CN103311529B - A kind of pod-like carbon coated manganese oxide composite material of core-shell structure and its preparation method and application - Google Patents
A kind of pod-like carbon coated manganese oxide composite material of core-shell structure and its preparation method and application Download PDFInfo
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- CN103311529B CN103311529B CN201310239612.1A CN201310239612A CN103311529B CN 103311529 B CN103311529 B CN 103311529B CN 201310239612 A CN201310239612 A CN 201310239612A CN 103311529 B CN103311529 B CN 103311529B
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 239000011258 core-shell material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229960003638 dopamine Drugs 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 5
- 229960000281 trometamol Drugs 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
- 238000005255 carburizing Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- 239000011572 manganese Substances 0.000 abstract description 4
- 239000011149 active material Substances 0.000 abstract description 3
- 239000002070 nanowire Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229920000428 triblock copolymer Polymers 0.000 abstract description 2
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 abstract 1
- 239000012286 potassium permanganate Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- -1 poly(ethylene oxide) Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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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 discloses a kind of pod-like carbon coated manganese oxide composite material of core-shell structure and its preparation method and application.Preparation method is as follows: first with triblock copolymer PEO-PPO-PEO (P123) and PVP for surfactant, take potassium permanganate as the presoma nano wire that manganese source carries out that hydro-thermal reaction obtains manganese; Then be carbon source with dopamine, gather dopamine, high temperature cabonization a period of time at presoma coated with uniform one deck thin layer, prepare and there is pod-like carbon coated manganese oxide composite material.Being coated with of carbon-coating is beneficial to the electronic conductivity improving manganese oxide, large space between manganese oxide active material can effectively be buffered in the volumetric expansion produced in repeated charge process, Electrochemical results shows that it has outstanding multiplying power and cycle performance as lithium ion battery negative material, is expected to obtain in field of lithium ion battery apply widely.
Description
Technical field
The invention belongs to new energy materials field, relate to a kind of lithium ion battery electrode material and its preparation method and application, be specifically related to one and there is pod-like carbon coated manganese oxide nucleocapsid combination electrode material.
Background technology
Within 1991, Sony corporation of Japan releases first business-like lithium ion battery first to market, and because it has larger energy density, the advantages such as longer cycle life, it occupies more and more important position in daily life.Along with the fast development of various portable electric appts, electric automobile and hybrid vehicle, the performance of people to energy storage device lithium ion battery it is also proposed higher requirement.Electrode material is that lithium ion battery needs one of key issue solved, the update of anode material for lithium-ion batteries is very frequent, from the LiFePO4 that initial cobalt acid lithium, nickle cobalt lithium manganate use up till now, spinel lithium manganate, the performance of material is become better and better.But the negative material of commercial lithium ion battery is then always based on material with carbon element.Many deficiencies such as the first charge-discharge efficiency that material with carbon element exists is low, specific capacity is low, organic solvent embeds altogether start to govern the development of whole lithium ion battery.Researcher, while improving material with carbon element performance as possible, also starts to develop new, that can be used as lithium ion battery negative, that performance is more superior material.
In recent years, because manganese oxide material has the advantages such as high theoretical capacity, wide electromotive force window, cheap and good fail safe as lithium ion battery negative material, the focus of research is become.But it also exists, and irreversible capacity is first higher, cyclical stability and the poor problem of high rate performance.The method of at present carrying out improving for manganese oxide material mainly contain pattern control and carbon coated, as document (X.Q.Yu, Y.He, J.P.Sun, etal.NanocrystallineMnOThinFilmAnodeforLithiumIonBatteri eswithLowOverpotentialElectrochemistryCommunications.200 9,11:791 ~ 794) prepare nanoscale MnO film by the method for pulsed laser deposition, under the discharge and recharge system of 0.125C, the removal lithium embedded capacity of MnO membrane electrode is 472mAhg
-1, the capacity after 25 times that circulates still can remain on more than 90%.Document (K.Zhong, X.Xia, B.Zhang, etal.MnOPowderasAnodeActiveMaterialsforLithiumIonBatteri es.JournalofPowerSources.2010,195:3300 ~ 3308) by after commercial MnO and sucrose mechanical mixture, obtained the MnO/C composite material of carbon coated by high temperature sintering.The charge/discharge capacity of this composite material can reach 650mAhg
-1, after carbon coated, the cycle performance of MnO is significantly improved.But first charge-discharge efficiency is lower than 65%, during discharge and recharge, the potential plateau difference of removal lithium embedded is excessive, also needs to improve its performance further.So we have proposed a kind of pod-like carbon coated manganese oxide core-shell composite material and preparation method thereof here, this material illustrates outstanding multiplying power and cycle performance as lithium ion battery negative material.
