CN110783541A - Based on cellulose-carbon nano tube-Li 4Ti 5O 12Hybrid battery negative electrode material - Google Patents

Based on cellulose-carbon nano tube-Li 4Ti 5O 12Hybrid battery negative electrode material Download PDF

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CN110783541A
CN110783541A CN201910998903.6A CN201910998903A CN110783541A CN 110783541 A CN110783541 A CN 110783541A CN 201910998903 A CN201910998903 A CN 201910998903A CN 110783541 A CN110783541 A CN 110783541A
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刘怀金
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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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 the technical field of lithium battery cathode materials, and discloses a lithium battery based on cellulose-carbon nano tube-Li 4Ti 5O 12The hybrid battery negative electrode material comprises the following raw materials: lithium titanate, titanium dioxide, cellulose, single-walled carbon nanotubes, oxalic acid and a titanate coupling agent. The cellulose-based carbon nanotube-Li 4Ti 5O 12Hybrid battery negative electrode material, Li 4Ti 5O 12Is a spinel solid solution composite oxide of metallic lithium and low potential transition metal titanium, and Li is modified by using acidified single-wall carbon nano tube 4Ti 5O 12Electrons can pass through the acidified single-walled carbon nanotubes and Li 4Ti 5O 12The interface is transferred from the negative electrode of the battery into the single-wall carbon nano-tubes, the contact area of the electrode material and the electrolyte is improved, and Li is increased 4Ti 5O 12The electron transport rate and conductivity of the electrode material, and also the Li generated in the full electrical process +The electrolyte is better transmitted into the electrolyte, the charging and discharging process of the battery is accelerated, and the working efficiency of the lithium ion battery is improved.

Description

Based on cellulose-carbon nano tube-Li 4Ti 5O 12Hybrid battery negative electrode material
Technical Field
The invention relates to the technical field of lithium battery cathode materials, in particular to a lithium battery cathode material based on cellulose-carbon nano tube-Li 4Ti 5O 12Hybrid battery negative electrode materials.
Background
The lithium ion battery is a secondary battery, and mainly realizes the charge and discharge process by the movement of lithium ions between the anode and the cathode of the battery, and in the charge and discharge process, Li +Ion is in twoThe electrodes are inserted and extracted back and forth: upon charging, Li +The lithium ion battery has the advantages of large energy density, high average output voltage, large output power, excellent cycle performance, long service life and the like.
However, the current lithium ion battery has low electron conduction rate and lithium ion diffusion coefficient, which results in low electrical conductivity of the electrode, affects the charge and discharge process and the energy storage system of the lithium ion battery, and simultaneously, the long-term charge and discharge process degrades the electrochemical performance of the anode and cathode materials of the lithium ion battery, and reduces the practicability and the applicability of the lithium ion battery.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a method based on cellulose-carbon nanotube-Li 4Ti 5O 12The hybrid battery cathode material solves the problems of low electron conduction rate and lithium ion diffusion coefficient and low electrode conductivity in the existing lithium ion battery, and also solves the problem of reduced electrochemical performance of the anode and cathode materials due to long-term charge-discharge process of the lithium ion battery.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: based on cellulose-carbon nano tube-Li 4Ti 5O 12The hybrid battery negative electrode material comprises the following raw materials in parts by weight: 50-70 parts of lithium titanate, 20-25 parts of titanium dioxide, 3-7 parts of cellulose, 2-5 parts of single-walled carbon nanotube, 4-10 parts of oxalic acid and 1-3 parts of titanate coupling agent.
Preferably, the lithium titanate has a molecular formula of Li 2TiO 3Wherein Li 2TiO 3The mass fraction is 93.5-95.8%.
Preferably, the titanium dioxide is TiO 2The content is 95.6-98.2%.
Preferably, the cellulose is lignin fiber, the length of the cellulose is 1000-1300 mu m, and the water content of the cellulose is 3.5-5.1%.
Preferably, the single-walled carbon nanotube is an allotrope of carbon, the length of the single-walled carbon nanotube is 4-8um, the outer diameter is 18-40nm, and the inner diameter is 2-4 nm.
Preferably, the mass fraction of COOH-COOH in the oxalic acid is 99.2-99.5%.
Preferably, the titanate coupling agent TMC-TTS is plant acidic monoalkoxy titanate.
Preferably, the cellulose-carbon nanotube-Li-based 4Ti 5O 12The preparation method of the hybrid battery negative electrode material comprises the following steps:
(1) preparation of novel lithium titanate composite oxide Li 4Ti 5O 12: weighing 50-70 parts of lithium titanate and 20-25 parts of titanium dioxide in turn, adding into a high-energy planetary ball mill, adding 200mL of distilled water and 300mL of ethanol, ball milling for 6-10h until the mixture completely passes through a 1200-mesh 1400-mesh sieve, washing the mixture with 1500-mesh 2000mL of distilled water, placing in an oven, heating to 80-85 ℃, and drying for 3-4h to obtain white particles Li 2TiO 3And TiO 2Mixture of Li 2TiO 3And TiO 2The mixture is put into a box-type resistance furnace, the temperature is raised to 760 ℃ and 770 ℃ at the heating rate of 5 ℃/min, the reaction is carried out for 8 to 10 hours, and the mixture is cooled to the room temperature after the reaction is completed to obtain the material lithium titanate composite oxide Li 4Ti 5O 12The spinel solid solution composite oxide consists of metal lithium and low-potential transition metal titanium.
