CN110534712A - A kind of black phosphorus-titanium dioxide-carbon compound cathode materials and preparation method and application - Google Patents

A kind of black phosphorus-titanium dioxide-carbon compound cathode materials and preparation method and application Download PDF

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Publication number
CN110534712A
CN110534712A CN201910683633.XA CN201910683633A CN110534712A CN 110534712 A CN110534712 A CN 110534712A CN 201910683633 A CN201910683633 A CN 201910683633A CN 110534712 A CN110534712 A CN 110534712A
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black phosphorus
ball
titanium dioxide
cathode materials
carbon compound
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欧阳柳章
周峰晨
刘军
胡仁宗
杨黎春
朱敏
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South China University of Technology SCUT
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South China University of Technology SCUT
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a kind of black phosphorus-titanium dioxide-carbon compound cathode materials and preparation method and application, the preparation under inert gas shielding atmosphere the following steps are included: carrying out ball-milling reaction for red phosphorus, obtaining nanoscale black phosphorus;Under inert gas shielding atmosphere, black phosphorus, titanium dioxide, carbon material are mixed, mixture is obtained, by mixture ball milling, obtains black phosphorus-titanium dioxide-carbon compound cathode materials.Carbon and black phosphorus are linked by C-P key, ensure that the close contact of black phosphorus and carbon material in charge and discharge process, alleviate volume change in black phosphorus process of intercalation.There are Ti-O-P key between titanium dioxide and black phosphorus, the utilization rate of active material black phosphorus can be effectively promoted, and promote the electron transfer rate of interface.Black phosphorus-titanium dioxide-carbon compound cathode materials prepared by the present invention show excellent cycle performance, higher reversible capacity as lithium ion battery negative material.

Description

A kind of black phosphorus-titanium dioxide-carbon compound cathode materials and preparation method and application
Technical field
The present invention relates to a kind of battery materials that can be used for preparing lithium ion battery, and in particular to a kind of black phosphorus-titanium dioxide Titanium-carbon compound cathode materials and the preparation method and application thereof.
Background technique
Lithium ion battery (LIB) is to develop more mature rechargeable battery at present, it not only has, and specific capacity is high, recycles The features such as service life length, memory-less effect, low self-discharge rate, and pollution is small, meets environmental requirement, can be widely used in electronic vapour The fields such as vehicle, aerospace, biomedical engineering.With the rapid development of science and technology worldwide, lithium ion battery The progress of technology has been unable to meet ever-increasing emerging energy application demand, usually requires that higher power/energy density With the longer service life, especially in power source market and power grid energy storage market.Therefore, there is height ratio capacity, length to follow The electrode material of ring service life and low cost plays a crucial role in energy storage market.
The theoretical capacity (372mAh/g) low compared to traditional commercial graphite cathode, elemental phosphorous theoretical lithium storage content is only Inferior to silicon, about 2596mAh/g, the great interest of researcher is caused.Black phosphorus is that a kind of most stable of phosphorus is same under normal temperature and pressure Plain obform body.Compared to red phosphorus (10-12S/m), electronic conductivity is up to 102S/m;Secondly have and layer as graphite-like Shape structure, interlayer are combined by Van der Waals force, can remove into the nanometer sheet of single layer or few layer.Its interlamellar spacing is 5.4 (big In the interlamellar spacing 3.4 of graphite), it is much larger than the ionic radius of lithium ion (1.52), is conducive to Li+In the migration of its interlayer, So as to realize high-multiplying power discharge specific capacity.However there are following two critical issues for phosphate material: (1) electron conduction of phosphorus Difference causes electrochemical redox reaction to be difficult to carry out;(2) volume expansion of phosphorus is larger (> 300%), causes phosphorus and conductive base The continuous broken growth of the contact variation, granule atomization and solid electrolyte film (SEI) of body.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art, the purpose of the present invention is to provide a kind of with high reversible capacity Black phosphorus-titanium dioxide-carbon compound cathode materials and the preparation method and application thereof.The preparation method passes through solid-phase ball milling technique, benefit With red phosphorus, TiO2, carbon as raw material, prepared using two step ball millings, preparation condition is mild, and simple process has scale application Use prospect.
An object of the present invention in black phosphorus by adding carbon, for improving the electric conductivity of electrode material.Secondly, carbon and Black phosphorus is linked by C-P key, ensure that the close contact of black phosphorus and carbon material in charge and discharge process, is alleviated in black phosphorus process of intercalation Volume change.
