CN111477852A - Composite anode material with network channel structure and preparation method and application thereof - Google Patents

Composite anode material with network channel structure and preparation method and application thereof Download PDF

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CN111477852A
CN111477852A CN202010295042.8A CN202010295042A CN111477852A CN 111477852 A CN111477852 A CN 111477852A CN 202010295042 A CN202010295042 A CN 202010295042A CN 111477852 A CN111477852 A CN 111477852A
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solid electrolyte
hard carbon
carbon
nano
network structure
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CN111477852B (en
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吉祥
刘柏男
罗飞
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Tianmu Energy Anode Material Co ltd
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Tianmu Energy Anode Material Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a composite cathode material with a network structure and a preparation method and application thereof; the composite cathode material comprises a hard carbon core and a shell coated outside the hard carbon core; the shell is a solid electrolyte layer formed by nano solid electrolyte particles; the hard carbon core comprises hard carbon materials and carbon nano tubes or carbon fibers which are dispersed among the hard carbon materials and are attached with nano solid electrolyte particles; the carbon nano tubes or the carbon fibers attached with the nano solid electrolyte particles form a network structure inside the hard carbon core and are communicated with the solid electrolyte layer; the size range of the hard carbon material is 1-40 um, and the range of Raman spectrum Id/Ig is 0.7-0.9; the diameter of the carbon nano tube or the carbon fiber is less than or equal to 1um, and the length of the carbon nano tube or the carbon fiber is less than or equal to 50 um; the size of the nano solid electrolyte particles is 1-200 nm; in the composite negative electrode material, according to the mass fraction, the hard carbon material: carbon nanotubes or carbon fibers: solid electrolyte layer ═ 30%, 100%: (0, 20% ], (0, 50% ]).

Description

Composite anode material with network channel structure and preparation method and application thereof
Technical Field
The invention relates to the technical field of materials, in particular to a composite anode material with a network channel structure and a preparation method and application thereof.
Background
At present, carbon materials have been widely used as negative electrode materials in lithium ion batteries.
The carbon negative electrode material mainly comprises various carbon materials such as artificial graphite, natural graphite, carbon nanotubes, hard carbon and the like, wherein the hard carbon material is used as amorphous carbon and has higher reversible capacity which theoretically reaches 700 mAh/g-1000 mAh/g and far exceeds the theoretical capacity 372mAh/g of graphitized carbon, and the irregular structure of the hard carbon can ensure the stable structure in the charging and discharging process, so that the lithium battery can have longer cycle life and better rate performance.
In the conventional liquid electrolyte, the unstable deposition process of lithium metal and the growth of dendrite cause a series of safety problems, which seriously hinder the development of the negative electrode of the lithium battery, and the appearance of the solid electrolyte perfectly solves the safety problem of the lithium battery.
Since 2000, solid electrolytes have been used in lithium batteries, such as lithium sulfur batteries and lithium air batteries, which use gaseous or liquid materials as electrodes, and have been more widely used in semi-solid, quasi-solid, and all-solid batteries. However, the solid electrolyte has obvious defects, the problem of electrode-solid electrolyte contact of the solid battery is similar to that of a short plate of a wooden barrel, and good contact between the electrode and the solid electrolyte is difficult to realize, so that the transmission efficiency of lithium ions is greatly limited.
The technical scheme of the existing lithium ion battery containing the solid electrolyte is mainly to mechanically mix the cathode particles, the solid electrolyte particles, the binder, the conductive additive and the like, or to mechanically mix the cathode particles and the solid electrolyte particles and then to sinter the mixture at high temperature for coating, or to simply disperse the solid electrolyte particles in the cathode material particles to form the composite material. The methods are still only point-to-point or single-layer face-to-face contact, and the problem of poor contact between the solid electrolyte and the negative electrode material still exists, so that the resistance is increased, and lithium ion transmission is hindered. Meanwhile, if a negative electrode material with large volume change in the charge and discharge process such as silicon is adopted, the problems of contact surface separation and rapid cycle capacity attenuation are caused.
Disclosure of Invention
The invention aims to provide a composite cathode material with a network structure and a preparation method and application thereof, aiming at the defects of the prior art, the network structure formed by carbon nano tubes or carbon fibers contained in a hard carbon core is adopted, and solid electrolyte particles are attached to the outer layers of the carbon nano tubes or the carbon fibers, so that the full-dimensional contact between the hard carbon material and the solid electrolyte is ensured, the contact surface resistance is effectively reduced, and the lithium ion transmission performance is improved.