(2) Preparing acidified single-wall carbon nanotubes: introducing N into a 500mL three-necked bottle 2Adding 200mL of distilled water, sequentially weighing 4-10 parts of oxalic acid and 2-5 parts of single-walled carbon nanotube, adding the oxalic acid and the single-walled carbon nanotube into a three-necked bottle, placing the three-necked bottle into an ultrasonic processor, carrying out ultrasonic treatment for 2-3h, placing the three-necked bottle into a constant-temperature water bath kettle after the ultrasonic treatment is finished, heating in water bath to 75-80 ℃, reacting for 20-24h, filtering the solution after the reaction is completed, obtaining a liquid, washing the obtained powdery granular black solid to be neutral by 3500-4000mL of distilled water, removing residual oxalic acid, finally placing the material into an oven, heating to 80-85 ℃, and drying for 3-4h to obtain the acidified single-necked solid of the black powdery solidWall carbon nanotube, MWCNTs-COOH nanoparticle.
(3) Based on cellulose-carbon nanotube-Li 4Ti 5O 12Hybrid battery negative electrode material: adding 100mL of distilled water and 150mL of glycerol into a 500mL beaker, and sequentially adding the Li prepared in the step (1) 4Ti 5O 12And (2) preparing MWCNTs-COOH nano particles, weighing 1-3 parts of titanate coupling agent and 3-7 parts of cellulose, sequentially adding the titanate coupling agent and the cellulose into a beaker, placing the beaker into a constant-temperature water bath kettle, heating to 60-65 ℃, uniformly stirring for 30-40min, after uniformly stirring, completely transferring the solution in the beaker into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a reaction kettle heating box, heating to 150 ℃ and 160 ℃, reacting for 10-12h, after completely reacting, performing suction filtration on the material through a Buchner funnel to obtain brown solid, washing the brown solid with 2500mL distilled water, placing the mixture into an oven, heating to 75-80 ℃, and drying for 4-5h to obtain gray solid cellulose-carbon nano tube-Li 4Ti 5O 12Hybrid composite material, gray solid cellulose-carbon nanotube-Li obtained 4Ti 5O 12Adding a proper amount of N-methyl pyrrolidone into the hybrid composite material to prepare slurry, uniformly coating the slurry on a copper foil, drying in vacuum to remove the solvent, and rolling by a roller press to obtain the cellulose-carbon nanotube-Li-based composite material 4Ti 5O 12Hybrid battery negative electrode materials.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
1. the cellulose-based carbon nanotube-Li 4Ti 5O 12Hybrid battery negative electrode material using Li 4Ti 5O 12Li as a main component of a negative electrode material for a lithium ion battery 4Ti 5O 12The lithium ion battery is a spinel solid solution composite oxide of metal lithium and low-potential transition metal titanium, and the special structure of the spinel solid solution composite oxide has the advantages of zero strain and no tension, so that lithium ions have good mobility in the charging and discharging processes, the charging and discharging cycle can reach more than thousands of times, and the service life of the lithium ion battery is greatly prolongedIts life is long.
2. The cellulose-based carbon nanotube-Li 4Ti 5O 12Hybrid battery negative electrode material, modification of Li by using acidified single-walled carbon nanotubes 4Ti 5O 12Electrons can pass through the acidified single-walled carbon nanotubes and Li 4Ti 5O 12The interface is transferred from the negative electrode of the battery into the single-wall carbon nano-tubes, the contact area of the electrode material and the electrolyte is improved, and Li is increased 4Ti 5O 12The electron transport rate and conductivity of the electrode material, and also the Li generated in the full electrical process +The electrolyte is better transmitted into the electrolyte, the charging and discharging process of the battery is accelerated, and the working efficiency of the lithium ion battery is improved.
3. The cellulose-based carbon nanotube-Li 4Ti 5O 12Hybrid battery negative electrode material formed by-OH structure in cellulose and COOH group in acidified single-walled carbon nanotube
Figure BDA0002240653010000041
In the structure of the utility model, the utility model has the advantages of simple structure, improved nucleophilicity of Li 4Ti 5O 12The performance of the lithium ion battery anode material is improved, the structural stability of the lithium ion battery anode material is improved, the stability and the service life of the cathode material are improved, and simultaneously, cellulose is used as a carbon source to modify Li 4Ti 5O 12The effectiveness of electron and ion transmission is increased, the conductivity of the cathode material is improved, the charge and discharge capacity of the lithium ion battery is increased, and the practicability and the applicability of the lithium ion battery are greatly improved.
