CN105633394A - Preparation method of graded Mn3O4 hollow microsphere material for high-performance lithium ion battery - Google Patents

Preparation method of graded Mn3O4 hollow microsphere material for high-performance lithium ion battery Download PDF

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Publication number
CN105633394A
CN105633394A CN201610015430.XA CN201610015430A CN105633394A CN 105633394 A CN105633394 A CN 105633394A CN 201610015430 A CN201610015430 A CN 201610015430A CN 105633394 A CN105633394 A CN 105633394A
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hollow microsphere
graduation
lithium ion
ion battery
microsphere material
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CN105633394B (en
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曾令兴
晨曦
黄晓霞
钱庆荣
陈庆华
黄宝铨
肖荔人
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Quangang Petrochemical Research Institute of Fujian Normal 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • 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
    • 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 graded Mn3O4 hollow microsphere material for a high-performance lithium ion battery. The preparation method comprises the following steps of adding 0.2-10g of manganese salt and 0.2-5g of cetyl trimethyl ammonium bromide (CTAB) into a reactor, and then adding 20-100mL of ethyl alcohol; violently stirring the mixture by a magnetic stirring device to make the mixture uniformly dissolved; adding the obtained solution into a polytetrafluoroethylene lining; loading the solution into a reaction kettle, placing the solution in a drying oven with 140-210 DEG C for 1-2 days; and naturally cooling the solution, centrifugally washing a sample, and then placing the sample in the drying oven, and drying the sample in air at a temperature of 70 DEG C, thereby obtaining the powder product, namely the graded Mn3O4 hollow microsphere material. The process is simple to operate, and is low in energy consumption and high in reproducibility, mass production can be achieved, and environmental requirement is met.

Description

High performance lithium ion battery graduation Mn3O4The preparation method of hollow microsphere material
Technical field
The invention belongs to field of lithium ion battery material, be more particularly to a kind of high-performance graduation Mn3O4The preparation method and application of hollow microsphere.
Background technology
Widely using of traditional fossil energy, result in serious environmental problem. Lithium ion battery is subject to the extensive concern of researcheres as a kind of clean energy resource. Along with the development of technology, the performance of lithium ion battery is proposed higher requirement by market. The performance of battery is mainly determined by the performance of electrode material. Therefore, specific capacity height, good stability, good rate capability lithium ion battery electrode material remain everybody pay close attention to focus. Lithium ion battery negative material industrial at present mainly has graphite, carbonaceous mesophase spherules and lithium titanate etc. But their specific capacity is relatively low, high rate performance is poor. Now, carbon based negative electrodes material, alloy type material are study the most several negative materials with transition metal oxide material. Transition metal oxide has a significantly high theoretical capacity, but general poorly conductive, and also in charge and discharge process, volume easily expands, and causes that cycle performance is poor. Improve the method for transition metal oxide negative material performance mainly by carbon cladding and synthesis hollow ball or graded structure etc., suppress electrode material volumetric expansion in charge and discharge process by special construction, improve specific capacity and the cyclical stability of material.
Mangano-manganic oxide has the spinel structure of distortion, because special construction heat stability is high, and manganese element mediates valence state, and chemical activity is higher. Mangano-manganic oxide is a kind of typical transition metal oxide, and theoretical capacity is up to 936mAh/g, but in charge and discharge process, deintercalation along with lithium ion, the volume of mangano-manganic oxide can expand, and thus can destroy the crystal structure of mangano-manganic oxide, causes that cycle life shortens. In order to improve charging and discharging capacity and the cycle performance of mangano-manganic oxide, it is necessary to mangano-manganic oxide is modified. The present invention is prepared the mangano-manganic oxide of graduation hollow microsphere structure by ethanol-thermal method, and its performance is greatly improved.
Summary of the invention
It is an object of the invention to provide a kind of high-performance graduation Mn3O4Hollow microsphere material and its preparation method and application, technique is simple, and favorable reproducibility can produce in a large number, and with low cost, energy consumption is low, meets environmental requirement.
