CN112736236B - Novel lithium ion battery anode material biomass carbon coated diphasic Li 4 Ti 5 O 12 -TiO 2 And applications thereof - Google Patents

Novel lithium ion battery anode material biomass carbon coated diphasic Li 4 Ti 5 O 12 -TiO 2 And applications thereof Download PDF

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CN112736236B
CN112736236B CN202110057349.9A CN202110057349A CN112736236B CN 112736236 B CN112736236 B CN 112736236B CN 202110057349 A CN202110057349 A CN 202110057349A CN 112736236 B CN112736236 B CN 112736236B
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lithium ion
biomass carbon
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anode material
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CN112736236A (en
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葛昊
田阳
尚婷婷
郭欣
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Liaoning University
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/36—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
    • 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 a novel lithium ion battery anode material biomass carbon coated double-phase Li 4 Ti 5 O 12 ‑TiO 2 And applications thereof. The invention uses the white wax tree wing peel and binary Li 4 Ti 5 O 12 ‑TiO 2 The micro-nano composite material composed of the compounds is applied to a lithium ion battery anode material, and on one hand, the two-phase Li is as follows 4 Ti 5 O 12 ‑TiO 2 The nano composite structure increases the grain boundary density of a large interface area, and on the other hand, the micron-sized carbonized wing peel has a macroporous structure, forms a network-shaped support for the product, not only can provide a conductive network, but also can reduce Li 4 Ti 5 O 12 、TiO 2 And (3) the agglomeration of the active sites of the reaction is increased, and the electronegativity of the material is improved, so that the electrochemical performance of the material is improved. The micro-nano composite material not only has a special structure, but also has the characteristics of a micrometer material and the special properties of a nanometer material.

Description

Novel lithium ion battery anode material biomass carbon coated diphasic Li 4 Ti 5 O 12 -TiO 2 And applications thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a biomass carbon coated double-phase Li 4 Ti 5 O 12 -TiO 2 A preparation method and application of the novel lithium ion battery cathode material.
Background
Rechargeable lithium ion batteries have a high energy density and a long cycle life and thus have been successfully used as power sources for portable electronic devices, and practical application storage of lithium ion batteries in electric vehicles and stationary electric energy depends largely on electrochemical properties of electrode materials, such as a large specific capacity,high rate capacity and good cycling stability. Graphite is commonly used as the negative electrode for commercial lithium ion batteries, but due to its low Li + Diffusion coefficient and serious safety issues show poor rate performance. Li (Li) 4 Ti 5 O 12 (LTO) is one of materials for replacing graphite as a negative electrode, li 4 Ti 5 O 12 Has a high theoretical specific capacity of 175mAh/g and Li 4 Ti 5 O 12 In Li + No significant volume change occurs during the intercalation/deintercalation of ions. In addition to LTO, tiO 2 Is also one of the negative electrode replacement materials of lithium ion batteries because of the rapid insertion/extraction of lithium during charge/discharge, the high insertion potential (2.0V) and the low volume change (3-4%) capability, and TiO 2 The theoretical capacity of (C) is as high as 336mAh/g. LTO and TiO, however 2 Have some disadvantages, such as LTO exhibiting low electron and ion conductivities and low rate capability, tiO 2 The diffusion rate is very low, thereby affecting the cycle performance and rate performance. LTO and TiO 2 Compounding has become an important and effective method of improving LTO electrode performance. LTO-TiO was synthesized by the molten salt method of Raman (Rahman) et al 2 Composite materials having high capacity and good rate capability. Wang et al synthetic rutile-capped two-phase LTO-TiO 2 The composite material has higher capacity than pure LTO at various rates.