In a first aspect, an embodiment of the present invention provides a composite anode material with a mesh structure, where the composite anode material includes a hard carbon core and an outer shell coated outside the hard carbon core;
the shell is a solid electrolyte layer formed by nano solid electrolyte particles;
the hard carbon core comprises hard carbon materials and carbon nano tubes or carbon fibers which are dispersed among the hard carbon materials and are attached with nano solid electrolyte particles; the carbon nano tubes or the carbon fibers attached with the nano solid electrolyte particles form a network structure inside the hard carbon core and are communicated with the solid electrolyte layer;
the hard carbon material specifically includes: the hard carbon material is prepared by taking one or a combination of more of glucose, sucrose, polyvinylpyrrolidone, starch polyvinylidene fluoride, novolac epoxy resin or polyvinyl chloride as a carbonization precursor; the size range of the hard carbon material is 1-40 um, and the range of Raman spectrum Id/Ig is 0.7-0.9; the diameter of the carbon nano tube or the carbon fiber is less than or equal to 1um, and the length of the carbon nano tube or the carbon fiber is less than or equal to 50 um; the size of the nano solid electrolyte particles is 1-200 nm;
in the composite negative electrode material, according to mass fraction, a hard carbon material: carbon nanotubes or carbon fibers: solid electrolyte layer ═ 30%, 100%: (0, 20% ], (0, 50% ]).
Preferably, the material of the nano solid electrolyte particles specifically comprises one or a combination of more of a perovskite type solid electrolyte material, a garnet type solid electrolyte material, a NASCION type solid electrolyte material and an L ISCION type solid electrolyte material.
Preferably, the surface layer of the hard carbon core is a hard carbon oxide layer obtained by oxidizing the hard carbon core.
In a second aspect, an embodiment of the present invention provides a preparation method of the composite anode material with a network structure, where the preparation method includes:
mixing carbon nano tubes or carbon fibers with nitric acid, uniformly stirring, and standing for 1-10 hours; carrying out suction filtration on the mixture obtained by mixing, and cleaning the mixture by using distilled water until the pH value is 6-8; adding nano solid electrolyte particles and distilled water, stirring, performing ultrasonic treatment, and drying; adding a carbonization precursor and distilled water, and uniformly stirring to form a hard carbon precursor mixture; the carbonized precursor includes: one or more of glucose, sucrose, polyvinylpyrrolidone, starch polyvinylidene fluoride, novolac epoxy resin or polyvinyl chloride;
carrying out hydrothermal treatment on the hard carbon precursor mixture, then washing and filtering until the filtrate is transparent and colorless, and then drying;
putting the dried sample into a reaction device, heating to 700-1300 ℃ at 1-10 ℃/min under a nitrogen atmosphere environment, preserving heat for 0.5-15 hours, and carbonizing the dried sample to obtain a hard carbon core with a network structure;
carrying out oxidation treatment on the hard carbon core with the network structure in an air atmosphere or in a hydrogen peroxide solution, then adding solid electrolyte nano particles and a solvent, uniformly stirring and drying; and (3) preserving the heat of the dried sample for 0.5 to 2 hours at 500 to 600 ℃ in nitrogen atmosphere to obtain the composite negative electrode material with the network structure.
Preferably, the material of the nano solid electrolyte particles specifically comprises one or a combination of more of a perovskite type solid electrolyte material, a garnet type solid electrolyte material, a NASCION type solid electrolyte material and an L ISCION type solid electrolyte material;
the solvent is specifically deionized water or ethanol.
Preferably, the hydrothermal treatment specifically comprises: pressure-heated hydrothermal treatment or non-pressure-heated hydrothermal treatment;
the pressure heating hydrothermal treatment comprises the following steps: the preparation is carried out in a hydrothermal kettle, the pressure is 0MPa to 10MPa, the heating temperature is 120 ℃ to 250 ℃, and the heat preservation time is 2 hours to 8 hours;
the heating temperature of the hydrothermal treatment without pressurizing and heating is 200-300 ℃, and the heat preservation time is 1-15 hours.
Preferably, the molar concentration of the nitric acid is 0.1 mol/L-5 mol/L.
Preferably, the oxidation treatment of the hard carbon core with the network structure in an air atmosphere specifically comprises: heating to 150-600 ℃ according to the heating rate of 0.5-10 ℃/min, and oxidizing the hard carbon core with the network structure for 1-10 hours in the air atmosphere;
the step of oxidizing the hard carbon core with the network structure in a hydrogen peroxide solution specifically comprises the following steps: mixing and stirring a hydrogen peroxide solution with the mass concentration of 1-40% and the hard carbon core with the network structure, and washing, filtering and drying the obtained product; wherein the stirring speed is 200 r/min-1000 r/min, and the stirring time is 1-10 hours.
In a third aspect, an embodiment of the present invention provides a negative electrode plate of a lithium ion battery, including the composite negative electrode material with a mesh structure according to the first aspect.
In a fourth aspect, an embodiment of the present invention provides a lithium ion battery, including the negative electrode tab of the third aspect.
