CN102034965B - Preparation method of manganese difluoride and graphite nanocomposite for cathode material of lithium ion battery - Google Patents
Preparation method of manganese difluoride and graphite nanocomposite for cathode material of lithium ion battery Download PDFInfo
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- CN102034965B CN102034965B CN201010535047A CN201010535047A CN102034965B CN 102034965 B CN102034965 B CN 102034965B CN 201010535047 A CN201010535047 A CN 201010535047A CN 201010535047 A CN201010535047 A CN 201010535047A CN 102034965 B CN102034965 B CN 102034965B
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Abstract
The invention provides a preparation method of a manganese difluoride and graphite nanocomposite for a cathode material of a lithium ion battery. The method comprises the following steps of: adding polyethylene glycol 2000 which serves as a surfactant into solution of manganous nitrate and solution of ammonium fluoride which serve as a manganese source and a fluorine source; mixing and stirring at normal temperature so as to produce white deposit; and introducing argon into the deposit in a tubular furnace and calcining under an air-isolated condition so as to obtain manganese difluoride powder. The manganese difluoride prepared by the method has a cubic blocky structure consisting of uniform nanoparticles. When taken as the cathode of the lithium ion battery, the nanocomposite obtained by mixing cubic manganese difluoride and graphite and performing ball milling represents high circulating performance. The method has a moderate preparation condition and simple equipment, and is safe and easy to operate. A synthesis product has high purity and stable property. Charging and discharging tests indicate that the nanocomposite has high electrochemical performance.
Description
Technical field
The present invention relates to the preparation method of lithium ion battery negative material manganese difluoride and Nano graphite compound, manganese difluoride is micron-sized cubic, and this cubic is made up of nano particle.
Background technology
Lithium ion battery begins flourish in eighties of last century the nineties.The Along with people's growth in the living standard; The a large amount of of portable type electronic product, electric bicycle and microcomputer popularize; People are to light weight, and volume is little, and energy density is big; The green power supply of long service life requires more and more, and lithium ion battery becomes the focus of research with its advantage that is difficult to compare.It is existing for a long time that the fluorine material is used for lithium ion battery, for example fluoride salt is used as electrolyte (LiPF
6); Organic fluoride as binding agent (PTFE) and (CFx) n as positive electrode etc.; Too high owing to electrode voltage for the carbon element negative material that improves commercial usefulness in addition, the unfavorable situation of the chemical property that voltage delay etc. cause is carried out fluorination treatment with fluorine to graphite surface.In addition, with metal fluoride during as electrode material, what it not only can carry out lithium ion takes off the embedding reaction, can also come storing energy through carrying out chemical conversioning reaction with lithium, and its capacity of emitting is far above taking off the embedding reaction, thereby obtains broad research in recent years.Naoko Yamakawa (J.Am.Chem.Soc.2009,131,10525) etc. are to FeF
3Charge and discharge process carried out detailed discussion, confirmed this conclusion: in many metal fluoride electrode materials, transition metal fluorides since relative molecular mass lower, specific capacity is high relatively, is the lithium ion battery electrode material that comparison value must be studied.In recent years, external Amatucci seminar, Maier seminar, Tarascon seminar and the Fu Zhengwen of Fudan University professor seminar are all studied it.For the manganese difluoride negative material, Fu Zhengwen teaches (Journal of Inorganic Materials, 2010; 25,145) etc. the method for usefulness pulsed laser deposition prepares it, and its chemical property has been carried out research and analysis; In first Zhou Xunhuan; Its irreversible capacity decay is bigger, and in process subsequently, cyclical stability is better.In Chinese patent, also there is not manganese difluoride to do the report of electrode material at present.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of lithium ion battery negative material manganese difluoride and Nano graphite compound.