Another object of the present invention is to improve the electronics and ionic conductivity of material by introducing titanium dioxide, is promoted Electrode reaction dynamics, releasable material stress.Secondly, there are Ti-O-P keys between titanium dioxide and black phosphorus, can effectively be promoted The utilization rate of active material black phosphorus, and promote the electron transfer rate of interface.
The purpose of the present invention is realized at least by one of following technical scheme.
The present invention provides a kind of black phosphorus-titanium dioxide-carbon compound cathode materials preparation methods, comprising the following steps:
(1) it prepares black phosphorus: under inert gas shielding atmosphere, red phosphorus being added in ball grinder with ball milling pearl and is sealed, is then carried out Ball-milling reaction obtains nanoscale black phosphorus;
(2) black phosphorus-titanium dioxide-carbon compound cathode materials are prepared: under inert gas shielding atmosphere, by black phosphorus, titanium dioxide, Carbon material mixing, obtains mixture, by mixture ball milling, obtains black phosphorus-titanium dioxide-carbon compound cathode materials.
Preferably, the ball milling in step (1) refers to that high energy deploys formula ball milling, rotational speed of ball-mill 800-1200rmp/min, ball Consuming time is 1-10h, and mass ratio, that is, ratio of grinding media to material of ball milling pearl and red phosphorus is (20 ~ 100): 1, the mode of ball milling is intermittent duty, Unidirectional operation 10-30min, 10-30min out of service.
Preferably, the ball milling in step (2) refers to that high energy deploys formula ball milling, and the revolving speed of ball milling is 800-1200rmp/min, Ball-milling Time is 2-10h, and mass ratio, that is, ratio of grinding media to material of ball milling pearl and mixture is (10-100): 1, the mode of ball milling is that interval is transported Row, unidirectional operation 10-30min, 10-30min out of service.
Preferably, the ball milling in step (2) refers to that planetary type ball-milling, the revolving speed of ball milling are 300-500rmp/min, ball milling Time is 2-10h, and mass ratio, that is, ratio of grinding media to material of ball milling pearl and mixture is (10-100): 1, the mode of ball milling is intermittent duty, Unidirectional operation 10-30min, 10-30min out of service.
Preferably, the carbon material in step (2) is one or more of expanded graphite, graphite, carbon black, Super P.
Preferably, the mass ratio that black phosphorus accounts for mixture in step (2) is 0.3-0.7, and titanium dioxide accounts for the quality of mixture Than for 0.1-0.3, remaining is carbon material.
Preferably, the inert gas is argon gas, and the pressure of inert gas is 0.1MPa.
Preferably, ball milling pearl is stainless steel ball.
The present invention also provides black phosphorus-titanium dioxide-carbon compound cathode materials of preparation method preparation.
The present invention also provides the black phosphorus-titanium dioxide-carbon compound cathode materials in lithium ion battery preparation Using.
Compared to the prior art, the invention has the advantages that and advantage:
1) black phosphorus prepared by the present invention-titanium dioxide-carbon compound cathode materials, carbon and black phosphorus is linked by C-P key, be ensure that and is filled The close contact of black phosphorus and carbon material in discharge process, alleviates volume change in black phosphorus process of intercalation, titanium dioxide and black phosphorus it Between there are Ti-O-P key, can effectively promote the utilization rate of active material black phosphorus, and promote the electron transfer rate of interface;
2) black phosphorus-titanium dioxide-carbon compound cathode materials prepared by the present invention are shown as lithium ion battery negative material (specific capacity is 935.8mAh/g after recycling 300 times under 2A/g current density, is held for excellent cycle performance, higher reversible capacity 83%) and outstanding high rate performance measuring conservation rate is (specific capacity is up to 947.4mAh/g under 7A/g current density);
3) black phosphorus-titanium dioxide-carbon compound cathode materials preparation method provided by the invention is simple to operation, sample preparation amount is big, Time-consuming is short, yield is high, and does not lead to the problem of secondary pollution to environment.
Detailed description of the invention
Fig. 1 is the circulation of black phosphorus-titanium dioxide made from embodiment 1-carbon compound cathode materials assembling lithium ion battery Performance curve;
Fig. 2 is the high rate performance of black phosphorus-titanium dioxide made from embodiment 1-carbon compound cathode materials assembling lithium ion battery Curve.
Specific embodiment
Below with reference to embodiment, invention is further described in detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
Present embodiments provide a kind of black phosphorus-titanium dioxide-carbon compound cathode materials preparation method, comprising the following steps:
(1) in 0.1MPa argon atmosphere glove box, original red phosphorus particle 1g is added in ball grinder, ratio of grinding media to material 50:1, into Row high energy deploys formula ball milling, Ball-milling Time 2h.Carrying out practically mode is unidirectional operation time 30min, time out of service 30min, number of run 4 times, rotational speed of ball-mill 1200rmp/min, after ball milling, in argon atmosphere glove box will material from ball It is taken out in grinding jar, obtains black phosphorus powder.