According to the composite cathode material with the network channel structure, the network channel structure is formed by the carbon nano tubes or the carbon fibers contained in the hard carbon core, and the solid electrolyte particles are attached to the outer layers of the carbon nano tubes or the carbon fibers, so that the hard carbon material can be in full-dimensional contact with the solid electrolyte, and the contact surface resistance is effectively reduced; the carbon nano tube or the carbon fiber has excellent conductivity, and lithium ions can be efficiently transmitted by virtue of the carbon nano tube or the carbon fiber, so that the lithium ion transmission performance and the rate capability of the battery are improved. The surface of the hard carbon core subjected to oxidation treatment is provided with a large number of pores, and the internal pore channel structure is exposed, so that a good contact surface is provided for the attachment of solid electrolyte particles, the solid electrolyte layer of the shell is ensured to be fully contacted with the internal network channel structure, and is connected with the solid electrolyte particles on the outer layer of the carbon nano tube into a whole; the hard carbon adopted by the invention is used as a cathode material, the problem of volume expansion does not need to be considered, the formed network structure cannot be damaged in the charging and discharging process, and the cycle stability is ensured. The composite cathode material provided by the invention can be used in liquid, semi-solid, quasi-solid and all-solid electrolyte lithium ion batteries.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
Fig. 1 is a schematic structural diagram of a hard carbon composite anode material with a network structure according to the present invention;
fig. 2 is a flowchart of a method for preparing a hard carbon composite anode material with a network structure according to an embodiment of the present invention;
fig. 3 is a Scanning Electron Microscope (SEM) image of the hard carbon composite negative electrode having a mesh structure obtained in example 1 of the present invention;
FIG. 4 is a comparison of the first cycle charge and discharge curves of button cells prepared from the samples obtained in example 1 and comparative example 1 of the present invention;
fig. 5 is a graph comparing the 20-week cycle capacity of button cells prepared from samples obtained in example 1 of the present invention and comparative example 1.
Detailed Description
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
The embodiment provides a composite anode material with a network channel structure and a preparation method and application thereof.
The composite anode material with the network structure provided by the embodiment of the invention comprises a hard carbon core and a shell coated outside the hard carbon core; the structure of which is schematically shown in figure 1.
The shell is a solid electrolyte layer formed by nano solid electrolyte particles;
the hard carbon core comprises hard carbon materials and carbon nanotubes or carbon fibers with attached nano solid electrolyte particles dispersed between the hard carbon materials, shown as carbon nanotubes in fig. 1. It can be seen that the surface thereof is adhered with a granular nano solid electrolyte. The carbon nano tubes or the carbon fibers of the nano solid electrolyte particles form a network structure inside the hard carbon core and are communicated with the solid electrolyte layer; the surface layer of the hard carbon core is provided with a hard carbon oxidation layer obtained by oxidizing the hard carbon core.
In the embodiment, the material of the nano solid electrolyte particles specifically includes one or a combination of several of a perovskite type solid electrolyte material, a garnet type solid electrolyte material, an NASCION type solid electrolyte material, and an L ISCION type solid electrolyte material, and the size of the nano solid electrolyte particles is 1-200 nm.
The hard carbon material specifically includes: the hard carbon material is prepared by taking one or a combination of more of glucose, sucrose, polyvinylpyrrolidone, starch polyvinylidene fluoride, novolac epoxy resin or polyvinyl chloride as a carbonization precursor; the size range of the hard carbon material is 1-40 um, and the range of Raman spectrum Id/Ig is 0.7-0.9.
The diameter of the carbon nano tube or the carbon fiber is less than or equal to 1um, and the length of the carbon nano tube or the carbon fiber is less than or equal to 50 um.
In the composite negative electrode material, according to the mass fraction, the hard carbon material: carbon nanotubes or carbon fibers: solid electrolyte layer ═ 30%, 100%: (0, 20% ], (0, 50% ]).
The preparation method of the composite anode material with the network channel structure can be prepared by the steps shown in fig. 2, and specifically comprises the following steps:
step 110, mixing the carbon nano tube or the carbon fiber with nitric acid, uniformly stirring, and standing for 1-10 hours; carrying out suction filtration on the mixture obtained by mixing, and cleaning the mixture by using distilled water until the pH value is 6-8; adding nano solid electrolyte particles and distilled water, stirring, performing ultrasonic treatment, and drying; adding a carbonization precursor and distilled water, and uniformly stirring to form a hard carbon precursor mixture;
specifically, the carbonization precursor comprises one or a combination of more of glucose, sucrose, polyvinylpyrrolidone, starch polyvinylidene fluoride, novolac epoxy resin or polyvinyl chloride, and the molar concentration of nitric acid is 0.1 mol/L-5 mol/L.
Step 120, carrying out hydrothermal treatment on the hard carbon precursor mixture, then washing and filtering until the filtrate is transparent and colorless, and then drying;
wherein, the hydrothermal treatment specifically comprises the following steps: pressure-heated hydrothermal treatment or non-pressure-heated hydrothermal treatment;
the pressure heating hydrothermal treatment comprises the following steps: the preparation is carried out in a hydrothermal kettle, the pressure is 0MPa to 10MPa, the heating temperature is 120 ℃ to 250 ℃, and the heat preservation time is 2 hours to 8 hours;
the heating temperature of the hydrothermal treatment without pressurizing and heating is 200-300 ℃, and the heat preservation time is 1-15 hours.
Step 130, placing the dried sample into a reaction device, heating to 700-1300 ℃ at a speed of 1-10 ℃/min under a nitrogen atmosphere environment, preserving heat for 0.5-15 hours, and carbonizing the dried sample to obtain a hard carbon core with a network structure;
step 140, oxidizing the hard carbon core with the network structure in an air atmosphere or in a hydrogen peroxide solution, then adding solid electrolyte nanoparticles and a solvent, uniformly stirring and drying; and (3) preserving the heat of the dried sample for 0.5 to 2 hours at 500 to 600 ℃ in nitrogen atmosphere to obtain the composite negative electrode material with the network structure.
