CN102983321A - Carbon-coated MnOx nano energy storage material with one-dimensional core-shell structure and preparation method thereof - Google Patents
Carbon-coated MnOx nano energy storage material with one-dimensional core-shell structure and preparation method thereof Download PDFInfo
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- CN102983321A CN102983321A CN2012105649565A CN201210564956A CN102983321A CN 102983321 A CN102983321 A CN 102983321A CN 2012105649565 A CN2012105649565 A CN 2012105649565A CN 201210564956 A CN201210564956 A CN 201210564956A CN 102983321 A CN102983321 A CN 102983321A
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Abstract
The invention discloses a carbon-coated MnOx nano energy storage material with a one-dimensional core-shell structure and a preparation method thereof. The energy storage material with a one-dimensional core-shell structure, which takes amorphous carbon as a shell and a MnOx nanowire as a core, is prepared by using a hydrothermal method through the processes of suction filtration, ultrasonic treatment, heat treatment, soaking and the like. According to the invention, the preparation processes are simple, and the prepared material has the advantages of high specific surface area, good electrical conductivity, good structure stability and good electrochemical cycle performance, and has a great application potential in the field of negative electrode materials for lithium secondary batteries.
Description
Technical field
The invention belongs to new forms of energy nanometer energy storage material field, be specifically related to a kind of one dimension core-shell structure carbon and coat MnO
xNanometer energy storage material and preparation method thereof.
Background technology
Along with the day by day exhaustion of traditional energy, the lithium rechargeable battery that represents as new forms of energy has received increasing concern.While is as the main power source of portable communication apparatus and portable electric appts, owing to it has the focus that becomes domestic and international research than excellent properties such as high output voltage and high-energy-densities.The demand of, high power capacity communication apparatus high-power for satisfying and electronic equipment, both at home and abroad the expert be devoted to study always have high power capacity, the lithium ion battery electrode material of good stability, economy, environmental protection, wherein the manganese oxide material is because its higher theoretical lithium memory capacity, be considered to a kind of most potential negative material, and be widely studied.
But, as the manganese oxide of negative material is low because of himself conductance, heavy-current discharge performance is poor, particularly in the situation of high-multiplying power discharge, its voltage platform is on the low side, energy density is less, has caused its cycle performance poor, and termination capacity can't be compared with its theoretical capacity.Therefore, for the electric conductivity that improves the manganese oxide material with and actual capacity and cycle performance in lithium ion battery applications, people are seeking how to improve the research of its circulating and reversible capacity and electric conductivity always.
There are some researches show when the size with the manganese oxide material is reduced to Nano grade and can effectively improve its discharge theoretical capacity, also having part Study to add other materials in the manganese oxide material forms and becomes again composite material, improve its electric conductivity with this, thereby also improve its cycle performance.A kind of MnO of preparation is provided (CN1438181A)
2The preparations of nanomaterials method: adopting potassium permanganate is the raw material material, take the alkylol APEO as reducing agent, surface dispersant and particle size stabilizer, makes nano-manganese dioxide by redox reaction.Document Chem. Commun., the MnO that 2012,48,6945 – 6947 propose
2The research of nano wire, their method is by preparing nano thread structure MnO
2Improved MnO
2As the chemical property of negative material, but do not change its poor electric conductivity, the poor shortcoming of cyclicity.Document Electrochemistry Communications 11 (2009) 795 – 798 have proposed the electrostatic spinning preparation and have had higher consistency MnO
2@Carbon composite material has effectively improved MnO
2Charge-discharge performance and conductivity, but its preparation equipment needed thereby more complicated, production efficiency is low, cost is higher.Therefore thereby effectively bring into play each composition in the nano composite material by artificial designing material structure and material composition takes off synergy realization composites performance raising in the process etc. in the lithium embedding and all remains further research.
In sum, the material of the manganese oxide of mentioning in most of document or the patent in theory all can not be eliminated the decline of its cycle performance effectively, thereby affects the application and development of manganese oxide material aspect the lithium electricity.The present compound preparation method of manganese oxide and other materials more complicated all in the patent meanwhile, and the manganese oxide material specific area for preparing is limited, poorly conductive, limited for its lithium memory property effect of raising.
Summary of the invention
The object of the invention is to for shortcomings and deficiencies of the prior art, provide a kind of one dimension core-shell structure carbon to coat MnO
xNanometer energy storage material and preparation method thereof, preparation technology is simple, prepared material has the advantage of high-specific surface area, good conductivity, structural stability and electrochemistry good cycle, in lithium secondary battery electrode negative material field huge application potential is arranged.