The preparation method of lithium ion battery negative material manganese difluoride of the present invention and Nano graphite compound may further comprise the steps:
1, be that 50% manganese nitrate solution is dissolved in the 150mL absolute ethyl alcohol and is made into colourless solution with 1.2～4.6mL mass fraction under the room temperature;
2, in the solution that step 1 obtains, add 2.0～4.0g Macrogol 2000 as surfactant, stir and obtain colourless solution;
3, under the room temperature 1.8～7.4g ammonium fluoride is dissolved in the 150mL distilled water, stirs, obtain colourless solution;
4, under condition of stirring, the solution that step 3 is obtained progressively is added drop-wise in the solution that step 2 obtains, and the ammonium fluoride of usefulness is excessive far away here, forms white precipitate; With the white precipitate centrifuge washing that obtains, the vacuum drying chamber inner drying at 80 ℃ obtains white powder; The white powder that obtains is calcined in tube furnace, fed under the situation of argon gas with secluding air, 420 ℃ were burnt 1～4 hour, and obtained the manganese difluoride powder;
5, manganese difluoride powder that step 4 is obtained and graphite are 1: 1 mixed by mass ratio, and under the situation that feeds argon gas, mechanical ball milling 4～6 hours obtains lithium ion battery negative material manganese difluoride and Nano graphite compound.
Effect of the present invention and advantage:
1. adopt manganese difluoride and the graphite nanometer composite material of the inventive method preparation to have favorable charge-discharge cycle performance and higher specific capacity, reversible capacities still have 330mAh/g after 30 weeks of circulation under with the current density of 100mA/g.
2. whole technical process is simple and safe, and productive rate is high.
3. compare with synthesizing the manganese difluoride electrode material before, synthesis condition is gentle, and equipment is simple, and handling safety is prone to row, and synthetic product purity is higher, stable in properties.Charge-discharge test has good electrochemical.
Further the present invention will be described below in conjunction with accompanying drawing and embodiment.
Description of drawings
Fig. 1 is the XRD diffraction pattern of the manganese difluoride powder of embodiment 2 gained.
Fig. 2 is the SEM figure of the manganese difluoride powder of embodiment 2 gained,
Fig. 3 is the SEM figure of 9,000 times of amplifications of the manganese difluoride powder of embodiment 2 gained,
Fig. 4 is the SEM figure of 80,000 times of amplifications of the manganese difluoride powder of embodiment 2 gained,
Visible from Fig. 2-4, the cubic structure of the manganese difluoride material that makes for forming by the granule of the about 100nm of diameter, this cube length of side is about 3 microns.
Fig. 5 is manganese difluoride and the Nano graphite compound powder of the embodiment 2 gained cycle performance of battery figure as the 100mA/g of lithium ion battery negative.
Embodiment
Embodiment 1
50% the manganese nitrate solution of 1.7mL is dissolved into wiring solution-forming in the 150mL absolute ethyl alcohol, in this solution, adds the 3.0g Macrogol 2000 as surfactant, stirring and dissolving forms colourless solution, is solution (1); The 2.8g ammonium fluoride is dissolved in the distilled water of 150mL and is made into colourless solution, be solution (2); Under condition of stirring, solution (2) progressively is added drop-wise in the solution (1), forms white precipitate; With the white precipitate centrifuge washing that obtains, the vacuum drying chamber inner drying at 80 ℃ obtains white powder; The white powder that obtains is calcined in tube furnace, fed under the situation of argon gas with secluding air, 420 ℃ were burnt 2 hours, and obtained the manganese difluoride powder; Is 1: 1 mixed with the manganese difluoride powder that obtains and graphite by mass ratio, and under the situation that feeds argon gas, mechanical ball milling 6 hours obtains the nano-complex of lithium ion battery negative material manganese difluoride and graphite.
Nano complexes material and acetylene black with lithium ion battery negative material manganese difluoride that makes and graphite; Polytetrafluoroethylene (FTFE) emulsion was according to 80: 10: 10 mixed; Add the isopropyl alcohol breakdown of emulsion and become electrode cream; It is rolled into the thick electrode film of 0.1mm, after the oven dry electrode film is pressed on the nickel foam collector, process electrode slice.In being full of the glove box of dry argon gas, carry out the assembling of simulated battery.The simulated battery that assembles is tested on battery test system, and the charging/discharging voltage scope is 3.0～0.3V, and current density is 100mA/g.
