CN109301209B - Preparation method of titanium dioxide modified phosphorus/carbon composite negative electrode material - Google Patents

Preparation method of titanium dioxide modified phosphorus/carbon composite negative electrode material Download PDF

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CN109301209B
CN109301209B CN201811134108.4A CN201811134108A CN109301209B CN 109301209 B CN109301209 B CN 109301209B CN 201811134108 A CN201811134108 A CN 201811134108A CN 109301209 B CN109301209 B CN 109301209B
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titanium dioxide
phosphorus
negative electrode
carbon composite
electrode material
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CN109301209A (en
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陶华超
张育坤
李金航
杨学林
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China Three Gorges University CTGU
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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
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • 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 preparation method of a titanium dioxide modified phosphorus/carbon composite negative electrode material, and belongs to the field of electrochemistry and new energy materials. The method directly and uniformly mixes red phosphorus, anthracite and nano titanium dioxide, and places the mixture into a high-energy ball milling tank filled with inert atmosphere for mechanical ball milling to obtain the titanium dioxide modified phosphorus/carbon composite material. The anthracite has low price and is suitable for low-cost large-scale production. The titanium dioxide modified phosphorus/carbon composite material prepared by the method is used as a negative electrode of a sodium ion battery, shows higher reversible specific capacity and good cycling stability, and has a certain application prospect when being used as a negative electrode material of the sodium ion battery.