Detailed Description
In order to achieve the purpose, the invention provides the following technical scheme: based on cellulose-carbon nano tube-Li 4Ti 5O 12The hybrid battery negative electrode material comprises the following raw materials in parts by weight: 50-70 parts of lithium titanate, 20-25 parts of titanium dioxide, 3-7 parts of cellulose, 2-5 parts of single-walled carbon nanotube, 4-10 parts of oxalic acid and 1-3 parts of titanic acidEster coupling agent, lithium titanate molecular formula is Li 2TiO 3Wherein Li 2TiO 3The mass fraction is 93.5-95.8%, and the TiO in the titanium dioxide is 295.6-98.2 percent of content, cellulose is lignin fiber, the length is 1000-1300 mu m, the water content is 3.5-5.1 percent, a single-walled carbon nanotube is an allotrope of carbon, the length of the single-walled carbon nanotube is 4-8 mu m, the outer diameter is 18-40nm, the inner diameter is 2-4nm, the mass fraction of COOH-COOH in oxalic acid is 99.2-99.5 percent, and a titanate coupling agent TMC-TTS plant acidic monoalkoxy titanate is based on the cellulose-carbon nanotube-Li titanate 4Ti 5O 12The preparation method of the hybrid battery negative electrode material comprises the following steps:
(1) preparation of novel lithium titanate composite oxide Li 4Ti 5O 12: weighing 50-70 parts of lithium titanate and 20-25 parts of titanium dioxide in turn, adding into a high-energy planetary ball mill, adding 200mL of distilled water and 300mL of ethanol, ball milling for 6-10h until the mixture completely passes through a 1200-mesh 1400-mesh sieve, washing the mixture with 1500-mesh 2000mL of distilled water, placing in an oven, heating to 80-85 ℃, and drying for 3-4h to obtain white particles Li 2TiO 3And TiO 2Mixture of Li 2TiO 3And TiO 2The mixture is put into a box-type resistance furnace, the temperature is raised to 760 ℃ and 770 ℃ at the heating rate of 5 ℃/min, the reaction is carried out for 8 to 10 hours, and the mixture is cooled to the room temperature after the reaction is completed to obtain the material lithium titanate composite oxide Li 4Ti 5O 12The spinel solid solution composite oxide consists of metal lithium and low-potential transition metal titanium.
(2) Preparing acidified single-wall carbon nanotubes: introducing N into a 500mL three-necked bottle 2Adding 200mL of distilled water, sequentially weighing 4-10 parts of oxalic acid and 2-5 parts of single-walled carbon nanotube, adding into a three-necked bottle, placing the three-necked bottle into an ultrasonic processor, carrying out ultrasonic treatment for 2-3h, placing the three-necked bottle into a constant-temperature water bath kettle after the ultrasonic treatment is finished, heating in water bath to 75-80 ℃, reacting for 20-24h, filtering the solution after the reaction is finished, washing the obtained powdery granular black solid to be neutral by 3500-4000mL of distilled water, removing residual oxalic acid, finally placing the material into an oven, heating to 80-85 ℃, and dryingDrying for 3-4h to obtain black powder solid acidified single-wall carbon nano-tubes and MWCNTs-COOH nano-particles.
(3) Based on cellulose-carbon nanotube-Li 4Ti 5O 12Hybrid battery negative electrode material: adding 100mL of distilled water and 150mL of glycerol into a 500mL beaker, and sequentially adding the Li prepared in the step (1) 4Ti 5O 12And (2) preparing MWCNTs-COOH nano particles, weighing 1-3 parts of titanate coupling agent and 3-7 parts of cellulose, sequentially adding the titanate coupling agent and the cellulose into a beaker, placing the beaker into a constant-temperature water bath kettle, heating to 60-65 ℃, uniformly stirring for 30-40min, after uniformly stirring, completely transferring the solution in the beaker into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a reaction kettle heating box, heating to 150 ℃ and 160 ℃, reacting for 10-12h, after completely reacting, performing suction filtration on the material through a Buchner funnel to obtain brown solid, washing the brown solid with 2500mL distilled water, placing the mixture into an oven, heating to 75-80 ℃, and drying for 4-5h to obtain gray solid cellulose-carbon nano tube-Li 4Ti 5O 12Hybrid composite material, gray solid cellulose-carbon nanotube-Li obtained 4Ti 5O 12Adding a proper amount of N-methyl pyrrolidone into the hybrid composite material to prepare slurry, uniformly coating the slurry on a copper foil, drying in vacuum to remove the solvent, and rolling by a roller press to obtain the cellulose-carbon nanotube-Li-based composite material 4Ti 5O 12Hybrid battery negative electrode materials.
The cellulose-based carbon nanotube-Li 4Ti 5O 12Hybrid battery negative electrode material using Li 4Ti 5O 12Li as a main component of a negative electrode material for a lithium ion battery 4Ti 5O 12The composite oxide is a spinel solid solution composite oxide of metal lithium and low-potential transition metal titanium, and the special structure of the composite oxide has the advantages of zero strain and no tension, so that lithium ions have good mobility in the charging and discharging processes, the charging and discharging cycle can reach more than thousands of times, the service life of the lithium ion battery is greatly prolonged, and the composite oxide is based on cellulose-carbon nanotube-Li 4Ti 5O 12Hybrid battery negative electrode material, produced byModification of Li using acidified single-walled carbon nanotubes 4Ti 5O 12Electrons can pass through the acidified single-walled carbon nanotubes and Li 4Ti 5O 12The interface is transferred from the negative electrode of the battery into the single-wall carbon nano-tubes, the contact area of the electrode material and the electrolyte is improved, and Li is increased 4Ti 5O 12The electron transport rate and conductivity of the electrode material, and also the Li generated in the full electrical process +The electrolyte is better transmitted into the electrolyte, the charging and discharging process of the battery is accelerated, and the working efficiency of the lithium ion battery is improved.