Summary of the invention
The object of this invention is to provide a kind of pod-like carbon coated manganese oxide composite material of core-shell structure and its preparation method and application, to overcome the defect that above-mentioned existing electrode material exists.Mentality of designing is as follows:
With the manganese presoma nano wire of water heat transfer for template, take dopamine as carbon source, the surface of nano wire is coated on uniformly by dopamine auto polymerization under the effect of dissolved oxygen, high temperature cabonization again, volume contraction while inner manganese presoma is converted into manganese oxide, cause between manganese oxide particle and produce large space, thus form pod-like pattern.In prepared composite material, carbon-coating is coated with the electrical conductivity performance being beneficial to and improving manganese oxide, effectively can improve the high rate performance of this material; Large space between manganese oxide active material, can the effectively volumetric expansion that produces in repeated charge process of padded coaming, guarantees the high cyclical stability of composite material.
The present invention is achieved by the following technical solutions:
A kind of pod-like carbon coated manganese oxide composite material of core-shell structure, described composite material has following structure: manganese oxide nano granule subsection filling, in the tube chamber of carbon nano-tube, forms pod-like nanometer nuclear shell nano-structure; Long 2 ~ 8 μm of described composite material, diameter is 50 ~ 150nm, and the coated thickness of carbon-coating is 10 ~ 20nm.
A preparation method for pod-like carbon coated manganese oxide composite material of core-shell structure, comprises the steps:
(1) by 50 ~ 200mgP123(poly(ethylene oxide)-PPOX-poly(ethylene oxide) triblock copolymer) be dissolved in after in water add 30 ~ 80mgPVP(PVP) stir to clarify, then add the 0.1MKMnO of 5 ~ 20ml
4solution stirs, at 150 ~ 180 DEG C, carry out hydro-thermal reaction 6 ~ 12h, cleans and collecting reaction product after being cooled to room temperature;
(2) 0.2 ~ 0.6gP123 is dissolved in 200 ~ 600ml water, then add the stirring of 0.25 ~ 0.75g tromethamine and obtain cushioning liquid, again products therefrom in step (1) is scattered in the described cushioning liquid of 40 ~ 200ml, cool to room temperature after ultrasonic 30 ~ 90min;
(3) in the product of step (2), 10 ~ 80mg dopamine is added while stirring, stirring reaction 3 ~ 24h at 10 ~ 40 DEG C, filtration washing collecting reaction product;
(4) the product carburizing reagent 2 ~ 4h at 600 ~ 900 DEG C in an inert atmosphere will obtained in (3), described pod-like carbon coated manganese oxide composite material of core-shell structure can be obtained, wherein, manganese oxide nano granule subsection filling, in the tube chamber of carbon nano-tube, forms pod-like nanometer nuclear shell nano-structure.
The carbon source of described carburizing reagent is the carbon that poly-dopamine decomposes produces.
Described inert atmosphere is argon gas.
The application of above-mentioned pod-like carbon coated manganese oxide composite material of core-shell structure, that is, be applied to lithium ion battery as negative material.
From above technical scheme and implementation method, the pod-like carbon coated manganese oxide core-shell composite material prepared by the present invention is used as lithium ion battery negative material can show outstanding chemical property.Carbon-coating is conducive to the electrical conductivity performance improving manganese oxide, effectively can improve the high rate performance of this material; Space between manganese oxide active material, can the effectively volumetric expansion that produces in repeated charge process of padded coaming, guarantees the high cyclical stability of composite material.