(2) in 0.1MPa argon atmosphere glove box, by 0.5g black phosphorus, 0.2g titanium dioxide, 0.3g expanded graphite with 5: The mixing of 2:3 mass ratio, is then added in ball grinder, ratio of grinding media to material 50:1, carries out high energy and deploys formula ball milling, Ball-milling Time 5h. Carrying out practically mode is unidirectional operation time 30min, time 30min out of service, and number of run 10 times, rotational speed of ball-mill is 1200rmp/min after ball milling, takes out material in argon gas glove box from ball grinder, obtains black phosphorus-titanium dioxide- Carbon compound cathode materials.
Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment are used for negative electrode of lithium ion battery: by black phosphorus- Titanium dioxide-carbon compound cathode materials, conductive agent (Super-P) and binder (sodium carboxymethylcellulose) are 70 in mass ratio: The ratio of 15:15, which is uniformly mixed to be coated on copper foil, is fabricated to electrode slice, is dried in vacuo;In argon atmosphere glove box, with gold Category lithium, which is used as, tests electrode assembling at button cell.Test condition is that charging and discharging currents density is 200mA/g or 2A/g, Charge and discharge blanking voltage is 0.01 ~ 2.0V.
The lithium ion battery of black phosphorus-titanium dioxide manufactured in the present embodiment-carbon compound cathode materials assembling discharges ratio for the first time Capacity is 1581.1mAh/g, and coulombic efficiency is 84.1% for the first time.Fig. 1 is that black phosphorus-titanium dioxide-carbon manufactured in the present embodiment is compound The cycle performance curve graph of the lithium ion battery of negative electrode material assembling.It can be seen that black phosphorus-titanium dioxide manufactured in the present embodiment Titanium-carbon compound cathode materials show higher specific capacity and preferable cycle life, 300 circulations under 2A/g current density Capacity is up to 935.8mAh/g, capacity retention ratio 83% afterwards.
Fig. 2 is the multiplying power of black phosphorus-titanium dioxide manufactured in the present embodiment-carbon compound cathode materials assembling lithium ion battery Performance chart.It can be seen that black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment are close in different electric currents There is stable specific capacity contribution to show excellent under degree even if reversible capacity is still up to 947.5mAh/g at 7A/g High rate performance.
Embodiment 2
Present embodiments provide a kind of black phosphorus-titanium dioxide-carbon compound cathode materials preparation method, comprising the following steps:
(1) in 0.1MPa argon atmosphere glove box, original red phosphorus particle 1g is added in ball grinder, ratio of grinding media to material 40:1, into Row high energy deploys formula ball milling, Ball-milling Time 5h.Carrying out practically mode is unidirectional operation time 30min, time out of service 30min, number of run 10 times, rotational speed of ball-mill 1100rmp/min, after ball milling, in argon atmosphere glove box will material from It is taken out in ball grinder, obtains black phosphorus powder.
(2) in 0.1MPa argon atmosphere glove box, by 0.5g black phosphorus, 0.1g titanium dioxide, 0.4g expanded graphite with 5: The mixing of 1:4 mass ratio, is then added in ball grinder, ratio of grinding media to material 50:1, carries out high energy and deploys formula ball milling, Ball-milling Time 5h. Carrying out practically mode is unidirectional operation time 30min, time 30min out of service, and number of run 10 times, rotational speed of ball-mill is 1200rmp/min after ball milling, takes out material in argon gas glove box from ball grinder, obtains black phosphorus-titanium dioxide- Carbon composite.
Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment are used for negative electrode of lithium ion battery: lithium-ion electric The preparation in pond and its test method are same as Example 1.Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment Reversible specific capacity is 1097.1mAh/g for the first time under 2A/g current density, and after recycling 200 times, reversible specific capacity is still up to 955.3mAh/g。
Embodiment 3
Present embodiments provide a kind of black phosphorus-titanium dioxide-carbon compound cathode materials preparation method, comprising the following steps:
(1) in 0.1MPa argon atmosphere glove box, original red phosphorus particle 1g is added in ball grinder, ratio of grinding media to material 20:1, into Row high energy deploys formula ball milling, Ball-milling Time 10h.Carrying out practically mode is unidirectional operation time 30min, time out of service 30min, number of run 20 times, rotational speed of ball-mill 1000rmp/min, after ball milling, in argon atmosphere glove box will material from It is taken out in ball grinder, obtains black phosphorus powder.