The size of the nano solid electrolyte particles is 1-200 nm, the nano solid electrolyte particles specifically comprise one or a combination of more of a perovskite type solid electrolyte material, a garnet type solid electrolyte material, an NASCION type solid electrolyte material and an L ISCION type solid electrolyte material, and a solvent can specifically adopt deionized water or ethanol.
The oxidation treatment of the hard carbon core with the network structure in the air atmosphere can specifically adopt the following modes: heating to 150-600 ℃ according to the heating rate of 0.5-10 ℃/min, and oxidizing the hard carbon core with the network structure for 1-10 hours in the air atmosphere; the oxidation treatment of the hard carbon core with the network structure in the hydrogen peroxide solution can specifically adopt the following modes: mixing and stirring a hydrogen peroxide solution with the mass concentration of 1-40% and a hard carbon core with a network structure, and washing, filtering and drying the materials; wherein the stirring speed is 200 r/min-1000 r/min, and the stirring time is 1-10 hours.
The composite cathode material prepared by the method has the core made of hard carbon, the surface of the core is provided with an oxidation layer, the shell is a solid electrolyte layer, and a network structure formed by carbon nano tubes or carbon fibers attached with the solid electrolyte is dispersed in the hard carbon core and can be communicated with the solid electrolyte outer layer of the shell. The network channel structure ensures the full contact of the cathode material and the solid electrolyte, and the contact is not limited to simple point-to-point one-dimensional contact or face-to-face two-dimensional contact any more, but the hard carbon cathode is in full-dimensional contact with the solid electrolyte, so that the contact surface resistance is effectively reduced.
In addition, the step of adding the carbon nanotubes or the carbon fibers is added during the preparation of the negative electrode material, which is completely different from the step of adding the carbon nanotubes or the carbon fibers in the pulping and coating process of the negative electrode plate in the prior art, and the carbon nanotubes or the carbon fibers are conductive agents instead of negative electrode active materials in the embodiment. The carbon nano tube or the carbon fiber provides a quick channel for lithium ion transmission, and the good rate performance of the composite material is guaranteed.
The hard carbon cathode adopted in the embodiment guarantees the stability of the solid electrolyte structure layer, and prevents the problems of surface falling, resistance increase and the like.
The composite negative electrode material provided by the invention can be used for preparing a negative electrode plate and is used in liquid, semi-solid, quasi-solid and all-solid electrolyte lithium ion batteries.
In order to better understand the technical solutions provided by the present invention, the following description respectively describes specific processes for preparing a lithium battery cathode material by using several methods provided by the above embodiments of the present invention, and methods for applying the same to a secondary battery and battery characteristics.
Example 1
The embodiment provides a method for preparing a composite anode material with a network channel structure, which comprises the following steps:
step 1, adding 20g of carbon nano tube into 50ml of nitric acid (the molar concentration is 2 mol/L), uniformly stirring, standing for 5 hours, carrying out suction filtration on the mixture, cleaning the mixture by using distilled water until the pH value is 7.0, and adding 2g of solid electrolyte L i with the particle size of 50nm7Ca3Zr2O12Stirring the nano particles and distilled water, performing ultrasonic treatment, and drying to obtain a dried substance;
step 2: adding 100g of glucose into the dried substance obtained in the step 1, adding 50ml of distilled water, uniformly stirring, and heating for 6 hours at the temperature of 200 ℃ under the pressure of 7Mpa in a hydrothermal kettle to obtain black powder;
and step 3: washing the black powder obtained in the step 3 with deionized water until the filtrate is transparent and colorless, drying the filtrate for 10 hours at 100 ℃, putting the filtrate into a tubular furnace, heating the filtrate to 1000 ℃ at the heating rate of 3 ℃/min under nitrogen atmosphere, and preserving the heat for 6 hours;
and 4, step 4: heating the sample obtained in the step 3 to 300 ℃ at the heating rate of 3 ℃/min in the air atmosphere, and preserving the heat for 2 hours;
step 5, mixing the sample obtained in step 4 with 30g of solid electrolyte L i with the particle size of 50nm7Ca3Zr2O12Mixing the nano particles, adding 50ml of distilled water, uniformly stirring, drying, putting into heating equipment, and keeping the temperature at 500 ℃ for 2 hours in a nitrogen atmosphere environment to obtain the composite cathode material with the network structure.
Mixing the prepared material and commercial graphite A which is purchased in the market according to a proportion to obtain a lithium ion battery cathode material with a specific capacity of 350mAh/g, uniformly mixing the obtained cathode material with 2% of carbon black, 2% of sodium cellulose acetate and 3% of styrene butadiene rubber in a polyvinylidene fluoride (PVDF) solvent to obtain battery slurry, coating the battery slurry on a copper foil, drying the battery slurry, cutting the battery slurry into wafers with the diameter of 14mm, performing vacuum drying at 100 ℃ for 12 hours, assembling the button cell on the lithium wafers in a glove box, and evaluating the structure and the electrochemical performance of the button cell through testing.
For better comparison, we prepared a comparative sample as follows.