Recently, researchers have reported and demonstrated that biomass carbon can also be used in lithium ion batteries. The biomass carbon material has the advantages of porous structure, large specific surface area, good conductivity, rich sources, environmental friendliness and the like, so that the biomass carbon material is widely focused by researchers, and the electrochemical performance of the biomass carbon material can be improved by adding the biomass carbon material into an electrode material as a high-conductivity material. Sun uses shaddock peel as biomass carbon of a lithium ion battery anode material, and the anode material shows higher specific capacity. In addition, many different types of leaves are also used as biomass carbon for electrode materials, such as maple leaves, ginkgo leaves, and the like. In summary, biomass carbon has been very popular for electrode materials. The biomass carbon is added into the electrode material to provide a three-dimensional network structure, which can be Li + Provides convenience and efficiencyChannels increase the specific surface area of the electrode material, increase the contact area with the electrolyte, and result in high lithium ion flux across the electrolyte/electrode interface. In a word, the work provides a simple, economical and efficient method for battery materials, and provides important application prospects for lithium ion battery cathodes.
Disclosure of Invention
The invention aims to provide a novel lithium ion battery anode material biomass carbon coated double-phase Li with good electrochemical performance 4 Ti 5 O 12 -TiO 2 Is prepared from the raw materials of the preparation method and application.
The technical scheme provided by the invention is that a novel lithium ion battery anode material biomass carbon coated diphasic Li 4 Ti 5 O 12 -TiO 2 The preparation method comprises the following steps: carbonizing wing peel and LiOH H 2 Dispersing O in deionized water in ultrasonic mode, namely, dispersing tetrabutyl titanate in absolute ethyl alcohol solution, adding tetrabutyl titanate into the absolute ethyl alcohol solution, fully stirring and mixing the absolute ethyl alcohol solution, transferring the absolute ethyl alcohol solution into a stainless steel reaction kettle, and carrying out hydrothermal treatment at 180 ℃ for 12-36h; collecting the precursor powder after the hydrothermal treatment, cross-washing with distilled water and ethanol to neutrality, vacuum drying at 80deg.C for 24-36h, placing in a tube furnace, calcining at 600-800deg.C for 1-3h under argon atmosphere, and grinding to obtain the target product biomass carbon-coated diphasic Li 4 Ti 5 O 12 -TiO 2 A composite material.
Furthermore, the novel lithium ion battery anode material biomass carbon coated double-phase Li 4 Ti 5 O 12 -TiO 2 The preparation method of the carbonized wing peel comprises the following steps: cleaning and drying the samara peel, grinding into powder, soaking in an activator solution, and magnetically stirring at 80 ℃ for 4 hours; filtering, vacuum drying at 80deg.C for 12 hr, placing in a tube furnace, calcining at 700-900deg.C for 1-3 hr under argon atmosphere, sequentially centrifuging with hydrochloric acid and distilled water, washing to neutrality, vacuum drying at 80deg.C for 12 hr, and grinding to obtain carbonized wing pericarp.
Further, the novel lithium ion battery anode material is biologicalCarbonaceous coated diphasic Li 4 Ti 5 O 12 -TiO 2 The activator solution is potassium hydroxide solution.
Furthermore, the novel lithium ion battery anode material biomass carbon coated double-phase Li 4 Ti 5 O 12 -TiO 2 The mass ratio of the samara peel to the potassium hydroxide=1:1-3.
Furthermore, the novel lithium ion battery anode material biomass carbon coated double-phase Li 4 Ti 5 O 12 -TiO 2 The calcination temperature was 800 ℃.
Furthermore, the novel lithium ion battery anode material biomass carbon coated double-phase Li 4 Ti 5 O 12 -TiO 2 The calcination temperature was 700 ℃.
Furthermore, the novel lithium ion battery anode material biomass carbon coated double-phase Li 4 Ti 5 O 12 -TiO 2 The samara skin is derived from fraxinus chinensis samara.
The biomass carbon coated diphasic Li provided by the invention 4 Ti 5 O 12 -TiO 2 As a negative electrode material in lithium ion batteries.
Further, the method comprises the following steps: uniformly stirring and coating a negative electrode material, a binder and a conductive agent on a copper foil to serve as a negative electrode of a lithium ion battery; the anode material is the biomass carbon coated double-phase Li 4 Ti 5 O 12 -TiO 2 。
The beneficial effects of the invention are as follows:
1. the material of the invention is easy to obtain, the micro-nano composite material is obtained by hydrothermal reaction in a reaction kettle, vacuum drying and high-temperature calcination, and the synthetic process condition is simple to operate, easy to control and easy to realize industrial production.
