CN105633455A - Lithium ion battery electrode material and preparation method thereof - Google Patents
Lithium ion battery electrode material and preparation method thereof Download PDFInfo
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- CN105633455A CN105633455A CN201610199621.6A CN201610199621A CN105633455A CN 105633455 A CN105633455 A CN 105633455A CN 201610199621 A CN201610199621 A CN 201610199621A CN 105633455 A CN105633455 A CN 105633455A
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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
- 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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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- 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
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Abstract
The invention relates to the field of lithium ion batteries, and in particular relates to a lithium ion battery electrode material and a preparation method thereof. The electrode material is simple in a synthetic method. The electrode material is good in stability; and when the electrode material is used as the lithium battery electrode material, the collapse is avoided in the charging and discharging process, and the multiplying power performance is good.
Description
Technical field
The present invention relates to field of lithium ion battery, in particular to a kind of lithium ion battery electrode material and its preparation method.
Background technology
Metal organic framework compound is as porous material due to its variable chemical structure, and excellent character receives to be paid close attention to widely. By rational design, metal organic framework compound can be widely used in gas storage, lithium ion stores, catalytic field. But, the chemical stability of metal organic framework compound often limits its application in practice, and many metal organic framework compound are easily decomposed in the presence of moisture or caved in. Such as, if in more complicated cases, when it is as the electrode materials of lithium ion battery, owing to the situation of electrolytic solution is more complicated, the stability of this metal organic framework compound is worse.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of lithium ion battery electrode material based on metal organic framework compound.
Another object of the present invention is to provide the preparation method of above-mentioned lithium ion battery electrode material.
A kind of lithium ion battery electrode material, this electrode materials chemical formula is C8H4N8Mn, wherein, C8H4N8For 5'-(pyrazine-2-base)-2H, 4'H-3,3'-join (1,2,4-triazole), described electrode materials is triclinic(crystalline)system,P1Spacer, unit cell parameters isa=10.386 (7),b=11.215 (3),c=13.317 (3),��=78.25 (5) o,��=86.53 (3) o,��=82.37 (3) o, V=1551.15 (1)3��
The preparation method of above-mentioned lithium ion battery electrode material is: by organic compound 5'-(pyrazine-2-base)-2H, 4'H-3,3'-connection (1,2,4-triazole) and manganous nitrate be dissolved in the middle of the mixed solvent of water and methyl alcohol, wherein the volume ratio of water and methyl alcohol is 1:1, at room temperature stir and form mixed liquor A, then described mixed liquor A is reacted at 60 DEG C backflow and within 24 hours, obtains mixed liquid B, finally slow cooling after described mixed liquid B under hydrothermal conditions reacting by heating is obtained described battery electrode material.
Described 5'-(pyrazine-2-base)-2H, 4'H-3,3'-connection (1,2,4-triazole) English be 5 '-(pyrazin-2-yl)-2H, 4 ' H-3,3 '-bi (1,2,4-triazole), chemical structural formula is as follows:
Further, described Heating temperature is 120 DEG C ~ 140 DEG C, and the reacting by heating time is 60 ~ 96 hours.
Further, described cooling is 2 DEG C/h ~ 5 DEG C/h and is down to room temperature.
Further, the mol ratio of described 5'-(pyrazine-2-base)-2H, 4'H-3,3'-connection (1,2,4-triazole) and manganous nitrate is 1:1 ~ 3.
Further, the mol ratio of described 5'-(pyrazine-2-base)-2H, 4'H-3,3'-connection (1,2,4-triazole) and manganous nitrate is 1:2.
The application of described battery electrode material in lithium ion battery.
The present invention has following useful effect:
The electrode materials synthetic method of the present invention is simple, and selected part is only containing atom N, so this electrode materials good stability, when it is as electrode material of lithium battery, in charge and discharge process, it mainly utilizes the atom N in triazole ring to carry out the migration of lithium ion for it, so its Stability Analysis of Structures, do not cave in the process of discharge and recharge.
Accompanying drawing explanation
Fig. 1 is the coordination environment figure of electrode materials with metal center Mn of the present invention.
Fig. 2 is the three-dimensional structure schematic diagram of the electrode materials of the present invention.
The electrode materials that Fig. 3 is the present invention works as the cycle performance figure that current density is 100mA/g.
Fig. 4 is the electrode materials of the present invention high rate performance figure under different current density.
Embodiment
Below in conjunction with embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention, is not limitation of the invention.