Comparative example 1
Step 1: 100g of glucose is taken, 100ml of distilled water is added, and after uniform ultrasonic stirring, the mixture is heated for 6 hours in a hydrothermal kettle under the conditions of 5MPa and 150 ℃ to obtain black powder.
Step 2: washing the obtained black powder with deionized water until the filtrate is transparent and colorless, drying at 100 deg.C for 15 hr, placing into a tube furnace, heating to 1000 deg.C at a heating rate of 3 deg.C/min under nitrogen atmosphere, and keeping the temperature for 8 hr. After cooling, the hard carbon negative electrode used for comparison was obtained.
Comparative example 2
Step 1: taking 100g of sucrose and 20g of carbon nano tube, adding 50ml of distilled water, uniformly stirring, and heating for 6 hours in a hydrothermal kettle at the temperature of 150 ℃ under the pressure of 5Mpa to obtain black powder;
and step 3: washing the black powder obtained in the step 3 with deionized water until the filtrate is transparent and colorless, drying the filtrate for 6 hours at 100 ℃, putting the filtrate into a tube furnace, heating the filtrate to 1150 ℃ at the heating rate of 1 ℃/min under nitrogen atmosphere, and preserving the heat for 7 hours;
and 4, step 4: and (3) adding the sample obtained in the step (3) into a 5% hydrogen peroxide solution, soaking for 3 hours, and drying at 100 ℃ for 3 hours to obtain the hard carbon negative electrode used for comparison.
Example 2
The embodiment provides a method for preparing a composite anode material with a network channel structure, which comprises the following steps:
step 1, adding 20g of carbon nano tube into 50ml of nitric acid (the molar concentration is 4 mol/L), uniformly stirring, standing for 6 hours, carrying out suction filtration on the mixture, cleaning the mixture by using distilled water until the pH value is 6.8, and adding 3g of solid electrolyte L i with the particle size of 50nm7Ca3Zr2O12Mixing the nanoparticles with distilled water, and ultrasonic treatingDrying after treatment;
step 2: taking 100g of polyvinylpyrrolidone, adding the dried substance obtained in the step 1, adding 50ml of distilled water, uniformly stirring, and heating for 6 hours at the temperature of 200 ℃ under the pressure of 7Mpa in a hydrothermal kettle to obtain black powder;
and step 3: washing the black powder obtained in the step 3 with deionized water until the filtrate is transparent and colorless, drying the filtrate for 6 hours at 100 ℃, putting the filtrate into a tube furnace, heating the filtrate to 1100 ℃ at the heating rate of 1 ℃/min under nitrogen atmosphere, and preserving the heat for 8 hours;
and 4, step 4: heating the sample obtained in the step 3 to 500 ℃ at the heating rate of 3 ℃/min in the air atmosphere, and preserving the heat for 2 hours;
step 5, mixing the sample obtained in step 4 with 30g of solid electrolyte L i with the particle size of 50nm7Ca3Zr2O12Mixing the nano particles, adding 50ml of distilled water, uniformly stirring, drying, putting into heating equipment, and keeping the temperature of 600 ℃ for 3 hours under a nitrogen atmosphere environment to obtain the composite cathode material with the network structure.
Example 3
The embodiment provides a method for preparing a composite anode material with a network channel structure, which comprises the following steps:
step 1, adding 20g of carbon nano tube into 80ml of nitric acid (the molar concentration is 1 mol/L), uniformly stirring, standing for 10 hours, carrying out suction filtration on the mixture, cleaning the mixture by using distilled water until the pH value is 7.3, and adding 3g of solid electrolyte L i with the particle size of 50nm7Ca3Zr2O12Stirring the nano particles and distilled water, performing ultrasonic treatment, and drying to obtain a dried substance;
step 2: taking 100g of polyvinylpyrrolidone, adding the dried substance obtained in the step 1, adding 50ml of alcohol, uniformly stirring, and heating for 3 hours at 200 ℃ under 0Mpa in a hydrothermal kettle to obtain a black jelly;
and step 3: drying the black jelly obtained in the step 3 at 100 ℃ for 2 hours, then placing the black jelly into a tube furnace, heating the black jelly to 1100 ℃ at the heating rate of 1 ℃/min under nitrogen atmosphere, and preserving heat for 2 hours;
and 4, step 4: heating the sample obtained in the step 3 to 500 ℃ at the heating rate of 3 ℃/min in the air atmosphere, and preserving the heat for 2 hours;
step 5, mixing the sample obtained in step 4 with 30g of solid electrolyte L i with the particle size of 50nm7Ca3Zr2O12Mixing the nano particles, adding 50ml of distilled water, uniformly stirring, drying, putting into heating equipment, and keeping the temperature of 500 ℃ for 4 hours in a nitrogen atmosphere environment to obtain the composite cathode material with the network structure.