2. The invention takes the samara peel of the natural plant ash tree as a carbon source, the main components of the samara peel are cellulose, hemicellulose and lignin, the samara peel is carbonized into functional carbon through high-temperature pyrolysis, the carbonization process is relatively simple, and the samara peel has a unique micron-sized pore structure, so that the initial coulomb efficiency is higher. The fraxinus chinensis is widely distributed in various provinces in south and north China, and has the advantages of rich sources, environmental protection, sustainable regeneration and the like.
3. The invention uses the white wax tree wing peel and binary Li 4 Ti 5 O 12 -TiO 2 The micro-nano composite material composed of the compounds is applied to a lithium ion battery anode material, and on one hand, the two-phase Li is as follows 4 Ti 5 O 12 -TiO 2 The nano composite structure increases the grain boundary density of a large interface area, and on the other hand, the micron-sized carbonized wing peel has a macroporous structure, forms a network-shaped support for the product, not only can provide a conductive network, but also can reduce Li 4 Ti 5 O 12 -TiO 2 And (3) the agglomeration of the active sites of the reaction is increased, and the electronegativity of the material is improved, so that the electrochemical performance of the material is improved. The micro-nano composite material not only has a special structure, but also contains the characteristics of the micro-material and the special properties of the nano-material.
Drawings
FIG. 1 shows carbonized Chinese ash skin (a) and Li prepared by the present invention 4 Ti 5 O 12 -TiO 2 SEM image of composite (b).
Figure 2 is an XRD pattern of carbonized fraxinus mandshurica fruit peel prepared in accordance with the present invention.
FIG. 3 is Li prepared according to the present invention 4 Ti 5 O 12 -TiO 2 XRD pattern of the C composite.
FIG. 4 shows carbonized Chinese ash skin (a) and Li prepared by the present invention 4 Ti 5 O 12 -TiO 2 -raman plot of composite material (b).
Detailed Description
The invention is further explained below in connection with specific embodiments, but is not intended to limit the scope of the invention.
In order to improve the electrochemical performance of a lithium ion battery and find a suitable substitute of a negative electrode material lithium titanate, the invention provides a novel biomass carbon-coated double-phase Li of the negative electrode material of the lithium ion battery 4 Ti 5 O 12 -TiO 2 Is prepared from the raw materials of the preparation method and application. The technical proposal is as follows:
preparation of biomass porous carbon material-carbonized white wax tree wing pericarp
1) Dissolving potassium hydroxide in distilled water at room temperature to prepare potassium hydroxide solution;
preferably, the concentration of potassium hydroxide solution is 40-60mg/mL.
More preferably, the concentration of potassium hydroxide solution is 50mg/mL.
2) Cleaning and oven drying Chinese ash bark, grinding into powder, soaking in potassium hydroxide solution, and magnetically stirring at 80deg.C for 4 hr; filtering the processed ash tree wing skin powder, vacuum drying at 80 ℃ for 12 hours, placing in a tube furnace, calcining at 700-900 ℃ for 1-3 hours under argon atmosphere, sequentially using hydrochloric acid and distilled water for centrifugal washing, vacuum drying at 80 ℃ for 12 hours, and grinding to obtain the target product carbonized ash tree wing skin.
Preferably, the mass ratio of the white wax tree wing pericarp to the potassium hydroxide=1:1-3.
Preferably, the calcination temperature is 800 ℃ and the calcination time is 2 hours.
The potassium hydroxide solution is used as an activating agent, micropores and mesopores can be introduced into a carbon skeleton of the biomass porous carbon, the pore volume of the micropores and the mesopores is increased, the specific surface area is increased, and therefore performances in the aspects of energy storage and energy conversion are improved. K in the reaction process + Can be embedded into carbon lattice of carbon skeleton to expand the carbon lattice, and finally acid washing to remove K + And compounds thereof, thus forming a porous structure.