The cellulose-based carbon nanotube-Li 4Ti 5O 12Hybrid battery negative electrode material formed by-OH structure in cellulose and COOH group in acidified single-walled carbon nanotube
Figure BDA0002240653010000061
In the structure of the utility model, the utility model has the advantages of simple structure,
Figure BDA0002240653010000062
improved nucleophilicity of Li 4Ti 5O 12The performance of the lithium ion battery anode material is improved, the structural stability of the lithium ion battery anode material is improved, the stability and the service life of the cathode material are improved, and simultaneously, cellulose is used as a carbon source to modify Li 4Ti 5O 12The effectiveness of electron and ion transmission is increased, the conductivity of the cathode material is improved, the charge and discharge capacity of the lithium ion battery is increased, and the practicability and the applicability of the lithium ion battery are greatly improved.
Example 1:
(1) preparation of novel lithium titanate composite oxide Li 4Ti 5O 12: weighing 70 parts of lithium titanate and 20 parts of titanium dioxide in turn, adding the lithium titanate and the titanium dioxide into a high-energy planetary ball mill, adding 200mL of distilled water and 300mL of ethanol, ball milling for 6-10h until the mixture completely passes through a 1200-mesh and 1400-mesh sieve, washing the mixture through 1500-mesh and 2000mL of distilled water, placing the mixture into an oven, heating the mixture to 80-85 ℃, and drying the mixture for 3-4h to obtain white particles Li 2TiO 3And TiO 2Mixture of Li 2TiO 3And TiO 2Mixture ofPutting the lithium titanate into a box-type resistance furnace, heating to 770 ℃ at the heating rate of 5 ℃/min, reacting for 8-10h, and cooling to room temperature after complete reaction to obtain the material lithium titanate composite oxide Li 4Ti 5O 12Spinel solid solution composite oxide component 1 of metallic lithium and low potential transition metal titanium
(2) Preparing acidified single-wall carbon nanotubes: introducing N into a 500mL three-necked bottle 2Adding 200mL of distilled water, sequentially weighing 4 parts of oxalic acid and 2 parts of single-walled carbon nanotube, adding the oxalic acid and the single-walled carbon nanotube into a three-necked bottle, placing the three-necked bottle into an ultrasonic processor, carrying out ultrasonic treatment for 2-3h, placing the three-necked bottle into a constant-temperature water bath kettle after the ultrasonic treatment, heating in water bath to 75-80 ℃, reacting for 20-24h, filtering the solution to obtain liquid after the reaction is completed, washing the obtained powdery black granular solid to be neutral by 3500-4000mL of distilled water, removing residual oxalic acid, finally placing the material in an oven, heating to 80-85 ℃, and drying for 3-4h to obtain the acidified single-walled carbon nanotube of the black powdery solid, wherein the MWCNTs-COOH nanoparticle component is 1
(3) Based on cellulose-carbon nanotube-Li 4Ti 5O 12Hybrid battery negative electrode material: adding 100mL of distilled water and 150mL of glycerol into a 500mL beaker, and sequentially adding the Li prepared in the step (1) 4Ti 5O 12And (2) weighing 1 part of titanate coupling agent and 3 parts of cellulose, sequentially adding the titanate coupling agent and the cellulose into a beaker, placing the beaker into a constant-temperature water bath kettle, heating to 60-65 ℃, uniformly stirring for 30-40min, uniformly stirring, completely transferring the solution in the beaker into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a reaction kettle heating box, heating to 150 ℃ and 160 ℃, reacting for 10-12h, after the reaction is completed, performing suction filtration on the material through a Buchner funnel to obtain brown solid, washing the brown solid with 2500mL of distilled water, placing the washed solid in a drying box, heating to 75-80 ℃, and drying for 4-5h to obtain gray solid cellulose-carbon nanotube-Li 4Ti 5O 12Hybrid composite component 1, gray solid cellulose-carbon nanotube-Li obtained 4Ti 5O 12Adding a proper amount of N-methyl pyrrolidone into the hybrid composite material to prepare slurry, and uniformly mixingEvenly coating on copper foil, vacuum drying to remove solvent, and rolling by roller press to obtain the final product 4Ti 5O 12Hybrid battery negative electrode material 1.
