CN112599762B - TiO 2 2 Negative electrode material of CNF battery and preparation method thereof - Google Patents

TiO 2 2 Negative electrode material of CNF battery and preparation method thereof Download PDF

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CN112599762B
CN112599762B CN202011469111.9A CN202011469111A CN112599762B CN 112599762 B CN112599762 B CN 112599762B CN 202011469111 A CN202011469111 A CN 202011469111A CN 112599762 B CN112599762 B CN 112599762B
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CN112599762A (en
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廖强
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Nanjing Guoxuan Battery 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
    • H01M4/48—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
    • 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
    • H01M4/62—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
    • H01M2004/026—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 discloses aTiO 2 a/CNF battery cathode material and a preparation method thereof, relating to the technical field of lithium ion battery cathode materials, wherein the TiO is 2 The negative electrode material of CNF battery is prepared by using carbon nano-cellulose as matrix and loading layered TiO on the matrix 2 A hybrid; the layered TiO 2 The hybrid being a multilayer Ti 3 C 2 T x The material is prepared from a precursor; the preparation of the anode material comprises the following steps: a plurality of layers of Ti 3 C 2 T x Dispersing the material in an ethanol solution, adding nano-cellulose, performing ultrasonic dispersion, aging, centrifugally washing, performing vacuum drying, calcining in an inert atmosphere, cooling, washing, and drying to obtain the nano-cellulose/nano-cellulose composite material. The invention utilizes Ti 3 C 2 T x Obtaining TiO by heat treatment 2 Hybrid and first mixing CNF with TiO 2 The lithium ion battery cathode material prepared by compounding the hybrid solves the problems of low specific capacity and poor layered stability of a single carbon-based material, obtains good cycle stability and reversibility, realizes improvement of the electrochemical characteristics of the carbon-based material, and is an ideal choice of the cathode material.

Description

TiO (titanium dioxide) 2 Negative electrode material of CNF battery and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to TiO 2 A CNF battery negative electrode material and a preparation method thereof.
Background
With the wide application of electronic products and new energy automobiles, lithium ion batteries have been permeated in various fields, and meanwhile, commercial graphite negative electrode materials have been difficult to meet the development of green energy and low-carbon economy, so that the development of high-specific-capacity negative electrode materials has a very important significance for the research of lithium ion batteries. The excellent cathode material ensures that the battery has high energy, good cycle stability and long service life, and also ensures safety so as to adapt to the development of novel cathode materials.
The carbon-based material has been favored by researchers because of its advantages of low density, simple synthesis, designable structure, and good stability. However, research on negative electrode materials is mainly focused on graphite-based and non-graphite-based carbons, and although these materials have good cycle performance and safety performance, they have low lithium intercalation capacity and are easy to precipitate lithium, and are not suitable for large-current discharge, so that practical applications thereof are limited.
At present, titanium dioxide (TiO) 2 ) The lithium ion battery is environment-friendly, low in cost, stable in structure in the process of lithium ion intercalation/deintercalation, capable of avoiding deposition of metal lithium, high in safety and high in development potential in high-energy storage. But TiO 2 2 MaterialThe poor electronic conductivity and the poor lithium ion diffusion affect the use effect thereof, and other materials need to be compounded to solve the problems.
Patent CN108448073A discloses C @ TiO with adjustable proportion 2 The composite negative electrode material is prepared through adding tetrabutyl titanate into glycol, hydrolyzing to form precursor, and calcining the precursor in inert gas to form C @ TiO 2 And (3) compounding the negative electrode material. The C in the composite material is wrapped with TiO 2 The cathode material has a stable structure in the charging and discharging process, and the conductivity of the material is improved by introducing carbon base, so that the C @ TiO 2 The composite negative electrode material not only has high capacity, but also has good rate performance. However, the above-mentioned C @ TiO 2 The composite material takes ethylene glycol as a carbon source, and has the problems of small specific surface area, higher cost, deficient source and the like.
Disclosure of Invention
Based on the technical problems in the prior art, the invention provides TiO 2 CNF battery negative electrode material and preparation method thereof, CNF and TiO are firstly mixed 2 The hybrid is compounded, and the obtained composite material is used as the lithium ion battery cathode material, so that the problems of low specific capacity and poor layered stability of a single carbon-based material are solved, and good cycle stability and reversibility are obtained.