(II) Biomass carbon-coated diphasic Li 4 Ti 5 O 12 -TiO 2 Micro-nano composite material (Li) 4 Ti 5 O 12 -TiO 2 Preparation of-C)
1) Carbonizing the white wax tree wing peel and LiOH H at room temperature 2 Dispersing O in deionized water in ultrasonic mode, namely, dispersing tetrabutyl titanate in absolute ethyl alcohol solution, adding tetrabutyl titanate into the absolute ethyl alcohol solution, fully mixing, transferring the obtained mixture into a stainless steel reaction kettle, and carrying out hydrothermal treatment at 180 ℃ for 12-36h; centrifuging the precursor powder after the hydrothermal treatmentSeparating, collecting precipitate, cross-centrifuging with distilled water and ethanol, washing to neutrality, and vacuum drying at 80deg.C for 24-36 hr.
Preferably, the hydrothermal treatment temperature is 180 ℃ and the hydrothermal treatment time is 24 hours.
2) Placing the precursor powder obtained in the step 1) into a tube furnace, calcining for 1-3h at 600-800 ℃ in an argon atmosphere, and grinding to obtain a target product biomass carbon-coated dual-phase Li 4 Ti 5 O 12 -TiO 2 Micro-nano composite material, denoted as Li 4 Ti 5 O 12 -TiO 2 -C。
Preferably, the calcination temperature is 700 ℃ and the calcination time is 2 hours.
(III) lithium ion button cell
By Li 4 Ti 5 O 12 -TiO 2 And (3) taking the C composite material as a negative electrode material, adding a proper amount of conductive agent and binder, uniformly mixing to form paste, uniformly coating the paste on a copper foil to serve as a negative electrode, and taking a lithium sheet as a positive electrode to assemble the lithium ion battery.
Preferably, the conductive agent is acetylene black.
Preferably, the binder is PVDF.
Preferably, li is as follows 4 Ti 5 O 12 -TiO 2 -C composite material, acetylene black, PVDF= (6-8): (3-1): 1.
Example 1
Biomass carbon coated diphasic Li 4 Ti 5 O 12 -TiO 2 Micro-nano composite material (Li) 4 Ti 5 O 12 -TiO 2 -C) the preparation method is as follows:
1) Grinding dried white wax tree wing skin into powder, weighing 2.5g white wax tree wing skin powder, adding into 50mL potassium hydroxide solution with concentration of 50mg/mL for activation, and magnetically stirring at 80 ℃ for 4h. Filtering, and vacuum drying the activated ash bark powder at 80deg.C for 12 hr. Then placing the mixture in a tube furnace, calcining for 2 hours at 800 ℃ under argon atmosphere, sequentially centrifugally washing the obtained product to be neutral by hydrochloric acid and distilled water, vacuum drying for 12 hours at 80 ℃, and grinding to obtain the target product carbonized white wax tree wing pericarp.
2) Taking 0.04g and 0.168g of carbonized white wax tree wing skin obtained in the step 1) 2 Dispersing O in 30mL of deionized water by ultrasonic wave, namely a solution A, dispersing 1.7mL of tetrabutyl titanate in 25mL of absolute ethyl alcohol solution, namely a solution B, adding the solution A into the solution B, fully stirring and uniformly mixing, transferring to a stainless steel reaction kettle, and carrying out hydrothermal treatment at 180 ℃ for 24 hours; centrifugally separating the precursor powder after the hydrothermal treatment, collecting precipitate, washing to neutrality by intersecting and centrifugally washing with distilled water and ethanol, vacuum drying at 80 ℃ for 24 hours, finally placing in a tube furnace, calcining at 700 ℃ for 2 hours under argon atmosphere, and grinding to obtain a target product Li 4 Ti 5 O 12 -TiO 2 -C composite material.
(II) characterization of materials
FIG. 1 shows carbonized Chinese ash skin (a) and Li prepared by the present invention 4 Ti 5 O 12 -TiO 2 SEM image of composite (b). As can be seen from FIG. 1 a, the carbonized Chinese ash skin material prepared by the invention has a macroporous structure of 1-2 μm. As can be seen from FIG. 1 b, li prepared according to the present invention 4 Ti 5 O 12 -TiO 2 the-C composite material presents a micro-nano composite structure, and nano-scale Li 4 Ti 5 O 12 -TiO 2 The biphasic compound is inlaid on the macroporous structure of the micron-sized biomass carbon. In addition, a large number of gaps can be seen in the product, and due to the porous structure of the biomass, a network-like support is formed for the product, so that not only a conductive network can be provided, but also Li can be reduced 4 Ti 5 O 12 、TiO 2 Is not limited, and is not limited.