Embodiment 2
50% the manganese nitrate solution of 4.4mL is dissolved into wiring solution-forming in the 150mL absolute ethyl alcohol, in this solution, adds the 3.0g Macrogol 2000 as surfactant, stirring and dissolving forms colourless solution, is solution (1); The 5.6g ammonium fluoride is dissolved in the distilled water of 150mL and is made into colourless solution, be solution (2); Under the situation of vigorous stirring, solution (2) progressively is added drop-wise in the solution (1), forms white precipitate; With the white precipitate centrifuge washing that obtains, the vacuum drying chamber inner drying at 80 ℃ obtains white powder; The white powder that obtains is calcined in tube furnace, fed under the situation of argon gas with secluding air, 420 ℃ were burnt 2 hours, and obtained the manganese difluoride powder; Is 1: 1 mixed with the manganese difluoride powder that obtains and graphite by mass ratio, and under the situation that feeds argon gas, mechanical ball milling 4 hours obtains the nano-complex of lithium ion battery negative material manganese difluoride and graphite.
Nano complexes material and acetylene black with lithium ion battery negative material manganese difluoride that makes and graphite; Polytetrafluoroethylene (FTFE) emulsion was according to 80: 10: 10 mixed; Add the isopropyl alcohol breakdown of emulsion and become electrode cream; It is rolled into the thick electrode film of 0.1mm, after the oven dry electrode film is pressed on the nickel foam collector, process electrode slice.In being full of the glove box of dry argon gas, carry out the assembling of simulated battery.The simulated battery that assembles is tested on battery test system, and the charging/discharging voltage scope is 3.0～0.3V, and current density is 100mA/g.Manganese difluoride and Nano graphite compound powder are seen Fig. 5 as the cycle performance of battery figure of the 100mA/g of lithium ion battery negative.
The XRD diffraction pattern of the manganese difluoride powder of gained is seen Fig. 1; The SEM figure of manganese difluoride powder sees Fig. 2, Fig. 3, Fig. 4; Visible by figure, the cubic structure of the manganese difluoride material that makes for forming by the granule of the about 100nm of diameter, this cube length of side is about 3 microns.
Embodiment 3
50% the manganese nitrate solution of 3.5mL is dissolved into wiring solution-forming in the 150mL absolute ethyl alcohol, in this solution, adds the 3.0g Macrogol 2000 as surfactant, stirring and dissolving forms colourless solution, is solution (1); The distilled water that the 3.3g ammonium fluoride is dissolved in 150mL is merely hit and is made into colourless solution, is solution (2); Under the situation of vigorous stirring, solution (2) progressively is added drop-wise in the solution (1), forms white precipitate; With the white precipitate centrifuge washing that obtains, the vacuum drying chamber inner drying at 80 ℃ obtains white powder; The white powder that obtains is calcined in tube furnace, fed under the situation of argon gas with secluding air, 420 ℃ were burnt 4 hours, and obtained the manganese difluoride powder; Is 1: 1 mixed with the manganese difluoride powder that obtains and graphite by mass ratio, and under the situation that feeds argon gas, mechanical ball milling 5 hours obtains the nano-complex of lithium ion battery negative material manganese difluoride and graphite.
Nano complexes material and acetylene black with lithium ion battery negative material manganese difluoride that makes and graphite; Polytetrafluoroethylene (FTFE) emulsion was according to 80: 10: 10 mixed; Add the isopropyl alcohol breakdown of emulsion and become electrode cream; It is rolled into the thick electrode film of 0.1mm, after the oven dry electrode film is pressed on the nickel foam collector, process electrode slice.In being full of the glove box of dry argon gas, carry out the assembling of simulated battery.The simulated battery that assembles is tested on battery test system, and the charging/discharging voltage scope is 3.0～0.3V, and current density is 100mA/g.
Embodiment 4
50% the manganese nitrate solution of 2.3mL is dissolved into wiring solution-forming in the 150mL absolute ethyl alcohol, in this solution, adds the 3.0g Macrogol 2000 as surfactant, stirring and dissolving forms colourless solution, is solution (1); The distilled water that the 3.0g ammonium fluoride is dissolved in 150mL is merely hit and is made into colourless solution, is solution (2); Under the situation of vigorous stirring, solution (2) progressively is added drop-wise in the solution (1), forms white precipitate; With the white precipitate centrifuge washing that obtains, the vacuum drying chamber inner drying at 80 ℃ obtains white powder; The white powder that obtains is calcined in tube furnace, fed under the situation of argon gas with secluding air, 420 ℃ were burnt 1 hour, and obtained the manganese difluoride powder; Is 1: 1 mixed with the manganese difluoride powder that obtains and graphite by mass ratio, and under the situation that feeds argon gas, mechanical ball milling 4 hours obtains the nano-complex of lithium ion battery negative material manganese difluoride and graphite.