Example 2
(1) Preparation of novel lithium titanate composite oxide Li 4Ti 5O 12: weighing 66 parts of lithium titanate and 21 parts of titanium dioxide in turn, adding the weighed materials into a high-energy planetary ball mill, adding 200mL of distilled water and 300mL of ethanol, ball-milling for 6-10h until the mixture completely passes through a 1200-mesh and 1400-mesh sieve, washing the mixture through 1500-mesh and 2000mL of distilled water, placing the mixture into an oven, heating the mixture to 80-85 ℃, and drying the mixture for 3-4h to obtain white particles Li 2TiO 3And TiO 2Mixture of Li 2TiO 3And TiO 2The mixture is put into a box-type resistance furnace, the temperature is raised to 760 ℃ and 770 ℃ at the heating rate of 5 ℃/min, the reaction is carried out for 8 to 10 hours, and the mixture is cooled to the room temperature after the reaction is completed to obtain the material lithium titanate composite oxide Li 4Ti 5O 12And a spinel solid solution composite oxide component 2 composed of metallic lithium and a low-potential transition metal titanium.
(2) Preparing acidified single-wall carbon nanotubes: introducing N into a 500mL three-necked bottle 2Adding 200mL of distilled water, sequentially weighing 5 parts of oxalic acid and 3 parts of single-walled carbon nanotube, adding the oxalic acid and the single-walled carbon nanotube into a three-necked bottle, placing the three-necked bottle into an ultrasonic processor, carrying out ultrasonic treatment for 2-3h, placing the three-necked bottle into a constant-temperature water bath kettle after the ultrasonic treatment, heating in a water bath to 75-80 ℃, reacting for 20-24h, filtering the solution after the reaction is completed to obtain liquid, washing the obtained black solid powder particles to be neutral by 3500-4000mL of distilled water, removing residual oxalic acid, finally placing the material in an oven, heating to 80-85 ℃, and drying for 3-4h to obtain the acidified single-walled carbon nanotube of the black powder solid, and the MWCNTs-COOH nanoparticle component 2.
(3) Based on cellulose-carbon nanotube-Li 4Ti 5O 12Hybrid battery negative electrode material: adding 100mL of distilled water and 150mL of glycerol into a 500mL beaker, and sequentially adding the Li prepared in the step (1) 4Ti 5O 12And MWCNTs-prepared in step (2)COOH nano particles are weighed, 1 part of titanate coupling agent and 4 parts of cellulose are sequentially added into a beaker, the beaker is placed into a constant-temperature water bath kettle and heated to 60-65 ℃, the solution is stirred for 30-40min at a constant speed, after the uniform stirring, the solution in the beaker is completely transferred into a hydrothermal reaction kettle, the hydrothermal reaction kettle is placed into a reaction kettle heating box and heated to 160 ℃ plus 150 ℃, the reaction lasts 10-12h, after the reaction is completed, the material is filtered by a Buchner funnel to obtain brown solid, the brown solid is washed by 2500mL of distilled water and heated to 75-80 ℃ in an oven, and the brown solid is dried for 4-5h to obtain gray solid cellulose-carbon nano tube-Li 4Ti 5O 12Hybrid composite component 1, gray solid cellulose-carbon nanotube-Li obtained 4Ti 5O 12Adding a proper amount of N-methyl pyrrolidone into the hybrid composite material to prepare slurry, uniformly coating the slurry on a copper foil, drying in vacuum to remove the solvent, and rolling by a roller press to obtain the cellulose-carbon nanotube-Li-based composite material 4Ti 5O 12Hybrid battery negative electrode material 2.
Example 3
(1) Preparation of novel lithium titanate composite oxide Li 4Ti 5O 12: sequentially weighing 59 parts of lithium titanate and 23 parts of titanium dioxide, adding the lithium titanate and the titanium dioxide into a high-energy planetary ball mill, adding 200mL of distilled water and 300mL of ethanol, ball-milling for 6-10h until the mixture completely passes through a 1200-mesh and 1400-mesh sieve, washing the mixture through 1500-mesh and 2000mL of distilled water, placing the mixture in an oven, heating to 80-85 ℃, and drying for 3-4h to obtain white particles Li 2TiO 3And TiO 2Mixture of Li 2TiO 3And TiO 2The mixture is put into a box-type resistance furnace, the temperature is raised to 760 ℃ and 770 ℃ at the heating rate of 5 ℃/min, the reaction is carried out for 8 to 10 hours, and the mixture is cooled to the room temperature after the reaction is completed to obtain the material lithium titanate composite oxide Li 4Ti 5O 12And a spinel solid solution composite oxide component 3 of metallic lithium and low potential transition metal titanium.
(2) Preparing acidified single-wall carbon nanotubes: introducing N into a 500mL three-necked bottle 2Adding 200mL of distilled water, sequentially weighing 7 parts of oxalic acid and 4 parts of single-walled carbon nanotube, and adding into a three-necked flaskPutting a three-necked bottle into an ultrasonic processor, carrying out ultrasonic treatment for 2-3h, after the ultrasonic treatment is finished, putting the three-necked bottle into a constant-temperature water bath kettle, heating in water bath to 75-80 ℃, reacting for 20-24h, filtering the solution after the reaction is finished, washing the obtained black solid powder particles to be neutral by 3500-4000mL distilled water, removing residual oxalic acid, finally putting the material into an oven, heating to 80-85 ℃, and drying for 3-4h to obtain the acidified single-walled carbon nanotube of the black solid powder, namely the MWCNTs-COOH nanoparticle component 3.