For achieving the above object, the present invention adopts following technical scheme:
A kind of one dimension core-shell structure carbon coats MnO
xThe preparation method of nanometer energy storage material comprises the steps:
(1) adopt hydro thermal method to prepare MnO
2Nano wire;
(2) ethanolic solution of preparation 20-40mL macromolecule organic takes by weighing the MnO of 0.5-1.5g step (1)
2Nano wire is distributed to wherein, and ultrasonic processing, filtration, drying obtain being distributed in the MnO in the macromolecule organic
2Nano wire;
(3) with the MnO in the macromolecule organic of being distributed in of step (2)
2Nano wire carries out high-temperature heat treatment under protective atmosphere, cooling obtains one dimension core-shell structure carbon and coats MnO
xThe nanometer energy storage material.
Described MnO
xBe Mn
3O
4, MnO
2, MnO, Mn
2The mixture of one or more among the O.
The ethanolic solution of the described macromolecule organic of step (2) is the ethanolic solution of polyvinylpyrrolidone (PVP), and its concentration is 0.1-1.5mol/L.
The described high-temperature heat treatment of carrying out under protective atmosphere of step (3) refers to be full of in the tube furnace of argon gas or nitrogen, 500-700 ℃ of lower heating 2-5h.
The method can take full advantage of the high capacity characteristics of manganese oxide material aspect lithium ion battery, and preparation is take the manganese oxide nano wire as mainly discharging and recharging the lithium ion battery negative material of material; In addition, the adding of amorphous carbon overcomes the deformation in charge and discharge process of manganese oxide nano wire breaks even breaks away from and the drawback of the electrode material poorly conductive that causes, thereby obtains a kind ofly to have high power capacity, higher rate charge-discharge speed and capacity and the one dimension shell nuclear carbon of good circulation performance and coat MnO
xThe preparation method of nano wire energy storage material.
Beneficial effect of the present invention is: the ion cathode material lithium of the present invention's preparation is a kind of with amorphous carbon coating MnO
xOne dimension shell nuclear nano thread structure, compared with prior art, this invention is because priority adopts hydro thermal method and infusion method, not only possessed nano-material the high-specific surface area effect but also possess 1-dimention nano functional material design feature.Simultaneously, with carbon the effective parcel of manganese oxide and isolation are got up, effectively prevented its reuniting effect in charge and discharge process, and improved structural stability, conductivity and the cyclicity stability of composite material.In addition, simple process of the present invention, easy to operate, material composition are easy to regulation and control, are the effective ways that preparation comprises high performance lithium ion battery electrode material nano-functional material.
Description of drawings
Fig. 1 is that single one dimension core-shell structure carbon coats MnO
xThe structural representation of nano wire energy storage material, wherein (1) is that shell, (2) are nuclear.
Fig. 2 is MnO
2The scanning electron microscope (SEM) photograph of nano wire.
Fig. 3 is the MnO that is distributed among the PVP
2The scanning electron microscope (SEM) photograph of nano wire.
Fig. 4 is that one dimension core-shell structure carbon coats MnO
xThe scanning electron microscope (SEM) photograph of nano wire energy storage material.MnO wherein
xBe Mn
3O
4, MnO
2, MnO, Mn
2The mixture of one or more among the O.
Embodiment
The present invention aims to provide a kind of one dimension shell nuclear carbon and coats MnO
xThe preparation method of nano wire energy storage material shows by reference to the accompanying drawings and concrete execution mode illustrates.
1) taking by weighing quality is that 1.64g five hydration manganese acetates, 1.59g potassium peroxydisulfate, 2.47g ammonium nitrate dissolve in respectively in 10ml, 20ml, the 10ml deionized water, ultrasonic processing 10min, solution is mixed again ultrasonic 10min, transfer to the 60ml hydrothermal reaction kettle, place 140 ℃ of lower heat treatment 12h of baking oven, deionized water, alcohol wash are used in cooling successively, place 50 ℃ of lower dry 24h of baking oven, obtain MnO
2Nano wire; Fig. 2 is MnO
2The scanning electron microscope (SEM) photograph of nano wire;
2) take by weighing 0.7gPVP and be dissolved in the 20ml ethanol, be stirred to homogeneous solution, take by weighing again the MnO in the 0.5g step 1)
2Nano wire is distributed to the PVP ethanolic solution, and ultrasonic 2h behind filtration, the dry 12h, can obtain being distributed in the MnO among the PVP
2Nano wire; Fig. 3 is the MnO that is distributed among the PVP
2The scanning electron microscope (SEM) photograph of nano wire;
3) take by weighing 0.8g step 2) in be distributed in MnO among the PVP
2Nano wire places the tube furnace of Ar gas protection, and 500 ℃ of heat treatment 2h are cooled to room temperature, can obtain one dimension core-shell structure carbon and coat MnO
xNano wire energy storage material, wherein MnO
xBe Mn
3O
4, MnO
2, MnO, Mn
2The mixture of one or more among the O; Fig. 4 is that one dimension core-shell structure carbon coats MnO
xThe scanning electron microscope (SEM) photograph of nano wire energy storage material.