Fig. 2 is an XRD pattern of the prepared carbonized fraxinus chinensis wing pericarp, and it can be seen from fig. 2 that there is a distinct graphite type carbon characteristic peak at 2θ=26°.
FIG. 3 is Li produced 4 Ti 5 O 12 -TiO 2 XRD pattern of the C composite. As can be clearly seen from the figure, the composite material prepared has spinel type Li 4 Ti 5 O 12 Characteristic peaks and rutile TiO of (2) 2 Is characterized by lower biochar content and weaker diffractionThe shot intensity results in no significant biochar diffraction peaks in the XRD pattern of the composite. In addition, li 4 Ti 5 O 12 Diffraction peaks and TiO of (2) 2 Is strong and sharp, indicating that Li is prepared 4 Ti 5 O 12 -TiO 2 The C composite material has very high crystallinity, and the addition of biochar does not affect Li 4 Ti 5 O 12 And TiO 2 Is a structure of (a).
FIG. 4 shows carbonized Chinese ash skin (a) and Li prepared by the present invention 4 Ti 5 O 12 -TiO 2 -raman plot of composite material (b). As can be seen from FIG. 4, li prepared by the present invention 4 Ti 5 O 12 -TiO 2 -C composite at 1345cm -1 、1588cm -1 The presence of D and G peaks demonstrates the presence of carbon in the composite, the ratio r=i of the peak intensities of the D and G bands D /I G Is an important index reflecting the graphitization degree of the carbon layer. The smaller the R value, the higher the graphitization degree of the carbon layer and the higher the ordering degree of the carbon layer. Li prepared by the invention 4 Ti 5 O 12 -TiO 2 The R value of the-C composite is about 0.9, which indicates Li 4 Ti 5 O 12 -TiO 2 The carbon layer in the-C composite material has higher graphitization degree, and the structure is beneficial to improving the conductivity of the material.
Description of the products prepared according to the present invention with reference to FIGS. 1, 2, 3 and 4 are Li 4 Ti 5 O 12 、TiO 2 And biochar complexes.
Example 2
Biomass carbon coated diphasic Li 4 Ti 5 O 12 -TiO 2 Micro-nano composite material (Li) 4 Ti 5 O 12 -TiO 2 -C) the preparation method is as follows:
1) Grinding dried white wax tree wing skin into powder, weighing 2.5g white wax tree wing skin powder, adding into 50mL potassium hydroxide solution with concentration of 50mg/mL for activation, and magnetically stirring at 80 ℃ for 4h. Filtering, and vacuum drying the activated ash bark powder at 80deg.C for 12 hr. Then placing the mixture in a tube furnace, calcining for 2 hours at 800 ℃ under argon atmosphere, sequentially centrifugally washing the obtained product to be neutral by hydrochloric acid and distilled water, vacuum drying for 12 hours at 80 ℃, and grinding to obtain the target product carbonized white wax tree wing pericarp.
2) Taking 0.05g and 0.168g of carbonized white wax tree wing skin obtained in the step 1) 2 Dispersing O in 30mL of deionized water by ultrasonic wave, namely a solution A, dispersing 1.7mL of tetrabutyl titanate in 25mL of absolute ethyl alcohol solution, namely a solution B, adding the solution A into the solution B, fully stirring and uniformly mixing, transferring to a stainless steel reaction kettle, and carrying out hydrothermal treatment at 180 ℃ for 24 hours; centrifugally separating the precursor powder after the hydrothermal treatment, collecting precipitate, washing to neutrality by intersecting and centrifugally washing with distilled water and ethanol, vacuum drying at 80 ℃ for 24 hours, finally placing in a tube furnace, calcining at 700 ℃ for 2 hours under argon atmosphere, and grinding to obtain a target product Li 4 Ti 5 O 12 -TiO 2 -C composite material.