The invention provides TiO 2 The negative electrode material of CNF battery is prepared by using carbon nano-cellulose as matrix and loading layered TiO on the matrix 2 A hybrid; the layered TiO 2 The hybrid being a multilayer Ti 3 C 2 T x The material is prepared by a precursor.
The invention also provides the TiO 2 The preparation method of the negative electrode material of the CNF battery comprises the following steps:
s1, forming a plurality of layers of Ti 3 C 2 T x Dispersing the material in ethanol solution, adding carbon nano cellulose, performing ultrasonic dispersion, aging, centrifugally washing, and vacuum drying to obtain Ti 3 C 2 T x A nanocellulose composite;
s2, mixing Ti 3 C 2 T x Calcining the/nano-cellulose composite material in inert atmosphere, cooling, washing and drying to obtain TiO 2 a/CNF composite material.
Preferably, in S1, multiple layers of Ti 3 C 2 T x The material is Ti 3 AlC 2 Is prepared by acid etching reaction of raw materials; the specific operation is as follows: under the condition of stirring, adding Ti 3 AlC 2 Adding into acid etching agent, sealing, stirring, reacting, centrifuging, washing, and vacuum drying to obtain multilayer Ti 3 C 2 T x A material; wherein the etchant is hydrofluoric acid aqueous solution.
Preferably, in S1, multiple layers of Ti 3 C 2 T x The weight-volume ratio g/mL of the material to the ethanol solution is 0.1-0.3: 20 to 40; preferably, a plurality of layers of Ti 3 C 2 T x The weight ratio of the material to the carbon nano-cellulose is 1-3: 3.
preferably, in S1, ultrasonic dispersion is carried out for 5-10 min, and standing and aging are carried out for 12-24 h.
Preferably, in S2, the calcining temperature is 600-800 ℃, and the calcining time is 6-8 h; preferably, the temperature rising rate of the calcination is 1 to 3 ℃/min.
Preferably, ti is added 3 AlC 2 Adding into acid etching agent, sealing and stirring for reaction, wherein the stirring speed is 100-300 rpm, and the reaction time is 24-72 h.
Preferably, the etchant is 40wt% aqueous hydrofluoric acid, ti 3 AlC 2 And the weight volume ratio g/mL of the etching agent is 1.0-3.0: 10 to 15.
Compared with the prior art, the beneficial effects of the invention are embodied in the following aspects:
1.TiO 2 in the preparation of the/CNF composite material, the carbon nano-cellulose has larger contact area and strong van der Waals force, so that Ti 3 C 2 T x Can be well dispersed on the surface of the carbon nano tube, and is calcined in inert atmosphere to prepare CNF (carbon nano tube) supported layered TiO 2 Composite structures of hybrids. In the invention, tiO is mixed with 2 The nano particles are well dispersed and loaded on the CNF, and the electrochemical performance of the negative electrode material is effectively improved.
2. The carbon-based negative electrode material prepared by taking the nano-cellulose as the raw material has higher specific surface area, lower cost and abundant sources, and becomes a battery material with potential application value.
3. The invention utilizes Ti 3 C 2 T x Obtaining TiO by heat treatment 2 Hybrid and first mixing CNF with TiO 2 The obtained composite material is used as the lithium ion battery cathode material, so that the problems of low specific capacity and poor layered stability of a single carbon-based material are solved, good cycle stability and reversibility are obtained, and the electrochemical characteristics of the carbon-based material are improved due to the improvement of the conductivity and the increase of the surface area, so that the composite material is an ideal choice of the cathode material.
4. The invention can enhance the electrochemical performance of the cathode material by the synergistic effect among the multi-component, and reasonably uses TiO with high lithium intercalation potential 2 The problem that dendritic lithium is formed by the carbon-based negative electrode material is solved, and meanwhile, the nano-cellulose can meet the development of green energy and low-carbon economy. Therefore, compared with the traditional graphite material, the prepared composite negative electrode material has a novel structure, and provides a certain technical reference and theoretical basis for the carbon-based negative electrode material.