1) taking by weighing quality is that 2.45 five hydration manganese acetates, 2.38g potassium peroxydisulfate, 2.44g ammonium nitrate dissolve in respectively 10ml, 30ml, 10ml deionized water, be labeled as respectively A, B, C, to mix behind A, B, the ultrasonic 10min of C, transfer in the 80ml hydrothermal reaction kettle, place 120 ℃ of lower heat treatment 12h of baking oven, cooling, use successively deionized water, alcohol, deionized water, alcohol wash four times after, place 75 ℃ of lower dry 24h of baking oven, namely obtain MnO
2Nano wire;
2) get 0.8gPVP and be dissolved in the 25ml ethanol, stir 1h, then take by weighing the MnO in the step 1)
2Nano wire 0.7g is distributed in the PVP ethanolic solution, leaves standstill 1h behind the ultrasonic 2h again, and filtration, drying obtain being distributed in the MnO among the PVP
2Nano wire;
3) take by weighing 1.0g step 2) in be distributed in MnO among the PVP
2Nano wire places in the tube furnace under the nitrogen protection, 550 ℃ of heat treatment 3h, and cooling can obtain one dimension core-shell structure carbon and coat MnO
xNano wire energy storage material, wherein MnO
xBe Mn
3O
4, MnO
2, MnO, Mn
2The mixture of one or more among the O.
Embodiment 3
1) getting respectively 2mmol five hydration manganese acetates, 2mmol potassium peroxydisulfate, 3mmol ammonium nitrate dissolves in respectively in 20ml, 35ml, the 15ml deionized water, mix behind the ultrasonic processing 10min, transfer in the 100ml hydrothermal reaction kettle behind the ultrasonic 10min again, with being placed on 160 ℃ of lower heat treatment 12h in the baking oven, after the cooling, use successively deionized water, alcohol wash, place again 50 ℃ of lower dry 48h of baking oven, namely obtain MnO
2Nano wire;
2) get 1.2gPVP and be dissolved in the 40ml ethanol, then get the MnO in the step 1)
2Nano thread structure material 0.8g is distributed to wherein in situation about stirring, and ultrasonic 2h filters, and drying obtains being distributed in the MnO among the PVP
2Nano wire;
3) with step 2) in be distributed in MnO among the PVP
2Nano wire in Ar atmosphere pipe type stove in, 600 ℃ of heat treatment 3h, be cooled to room temperature after, can obtain one dimension core-shell structure carbon and coat MnO
xNano wire energy storage material, wherein MnO
xBe Mn
3O
4, MnO
2, MnO, Mn
2The mixture of one or more among the O.
The above only is preferred embodiment of the present invention, and all equalizations of doing according to the present patent application claim change and modify, and all should belong to covering scope of the present invention.
Claims (5)
1. an one dimension core-shell structure carbon coats MnO
xThe preparation method of nanometer energy storage material is characterized in that: comprise the steps:
(1) adopt hydro thermal method to prepare MnO
2Nano wire;
(2) ethanolic solution of preparation 20-40mL macromolecule organic takes by weighing the MnO of 0.5-1.5g step (1)
2Nano wire is distributed to wherein, and ultrasonic processing, filtration, drying obtain being distributed in the MnO in the macromolecule organic
2Nano wire;
(3) with the MnO in the macromolecule organic of being distributed in of step (2)
2Nano wire carries out high-temperature heat treatment under protective atmosphere, cooling obtains one dimension core-shell structure carbon and coats MnO
xThe nanometer energy storage material.
2. one dimension core-shell structure carbon according to claim 1 coats MnO
xThe preparation method of nanometer energy storage material is characterized in that: described MnO
xBe Mn
3O
4, MnO
2, MnO, Mn
2The mixture of one or more among the O.