Description

Preparation method of titanium dioxide modified phosphorus/carbon composite negative electrode material
Technical Field
The invention discloses a titanium dioxide modified phosphorus/carbon composite negative electrode material and a preparation method thereof, belonging to the field of electrochemistry and new energy materials.
Technical Field
The electrochemical energy storage technology is a key component of a future renewable energy source-friendly power grid, and has high energy efficiency, stability and adaptability. Due to the significant cost advantage and abundance of sodium resources, sodium ion batteries are likely to compete with widely used lithium ion batteries and change the landscape for electrochemical energy storage. Sodium and lithium are elements of the same main group and have similar physicochemical properties, and sodium-ion batteries have a similar working principle as lithium-ion batteries. Due to similar intercalation chemistry as LIB, including NaxNiO2，Na2/3Fe1/2Mn1/2O2，Na3V2（PO4）3And Na3V2（PO4）2F3Various cathode materials have been developed by simulating the counterparts in LIBs and show better electrochemical performance. The challenge of developing sodium ion anodes is great, particularly in developing new anode materials with high specific capacity and long-term cycling stability. Based on this, research and development of sodium ion batteries are slow to some extentSolving the problem of limited battery development caused by insufficient lithium resources. The main problem hindering the practicability of the sodium ion battery at present is that no electrode material with excellent performance, safety and stability exists, and once the research is successful, the sodium ion battery has larger market competitive advantage than the lithium ion battery in the large-scale energy storage field.
Phosphorus (P) due to its low cost and high theoretical capacity (2595 mAh g)-1) Has potential use value. However, due to the inherently low conductivity (≈ 10)-14 S cm-1) And has a large volume change (. apprxeq.300%), insufficient cycling stability and poor rate performance. Previous reports indicate that forming P-based compounds by alloying P with other conductive materials is an effective strategy to improve conductivity and buffer volume effects. These conductive materials are typically electrochemically inert components such as Fe and Ni, resulting in a lower utilization of the electrode. In addition, most of the reported P-based materials have low practical ability, fast capacity fading, and poor cycle stability due to large reaction irreversibility caused by aggregation and pulverization, so that the composition of red phosphorus with a carbon material has been studied more to improve the stability. Common methods are ball milling and steam adsorption. For example, Kim and the like utilize a ball milling method to prepare an amorphous red phosphorus/carbon black composite material which is used for a sodium ion battery cathode for the first time. (Kim Y, Park Y, Choi A, Choi N S, Kim J, Lee J, Ryu J H, OhS M, Lee K T. Advanced Materials, 2013, 25 (22): 3045.) Wang and the like directly and separately place porous carbon and red phosphorus in a container, heat the container to 450 ℃ and preserve heat for 3 hours to successfully prepare the red phosphorus-porous carbon composite material for the first time, and fill the blank of the electrode material of the red phosphorus-based secondary battery. (Wang L, He X, Li J, Sun W, Gao J, Guo J, Jiang C. Angewandte Chemie International Edition, 2012, 51 (36): 9034.).
Disclosure of Invention
The invention aims to provide a preparation method of a titanium dioxide modified phosphorus/carbon composite negative electrode material. The invention utilizes cheap anthracite as a carbon source, red phosphorus as a phosphorus source and titanium dioxide as an intermediate layer to modify the aggregation and expansion of the phosphorus-based material. Anthracite as one new kind of carbon material contains both soft carbon and small amount of hard carbon, and compared with single carbon source, it has raised specific capacity and improved conductivity. Compared with the existing carbon material, the anthracite greatly reduces the production cost and is suitable for large-scale commercial production.
The method comprises the steps of uniformly mixing red phosphorus, anthracite and titanium dioxide, and placing the mixture into a ball milling tank filled with inert atmosphere for ball milling to finally form the titanium dioxide modified phosphorus/carbon composite negative electrode material. The preparation process comprises the following steps:
(1) uniformly mixing red phosphorus, anthracite and titanium dioxide, wherein the mass ratio of the red phosphorus to the anthracite is 0.4-3: 1. The titanium dioxide accounts for 5 to 20 percent of the total mass fraction of the phosphorus-carbon composite material.
(2) And (3) placing the mixture of the red phosphorus, the anthracite and the titanium dioxide in a ball milling tank filled with inert gas for ball milling, wherein the ball milling rotation speed is 400-1200 rpm, and the ball milling time is 4-48 h.
The prepared titanium dioxide modified phosphorus/carbon composite negative electrode material is of a granular structure, and the diameter of the titanium dioxide modified phosphorus/carbon composite negative electrode material is 0.1-1 micron.
The titanium dioxide modified phosphorus/carbon composite negative electrode material provided by the invention has the following beneficial effects:
(1) the method adopts a P-O chemical bond to fix simple substance phosphorus.
(2) The titanium dioxide modified phosphorus/carbon composite material prepared by the method has better cycle performance when used as a cathode of a sodium ion battery.
(3) The titanium dioxide modified phosphorus/carbon composite material prepared by the method has higher reversible specific capacity when being used as a cathode of a sodium ion battery;
(4) the preparation process is simple and easy for industrial production.
According to the technical scheme, the high-activity nano titanium dioxide can react with phosphorus to form a P-O bond in the high-energy ball milling process, and the elemental phosphorus is fixed by adopting the P-O chemical bond, so that the volume effect of the phosphorus in the charging and discharging processes is relieved, and the circulation stability of the phosphorus is kept. Meanwhile, the anthracite contains soft carbon and hard carbon, and the two-phase carbon source improves the specific capacity and the conductivity of the whole electrode. The anthracite has low price and is suitable for low-cost large-scale production.