Drawings
FIG. 1 is a flow chart of the preparation process of the present invention;
FIG. 2 shows TiO prepared in example 1 of the present invention 2 XRD pattern of/CNF composite material;
FIG. 3 is a diagram of TiO prepared in example 1 of the present invention 2 Raman spectra of/CNF composites;
FIG. 4 is a diagram showing the preparation of TiO in example 1 of the present invention 2 SEM images of the raw materials and products of the/CNF composite; wherein (a) Ti 3 C 2 T x Carbon nanocellulose, (b) TiO 30 μm in scale 2 TiO 5 μm on scale of/CNF (d) 2 /CNF；
FIG. 5 is a diagram showing the preparation of TiO in example 1 of the present invention 2 TEM images of the starting materials and products of the/CNF composite; wherein (a) is 1 μm TiO 2 Transmission plot of/CNF, (b) 100nm TiO scale 2 (iii) CNF transmission plot, (c) 50nm TiO scale 2 CNF transmission diagram, (d) TiO 2 a/CNF transmission diffraction analysis chart;
FIG. 6 shows TiO prepared in example 1 of the present invention 2 BET and XPS plots of/CNF composites; wherein (a) TiO 2 Specific surface area of the/CNF (b) TiO 2 CNF pore size distribution plot, (c) TiO 2 X-ray photoelectron spectrum of/CNF, and (d) valence diagram of Ti element.
Detailed Description
Referring to FIG. 1, the present invention provides a TiO compound 2 The preparation process flow chart of the/CNF battery negative electrode material is that carbon nano-cellulose and a plurality of layers of Ti are mixed 3 C 2 T x Mixing the solutions to obtain Ti-loaded surface 3 C 2 T x Nano carbon fiber composite material Ti 3 C 2 T x The TiO is obtained by heat treatment and carbonization of the/nano-cellulose composite material 2 a/CNF composite material.
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
Step 1, preparing Ti 3 C 2 T x Material
Weighing 10mL of 40% HF aqueous solution in a polytetrafluoroethylene reaction kettle, and weighing Ti 3 AlC 2 Precursor 1.0g, stirring Ti at room temperature under the condition of magnetic stirring rotation speed of 100r/min 3 AlC 2 Slowly adding HF aqueous solution into the precursor within 1.0min, sealing the reaction kettle, and keeping the stirring time for 24h. Deionized water was added to the resulting product, and the mixture was centrifuged at 3500rpm for 3min each time. At the final centrifugation, the supernatant had a pH around 7.0. The obtained product is dried in a vacuum drying oven at 60 ℃.
Step 2, preparing Ti 3 C 2 T x Nano cellulose composite material
At room temperature, the Ti prepared in the step 1 is added 3 C 2 T x 0.1g of the mixture is weighed and evenly dispersed in 20mL of ethanol solution, 0.3g of carbon nano-cellulose is added, ultrasonic dispersion is carried out, and standing and aging are carried out for 12 hours. Finally, by distillationWater and absolute ethyl alcohol are centrifugally washed for 3 to 5 times respectively, and vacuum drying is carried out at the temperature of 60 ℃.
Step 3, preparing TiO 2 /CNF composite material
Preparing Ti by the step 2 3 C 2 T x The/nanocellulose composite is transferred to a tube furnace in N 2 The calcination was carried out for 8h at 600 ℃ under a stream-protecting atmosphere. Cooling to room temperature to obtain TiO 2 a/CNF composite material.
For the prepared TiO 2 the/CNF composite was characterized and tested.
FIG. 2 shows TiO prepared in example 1 2 XRD pattern of/CNF composite material; in TiO 2 In the/CNF sample, in addition to the carbon peaks at 22 DEG and 44 DEG, other main diffraction peaks were associated with TiO 2 The JCPDS cards are consistent.
FIG. 3 is a diagram of TiO prepared in example 1 of the present invention 2 Raman plots of the/CNF composites; in the figure, D represents amorphous carbon, G represents graphite graphitized carbon, and the intensity of the peak at G is larger than that at D, which shows that TiO 2 the/CNF negative electrode material has high graphitization degree.
FIG. 4 is a diagram showing TiO preparation in example 1 of the present invention 2 SEM images of the raw material and the product of the/CNF composite material; as can be seen from a comparison of FIG. b with FIGS. c and d, tiO was added 2 Loaded on the CNF backbone.