Example 4
The embodiment provides a method for preparing a composite anode material with a network channel structure, which comprises the following steps:
step 1, adding 20g of carbon nano tube into 30ml of nitric acid (the molar concentration is 5 mol/L), uniformly stirring, standing for 2h, carrying out suction filtration on the mixture, cleaning the mixture by using distilled water until the pH value is 7.3, and adding 4g of solid electrolyte L i with the particle size of 20nm7K3Ta2O12Stirring the nano particles and distilled water, performing ultrasonic treatment, and drying to obtain a dried substance;
step 2: taking 100g of sodium carboxymethylcellulose, adding the dried substance obtained in the step 1, adding 50ml of distilled water, uniformly stirring, and heating for 6 hours at the temperature of 150 ℃ under the pressure of 6Mpa in a hydrothermal kettle to obtain black powder;
and step 3: washing the black powder obtained in the step 3 with deionized water until the filtrate is transparent and colorless, drying the filtrate for 6 hours at 100 ℃, putting the filtrate into a tube furnace, heating the filtrate to 1150 ℃ at the heating rate of 1 ℃/min under nitrogen atmosphere, and preserving the heat for 6 hours;
and 4, step 4: adding the sample obtained in the step 3 into a 3% hydrogen peroxide solution, soaking for 5 hours, and drying at 70 ℃ for 10 hours;
step 5, mixing the sample obtained in step 4 with 30g of solid electrolyte L i with the particle size of 20nm7K3Ta2O12Mixing, adding 50ml of distilled water, uniformly stirring, drying, putting into heating equipment, and keeping the temperature at 400 ℃ for 4 hours under a nitrogen atmosphere environment to obtain the composite cathode material with the network structure.
Example 5
The embodiment provides a method for preparing a composite anode material with a network channel structure, which comprises the following steps:
step 1, adding 20g of carbon nano tube into 30ml of nitric acid (the molar concentration is 5 mol/L), uniformly stirring, standing for 4 hours, carrying out suction filtration on the mixture, cleaning the mixture by using distilled water until the pH value is 6.5, and adding 5g of solid electrolyte L i with the particle size of 20nm7K3Ta2O12Stirring the nano particles and distilled water, performing ultrasonic treatment, and drying to obtain a dried substance;
step 2: adding 100g of sucrose into the dried product obtained in the step 1, adding 50ml of distilled water, uniformly stirring, and heating for 6 hours in a hydrothermal kettle at the temperature of 150 ℃ under the pressure of 5Mpa to obtain black powder;
and step 3: washing the black powder obtained in the step 3 with deionized water until the filtrate is transparent and colorless, drying the filtrate for 6 hours at 100 ℃, putting the filtrate into a tube furnace, heating the filtrate to 1100 ℃ at the heating rate of 1 ℃/min under nitrogen atmosphere, and preserving the heat for 6 hours;
and 4, step 4: adding the sample obtained in the step 3 into a 3% hydrogen peroxide solution, soaking for 5 hours, and drying at 100 ℃ for 3 hours;
step 5, mixing the sample obtained in the step 4 with 20g of solid electrolyte L i with the particle size of 20nm7K3Ta2O12Mixing the nano particles, adding 50ml of distilled water, uniformly stirring, drying, putting into heating equipment, and keeping the temperature of 500 ℃ for 4 hours in a nitrogen atmosphere environment to obtain the composite cathode material with the network structure.
Example 6
The embodiment provides a method for preparing a composite anode material with a network channel structure, which comprises the following steps:
step 1, adding 20g of carbon fiber into 80ml of nitric acid (the molar concentration is 1 mol/L), uniformly stirring, standing for 10 hours, carrying out suction filtration on the mixture, cleaning the mixture by using distilled water until the pH value is 7.1, and adding 4g of solid electrolyte L i with the particle size of 20nm7K3Ta2O12Stirring the nano particles and distilled water, performing ultrasonic treatment, and drying to obtain a dried substance;
step 2: taking 100g of polyvinylpyrrolidone, adding the dried substance obtained in the step 1, adding 50ml of alcohol, uniformly stirring, and heating for 5 hours in a hydrothermal kettle at the temperature of 120 ℃ under 10Mpa to obtain a black jelly;
and step 3: drying the black jelly obtained in the step 3 at 100 ℃ for 2 hours, then placing the black jelly into a tube furnace, heating the black jelly to 1100 ℃ at the heating rate of 10 ℃/min under nitrogen atmosphere, and preserving heat for 2 hours;
and 4, step 4: heating the sample obtained in the step 3 to 400 ℃ at the heating rate of 1 ℃/min in the air atmosphere, and preserving the heat for 5 hours;
step 5, mixing the sample obtained in the step 4 with 20g of solid electrolyte L i with the particle size of 20nm7K3Ta2O12Mixing the nano particles, adding 60ml of distilled water, uniformly stirring, drying, putting into heating equipment, and keeping the temperature of 400 ℃ for 4 hours in a nitrogen atmosphere environment to obtain the composite cathode material with the network structure.