Titanium dioxide and phosphorus can form a P-O chemical bond in the high-energy ball milling process, and elemental phosphorus is fixed in a P-O chemical bond mode, so that the stability of phosphorus in the circulating process is improved.
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of the titanium dioxide modified phosphorus/carbon anode material prepared in example 1 of the present invention.
Fig. 2 is Scanning Electron Microscope (SEM) photographs at different magnifications of the titanium dioxide modified phosphorus/carbon negative electrode material prepared in example 1 of the present invention, wherein a is a drawing at a magnification of 1000, b is a drawing at a magnification of 2000, c is a drawing at a magnification of 5000, and d is a drawing at a magnification of 10000.
Fig. 3 is a high resolution P2P X-ray photoelectron spectroscopy (XPS) of the titanium dioxide modified phosphorus/carbon anode material prepared in example 1 of the present invention.
Fig. 4 is a first 3 times charge and discharge curve of the titanium dioxide modified phosphorus/carbon negative electrode material prepared in example 1 of the present invention as a negative electrode material of a sodium ion battery.
Fig. 5 shows the cycle stability performance of the titanium dioxide modified phosphorus/carbon anode material prepared in example 1 of the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1: titanium dioxide modified phosphorus/carbon composite negative electrode material I
Anthracite tailings (0.4 g), red phosphorus (0.6 g) and titanium dioxide (0.1 g) are subjected to ball milling for 20 hours at the rotating speed of 1200 rpm, and after the materials are cooled and sieved, the negative electrode material of the titanium dioxide modified phosphorus/carbon sodium ion battery is obtained, and fig. 1 is an XRD (X-ray diffraction) spectrum of the prepared titanium dioxide modified phosphorus/carbon composite negative electrode material. The atlas shows that the prepared titanium dioxide modified phosphorus/carbon negative electrode material is an amorphous material, and the main peak is still the diffraction peak of P. Fig. 2 is an SEM photograph of the prepared titanium dioxide-modified phosphorus/carbon composite anode material, and it can be seen that the material has a granular structure with a diameter of about 0.1 to 1 μm. FIG. 3 is a high resolution XPS P2P spectrum of the prepared titanium dioxide modified phosphorus/carbon composite anode material, and after the peak fitting of the original data, it can be seen that 12 is the peak value9.4 eV and 130.1 eV correspond to P2P for elemental phosphorus, respectively3/2And P2P1/2This corresponds to a P-O bond at 133.0 eV, indicating the presence of a stronger P-O bond in the composite. The P-O bond can fix the simple substance phosphorus, avoid the fragmentation and the falling off in the circulating process and keep the structural integrity of the electrode.
Mixing the titanium dioxide modified phosphorus/carbon composite negative electrode material prepared by the method with conductive agent carbon black and binder polyvinylidene fluoride (dissolved in nitrogen methyl pyrrolidone) according to the mass ratio of 8: 1: and 1, smearing, and drying the smeared electrode in vacuum to serve as a working electrode. The sodium sheet is a counter electrode, and the electrolyte is general sodium ion battery electrolyte 1M NaClO4Dissolving in DMC EC EMC =1:1:1 electrolyte to prepare 2025 type button cell, and adding 100 mA g-1The current density of charge and discharge, the charge and discharge curve of the previous 3 times is shown in FIG. 4. As can be seen, the first discharge capacity of the material is 1125 mAh g-1And under the condition that the test voltage is 0-2.5V, the first reversible charging capacity is 941 mAh g-1The first coulombic efficiency reaches up to 83.7 percent, and the reversible capacities of the second time and the third time are 940 mAh g and 937 mAh g respectively-1. FIG. 5 shows that the titanium dioxide modified phosphorus/carbon composite negative electrode material is at 100 mA g-1The cycle performance under the current density shows that the reversible charge capacity of the titanium dioxide modified phosphorus/carbon composite negative electrode material is still 821 mAh g after 80 cycles-1。
Example 2: titanium dioxide modified phosphorus/carbon composite negative electrode material II
Anthracite (0.4 g), red phosphorus (0.6 g) and titanium dioxide (0.1 g) are subjected to ball milling for 12 hours at the rotating speed of 800 rpm, and after the materials are cooled and screened, the negative electrode material of the titanium dioxide modified phosphorus/carbon sodium ion battery is obtained. The electrode material was tested under the conditions described in example 1, using titanium dioxide modified phosphorus/carbon as the negative electrode material for sodium ion batteries at 100 mA g-1The current density is charged and discharged, and the first reversible capacity is 810 mAh g under the condition that the test voltage is 0-2.5V-1The first coulombic efficiency is 78.5%, and the reversible capacity after 80 cycles is 620 mAh g-1。
Example 3: titanium dioxide modified phosphorus/carbon composite negative electrode material III
And (3) performing ball milling on anthracite tailings (0.4 g), red phosphorus (0.6 g) and titanium dioxide (0.1 g) for 8 hours at the rotating speed of 600 rpm, and cooling and screening the materials to obtain the titanium dioxide modified phosphorus/carbon sodium ion battery cathode material. The electrode material was tested under the conditions described in example 1, using titanium dioxide modified phosphorus/carbon as the negative electrode material for sodium ion batteries at 100 mA g-1Charging and discharging at current density, and first reversible capacity of 786 mAh g under test voltage of 0-2.5V-1The first coulombic efficiency is 75.6 percent, and the reversible capacity after 80 cycles is 574 mAh g-1。
Example 4: titanium dioxide modified phosphorus/carbon composite anode material IV
And (3) performing ball milling on anthracite tailings (0.4 g), red phosphorus (0.6 g) and titanium dioxide (0.1 g) for 4 hours at the rotating speed of 400 rpm, and cooling and screening the materials to obtain the titanium dioxide modified phosphorus/carbon sodium ion battery cathode material. The electrode material was tested under the conditions described in example 1, using titanium dioxide modified phosphorus/carbon as the negative electrode material for sodium ion batteries at 100 mA g-1Charging and discharging at current density, and first reversible capacity of 695 mAh g under test voltage of 0-2.5V-1The first coulombic efficiency is 64.3 percent, and the reversible capacity after 80 cycles is 352 mAh g-1。