3. one dimension core-shell structure carbon according to claim 1 coats MnO
xThe preparation method of nanometer energy storage material is characterized in that: the ethanolic solution of the described macromolecule organic of step (2) is the ethanolic solution of polyvinylpyrrolidone, and its concentration is 0.1-1.5mol/L.
4. one dimension core-shell structure carbon according to claim 1 coats MnO
xThe preparation method of nanometer energy storage material is characterized in that: the described high-temperature heat treatment of carrying out under protective atmosphere of step (3) refers to be full of in the tube furnace of argon gas or nitrogen, 500-700 ℃ of lower heating 2-5h.
5. the one dimension core-shell structure carbon that makes of the method for claim 1 coats MnO
xThe nanometer energy storage material.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103633304A (en) * | 2013-12-06 | 2014-03-12 | 福州大学 | Method for preparing coaxially-composite nano material by using carbon nano tube as core |
| CN103769579A (en) * | 2014-01-26 | 2014-05-07 | 江苏鹰球集团有限公司 | Method for preparing carbon-encapsulated Cu/Mn2O composite porous material |
| CN104993143A (en) * | 2015-05-25 | 2015-10-21 | 西北工业大学 | Preparation method of self-support lithium ion battery cathode material |
| CN105047899A (en) * | 2015-06-16 | 2015-11-11 | 田东 | Synthesis method of lithium-ion cathode material LiMn2O4/C |
| CN105914051A (en) * | 2016-06-02 | 2016-08-31 | 安徽师范大学 | One-dimensional MnO2@NiMoO4 core shell heterojunction composite material and preparation method and application thereof |
| CN106229499A (en) * | 2016-09-18 | 2016-12-14 | 陕西科技大学 | A kind of preparation method of lithium ion battery MnO/Super P nanometer anode material |
| CN108703417A (en) * | 2018-06-08 | 2018-10-26 | 佛山市南海区佳妍内衣有限公司 | Anti-bacterial briefs based on far-infrared physiotherapy |
| CN110828799A (en) * | 2019-10-31 | 2020-02-21 | 北京科技大学 | Water-system zinc ion battery MnOx@ C cathode material and preparation method thereof |
| CN113823777A (en) * | 2021-08-11 | 2021-12-21 | 中国地质大学（武汉） | Porous nitrogen-doped carbon coaxial coating manganese dioxide nanotube and preparation method and application thereof |
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| CN105702923B (en) * | 2016-01-29 | 2018-08-10 | 中国科学院宁波材料技术与工程研究所 | A kind of manganese oxide/carbon/carbon nanotube hybrid material and its preparation method and application |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103633304A (en) * | 2013-12-06 | 2014-03-12 | 福州大学 | Method for preparing coaxially-composite nano material by using carbon nano tube as core |
| CN103769579A (en) * | 2014-01-26 | 2014-05-07 | 江苏鹰球集团有限公司 | Method for preparing carbon-encapsulated Cu/Mn2O composite porous material |
| CN103769579B (en) * | 2014-01-26 | 2016-05-25 | 江苏鹰球集团有限公司 | The preparation method of the coated Cu/Mn2O composite porous material of a kind of carbon |
| CN104993143A (en) * | 2015-05-25 | 2015-10-21 | 西北工业大学 | Preparation method of self-support lithium ion battery cathode material |
| CN105047899A (en) * | 2015-06-16 | 2015-11-11 | 田东 | Synthesis method of lithium-ion cathode material LiMn2O4/C |
| CN105914051A (en) * | 2016-06-02 | 2016-08-31 | 安徽师范大学 | One-dimensional MnO2@NiMoO4 core shell heterojunction composite material and preparation method and application thereof |
| CN105914051B (en) * | 2016-06-02 | 2019-04-16 | 安徽师范大学 | One-dimensional MnO2@NiMoO4Nucleocapsid heterojunction composite and its preparation method and application |
| CN106229499A (en) * | 2016-09-18 | 2016-12-14 | 陕西科技大学 | A kind of preparation method of lithium ion battery MnO/Super P nanometer anode material |
| CN108703417A (en) * | 2018-06-08 | 2018-10-26 | 佛山市南海区佳妍内衣有限公司 | Anti-bacterial briefs based on far-infrared physiotherapy |
| CN110828799A (en) * | 2019-10-31 | 2020-02-21 | 北京科技大学 | Water-system zinc ion battery MnOx@ C cathode material and preparation method thereof |
| CN113823777A (en) * | 2021-08-11 | 2021-12-21 | 中国地质大学（武汉） | Porous nitrogen-doped carbon coaxial coating manganese dioxide nanotube and preparation method and application thereof |
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