Embodiment 1
By 0.1mmol5'-(pyrazine-2-base)-2H, 4'H-3,3'-connection (1,2,4-triazole) and 0.2mmol manganous nitrate be dissolved in the middle of the mixed solvent of 10mL water and 10mL methyl alcohol, at room temperature form mixed liquor A after stirring and dissolving, then described mixed liquor A is reacted at 60 DEG C backflow and within 24 hours, obtains mixed liquid B, subsequently mixed liquid B is transferred in tetrafluoroethylene autoclave, place it in 130 DEG C of baking ovens and react 72 hours, being down to room temperature filtration with 5 DEG C/h afterwards and obtain described electrode materials, product rate is that 73.6%(is based on manganese).
Then above-mentioned electrode materials is carried out structural characterization.
The X ray diffracting data of this electrode materials visits on diffractometer in BrukerSmartApexCCD face, uses MoK��Radiation (��=0.71073), collects with �� scan mode and carries out Lp factor correction, and absorption correction uses SADABS program. Use direct method solution structure, then obtain whole non-hydrogen atom coordinate by difference fourier method, and obtain hydrogen atom position (C H1.083) with theoretical hydrogenation method, by method of least squares, structure is revised. Evaluation work completes with SHELXTL routine package on PC. This electrode materials structure is shown in Fig. 1, Fig. 2.
Resolve it will be seen that this electrode materials chemical formula is C after tested8H4N8Mn, wherein, C8H4N8For 5'-(pyrazine-2-base)-2H, 4'H-3,3'-join (1,2,4-triazole), described electrode materials is triclinic(crystalline)system,P1Spacer, unit cell parameters isa=10.386 (7),b=11.215 (3),c=13.317 (3),��=78.25 (5) o,��=86.53 (3) o,��=82.37 (3) o, V=1551.15 (1)3, Z=4.
From crystalline structure, this electrode materials belongs to triclinic(crystalline)system,P1Spacer, joins (1,2,4-triazole) containing a Mn atom and 5'-(pyrazine-2-base)-2H, a 4'H-3,3'-in this asymmetric cell, as shown in Figure 1. Wherein, Mn atom takes the 6 octahedral patterns of coordination and 6 atom N coordinations, and wherein 4 atom N take the pattern of chelating ligands, and remaining 2 atom N take the pattern of monodentate ligand; And 5'-(pyrazine-2-base)-2H, 4'H-3,3'-connection (1,2,4-triazole) and Mn atom can form the structure of a kind of cage shape, adjacent cage finally defines a kind of three-dimensional structure as shown in Figure 2, and the atom N in triazole ring is then distributed in the duct of a dimension, is conducive to the absorption of lithium ion.
Embodiment 2
By 0.1mmol5'-(pyrazine-2-base)-2H, 4'H-3,3'-connection (1,2,4-triazole) and 0.1mmol manganous nitrate be dissolved in the middle of the mixed solvent of 10mL water and 10mL methyl alcohol, at room temperature form mixed liquor A after stirring and dissolving, then described mixed liquor A is reacted at 60 DEG C backflow and within 24 hours, obtains mixed liquid B, subsequently mixed liquid B is transferred in tetrafluoroethylene autoclave, place it in 120 DEG C of baking ovens and react 96 hours, being down to room temperature filtration with 2 DEG C/h afterwards and obtain described electrode materials, product rate is that 56.3%(is based on manganese).
Embodiment 3
By 0.1mmol5'-(pyrazine-2-base)-2H, 4'H-3,3'-connection (1,2,4-triazole) and 0.3mmol manganous nitrate be dissolved in the middle of the mixed solvent of 10mL water and 10mL methyl alcohol, at room temperature form mixed liquor A after stirring and dissolving, then described mixed liquor A is reacted at 60 DEG C backflow and within 24 hours, obtains mixed liquid B, subsequently mixed liquid B is transferred in tetrafluoroethylene autoclave, place it in 140 DEG C of baking ovens and react 60 hours, being down to room temperature filtration with 4 DEG C/h afterwards and obtain described electrode materials, product rate is that 61.3%(is based on manganese).
Embodiment 4
Then as stand-by after above-mentioned electrode materials being pulverized, the electrochemical property test of electrode materials material is assembled into button cell (CR-2032) in the glove box of full Ar carry out, by active substance, acetylene black is dissolved in water with Xylo-Mucine according to the ratio that mass ratio is 7:2:1 to adjust into mixed slurry be coated with on Copper Foil, dry 12h at 80 DEG C, vacuum, punching can obtain electrode slice. Battery assemble in taking metal lithium sheet as to electrode, 1MLiPF6The solution being dissolved in EC/DEC (volume ratio is 1:1) is electrolytic solution, and Celgard2300 is barrier film, is made into CR-2032 button cell in glove box. 12h need to be left standstill in room temperature before battery testing. Charge and discharge cycles test adopts LANDCT-2001A battery test system, tests under room temperature under voltage range is 0.1-3.0V.