Example 7
The embodiment provides a method for preparing a composite anode material with a network channel structure, which comprises the following steps:
step 1, adding 20g of carbon fiber into 80ml of nitric acid (the molar concentration is 5 mol/L), uniformly stirring, standing for 5 hours, carrying out suction filtration on the mixture, cleaning the mixture by using distilled water until the pH value is 6.1, and adding 4g of solid electrolyte L i with the particle size of 20nm7K3Ta2O12Stirring the nano particles and distilled water, performing ultrasonic treatment, and drying to obtain a dried substance;
step 2: adding 500g of sucrose into the dried product obtained in the step 1, adding 100ml of distilled water, uniformly stirring, and heating for 15 hours in a hydrothermal kettle at the temperature of 250 ℃ under the pressure of 0.5Mpa to obtain a black jelly;
and step 3: drying the black jelly obtained in the step 3 at 100 ℃ for 2 hours, then placing the black jelly into a tube furnace, heating the black jelly to 1300 ℃ at the heating rate of 5 ℃/min under nitrogen atmosphere, and preserving heat for 0.5 hour;
and 4, step 4: heating the sample obtained in the step 3 to 150 ℃ at the heating rate of 1 ℃/min in the air atmosphere, and preserving the heat for 10 hours;
and 5: mixing the sample obtained in step 4 with 20g of granulesSolid electrolyte L i with size of 20nm7K3Ta2O12Mixing the nano particles, adding 60ml of distilled water, uniformly stirring, drying, putting into heating equipment, and keeping the temperature of 400 ℃ for 4 hours in a nitrogen atmosphere environment to obtain the composite cathode material with the network structure.
Example 8
The embodiment provides a method for preparing a composite anode material with a network channel structure, which comprises the following steps:
step 1, adding 20g of carbon fiber into 100ml of nitric acid (the molar concentration is 0.1 mol/L), uniformly stirring, standing for 10 hours, carrying out suction filtration on the mixture, cleaning the mixture by using distilled water until the pH value is 7.9, and adding 4g of solid electrolyte L i with the particle size of 20nm7K3Ta2O12Stirring the nano particles and distilled water, performing ultrasonic treatment, and drying to obtain a dried substance;
step 2: adding 200g of glucose into the dried substance obtained in the step 1, adding 150ml of distilled water, uniformly stirring, and heating for 8 hours at the temperature of 250 ℃ under 10Mpa in a hydrothermal kettle to obtain a black jelly;
and step 3: drying the black jelly obtained in the step 3 at 100 ℃ for 2 hours, then placing the black jelly into a tube furnace, heating the black jelly to 700 ℃ at the heating rate of 10 ℃/min under nitrogen atmosphere, and preserving heat for 15 hours;
and 4, step 4: heating the sample obtained in the step (3) to 200 ℃ at the heating rate of 1 ℃/min in the air atmosphere, and preserving the heat for 6 hours;
step 5, mixing the sample obtained in step 4 with 30g of solid electrolyte L i with the particle size of 20nm7K3Ta2O12Mixing the nano particles, adding 60ml of distilled water, uniformly stirring, drying, putting into heating equipment, and keeping the temperature of 300 ℃ for 5 hours under a nitrogen atmosphere environment to obtain the composite cathode material with the network structure.
The electrochemical performance of the button cell was evaluated by testing and reported in table 1 for each example and comparative example assembled as described in example 1 above.
Serial number Specific charging capacity (mAh/g) First week efficiency (%)
Example 1 457.3 75.2
Example 2 456.2 76.3
Example 3 444.1 76.4
Example 4 436.3 74.3
Example 5 455.7 74.6
Example 6 454.7 76.8
Example 7 446.5 75.3
Example 8 452.1 75.6
Comparative example 1 294.4 51.1
Comparative example 2 467.8 76.9
TABLE 1
As can be seen from the table, the presence of the carbon nanotubes or carbon fibers in the composite anode material with a mesh structure provided in the example of the present invention greatly improves the lithium intercalation capacity of the hard carbon material compared to comparative example 1, and the addition of the mesh structure of the solid electrolyte and the carbon nanotubes or carbon fibers improves the cycle stability compared to comparative example 2, and although the partial capacity is reduced, the cycle capacity of example 1 at 20 weeks is much higher than that of comparative example 1.
According to the composite cathode material with the network channel structure, the network channel structure is formed by the carbon nano tubes or the carbon fibers contained in the hard carbon core, and the solid electrolyte particles are attached to the outer layers of the carbon nano tubes or the carbon fibers, so that the hard carbon material can be in full-dimensional contact with the solid electrolyte, and the contact surface resistance is effectively reduced; the carbon nano tube or the carbon fiber has excellent conductivity, and lithium ions can be efficiently transmitted by virtue of the carbon nano tube or the carbon fiber, so that the lithium ion transmission performance and the rate capability of the battery are improved. The surface of the hard carbon core subjected to oxidation treatment is provided with a large number of pores, and the internal pore channel structure is exposed, so that a good contact surface is provided for the attachment of solid electrolyte particles, the solid electrolyte layer of the shell is ensured to be fully contacted with the internal network channel structure, and is connected with the solid electrolyte particles on the outer layer of the carbon nano tube into a whole; the hard carbon adopted by the invention is used as a cathode material, the problem of volume expansion does not need to be considered, the formed network structure cannot be damaged in the charging and discharging process, and the cycle stability is ensured. The composite cathode material provided by the invention can be used in liquid, semi-solid, quasi-solid and all-solid electrolyte lithium ion batteries.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. The composite negative electrode material with the network structure is characterized by comprising a hard carbon core and a shell coated outside the hard carbon core;
the shell is a solid electrolyte layer formed by nano solid electrolyte particles;
the hard carbon core comprises hard carbon materials and carbon nano tubes or carbon fibers which are dispersed among the hard carbon materials and are attached with nano solid electrolyte particles; the carbon nano tubes or the carbon fibers attached with the nano solid electrolyte particles form a network structure inside the hard carbon core and are communicated with the solid electrolyte layer;
the hard carbon material specifically includes: the hard carbon material is prepared by taking one or a combination of more of glucose, sucrose, polyvinylpyrrolidone, starch polyvinylidene fluoride, novolac epoxy resin or polyvinyl chloride as a carbonization precursor; the size range of the hard carbon material is 1-40 um, and the range of Raman spectrum Id/Ig is 0.7-0.9; the diameter of the carbon nano tube or the carbon fiber is less than or equal to 1um, and the length of the carbon nano tube or the carbon fiber is less than or equal to 50 um; the size of the nano solid electrolyte particles is 1-200 nm;
in the composite negative electrode material, according to mass fraction, a hard carbon material: carbon nanotubes or carbon fibers: solid electrolyte layer ═ 30%, 100%: (0, 20% ], (0, 50% ]).