(2) in 0.1MPa argon atmosphere glove box, by 0.6g black phosphorus, 0.2g titanium dioxide, 0.2g expanded graphite with 6: The mixing of 2:2 mass ratio, is then added in ball grinder, ratio of grinding media to material 50:1, carries out high energy and deploys formula ball milling, Ball-milling Time 5h. Carrying out practically mode is unidirectional operation time 30min, time 30min out of service, and number of run 10 times, rotational speed of ball-mill is 1200rmp/min after ball milling, takes out material in argon gas glove box from ball grinder, obtains black phosphorus-titanium dioxide- Carbon compound cathode materials.
Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment are used for negative electrode of lithium ion battery: lithium-ion electric The preparation in pond and its test method are same as Example 1.Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment Reversible specific capacity is 1072.4mAh/g for the first time under 2A/g current density, after recycling 250 times, reversible specific capacity 879mAh/g.
Embodiment 4
Present embodiments provide a kind of black phosphorus-titanium dioxide-carbon compound cathode materials preparation method, comprising the following steps:
(1) in 0.1MPa argon atmosphere glove box, original red phosphorus particle 1g is added in ball grinder, ratio of grinding media to material 100:1, into Row high energy deploys formula ball milling, Ball-milling Time 1h.Carrying out practically mode is unidirectional operation time 30min, time out of service 30min, number of run 2 times, rotational speed of ball-mill 1200rmp/min, after ball milling, in argon atmosphere glove box will material from ball It is taken out in grinding jar, obtains black phosphorus powder.
(2) in 0.1MPa argon atmosphere glove box, by 0.5g black phosphorus, 0.2g titanium dioxide, 0.3g expanded graphite with 5: The mixing of 2:3 mass ratio, is then added in ball grinder, ratio of grinding media to material 50:1, carries out high energy and deploys formula ball milling, Ball-milling Time 10h. Carrying out practically mode is unidirectional operation time 30min, time 30min out of service, and number of run 20 times, rotational speed of ball-mill is 1100rmp/min after ball milling, takes out material in argon gas glove box from ball grinder, obtains black phosphorus-titanium dioxide- Carbon composite.
Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment are used for negative electrode of lithium ion battery: lithium-ion electric The preparation in pond and its test method are same as Example 1.Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment Reversible specific capacity is 1107mAh/g for the first time under 2A/g current density, after recycling 200 times, reversible specific capacity 948.3mAh/g.
Embodiment 5(control)
Present embodiments provide a kind of preparation method of black phosphorus-carbon compound cathode materials, comprising the following steps:
(1) in 0.1MPa argon atmosphere glove box, original red phosphorus particle 1g is added in ball grinder, ratio of grinding media to material 60:1, into Row high energy deploys formula ball milling, Ball-milling Time 2h.Carrying out practically mode is unidirectional operation time 30min, time out of service 30min, number of run 4 times, rotational speed of ball-mill 1000rmp/min, after ball milling, in argon atmosphere glove box will material from ball It is taken out in grinding jar, obtains black phosphorus powder.
(2) in 0.1MPa argon atmosphere glove box, by 0.5g black phosphorus, 0g titanium dioxide, 0.5g expanded graphite with 5:0:5 Mass ratio mixing, is then added in ball grinder, ratio of grinding media to material 50:1, carries out high energy and deploys formula ball milling, Ball-milling Time 5h.Specifically Operational mode be unidirectional operation time 30min, time 30min out of service, number of run 10 times, rotational speed of ball-mill 1200rmp/ Min after ball milling, takes out material in argon gas glove box from ball grinder, obtains black phosphorus-carbon compound cathode materials.
Black phosphorus-carbon compound cathode materials manufactured in the present embodiment are used for negative electrode of lithium ion battery: the preparation of lithium ion battery And its test method is same as Example 1.Black phosphorus-carbon compound cathode materials manufactured in the present embodiment are first under 2A/g current density Secondary reversible specific capacity is 1077mAh/g, and after recycling 200 times, reversible specific capacity is only 480.3mAh/g, it is possible thereby to find, TiO2Addition can be obviously improved the chemical properties of phosphorous-based materials.