Fig. 3 is the electrode materials of the present invention under the 100mA/g cycle performance figure of first 200 times, as can be seen from figure we, the electrode materials first circle specific discharge capacity of the present invention is 212mAh/g, and in ensuing circulation, this electrode materials remains good cyclical stability always, specific discharge capacity is stabilized in about 160mAh/g always, this may be due to the atom N in three-dimensional structure special in this electrode materials, be conducive to the adsorption and desorption of Li, therefore, should have good cycle performance containing electrode materials.
Fig. 4 is the high rate performance figure of the electrode materials of the present invention, when current density is from 50 to 100,200, during 400mA/g, specific discharge capacity is distributed as 205,160,124,92mAh/g, even if under the multiplying power of 400mA/g, the capacity of battery still can keep battery at the 45% of the specific discharge capacity of 50mA/g, when current density returns to 50mA/g, the capacity of battery still can return to 204mAh/g, and these results fully show that the electrode materials of the present invention has excellent high rate performance.
The above embodiment only have expressed embodiments of the present invention; it describes comparatively concrete and detailed; but therefore can not be interpreted as the restriction to patent scope of the present invention; in every case the technical scheme adopting the form of equivalent replacement or equivalent transformation to obtain, all should drop within protection scope of the present invention.
Claims (8)
1. a lithium ion battery electrode material, it is characterised in that: this electrode materials chemical formula is C8H4N8Mn, wherein, C8H4N8For 5'-(pyrazine-2-base)-2H, 4'H-3,3'-join (1,2,4-triazole).
2. a kind of lithium ion battery electrode material according to claim 1, it is characterised in that, described electrode materials is triclinic(crystalline)system,P1Spacer, unit cell parameters isa=10.386 (7),b=11.215 (3),c=13.317 (3),��=78.25 (5) o,��=86.53 (3) o,��=82.37 (3) o, V=1551.15 (1)3��
3. the preparation method of lithium ion battery electrode material according to claim 1, it is characterized in that: by organic compound 5'-(pyrazine-2-base)-2H, 4'H-3,3'-connection (1,2,4-triazole) and manganous nitrate be dissolved in the middle of the mixed solvent of water and methyl alcohol, wherein the volume ratio of water and methyl alcohol is 1:1, at room temperature stir and form mixed liquor A, then described mixed liquor A is reacted at 60 DEG C backflow and within 24 hours, obtains mixed liquid B, finally slow cooling after described mixed liquid B under hydrothermal conditions reacting by heating is obtained described battery electrode material.
4. the preparation method of lithium ion battery electrode material according to claim 3, it is characterised in that: described Heating temperature is 120 DEG C ~ 140 DEG C, and the reacting by heating time is 60 ~ 96 hours.
5. the preparation method of lithium ion battery electrode material according to claim 3, it is characterised in that: described cooling is 2 DEG C/h ~ 5 DEG C/h and is down to room temperature.
6. the preparation method of lithium ion battery electrode material according to claim 3, it is characterised in that: the mol ratio of described 5'-(pyrazine-2-base)-2H, 4'H-3,3'-connection (1,2,4-triazole) and manganous nitrate is 1:1 ~ 3.
7. the preparation method of lithium ion battery electrode material according to claim 6, it is characterised in that: the mol ratio of described 5'-(pyrazine-2-base)-2H, 4'H-3,3'-connection (1,2,4-triazole) and manganous nitrate is 1:2.
8. the application of battery electrode material according to claim 1 in lithium ion battery.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106111197B (en) * | 2016-06-12 | 2018-07-24 | 山东师范大学 | Nano Pd particle1.6Au1.0The preparation method of alloy@Mn (II) MOF and application |
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| CN104538633A (en) * | 2014-12-15 | 2015-04-22 | 刘国政 | Lithium-ion battery electrode material and preparation method thereof |
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| CN102044674A (en) * | 2009-10-12 | 2011-05-04 | 中国科学院物理研究所 | Anode material for lithium ion battery and preparation method thereof |
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| CN104393270A (en) * | 2014-12-11 | 2015-03-04 | 刘国政 | Electrode material of lithium ion battery and preparation method of electrode material |
| CN104538633A (en) * | 2014-12-15 | 2015-04-22 | 刘国政 | Lithium-ion battery electrode material and preparation method thereof |
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Application publication date: 20160601 |