2. The composite anode material with the network structure as claimed in claim 1, wherein the material of the nano solid electrolyte particles specifically comprises one or more of a perovskite type solid electrolyte material, a garnet type solid electrolyte material, a NASCION type solid electrolyte material, and L ISCION type solid electrolyte material.
3. The composite anode material with the network structure according to claim 1, wherein the surface layer of the hard carbon core is a hard carbon oxide layer obtained by oxidizing the hard carbon core.
4. A method for preparing the composite anode material with the network structure according to any one of the claims 1 to 3, wherein the method comprises the following steps:
mixing carbon nano tubes or carbon fibers with nitric acid, uniformly stirring, and standing for 1-10 hours; carrying out suction filtration on the mixture obtained by mixing, and cleaning the mixture by using distilled water until the pH value is 6-8; adding nano solid electrolyte particles and distilled water, stirring, performing ultrasonic treatment, and drying; adding a carbonization precursor and distilled water, and uniformly stirring to form a hard carbon precursor mixture; the carbonized precursor includes: one or more of glucose, sucrose, polyvinylpyrrolidone, starch polyvinylidene fluoride, novolac epoxy resin or polyvinyl chloride;
carrying out hydrothermal treatment on the hard carbon precursor mixture, then washing and filtering until the filtrate is transparent and colorless, and then drying;
putting the dried sample into a reaction device, heating to 700-1300 ℃ at 1-10 ℃/min under a nitrogen atmosphere environment, preserving heat for 0.5-15 hours, and carbonizing the dried sample to obtain a hard carbon core with a network structure;
carrying out oxidation treatment on the hard carbon core with the network structure in an air atmosphere or in a hydrogen peroxide solution, then adding solid electrolyte nano particles and a solvent, uniformly stirring and drying; and (3) preserving the heat of the dried sample for 0.5 to 2 hours at 500 to 600 ℃ in nitrogen atmosphere to obtain the composite negative electrode material with the network structure.
5. The preparation method of claim 4, wherein the material of the nano solid electrolyte particles comprises one or more of perovskite type solid electrolyte material, garnet type solid electrolyte material, NASCION type solid electrolyte material, and L ISCION type solid electrolyte material;
the solvent is specifically deionized water or ethanol.
6. The preparation method according to claim 4, characterized in that the hydrothermal treatment is specifically: pressure-heated hydrothermal treatment or non-pressure-heated hydrothermal treatment;
the pressure heating hydrothermal treatment comprises the following steps: the preparation is carried out in a hydrothermal kettle, the pressure is 0MPa to 10MPa, the heating temperature is 120 ℃ to 250 ℃, and the heat preservation time is 2 hours to 8 hours;
the heating temperature of the hydrothermal treatment without pressurizing and heating is 200-300 ℃, and the heat preservation time is 1-15 hours.
7. The method according to claim 4, wherein the molar concentration of the nitric acid is 0.1 mol/L to 5 mol/L.
8. The preparation method according to claim 4, wherein the oxidation treatment of the hard carbon core with the network structure in an air atmosphere specifically comprises: heating to 150-600 ℃ according to the heating rate of 0.5-10 ℃/min, and oxidizing the hard carbon core with the network structure for 1-10 hours in the air atmosphere;
the step of oxidizing the hard carbon core with the network structure in a hydrogen peroxide solution specifically comprises the following steps: mixing and stirring a hydrogen peroxide solution with the mass concentration of 1-40% and the hard carbon core with the network structure, and washing, filtering and drying the obtained product; wherein the stirring speed is 200 r/min-1000 r/min, and the stirring time is 1-10 hours.
9. A negative pole piece of a lithium ion battery is characterized in that the negative pole piece comprises the composite negative pole material with the network structure of any one of claims 1 to 3.
10. A lithium ion battery, characterized in that the lithium ion battery comprises the negative electrode plate of claim 9.
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CN107959006A (en) * 2017-10-31 2018-04-24 华南理工大学 A kind of lignin-base hard carbon/carbon nano tube compound material and preparation method thereof and the application in lithium ion battery negative material
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