Embodiment 6
Present embodiments provide a kind of black phosphorus-titanium dioxide-carbon compound cathode materials preparation method, comprising the following steps:
(1) in 0.1MPa argon atmosphere glove box, original red phosphorus particle 1g is added in ball grinder, ratio of grinding media to material 50:1, into Row high energy deploys formula ball milling, Ball-milling Time 4h.Carrying out practically mode is unidirectional operation time 30min, time out of service 30min, number of run 8 times, rotational speed of ball-mill 1100rmp/min, after ball milling, in argon atmosphere glove box will material from ball It is taken out in grinding jar, obtains black phosphorus powder.
(2) in 0.1MPa argon atmosphere glove box, by 0.5g black phosphorus, 0.2g titanium dioxide, 0.3g expanded graphite with 5: The mixing of 2:3 mass ratio, is then added in ball grinder, ratio of grinding media to material 30:1, carries out high energy and deploys formula ball milling, Ball-milling Time 6h. Carrying out practically mode is unidirectional operation time 30min, time 30min out of service, and number of run 12 times, rotational speed of ball-mill is 1000rmp/min after ball milling, takes out material in argon gas glove box from ball grinder, obtains black phosphorus-titanium dioxide- Carbon compound cathode materials.
Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment are used for negative electrode of lithium ion battery: lithium-ion electric The preparation in pond and its test method are same as Example 1.Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment First discharge specific capacity is 1523.3mAh/g under 200mA/g current density, and initial charge specific capacity is 1255.2mAh/g, first Secondary coulombic efficiency is up to 82.4%.
Embodiment 7
Present embodiments provide a kind of black phosphorus-titanium dioxide-carbon compound cathode materials preparation method, comprising the following steps:
(1) in 0.1MPa argon atmosphere glove box, original red phosphorus particle 1g is added in ball grinder, ratio of grinding media to material 50:1, into Row high energy deploys formula ball milling, Ball-milling Time 2h.Carrying out practically mode is unidirectional operation time 30min, time out of service 30min, number of run 4 times, rotational speed of ball-mill 1100rmp/min, after ball milling, in argon atmosphere glove box will material from ball It is taken out in grinding jar, obtains black phosphorus powder.
(2) in 0.1MPa argon atmosphere glove box, by 0.5g black phosphorus, 0.2g titanium dioxide, 0.3g expanded graphite with 5: The mixing of 2:3 mass ratio, is then added in ball grinder, ratio of grinding media to material 10:1, carries out high energy and deploys formula ball milling, Ball-milling Time 8h. Carrying out practically mode is unidirectional operation time 30min, time 30min out of service, and number of run 16 times, rotational speed of ball-mill is 1100rmp/min after ball milling, takes out material in argon gas glove box from ball grinder, obtains black phosphorus-titanium dioxide- Carbon compound cathode materials.
Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment are used for negative electrode of lithium ion battery: lithium-ion electric The preparation in pond and its test method are same as Example 1.Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment First discharge specific capacity is 1578.3mAh/g under 200mA/g current density, and initial charge specific capacity is 1321.2mAh/g, first Secondary coulombic efficiency is up to 83.7%.
Embodiment 8
Present embodiments provide a kind of black phosphorus-titanium dioxide-carbon compound cathode materials preparation method, comprising the following steps:
(1) in 0.1MPa argon atmosphere glove box, original red phosphorus particle 1g is added in ball grinder, ratio of grinding media to material 50:1, into Row high energy deploys formula ball milling, Ball-milling Time 2h.Carrying out practically mode is unidirectional operation time 30min, time out of service 30min, number of run 4 times, rotational speed of ball-mill 1200rmp/min, after ball milling, in argon atmosphere glove box will material from ball It is taken out in grinding jar, obtains black phosphorus powder.
(2) in 0.1MPa argon atmosphere glove box, by 0.3g black phosphorus, 0.3g titanium dioxide, 0.4g expanded graphite with 3: The mixing of 3:4 mass ratio, is then added in ball grinder, ratio of grinding media to material 50:1, carries out high energy and deploys formula ball milling, Ball-milling Time 5h. Carrying out practically mode is unidirectional operation time 30min, time 30min out of service, and number of run 10 times, rotational speed of ball-mill is 1200rmp/min after ball milling, takes out material in argon gas glove box from ball grinder, obtains black phosphorus-titanium dioxide- Carbon compound cathode materials.
Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment are used for negative electrode of lithium ion battery: lithium-ion electric The preparation in pond and its test method are same as Example 1.Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment First discharge specific capacity is 1142.6mAh/g under 200mA/g current density, and initial charge specific capacity is 937.6mAh/g, first Secondary coulombic efficiency is up to 82.1%.