For achieving the above object, the present invention adopts the following technical scheme that
The present invention adopts ethanol-thermal method, synthesizes pure phase graduation Mn at a lower temperature3O4Hollow microsphere material. It is specific as follows:
A kind of high performance lithium ion battery graduation Mn of the present invention3O4The preparation method of hollow microsphere material, comprises the steps:
1) first the cetyl trimethylammonium bromide of the manganese salt of 0.2-10g and 0.2-5g is added reactor, add 20-100mL ethanol, be stirred vigorously 5-20 minute, so as to uniform dissolution becomes solution;
2) step 1) gained solution is added in polytetrafluoroethyllining lining, load reactor, put into 140-210 �� of C of baking oven and react 1-2 days, after natural cooling, centrifuge washing sample, then place in baking oven, dry with the temperature of 70 �� of C in atmosphere, i.e. scoring rank Mn3O4Hollow microsphere material.
Described manganese salt is manganese acetate, manganese nitrate, manganese carbonate or manganese chloride.
Described ethanol concentration expressed in percentage by volume is 95%.
The high performance lithium ion battery that the above-mentioned preparation method of the present invention prepares is classified Mn3O4Hollow microsphere material.
Described graduation Mn3O4Mangano-manganic oxide in hollow microsphere material is the mangano-manganic oxide of high-crystallinity, the diffraction maximum position of described high-crystallinity mangano-manganic oxide and JCPDSno.18-0803 standard diagram match, the graduation hollow microsphere structure that the mangano-manganic oxide hollow microsphere material of high-crystallinity is made up of nanometer sheet, the diameter of the hollow microsphere in graduation hollow microsphere structure is about 1 ��m, the diameter of the hollow space in graduation hollow microsphere structure is about 500nm, the thickness of the nanometer sheet in graduation hollow microsphere structure is about 10nm, the lattice fringe of the mangano-manganic oxide in graduation hollow microsphere structure is high-visible, the interplanar distance that the lattice fringe of described high-crystallinity mangano-manganic oxide nanocrystalline is corresponding is 0.309nm, with d in the X ray diffracting spectrum of tetragonal crystal system mangano-manganic oxide112Spacing matches.
The high performance lithium ion battery that the above-mentioned preparation method of the present invention prepares is classified Mn3O4The application of hollow microsphere material, its feature is described graduation Mn3O4Hollow microsphere materials application in lithium ion battery negative, the charge and discharge cycles 100 times when voltage be 0.02-3.0V, electric current density is 100mA/g, specific capacity is stable at 640mAh/g; When high current density 1A/g after charge and discharge cycles 250 times, specific capacity is up to 408mAh/g.
A kind of lithium ion battery of the present invention, including working electrode, reference electrode and to electrode, working electrode prepares as follows, is in mass ratio: the Mn that the arbitrary described preparation method of claim 1-3 prepares3O4Being coated in equably as working electrode on Copper Foil after hollow microsphere material politef acetylene black=75-90:5-10:5-15 mixed grinding, described reference electrode and electrode is lithium metal, electrolyte is 1MLiPF6EC+DMC+EMC solution, the volume ratio of described EC/DMC/EMC is 1/1/1.
Described EC is (ethylene carbonate); DMC is (dimethyl carbonate); EMC(Ethyl methyl carbonate).
The present invention has the great advantage that
1) effect of the cetyl trimethylammonium bromide used by the present invention is nucleator and derivant, hollow micro-sphere structure is played an important role, only the cetyl trimethylammonium bromide of the present invention, just can prepare the Mn of the present invention3O4Graduation hollow microsphere material, the Mn that the present invention is synthetically derived3O4Mn in graduation hollow microsphere material3O4For the mangano-manganic oxide of high-crystallinity, its diffraction maximum position and Mn3O4Standard diagram (JCPDSno.18-0803) match. Each corresponding indices of crystallographic plane are as shown in Figure 1. The experiment of scanned Electronic Speculum, transmission electron microscope obtains the graduation Mn of Fig. 23O4The SEM of hollow microsphere material TEM figure. As shown in Figure 2, the hollow microsphere graded structure that this complex is made up of nanometer sheet. Wherein, the diameter of hollow bead is about 1 ��m, and the diameter of its hollow space is about 500nm, and the thickness of nanometer sheet is about 10nm; By the f in Fig. 2 it can be seen that the lattice fringe of mangano-manganic oxide is high-visible, the interplanar distance that the lattice fringe of described high-crystallinity mangano-manganic oxide nanocrystalline is corresponding is 0.309nm, and this is with tetragonal crystal system Mn3O4X ray diffracting spectrum in d112Spacing matches.