(3) Based on cellulose-carbon nanotube-Li 4Ti 5O 12Hybrid battery negative electrode material: adding 100mL of distilled water and 150mL of glycerol into a 500mL beaker, and sequentially adding the Li prepared in the step (1) 4Ti 5O 12And (2) weighing 2 parts of titanate coupling agent and 5 parts of cellulose, sequentially adding the titanate coupling agent and the cellulose into a beaker, placing the beaker into a constant-temperature water bath kettle, heating to 60-65 ℃, uniformly stirring for 30-40min, uniformly stirring, completely transferring the solution in the beaker into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a reaction kettle heating box, heating to 160 ℃ for reaction at the temperature of 150- 4Ti 5O 12Hybrid composite component 3, gray solid cellulose-carbon nanotube-Li obtained 4Ti 5O 12Adding a proper amount of N-methyl pyrrolidone into the hybrid composite material to prepare slurry, uniformly coating the slurry on a copper foil, drying in vacuum to remove the solvent, and rolling by a roller press to obtain the cellulose-carbon nanotube-Li-based composite material 4Ti 5O 12Hybrid battery negative electrode material 3.
Example 4
(1) Preparation of novel lithium titanate composite oxide Li 4Ti 5O 12: 54 parts of lithium titanate and 24 parts of titanium dioxide are sequentially weighed and added into a high-energy planetary ball mill, 200mL of distilled water and 300mL of ethanol are added, ball milling is carried out for 6-10h,until the mixture completely passes through a 1200-1400 mesh sieve, washing the mixture by 1500-2000mL distilled water, placing the mixture in an oven, heating the mixture to 80-85 ℃, and drying the mixture for 3-4h to obtain white particles Li 2TiO 3And TiO 2Mixture of Li 2TiO 3And TiO 2The mixture is put into a box-type resistance furnace, the temperature is raised to 760 ℃ and 770 ℃ at the heating rate of 5 ℃/min, the reaction is carried out for 8 to 10 hours, and the mixture is cooled to the room temperature after the reaction is completed to obtain the material lithium titanate composite oxide Li 4Ti 5O 12And a spinel solid solution composite oxide component 4 of metallic lithium and a low-potential transition metal titanium.
(2) Preparing acidified single-wall carbon nanotubes: introducing N into a 500mL three-necked bottle 2Adding 200mL of distilled water, sequentially weighing 9 parts of oxalic acid and 4 parts of single-walled carbon nanotube, adding the oxalic acid and the single-walled carbon nanotube into a three-necked bottle, placing the three-necked bottle into an ultrasonic processor, carrying out ultrasonic treatment for 2-3h, placing the three-necked bottle into a constant-temperature water bath kettle after the ultrasonic treatment, heating in a water bath to 75-80 ℃, reacting for 20-24h, filtering the solution after the reaction is completed to obtain liquid, washing the obtained black solid powder particles to be neutral by 3500-4000mL of distilled water, removing residual oxalic acid, finally placing the material in an oven, heating to 80-85 ℃, and drying for 3-4h to obtain the acidified single-walled carbon nanotube of the black powder solid, and the MWCNTs-COOH nanoparticle component 4.
(3) Based on cellulose-carbon nanotube-Li 4Ti 5O 12Hybrid battery negative electrode material: adding 100mL of distilled water and 150mL of glycerol into a 500mL beaker, and sequentially adding the Li prepared in the step (1) 4Ti 5O 12And (2) weighing 3 parts of titanate coupling agent and 6 parts of cellulose, sequentially adding the titanate coupling agent and the cellulose into a beaker, placing the beaker into a constant-temperature water bath kettle, heating to 60-65 ℃, uniformly stirring for 30-40min, uniformly stirring, completely transferring the solution in the beaker into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a reaction kettle heating box, heating to 150-160 ℃, reacting for 10-12h, after the reaction is completed, performing suction filtration on the material through a Buchner funnel to obtain brown solid, washing the brown solid with 2500mL of distilled water, heating to 75-80 ℃ in a drying oven, and drying for 4-fold materials5h, obtaining gray solid cellulose-carbon nano tube-Li 4Ti 5O 12Hybrid composite component 4, gray solid cellulose-carbon nanotube-Li obtained 4Ti 5O 12Adding a proper amount of N-methyl pyrrolidone into the hybrid composite material to prepare slurry, uniformly coating the slurry on a copper foil, drying in vacuum to remove the solvent, and rolling by a roller press to obtain the cellulose-carbon nanotube-Li-based composite material 4Ti 5O 12Hybrid battery negative electrode material 4.