Example 3
Biomass carbon coated diphasic Li 4 Ti 5 O 12 -TiO 2 Micro-nano composite material (Li) 4 Ti 5 O 12 -TiO 2 -C) the preparation method is as follows:
1) Grinding dried white wax tree wing skin into powder, weighing 2.5g white wax tree wing skin powder, adding into 50mL potassium hydroxide solution with concentration of 50mg/mL for activation, and magnetically stirring at 80 ℃ for 4h. Filtering, and vacuum drying the activated ash bark powder at 80deg.C for 12 hr. Then placing the mixture in a tube furnace, calcining for 2 hours at 800 ℃ under argon atmosphere, sequentially centrifugally washing the obtained product to be neutral by hydrochloric acid and distilled water, vacuum drying for 12 hours at 80 ℃, and grinding to obtain the target product carbonized white wax tree wing pericarp.
2) Taking 0.06g and 0.168g of the carbonized white wax tree wing skin obtained in the step 1) 2 Dispersing O in 30mL of deionized water by ultrasonic wave, namely a solution A, dispersing 1.7mL of tetrabutyl titanate in 25mL of absolute ethyl alcohol solution, namely a solution B, adding the solution A into the solution B, fully stirring and uniformly mixing, transferring to a stainless steel reaction kettle, and carrying out hydrothermal treatment at 180 ℃ for 24 hours; centrifugally separating the precursor powder after the hydrothermal treatment,collecting precipitate, cross centrifuging with distilled water and ethanol, washing to neutrality, vacuum drying at 80deg.C for 24 hr, placing in a tube furnace, calcining at 700deg.C under argon atmosphere for 2 hr, and grinding to obtain target product Li 4 Ti 5 O 12 -TiO 2 -C composite material.
Example 4
Biomass carbon coated diphasic Li 4 Ti 5 O 12 -TiO 2 Application of the material as negative electrode material in lithium ion battery
The method for assembling the lithium ion battery comprises the following steps: li prepared in examples 1, 2 and 3 respectively using commercially available common acetylene black as a conductive material and PVDF as a binder 4 Ti 5 O 12 -TiO 2 -C as negative electrode material, li in mass ratio 4 Ti 5 O 12 -TiO 2 Mixing acetylene black and PVDF=8:1:1, uniformly coating the mixture on copper foil to serve as a negative electrode, and respectively assembling the positive electrode and the negative electrode into the button cell by using lithium sheets.
Electrochemical performance test:
in the form of commercially available Li 4 Ti 5 O 12 The material was used as a battery negative electrode material, a lithium sheet was used as a counter electrode, a button battery was assembled, and electrochemical performance was tested as a comparative example, and the results are shown in table 1.
TABLE 1 comparison of electrochemical properties of batteries prepared from different negative electrode materials (charge-discharge Rate 1C)
As can be seen from Table 1, compared with ordinary Li 4 Ti 5 O 12 Negative electrode material, li synthesized by the method of the invention 4 Ti 5 O 12 -TiO 2 the-C composite has better electrochemical properties. With the increase of biomass carbon quality, the electrochemical performance of the composite material synthesized by the method is firstly increased and then weakened, and the electrochemical performance of the composite material obtained by calcining the biomass carbon added with 0.05g in example 2 can be seen to be clearIs significantly higher than the composites of example 1 and example 3. And the raw materials adopt natural white wax tree wing peel, so that the method is environment-friendly and easy to obtain. Li synthesized by the method of the invention 4 Ti 5 O 12 -TiO 2 The C composite material shows good cycle stability during 100 charge and discharge cycles. On the one hand, the diphase Li under the premise of keeping the excellent properties of LTO 4 Ti 5 O 12 -TiO 2 The nano composite structure increases the grain boundary density of a large interface area, and on the other hand, the micron-sized carbonized wing peel has a macroporous structure, forms a network-shaped support for the product, not only can provide a conductive network, but also can reduce Li 4 Ti 5 O 12 、TiO 2 And (3) the agglomeration of the active sites of the reaction is increased, and the electronegativity of the material is improved, so that the electrochemical performance of the material is improved. The invention adopts an extremely simple hydrothermal method for one-step synthesis, which is beneficial to realizing the commercialization of the LTO anode material.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (5)