2) with the graduation Mn of the present invention3O4Hollow microsphere material has significantly high cyclical stability and large current density electrical characteristics as the lithium ion battery that lithium ion battery negative obtains. When voltage be 0.02-3.0V, electric current density is 100mA/g, classify Mn3O4After hollow microsphere circulates 100 times, specific capacity is stable at 640mAh/g, and Mn is described3O4Electrode material there is high specific capacity and good cyclical stability; Show the high rate during charging-discharging of excellence simultaneously, even if 250 specific capacities of charge and discharge cycles are stable at 408mAh/g when high current density 1A/g, Mn is also described3O4Electrode has the cyclical stability of excellence.
3) graduation Mn3O4Hollow microsphere material is a kind of good lithium ion battery negative material, and the present invention provides one first and prepares graduation Mn3O4The method of hollow microsphere material, the method technique is simple, excellent performance, and favorable reproducibility can produce in a large number, and with low cost, energy consumption is low, meets environmental requirement.
Accompanying drawing explanation
Fig. 1 is the graduation Mn of embodiment 1 gained3O4The XRD figure of hollow microsphere material.
Fig. 2 is the graduation Mn of embodiment 1 gained3O4The SEM/TEM figure of hollow microsphere material.
Fig. 3 is the graduation Mn of embodiment 1 gained3O4Hollow microsphere material cycle performance figure under 100mA/g electric current density.
Fig. 4 is the graduation Mn of embodiment 1 gained3O4Hollow microsphere material cycle performance under 1A/g electric current density and coulombic efficiency figure.
Fig. 5 is the graduation Mn of embodiment 1 gained3O4Hollow microsphere material high rate performance figure under 0.2-2A/g electric current density.
Detailed description of the invention
Following embodimentEC is (ethylene carbonate); DMC is (dimethyl carbonate); EMC(Ethyl methyl carbonate), ethanol is concentration expressed in percentage by volume is the industrial alcohol of 95%.
Embodiment 1
First the cetyl trimethylammonium bromide (CTAB) of the manganese acetate of 0.24g and 0.24g is added reactor, add 40mL ethanol, be stirred vigorously 5-20 minute, so as to uniform dissolution. Gained solution is added in polytetrafluoroethyllining lining, load reactor, put into 200 �� of C of baking oven and react 2 days. After natural cooling, centrifuge washing sample, then place in baking oven, dry with the temperature of 70 �� of C in atmosphere, obtain described graduation Mn3O4Hollow microsphere material. The Mn of Fig. 1 is obtained through XRD experiment3O4Graduation hollow microsphere material XRD figure, by Fig. 1 it can be seen that be synthetically derived the mangano-manganic oxide of high-crystallinity, its diffraction maximum position and Mn3O4Standard diagram (JCPDSno.18-0803) match. Each corresponding indices of crystallographic plane are as shown in Figure 1. The experiment of scanned Electronic Speculum, transmission electron microscope obtains the graduation Mn of Fig. 23O4The SEM of hollow microsphere material TEM figure. By the a-e in Fig. 2 it can be seen that the hollow microsphere graded structure that is made up of nanometer sheet of this complex. Wherein, the diameter of hollow bead is about 1 ��m, and the diameter of its hollow space is about 500nm, and the thickness of nanometer sheet is about 10nm; By the f in Fig. 2 it can be seen that the lattice fringe of mangano-manganic oxide is high-visible, the interplanar distance that the lattice fringe of described high-crystallinity mangano-manganic oxide nanocrystalline is corresponding is 0.309nm, and this is with