Claims (1)

1. A preparation method of a titanium dioxide modified phosphorus/carbon composite negative electrode material is characterized by comprising the following steps: uniformly mixing red phosphorus, anthracite and titanium dioxide, then placing the mixture into a ball milling tank filled with inert argon atmosphere, and mechanically milling for 4-48 h at the rotating speed of 1200 rpm to obtain a titanium dioxide modified phosphorus/carbon composite negative electrode material; the mass ratio of the red phosphorus to the anthracite tailing is 0.4-3:1, the titanium dioxide accounts for 5 to 20 percent of the total mass fraction of the phosphorus-carbon composite material.
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CN110400702A (en) * 2019-04-15 2019-11-01 南京工业大学 The composite material of a kind of extra small titanium dioxide granule and carbon and its application
CN110534712A (en) * 2019-07-26 2019-12-03 华南理工大学 A kind of black phosphorus-titanium dioxide-carbon compound cathode materials and preparation method and application
CN110838580B (en) * 2019-11-20 2023-03-31 长沙理工大学 Titanium dioxide ultrathin carbon bubble confinement high-load red phosphorus composite electrode material and preparation method thereof
CN111203247A (en) * 2020-02-24 2020-05-29 青岛旭晟东阳新材料有限公司 Red phosphorus-based semiconductor antibacterial photocatalyst and preparation method thereof
CN113937271A (en) * 2021-10-14 2022-01-14 宁波亿纬创能锂电池有限公司 Negative electrode material and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103337611A (en) * 2013-07-10 2013-10-02 厦门大学 Preparation method of graphene-titanium dioxide composite material
EP2715843A1 (en) * 2011-06-01 2014-04-09 Westfälische Wilhelms Universität Electrode material for lithium and lithium ion batteries
CN103825002A (en) * 2014-01-29 2014-05-28 浙江工业大学 Composite material using titanium dioxide as skeleton structure to clad phosphorus and application of composite material
CN106299292A (en) * 2016-09-12 2017-01-04 三峡大学 A kind of phosphorus/carbon compound cathode materials and preparation method thereof
CN106960965A (en) * 2017-03-07 2017-07-18 上海电力学院 A kind of preparation method of the different structural material supported precious metal nano-particle processed of black phosphorus titanium dioxide

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106025194B (en) * 2016-05-12 2019-04-02 安泰科技股份有限公司 A kind of black phosphorus base composite negative pole material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2715843A1 (en) * 2011-06-01 2014-04-09 Westfälische Wilhelms Universität Electrode material for lithium and lithium ion batteries
CN103337611A (en) * 2013-07-10 2013-10-02 厦门大学 Preparation method of graphene-titanium dioxide composite material
CN103825002A (en) * 2014-01-29 2014-05-28 浙江工业大学 Composite material using titanium dioxide as skeleton structure to clad phosphorus and application of composite material
CN106299292A (en) * 2016-09-12 2017-01-04 三峡大学 A kind of phosphorus/carbon compound cathode materials and preparation method thereof
CN106960965A (en) * 2017-03-07 2017-07-18 上海电力学院 A kind of preparation method of the different structural material supported precious metal nano-particle processed of black phosphorus titanium dioxide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
过渡金属氧化物负极材料及其储锂性能研究;肖涵;《中国博士学位论文全文数据库工程科技Ⅱ辑》;20160330;第52-62页 *

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