1. Novel lithium ion battery anode material biomass carbon coated diphasic Li 4 Ti 5 O 12 -TiO 2 The preparation method is characterized by comprising the following steps: carbonizing wing peel and LiOH H 2 Dispersing O in deionized water in ultrasonic mode, namely, dispersing tetrabutyl titanate in absolute ethyl alcohol solution, adding tetrabutyl titanate into the absolute ethyl alcohol solution, fully stirring and mixing, transferring the obtained mixture into a stainless steel reaction kettle, and carrying out hydrothermal treatment at 180 ℃ for 12-36h; collecting the precursor powder after the hydrothermal treatment, cross-washing with distilled water and ethanol to neutrality, vacuum drying at 80deg.C for 24-36h, placing in a tube furnace, calcining at 700deg.C for 1-3h under argon atmosphere, and grinding to obtain the target product biomass carbon-coated diphasic Li 4 Ti 5 O 12 -TiO 2 A composite material;
the preparation method of the carbonized wing peel comprises the following steps: cleaning and drying the samara peel, grinding into powder, soaking in an activator solution, and magnetically stirring at 80 ℃ for 4h; filtering, vacuum drying at 80deg.C for 12h, calcining at 800deg.C for 1-3h in a tube furnace under argon atmosphere, sequentially centrifuging with hydrochloric acid and distilled water, drying at 80deg.C for 12h, and grinding to obtain carbonized wing pericarp; the samara skin is derived from fraxinus chinensis samara.
2. The novel lithium ion battery anode material biomass carbon-coated dual-phase Li of claim 1 4 Ti 5 O 12 -TiO 2 The method is characterized in that the activator solution is potassium hydroxide solution.
3. The novel lithium ion battery anode material biomass carbon-coated dual-phase Li of claim 1 4 Ti 5 O 12 -TiO 2 The preparation method is characterized in that the mass ratio of the samara peel to the potassium hydroxide=1:1-3.
4. A biomass carbon-coated dual-phase Li prepared according to the method of any one of claims 1-3 4 Ti 5 O 12 -TiO 2 As a negative electrode material in lithium ion batteries.
5. The use according to claim 4, characterized in that the method is as follows: uniformly stirring and coating a negative electrode material, a binder and a conductive agent on a copper foil to serve as a negative electrode of a lithium ion battery; the anode material is the biomass carbon coated diphasic Li according to any one of claims 1-3 4 Ti 5 O 12 -TiO 2 。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102324511A (en) * 2011-10-09 2012-01-18 北京科技大学 Preparation method for lithium ion battery composite cathode material
CN104638255A (en) * 2015-02-02 2015-05-20 斌源材料科技（上海）有限公司 Lithium titanate/carbon composite material and method for preparing material
CN106816593A (en) * 2017-03-03 2017-06-09 辽宁大学 A kind of lithium ion battery negative material Li4Ti5O12/TiO2Nano-chip arrays and its preparation method and application
CN106848251A (en) * 2017-03-15 2017-06-13 北京朗盛特耐科技有限公司 A kind of preparation method of CNT lithium titanate composite anode material
CN111268677A (en) * 2020-01-20 2020-06-12 辽宁大学 Preparation method and application of novel lithium ion battery negative electrode material carbonized grape seed

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102324511A (en) * 2011-10-09 2012-01-18 北京科技大学 Preparation method for lithium ion battery composite cathode material
CN104638255A (en) * 2015-02-02 2015-05-20 斌源材料科技（上海）有限公司 Lithium titanate/carbon composite material and method for preparing material
CN106816593A (en) * 2017-03-03 2017-06-09 辽宁大学 A kind of lithium ion battery negative material Li4Ti5O12/TiO2Nano-chip arrays and its preparation method and application
CN106848251A (en) * 2017-03-15 2017-06-13 北京朗盛特耐科技有限公司 A kind of preparation method of CNT lithium titanate composite anode material
CN111268677A (en) * 2020-01-20 2020-06-12 辽宁大学 Preparation method and application of novel lithium ion battery negative electrode material carbonized grape seed

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