a mixture 2; and then blending the mixture 1 and the mixture 2, and uniformly dispersing to obtain precursor slurry.
8. The lithium ion battery cathode material according to claim 1, wherein the filling process in step 3 is:
pretreating the porous main conducting network structure material, wherein the pretreatment comprises surface activation or/and surfactant addition;
before filling, placing the porous main conducting network structure material in a vacuum environment for vacuumizing, discharging air in a hole structure to make space for filling a precursor, and then placing the porous main conducting network structure material in precursor slurry for starting filling;
in the filling process, pressure is applied to extrude the precursor into the hole; the temperature is increased, and the viscosity of the precursor is reduced; and (5) adding mechanical disturbance and opening the hole opening.
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