tetragonal crystal system Mn3O4X ray diffracting spectrum in d112Spacing matches, and illustrates that embodiment 1 can obtain the mangano-manganic oxide of pure phase. Lithium ion battery assembles: each component is in mass ratio: above-mentioned prepared graduation Mn3O4Hollow microsphere material: politef: be coated on Copper Foil after acetylene black=75:10:15 mixed grinding to work electrode equably, reference electrode and electrode is lithium metal, electrolyte is by 1MLiPF6EC+DMC+EMC (wherein EC/DMC/EMC=1/1/1v/v/v) solution. All assemblings all carry out in glove box. See shown in Fig. 3, Fig. 4 and Fig. 5, Mn3O4Graduation-carbon composite is charge and discharge cycles 100 times when voltage be 0.02-3.0V, electric current density is 100mA/g, and specific capacity is stable at 640mAh/g; Show the high rate during charging-discharging of excellence, even if when high current density 1A/g after charge and discharge cycles 250 times, specific capacity is up to 408mAh/g simultaneously; This graduation Mn is described3O4Hollow microsphere material has the charge-discharge characteristic of long circulation life, has a good application prospect.
Embodiment 2
First the cetyl trimethylammonium bromide (CTAB) of the manganese nitrate of 2.4g and 0.9g is added reactor, add 25mL ethanol, be stirred vigorously 15 minutes, so as to uniform dissolution. Gained solution is added in polytetrafluoroethyllining lining, load reactor, put into 180 �� of C of baking oven and react 2 days. After natural cooling, centrifuge washing sample, then place in baking oven, dry with the temperature of 70 �� of C in atmosphere, obtain described graduation Mn3O4Hollow microsphere material. Lithium ion battery assembles: classify Mn in mass ratio3O4Hollow microsphere material: politef: be coated on Copper Foil after acetylene black=80:10:10 mixed grinding to work electrode equably, reference electrode and electrode is lithium metal, electrolyte is by 1MLiPF6EC+DMC+EMC (EC/DMC/EMC=1/1/1v/v/v) solution. All assemblings all carry out in glove box.
Embodiment 3
First the cetyl trimethylammonium bromide (CTAB) of the manganese carbonate of 1g and 0.8g is added reactor, add 50mL ethanol, be stirred vigorously 20 minutes, so as to uniform dissolution. Gained solution is added in polytetrafluoroethyllining lining, load reactor, put into 180 �� of C of baking oven and react 1 day. After natural cooling, centrifuge washing sample, then place in baking oven, dry with the temperature of 70 �� of C in atmosphere, obtain described graduation Mn3O4Hollow microsphere material. Lithium ion battery assembles: classify Mn in mass ratio3O4Hollow microsphere material: politef: being coated on Copper Foil after acetylene black=75:10:15 mixed grinding to work electrode equably, be LiMn2O4 to electrode, electrolyte is 1MLiPF6EC+DMC+EMC (EC/DMC/EMC=1/1/1v/v/v) solution. All assemblings all carry out in glove box.
Embodiment 4
First the cetyl trimethylammonium bromide (CTAB) of the manganese chloride of 5g and 2g is added reactor, add 80mL ethanol, be stirred vigorously 20 minutes, so as to uniform dissolution. Gained solution is added in polytetrafluoroethyllining lining, load reactor, put into 200 �� of C of baking oven and react 2 days. After natural cooling, centrifuge washing sample, then place in baking oven, dry with the temperature of 70 �� of C in atmosphere, obtain described graduation Mn3O4Hollow microsphere material. Lithium ion battery assembles: classify Mn in mass ratio3O4Hollow microsphere material: politef: being coated on Copper Foil after acetylene black=85:5:10 mixed grinding to work electrode equably, be LiMn2O4 to electrode, electrolyte is 1MLiPF6EC+DMC+EMC (EC/DMC/EMC=1/1/1v/v/v) solution. All assemblings all carry out in glove box.