Nano complexes material and acetylene black with lithium ion battery negative material manganese difluoride that makes and graphite; Polytetrafluoroethylene (FTFE) emulsion was according to 80: 10: 10 mixed; Add the isopropyl alcohol breakdown of emulsion and become electrode cream; It is rolled into the thick electrode film of 0.1mm, after the oven dry electrode film is pressed on the nickel foam collector, process electrode slice.In being full of the glove box of dry argon gas, carry out the assembling of simulated battery.The simulated battery that assembles is tested on battery test system, and the charging/discharging voltage scope is 3.0～0.3V, and current density is 100mA/g.
The XRD diffraction pattern of the manganese difluoride powder of embodiment 1,3 and embodiment 4 gained, the SEM of manganese difluoride powder figure, manganese difluoride and Nano graphite compound powder be as the cycle performance of battery of the 100mA/g of lithium ion battery negative, identical with embodiment 2.
Claims (1)
1. prepare the method for lithium ion battery negative material manganese difluoride and Nano graphite compound, it is characterized in that may further comprise the steps:
1) be that 50% manganese nitrate solution is dissolved in the 150mL absolute ethyl alcohol and is made into colourless solution with 1.2～4.6mL mass fraction under the room temperature;
2) in the solution that step 1) obtains, add 2.0～4.0g Macrogol 2000 as surfactant, stir and obtain colourless solution;
3) under the room temperature 1.8～7.4g ammonium fluoride is dissolved in the 150mL distilled water, stirs, obtain colourless solution;
4) under condition of stirring, the solution that step 3) is obtained progressively is added drop-wise to step 2) in the solution that obtains, the ammonium fluoride of usefulness is excessive far away, forms white precipitate; With the white precipitate centrifuge washing that obtains, the vacuum drying chamber inner drying at 80 ℃ obtains white powder; The white powder that obtains is calcined in tube furnace, fed under the situation of argon gas with secluding air, 420 ℃ were burnt 1～4 hour, and obtained the manganese difluoride powder;
5) manganese difluoride powder that step 4) is obtained and graphite are 1: 1 mixed by mass ratio, and under the situation that feeds argon gas, mechanical ball milling 4～6 hours obtains lithium ion battery negative material manganese difluoride and Nano graphite compound.
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| CN105314685A (en) * | 2014-07-31 | 2016-02-10 | 中国科学院上海硅酸盐研究所 | High-performance nano manganous fluoride cathode material and preparation method therefor |
| CN108172771A (en) * | 2016-12-07 | 2018-06-15 | 中国科学院上海硅酸盐研究所 | A kind of manganous fluoride/carbon composite and its preparation method and application |
| CN115893496B (en) * | 2022-11-10 | 2024-02-20 | 北京科技大学 | Composite anode material MnF2@C of lithium ion battery and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1812168A (en) * | 2005-01-26 | 2006-08-02 | 中国科学院金属研究所 | Modified method for lithium ion cell negative electrode material |
| CN101014541A (en) * | 2004-09-10 | 2007-08-08 | 昭和电工株式会社 | Process for producing manganese fluoride |
| CN101027255A (en) * | 2004-09-23 | 2007-08-29 | 阿斯特电子公司 | Method of manufacturing manganese tetrafluoride |
| CN101673818A (en) * | 2009-10-15 | 2010-03-17 | 中国工程物理研究院电子工程研究所 | Lithium ion battery cathode and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101014541A (en) * | 2004-09-10 | 2007-08-08 | 昭和电工株式会社 | Process for producing manganese fluoride |
| CN101027255A (en) * | 2004-09-23 | 2007-08-29 | 阿斯特电子公司 | Method of manufacturing manganese tetrafluoride |
| CN1812168A (en) * | 2005-01-26 | 2006-08-02 | 中国科学院金属研究所 | Modified method for lithium ion cell negative electrode material |
| CN101673818A (en) * | 2009-10-15 | 2010-03-17 | 中国工程物理研究院电子工程研究所 | Lithium ion battery cathode and preparation method thereof |
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