Example 5
(1) Preparation of novel lithium titanate composite oxide Li 4Ti 5O 12: weighing 50 parts of lithium titanate and 25 parts of titanium dioxide in turn, adding the lithium titanate and the titanium dioxide into a high-energy planetary ball mill, adding 200mL of distilled water and 300mL of ethanol, ball milling for 6-10h until the mixture completely passes through a 1200-mesh and 1400-mesh sieve, washing the mixture through 1500-mesh and 2000mL of distilled water, placing the mixture into an oven, heating the mixture to 80-85 ℃, and drying the mixture for 3-4h to obtain white particles Li 2TiO 3And TiO 2Mixture of Li 2TiO 3And TiO 2The mixture is put into a box-type resistance furnace, the temperature is raised to 760 ℃ and 770 ℃ at the heating rate of 5 ℃/min, the reaction is carried out for 8 to 10 hours, and the mixture is cooled to the room temperature after the reaction is completed to obtain the material lithium titanate composite oxide Li 4Ti 5O 12Spinel solid solution composite oxide component 5 of metallic lithium and low potential transition metal titanium
(2) Preparing acidified single-wall carbon nanotubes: introducing N into a 500mL three-necked bottle 2Adding 200mL of distilled water, sequentially weighing 10 parts of oxalic acid and 5 parts of single-walled carbon nanotube, adding the oxalic acid and the single-walled carbon nanotube into a three-necked bottle, placing the three-necked bottle into an ultrasonic processor, carrying out ultrasonic treatment for 2-3h, placing the three-necked bottle into a constant-temperature water bath kettle after the ultrasonic treatment, heating in a water bath to 75-80 ℃, reacting for 20-24h, filtering the solution after the reaction is completed to obtain liquid, washing the obtained black solid powder particles to be neutral by 3500-4000mL of distilled water, removing residual oxalic acid, finally placing the material in an oven, heating to 80-85 ℃, and drying for 3-4h to obtain the acidified single-walled carbon nanotube of the black powder solid, and the MWCNTs-COOH nanoparticle component 5.
(3) Based on cellulose-carbon nanotube-Li 4Ti 5O 12Hybrid battery negative electrode material: adding 100mL of distilled water and 150mL of glycerol into a 500mL beaker, and sequentially adding the Li prepared in the step (1) 4Ti 5O 12And (2) weighing 3 parts of titanate coupling agent and 7 parts of cellulose, sequentially adding the titanate coupling agent and the cellulose into a beaker, placing the beaker into a constant-temperature water bath kettle, heating to 60-65 ℃, uniformly stirring for 30-40min, uniformly stirring, completely transferring the solution in the beaker into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a reaction kettle heating box, heating to 150 ℃ and 160 ℃, reacting for 10-12h, after the reaction is completed, performing suction filtration on the material through a Buchner funnel to obtain brown solid, washing the brown solid with 2500mL of distilled water, placing the washed solid in a drying box, heating to 75-80 ℃, and drying for 4-5h to obtain gray solid cellulose-carbon nanotube-Li 4Ti 5O 12Hybrid composite component 5, gray solid cellulose-carbon nanotube-Li obtained 4Ti 5O 12Adding a proper amount of N-methyl pyrrolidone into the hybrid composite material to prepare slurry, uniformly coating the slurry on a copper foil, drying in vacuum to remove the solvent, and rolling by a roller press to obtain the cellulose-carbon nanotube-Li-based composite material 4Ti 5O 12Hybrid battery negative electrode material 5.

Claims (8)

1. Based on cellulose-carbon nano tube-Li 4Ti 5O 12The hybrid battery cathode material comprises the following raw materials in parts by weight, and is characterized in that: 50-70 parts of lithium titanate, 20-25 parts of titanium dioxide, 3-7 parts of cellulose, 2-5 parts of single-walled carbon nanotube, 4-10 parts of oxalic acid and 1-3 parts of titanate coupling agent.
2. The cellulose-carbon nanotube-Li-based material of claim 1 4Ti 5O 12The hybrid battery negative electrode material is characterized in that: the molecular formula of the lithium titanate is Li 2TiO 3Wherein Li 2TiO 3The mass fraction is 93.5-95.8%.
3. The cellulose-carbon nanotube-Li-based material of claim 1 4Ti 5O 12The hybrid battery negative electrode material is characterized in that: TiO in the titanium dioxide 2The content is 95.6-98.2%.
4. The cellulose-carbon nanotube-Li-based material of claim 1 4Ti 5O 12The hybrid battery negative electrode material is characterized in that: the cellulose is lignin fiber, the length of the cellulose is 1000-1300 mu m, and the water content of the cellulose is 3.5-5.1%.
5. The cellulose-carbon nanotube-Li-based material of claim 1 4Ti 5O 12The hybrid battery negative electrode material is characterized in that: the single-walled carbon nanotube is an allotrope of carbon, the length of the single-walled carbon nanotube is 4-8um, the outer diameter is 18-40nm, and the inner diameter is 2-4 nm.
6. The cellulose-carbon nanotube-Li-based material of claim 1 4Ti 5O 12The hybrid battery negative electrode material is characterized in that: the mass fraction of COOH-COOH in the oxalic acid is 99.2-99.5%.
7. The cellulose-carbon nanotube-Li-based material of claim 1 4Ti 5O 12The hybrid battery negative electrode material is characterized in that: the titanate coupling agent TMC-TTS plant acidic monoalkoxyl titanate.