FIG. 5 is a diagram showing the preparation of TiO in example 1 of the present invention 2 TEM images of the starting materials and products of the/CNF composite; tiO as shown in the figures (a) and (b) 2 The particles are surrounded by carbon, indicating TiO 2 The formation of the particle structure and CNF; (c) Is TiO 2 CNF high resolution TEM; (d) SAED confirmed TiO 2 The lattice characteristics of the nanoparticles.
FIG. 6 shows TiO prepared in example 1 of the present invention 2 BET and XPS profiles of/CNF composites; FIG. A is TiO 2 The CNF sample has a representative IV-type isothermal curve at a relative pressure of 0.4-1.0, has an obvious hysteresis loop and represents a mesoporous structure of the composite material. The specific surface area of the sample is 251.59m 2 (ii) in terms of/g. And (b) the pore diameter is mainly distributed below 5 nm. (c) TiO 2 2 XPS scanning spectrum of/CNF shows that the composite materialThe existence of Ti, C, O and F elements in the material, and (d) the Ti 2p has two main peaks at 459.2eV and 464.9eV, which respectively correspond to Ti-O (2 p 3/2) and Ti-O (2 p 1/2). This fact confirms the use of Ti 3 C 2 Tx to TiO 2 Complete phase transition of the phases.
Example 2
Step 1, preparing Ti 3 C 2 T x Material
Weighing 12mL of 40% HF aqueous solution in a polytetrafluoroethylene reaction kettle, and weighing Ti 3 AlC 2 1.0g of precursor, and stirring Ti at room temperature under the condition of magnetic stirring rotation speed of 200r/min 3 AlC 2 The precursor is slowly added with HF aqueous solution within 2.0min, the reaction kettle is sealed, and the stirring time lasts 24h. Deionized water is added into the obtained product, and centrifugal separation is carried out at the rotating speed of 3500rpm for 3min each time. At the final centrifugation, the supernatant had a pH around 7.0. The obtained product is dried in a vacuum drying oven at 60 ℃.
Step 2, preparing Ti 3 C 2 T x Nano-cellulose composite material
At room temperature, the Ti prepared in the step 1 is added 3 C 2 T x 0.2g of the mixture is weighed and evenly dispersed in 30mL of ethanol solution, 0.3g of carbon nano-cellulose is added, ultrasonic dispersion is carried out, and standing and aging are carried out for 12 hours. Finally, centrifugal washing is carried out for 3-5 times by distilled water and absolute ethyl alcohol respectively, and vacuum drying is carried out at 60 ℃.
Step 3, preparing TiO 2 /CNF composite material
Preparing Ti by the step 2 3 C 2 T x The/nanocellulose composite is transferred to a tube furnace in N 2 Calcination was carried out at 700 ℃ for 7h under a protective atmosphere of steam. Cooling to room temperature to obtain TiO 2 a/CNF composite material.
Example 3
Step 1, preparing Ti 3 C 2 T x Material
Weighing 15mL of 40% HF aqueous solution in a polytetrafluoroethylene reaction kettle, and weighing Ti 3 AlC 2 Precursor 2.0g, stirring Ti at room temperature under the condition of magnetic stirring speed of 300r/min 3 AlC 2 Slowly adding HF aqueous solution into the precursor within 3.0min, sealing the reaction kettle, and keeping the stirring time for 48h. Deionized water is added into the obtained product, and centrifugal separation is carried out at the rotating speed of 3500rpm for 3min each time. At the final centrifugation, the supernatant had a pH around 7.0. The obtained product is dried in a vacuum drying oven at 60 ℃.
Step 2, preparing Ti 3 C 2 T x Nano cellulose composite material
At room temperature, the Ti prepared in the step 1 is added 3 C 2 T x 0.3g of the solution is weighed and evenly dispersed in 40mL of ethanol solution, 0.3g of carbon nano-cellulose is added, ultrasonic dispersion is carried out, and standing and aging are carried out for 12 hours. Finally, centrifugal washing is carried out for 3-5 times by distilled water and absolute ethyl alcohol respectively, and vacuum drying is carried out at 60 ℃.
Step 3, preparing TiO 2 /CNF composite material
Preparing Ti by the step 2 3 C 2 T x The/nanocellulose composite is transferred to a tube furnace in N 2 The calcination was carried out at 800 ℃ for 6h under a stream-protecting atmosphere. Cooling to room temperature to obtain TiO 2 a/CNF composite material.