The foregoing is only presently preferred embodiments of the present invention, all equalizations done according to present patent application scope change and modify, and all should belong to the covering scope of the present invention.

Claims (7)

1. a high performance lithium ion battery graduation Mn3O4The preparation method of hollow microsphere material, comprises the steps:
1) first the cetyl trimethylammonium bromide of the manganese salt of 0.2-10g and 0.2-5g is added reactor, add 20-100mL ethanol, be stirred vigorously 5-20 minute, so as to uniform dissolution becomes solution;
2) step 1) gained solution is added in polytetrafluoroethyllining lining, load reactor, put into 140-210 �� of C of baking oven and react 1-2 days, after natural cooling, centrifuge washing sample, then place in baking oven, dry with the temperature of 70 �� of C in atmosphere, i.e. scoring rank Mn3O4Hollow microsphere material.
2. high performance lithium ion battery according to claim 1 graduation Mn3O4The preparation method of hollow microsphere material, it is characterised in that described manganese salt is manganese acetate, manganese nitrate, manganese carbonate or manganese chloride.
3. high performance lithium ion battery according to claim 1 graduation Mn3O4The preparation method of hollow microsphere material, it is characterised in that described ethanol concentration expressed in percentage by volume is 95%.
4. the high performance lithium ion battery graduation Mn that the arbitrary described preparation method of claim 1-3 prepares3O4Hollow microsphere material.
5. high performance lithium ion battery according to claim 4 graduation Mn3O4Hollow microsphere material, it is characterised in that: described graduation Mn3O4Mangano-manganic oxide in hollow microsphere material is the mangano-manganic oxide of high-crystallinity, the diffraction maximum position of described high-crystallinity mangano-manganic oxide and JCPDSno.18-0803 standard diagram match, the graduation hollow microsphere structure that the mangano-manganic oxide hollow microsphere material of high-crystallinity is made up of nanometer sheet, the diameter of the hollow microsphere in graduation hollow microsphere structure is about 1 ��m, the diameter of the hollow space in graduation hollow microsphere structure is about 500nm, the thickness of the nanometer sheet in graduation hollow microsphere structure is about 10nm, the lattice fringe of the mangano-manganic oxide in graduation hollow microsphere structure is high-visible, the interplanar distance that the lattice fringe of described high-crystallinity mangano-manganic oxide nanocrystalline is corresponding is 0.309nm, with d in the X ray diffracting spectrum of tetragonal crystal system mangano-manganic oxide112Spacing matches.
6. the high performance lithium ion battery graduation Mn that the arbitrary described preparation method of claim 1-3 prepares3O4The application of hollow microsphere material, it is characterised in that: described graduation Mn3O4Hollow microsphere materials application in lithium ion battery negative, the charge and discharge cycles 100 times when voltage be 0.02-3.0V, electric current density is 100mA/g, specific capacity is stable at 640mAh/g; When high current density 1A/g after charge and discharge cycles 250 times, specific capacity is up to 408mAh/g.
7. a lithium ion battery, including working electrode, reference electrode and to electrode, it is characterised in that: be in mass ratio: the Mn that the arbitrary described preparation method of claim 1-3 prepares3O4Being coated in equably as working electrode on Copper Foil after hollow microsphere material politef acetylene black=75-90:5-10:5-15 mixed grinding, described reference electrode and electrode is lithium metal, electrolyte is 1MLiPF6EC+DMC+EMC solution, the volume ratio of described EC/DMC/EMC is 1/1/1.
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CN110498454A (en) * 2019-07-30 2019-11-26 复旦大学 A kind of spinel type nanometer crystalline substance material and its preparation method and application

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Publication number Priority date Publication date Assignee Title
CN106328919A (en) * 2016-09-26 2017-01-11 福州大学 Lithium ion battery cathode material microgranitic trimanganese tetroxide, and preparation method and application thereof
CN110498454A (en) * 2019-07-30 2019-11-26 复旦大学 A kind of spinel type nanometer crystalline substance material and its preparation method and application

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