Embodiment 9
Present embodiments provide a kind of black phosphorus-titanium dioxide-carbon compound cathode materials preparation method, comprising the following steps:
(1) in 0.1MPa argon atmosphere glove box, original red phosphorus particle 1g is added in ball grinder, ratio of grinding media to material 50:1, into Row high energy deploys formula ball milling, Ball-milling Time 2h.Carrying out practically mode is unidirectional operation time 30min, time out of service 30min, number of run 4 times, rotational speed of ball-mill 1200rmp/min, after ball milling, in argon atmosphere glove box will material from ball It is taken out in grinding jar, obtains black phosphorus powder.
(2) in 0.1MPa argon atmosphere glove box, by 0.5g black phosphorus, 0.2g titanium dioxide, 0.3g expanded graphite with 5: The mixing of 2:3 mass ratio, is then added in ball grinder, ratio of grinding media to material 50:1, carries out planetary type ball-milling, Ball-milling Time 10h.Specifically Operational mode be unidirectional operation time 30min, time 30min out of service, number of run 20 times, rotational speed of ball-mill 500rmp/ Min after ball milling, takes out material in argon gas glove box from ball grinder, obtains black phosphorus-titanium dioxide-carbon Compound Negative Pole material.
Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment are used for negative electrode of lithium ion battery: lithium-ion electric The preparation in pond and its test method are same as Example 1.Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment First discharge specific capacity is 1440.3mAh/g under 200mA/g current density, and initial charge specific capacity is 1134.3mAh/g, first Secondary coulombic efficiency is up to 78.8%.
Embodiment 10
Present embodiments provide a kind of black phosphorus-titanium dioxide-carbon compound cathode materials preparation method, comprising the following steps:
(1) in 0.1MPa argon atmosphere glove box, original red phosphorus particle 1g is added in ball grinder, ratio of grinding media to material 40:1, into Row high energy deploys formula ball milling, Ball-milling Time 2h.Carrying out practically mode is unidirectional operation time 30min, time out of service 30min, number of run 4 times, rotational speed of ball-mill 1200rmp/min, after ball milling, in argon atmosphere glove box will material from ball It is taken out in grinding jar, obtains black phosphorus powder.
(2) in 0.1MPa argon atmosphere glove box, by 0.5g black phosphorus, 0.2g titanium dioxide, 0.3g expanded graphite with 5: The mixing of 2:3 mass ratio, is then added in ball grinder, ratio of grinding media to material 50:1, carries out planetary type ball-milling, Ball-milling Time 5h.Specifically Operational mode be unidirectional operation time 30min, time 30min out of service, number of run 10 times, rotational speed of ball-mill 500rmp/ Min after ball milling, takes out material in argon gas glove box from ball grinder, obtains black phosphorus-titanium dioxide-carbon Compound Negative Pole material.
Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment are used for negative electrode of lithium ion battery: lithium-ion electric The preparation in pond and its test method are same as Example 1.Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment First discharge specific capacity is 1432.5mAh/g under 200mA/g current density, and initial charge specific capacity is 1108.6mAh/g, first Secondary coulombic efficiency is up to 77.4%.
Embodiment 11
Present embodiments provide a kind of black phosphorus-titanium dioxide-carbon compound cathode materials preparation method, comprising the following steps:
(1) in 0.1MPa argon atmosphere glove box, original red phosphorus particle 1g is added in ball grinder, ratio of grinding media to material 50:1, into Row high energy deploys formula ball milling, Ball-milling Time 2h.Carrying out practically mode is unidirectional operation time 30min, time out of service 30min, number of run 4 times, rotational speed of ball-mill 1200rmp/min, after ball milling, in argon atmosphere glove box will material from ball It is taken out in grinding jar, obtains black phosphorus powder.
(2) in 0.1MPa argon atmosphere glove box, by 0.5g black phosphorus, 0.2 titanium dioxide, 0.3g expanded graphite with 5:2: The mixing of 3 mass ratioes, is then added in ball grinder, ratio of grinding media to material 50:1, carries out planetary type ball-milling, Ball-milling Time 10h.Specific fortune Row mode be unidirectional operation time 30min, time 30min out of service, number of run 20 times, rotational speed of ball-mill 300rmp/ Min after ball milling, takes out material in argon gas glove box from ball grinder, obtains black phosphorus-titanium dioxide-carbon Compound Negative Pole material.
Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment are used for negative electrode of lithium ion battery: lithium-ion electric The preparation in pond and its test method are same as Example 1.Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment First discharge specific capacity is 1438.2mAh/g under 200mA/g current density, and initial charge specific capacity is 1123.7mAh/g, first Secondary coulombic efficiency is up to 78.1%.