8. The cellulose-carbon nanotube-Li-based material of claim 1 4Ti 5O 12The hybrid battery negative electrode material is characterized in that: the cellulose-carbon nanotube-Li-based 4Ti 5O 12The preparation method of the hybrid battery negative electrode material comprises the following steps:
(1) preparation of novel lithium titanate composite oxide Li 4Ti 5O 12: weighing 50-70 parts of lithium titanate and 20-25 parts of titanium dioxide in turn, adding into a high-energy planetary ball mill, adding 200mL of distilled water and 300mL of ethanol, ball milling for 6-10h until the mixture completely passes through a 1200-mesh 1400-mesh sieve, washing the mixture with 1500-mesh 2000mL of distilled water, placing in an oven, heating to 80-85 ℃, and drying for 3-4h to obtain white particles Li 2TiO 3And TiO 2Mixture of Li 2TiO 3And TiO 2The mixture is put into a box-type resistance furnace, the temperature is raised to 760 ℃ and 770 ℃ at the heating rate of 5 ℃/min, the reaction is carried out for 8 to 10 hours, and the mixture is cooled to the room temperature after the reaction is completed to obtain the material lithium titanate composite oxide Li 4Ti 5O 12The spinel solid solution composite oxide consists of metal lithium and low-potential transition metal titanium.
(2) Preparing acidified single-wall carbon nanotubes: introducing N into a 500mL three-necked bottle 2Adding 200mL of distilled water, sequentially weighing 4-10 parts of oxalic acid and 2-5 parts of single-walled carbon nanotube, adding into a three-necked bottle, placing the three-necked bottle into an ultrasonic processor, carrying out ultrasonic treatment for 2-3h, placing the three-necked bottle into a constant-temperature water bath kettle after the ultrasonic treatment is finished, heating in water bath to 75-80 ℃, reacting for 20-24h, filtering out the solution after the reaction is completed, washing the obtained powdery black granular solid to be neutral by 3500-4000mL of distilled water, removing residual oxalic acid, finally placing the material in an oven, heating to 80-85 ℃, and drying for 3-4h to obtain the acidified single-walled carbon nanotube and MWCNTs-COOH nano particle of the black powdery solid.
(3) Based on cellulose-carbon nanotube-Li 4Ti 5O 12Hybrid battery negative electrode material: adding 100mL of distilled water and 150mL of glycerol into a 500mL beaker, and sequentially adding the Li prepared in the step (1) 4Ti 5O 12And (2) preparing MWCNTs-COOH nano particles, weighing 1-3 parts of titanate coupling agent and 3-7 parts of cellulose, sequentially adding the titanate coupling agent and the cellulose into a beaker, placing the beaker into a constant-temperature water bath kettle, heating to 60-65 ℃, uniformly stirring for 30-40min, after uniformly stirring, completely transferring the solution in the beaker into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a reaction kettle heating box, heating to 160 ℃ at 150 ℃, reacting for 10-12h,after the reaction is completed, the material is filtered by a Buchner funnel to obtain brown solid, and the brown solid is washed clean by 2000-2500mL distilled water and is placed in an oven to be heated to 75-80 ℃ and dried for 4-5h to obtain gray solid cellulose-carbon nano tube-Li 4Ti 5O 12Hybrid composite material, gray solid cellulose-carbon nanotube-Li obtained 4Ti 5O 12Adding a proper amount of N-methyl pyrrolidone into the hybrid composite material to prepare slurry, uniformly coating the slurry on a copper foil, drying in vacuum to remove the solvent, and rolling by a roller press to obtain the cellulose-carbon nanotube-Li-based composite material 4Ti 5O 12Hybrid battery negative electrode materials.
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Cited By (4)

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CN112289990A (en) * 2020-04-20 2021-01-29 董荣芳 Application of composite nano material as battery negative electrode material
CN112736234A (en) * 2021-01-15 2021-04-30 辽宁大学 Novel lithium ion battery cathode material based on biomass/carbon nanotube composite modified lithium titanate and application thereof
CN114843494A (en) * 2022-03-04 2022-08-02 大连海事大学 Rare earth titanate electrode material with tube centerline structure and preparation method thereof
CN115084469A (en) * 2022-06-30 2022-09-20 合肥国轩高科动力能源有限公司 Lithium ion battery cathode composite material and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112289990A (en) * 2020-04-20 2021-01-29 董荣芳 Application of composite nano material as battery negative electrode material
CN112736234A (en) * 2021-01-15 2021-04-30 辽宁大学 Novel lithium ion battery cathode material based on biomass/carbon nanotube composite modified lithium titanate and application thereof
CN112736234B (en) * 2021-01-15 2024-02-20 辽宁大学 Novel lithium ion battery anode material based on biomass/carbon nanotube composite modified lithium titanate and application thereof
CN114843494A (en) * 2022-03-04 2022-08-02 大连海事大学 Rare earth titanate electrode material with tube centerline structure and preparation method thereof
CN114843494B (en) * 2022-03-04 2024-02-20 大连海事大学 Rare earth titanate electrode material with tube centerline structure and preparation method thereof
CN115084469A (en) * 2022-06-30 2022-09-20 合肥国轩高科动力能源有限公司 Lithium ion battery cathode composite material and preparation method thereof

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