Example 4
Step 1, preparing Ti 3 C 2 T x Material
Weighing 12mL of 40% HF aqueous solution in a polytetrafluoroethylene reaction kettle, and weighing Ti 3 AlC 2 Precursor 3.0g, stirring Ti at room temperature under the condition of magnetic stirring speed of 300r/min 3 AlC 2 Slowly adding HF aqueous solution into the precursor within 3.0min, sealing the reaction kettle, and keeping the stirring time for 48h. Deionized water is added into the obtained product, and centrifugal separation is carried out at the rotating speed of 3500rpm for 3min each time. At the last centrifugation, the supernatant had a pH around 7.0. The obtained product is dried in a vacuum drying oven at 60 ℃.
Step 2, preparing Ti 3 C 2 T x Nano cellulose composite material
At room temperature, the Ti prepared in the step 1 is added 3 C 2 T x 0.2g was weighed, uniformly dispersed in 40mL of an ethanol solution, and 0 was added.3g of carbon nano-cellulose, performing ultrasonic dispersion, and standing and aging for 12 hours. Finally, centrifugal washing is carried out for 3-5 times by distilled water and absolute ethyl alcohol respectively, and vacuum drying is carried out at 60 ℃.
Step 3, preparing TiO 2 /CNF composite material
Preparing Ti by the step 2 3 C 2 T x The/nanocellulose composite is transferred to a tube furnace in N 2 The calcination was carried out for 8h at 600 ℃ under a stream-protecting atmosphere. Cooling to room temperature to obtain TiO 2 a/CNF composite material.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (5)

1. TiO (titanium dioxide) 2 The preparation method of the negative electrode material of the CNF battery is characterized in that carbon nano-cellulose is taken as a substrate, and layered TiO is loaded on the substrate 2 A hybrid; the layered TiO 2 The hybrid being a multilayer Ti 3 C 2 T x The material is prepared by taking a precursor as a raw material, and the preparation method specifically comprises the following steps:
s1, forming a plurality of layers of Ti 3 C 2 T x Dispersing the material in ethanol solution, adding carbon nano-cellulose, performing ultrasonic dispersion, aging, centrifugally washing, and vacuum drying to obtain Ti 3 C 2 T x A nanocellulose composite; the multilayer Ti 3 C 2 T x The weight ratio of the material to the carbon nano-cellulose is 1-3: 3; the multilayer Ti 3 C 2 T x The material is Ti 3 AlC 2 Is prepared by acid etching reaction of raw materials; the specific operation is as follows: under the condition of stirring, adding Ti 3 AlC 2 Adding into acid etching agent, sealing, stirring, reacting, centrifuging, washing, and vacuum drying to obtain multilayer Ti 3 C 2 T x A material; wherein the etchant is hydrofluoric acid water solubleLiquid;
s2, mixing Ti 3 C 2 T x Calcining the/nano-cellulose composite material in inert atmosphere, cooling, washing and drying to obtain TiO 2 a/CNF composite; the calcining temperature is 600-800 ℃, and the calcining time is 6-8 h; the temperature rising speed of the calcination is 1 to 3 ℃/min.
2. The TiO of claim 1 2 The preparation method of the negative electrode material of the CNF battery is characterized in that in S1, multiple layers of Ti are arranged 3 C 2 T x The weight-volume ratio g/mL of the material to the ethanol solution is 0.1-0.3: 20 to 40.
3. The TiO of claim 1 2 The preparation method of the negative electrode material of the CNF battery is characterized in that in S1, ultrasonic dispersion is carried out for 5-10 min, and standing and aging are carried out for 12-24 h.
4. The TiO of claim 1 2 The preparation method of the negative electrode material of the CNF battery is characterized in that Ti is added 3 AlC 2 Adding into acid etching agent, sealing and stirring for reaction, wherein the stirring speed is 100-300 rpm, and the reaction time is 24-72 h.
5. The TiO of claim 1 2 The preparation method of the negative electrode material of the CNF battery is characterized in that the etching agent is 40wt% hydrofluoric acid aqueous solution and Ti 3 AlC 2 And the weight volume ratio g/mL of the etching agent is 1.0-3.0: 10 to 15.
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