Embodiment 12
Present embodiments provide a kind of black phosphorus-titanium dioxide-carbon compound cathode materials preparation method, comprising the following steps:
(1) in 0.1MPa argon atmosphere glove box, original red phosphorus particle 1g is added in ball grinder, ratio of grinding media to material 50:1, into Row high energy deploys formula ball milling, Ball-milling Time 2h.Carrying out practically mode is unidirectional operation time 30min, time out of service 30min, number of run 4 times, rotational speed of ball-mill 1200rmp/min, after ball milling, in argon atmosphere glove box will material from ball It is taken out in grinding jar, obtains black phosphorus powder.
(2) in 0.1MPa argon atmosphere glove box, by 0.5g black phosphorus, 0.2g titanium dioxide, 0.3g expanded graphite with 5: The mixing of 2:3 mass ratio, is then added in ball grinder, ratio of grinding media to material 30:1, carries out planetary type ball-milling, Ball-milling Time 10h.Specifically Operational mode be unidirectional operation time 30min, time 30min out of service, number of run 20 times, rotational speed of ball-mill 500rmp/ Min after ball milling, takes out material in argon gas glove box from ball grinder, obtains black phosphorus-titanium dioxide-carbon Compound Negative Pole material.
Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment are used for negative electrode of lithium ion battery: lithium-ion electric The preparation in pond and its test method are same as Example 1.Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment First discharge specific capacity is 1424.3mAh/g under 200mA/g current density, and initial charge specific capacity is 1071.8mAh/g, first Secondary coulombic efficiency is up to 75.2%.
Embodiment 13
Present embodiments provide a kind of black phosphorus-titanium dioxide-carbon compound cathode materials preparation method, comprising the following steps:
(1) in 0.1MPa argon atmosphere glove box, original red phosphorus particle 1g is added in ball grinder, ratio of grinding media to material 50:1, into Row high energy deploys formula ball milling, Ball-milling Time 2h.Carrying out practically mode is unidirectional operation time 30min, time out of service 30min, number of run 4 times, rotational speed of ball-mill 1200rmp/min, after ball milling, in argon atmosphere glove box will material from ball It is taken out in grinding jar, obtains black phosphorus powder.
(2) in 0.1MPa argon atmosphere glove box, by 0.6g black phosphorus, 0.2g titanium dioxide, 0.2g expanded graphite with 6: The mixing of 2:2 mass ratio, is then added in ball grinder, ratio of grinding media to material 100:1, carries out planetary type ball-milling, Ball-milling Time 2h.Specifically Operational mode be unidirectional operation time 30min, time 30min out of service, number of run 20 times, rotational speed of ball-mill 500rmp/ Min after ball milling, takes out material in argon gas glove box from ball grinder, obtains black phosphorus-titanium dioxide-carbon Compound Negative Pole material.
Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment are used for negative electrode of lithium ion battery: lithium-ion electric The preparation in pond and its test method are same as Example 1.Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment First discharge specific capacity is 1830.2mAh/g under 200mA/g current density, and initial charge specific capacity is 1409.3mAh/g, first Secondary coulombic efficiency is up to 76.9%.
Embodiment 14
Present embodiments provide a kind of black phosphorus-titanium dioxide-carbon compound cathode materials preparation method, comprising the following steps:
(1) in 0.1MPa argon atmosphere glove box, original red phosphorus particle 1g is added in ball grinder, ratio of grinding media to material 50:1, into Row high energy deploys formula ball milling, Ball-milling Time 2h.Carrying out practically mode is unidirectional operation time 30min, time out of service 30min, number of run 4 times, rotational speed of ball-mill 1200rmp/min, after ball milling, in argon atmosphere glove box will material from ball It is taken out in grinding jar, obtains black phosphorus powder.
(2) in 0.1MPa argon atmosphere glove box, by 0.5g black phosphorus, 0.1g titanium dioxide, 0.4g expanded graphite with 5: The mixing of 1:4 mass ratio, is then added in ball grinder, ratio of grinding media to material 80:1, carries out planetary type ball-milling, Ball-milling Time 8h.Specifically Operational mode be unidirectional operation time 30min, time 30min out of service, number of run 16 times, rotational speed of ball-mill 500rmp/ Min after ball milling, takes out material in argon gas glove box from ball grinder, obtains black phosphorus-titanium dioxide-carbon Compound Negative Pole material.
Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment are used for negative electrode of lithium ion battery: lithium-ion electric The preparation in pond and its test method are same as Example 1.Black phosphorus-titanium dioxide-carbon compound cathode materials manufactured in the present embodiment First discharge specific capacity is 1488.3mAh/g under 200mA/g current density, and initial charge specific capacity is 1123.9mAh/g, first Secondary coulombic efficiency is up to 75.5%.
Above embodiments only illustrate as specific implementation case of the invention, but embodiments of the present invention are not by described The limitation of embodiment, the carbon material can also be other any without departing from this hair to be any in graphite, carbon black, Super P Made changes, modifications, substitutions, combinations, simplifications under bright spiritual essence and principle, should be equivalent substitute mode, all wrap Containing within protection scope of the present invention.

Claims (10)

1. a kind of black phosphorus-titanium dioxide-carbon compound cathode materials preparation method, which comprises the following steps:
(1) it prepares black phosphorus: under inert gas shielding atmosphere, red phosphorus being added in ball grinder with ball milling pearl and is sealed, is then carried out Ball-milling reaction obtains nanoscale black phosphorus;
(2) black phosphorus-titanium dioxide-carbon compound cathode materials are prepared: under inert gas shielding atmosphere, by black phosphorus, titanium dioxide, Carbon material mixing, obtains mixture, by mixture ball milling, obtains black phosphorus-titanium dioxide-carbon compound cathode materials.
2. black phosphorus according to claim 1-titanium dioxide-carbon compound cathode materials preparation method, which is characterized in that step Suddenly the ball milling in (1) refers to that high energy deploys formula ball milling, rotational speed of ball-mill 800-1200rmp/min, Ball-milling Time 1-10h, ball Mass ratio, that is, the ratio of grinding media to material for grinding pearl and red phosphorus is (20 ~ 100): 1, the mode of ball milling is intermittent duty, unidirectional operation 10-30min, 10-30min out of service.
3. black phosphorus according to claim 1-titanium dioxide-carbon compound cathode materials preparation method, which is characterized in that step Suddenly the ball milling in (2) refers to that high energy deploys formula ball milling, and the revolving speed of ball milling is 800-1200rmp/min, Ball-milling Time 2-10h, Mass ratio, that is, ratio of grinding media to material of ball milling pearl and mixture is (10-100): 1, the mode of ball milling is intermittent duty, unidirectional operation 10- 30min, 10-30min out of service.
4. black phosphorus according to claim 1-titanium dioxide-carbon compound cathode materials preparation method, which is characterized in that step Suddenly the ball milling in (2) refers to that planetary type ball-milling, the revolving speed of ball milling are 300-500rmp/min, Ball-milling Time 2-10h, ball milling pearl Mass ratio, that is, ratio of grinding media to material with mixture is (10-100): 1, the mode of ball milling is intermittent duty, and unidirectional operation 10-30min stops Only run 10-30min.
5. black phosphorus according to claim 1-titanium dioxide-carbon compound cathode materials preparation method, which is characterized in that step Suddenly the carbon material in (2) is one or more of expanded graphite, graphite, carbon black, Super P.
6. black phosphorus according to claim 1-titanium dioxide-carbon compound cathode materials preparation method, which is characterized in that step Suddenly the mass ratio that black phosphorus accounts for mixture in (2) is 0.3-0.7, and the mass ratio that titanium dioxide accounts for mixture is 0.1-0.3, remaining is Carbon material.
7. black phosphorus according to claim 1-titanium dioxide-carbon compound cathode materials preparation method, which is characterized in that institute Stating inert gas is argon gas.
8. black phosphorus according to claim 1-titanium dioxide-carbon compound cathode materials preparation method, which is characterized in that ball Mill pearl is stainless steel ball.
9. black phosphorus-titanium dioxide-carbon compound cathode materials of any one of claim 1 to the 8 preparation method preparation.
10. application of the black phosphorus-titanium dioxide-carbon compound cathode materials as claimed in claim 9 in lithium ion battery preparation.
CN201910683633.XA 2019-07-26 2019-07-26 A kind of black phosphorus-titanium dioxide-carbon compound cathode materials and preparation method and application Pending CN110534712A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110931717A (en) * 2019-12-06 2020-03-27 浙江埃登达新能源材料有限公司 Ball-milling negative electrode bag and preparation method thereof
CN112018363A (en) * 2020-08-31 2020-12-01 中国科学技术大学 Black phosphorus-based composite negative electrode material, preparation method thereof and application thereof in metal secondary battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110931717A (en) * 2019-12-06 2020-03-27 浙江埃登达新能源材料有限公司 Ball-milling negative electrode bag and preparation method thereof
CN112018363A (en) * 2020-08-31 2020-12-01 中国科学技术大学 Black phosphorus-based composite negative electrode material, preparation method thereof and application thereof in metal secondary battery

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