Accompanying drawing explanation
Fig. 1 is the XRD curve of embodiment 1 product;
Fig. 2 is the transmission electron microscope photo of embodiment 1 product;
Fig. 3 has the electrochemical property test result that pod-like carbon coated manganese oxide core-shell composite material is lithium cell cathode material prepared by embodiment 1.
Embodiment
Elaborate to embodiments of the invention below, the present embodiment is implemented under premised on technical solution of the present invention, give detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
50mgP123 is dissolved in and adds 50mgPVP after in water and stir to clarify, then add 0.1MKMnO
4solution 6ml stirs, and carries out hydro-thermal reaction 8h at 150 DEG C, cleans and collecting reaction product after being cooled to room temperature.0.2gP123 is dissolved in 200ml water, then adds the stirring of 0.25g tromethamine and obtain cushioning liquid, more above-mentioned products therefrom is scattered in described cushioning liquid 100ml, cool to room temperature after ultrasonic 30min.20mg dopamine is added while stirring, stirred at ambient temperature reaction 5h, filtration washing collecting reaction product in above-mentioned solution.Then by the product obtained in argon gas atmosphere 850 DEG C carry out high temperature cabonization 2h, obtain pod-like carbon coated manganese oxide core-shell composite material, the XRD curve of product as shown in Figure 1, the transmission electron microscope photo of product as shown in Figure 2.CR2016 type button cell is adopted to test its chemical property.Fig. 3 is the rate charge-discharge test result figure of material, and as can be seen from the figure along with the increase of current density, its capacity suppression ratio is comparatively slow, illustrates that this material has good rate charge-discharge performance.And the circulation volume several times under each multiplying power keeps stable, when current density returns low range, capacity can well recover, and proves that this material has good cyclical stability.
Embodiment 2
50mgP123 is dissolved in and adds 30mgPVP after in water and stir to clarify, then add 0.1MKMnO
4solution 8ml stirs, and carries out hydro-thermal reaction 10h at 160 DEG C, cleans and collecting reaction product after being cooled to room temperature.0.4gP123 is dissolved in 400ml water, then adds the stirring of 0.5g tromethamine and obtain cushioning liquid, more above-mentioned products therefrom is scattered in described cushioning liquid 40ml, cool to room temperature after ultrasonic 60min.40mg dopamine is added while stirring, stirred at ambient temperature reaction 10h, filtration washing collecting reaction product in above-mentioned solution.Then by the product obtained in argon gas atmosphere 750 DEG C carry out high temperature cabonization 4h, obtain pod-like carbon coated manganese oxide core-shell composite material.Electro-chemical test part with embodiment 1, the prepared materials show experimental result almost identical with embodiment 1.
Embodiment 3
50mgP123 is dissolved in and adds 80mgPVP after in water and stir to clarify, then add 0.1MKMnO
4solution 20ml stirs, and carries out hydro-thermal reaction 12h at 180 DEG C, cleans and collecting reaction product after being cooled to room temperature.0.6gP123 is dissolved in 500ml water, then adds the stirring of 0.75g tromethamine and obtain cushioning liquid, more above-mentioned products therefrom is scattered in described cushioning liquid 200ml, cool to room temperature after ultrasonic 90min.80mg dopamine is added while stirring, stirred at ambient temperature reaction 24h, filtration washing collecting reaction product in above-mentioned solution.Then by the product obtained in argon gas atmosphere 900 DEG C carry out high temperature cabonization 2h, obtain pod-like carbon coated manganese oxide core-shell composite material.Electro-chemical test part with embodiment 1, the prepared materials show experimental result almost identical with embodiment 1.
Claims (3)
1. a preparation method for pod-like carbon coated manganese oxide composite material of core-shell structure, is characterized in that, comprise the steps:
(1) 50 ~ 200mgP123 is dissolved in adds 30 ~ 80mgPVP after in water and stir to clarify, then add the 0.1MKMnO of 5 ~ 20ml
4solution stirs, at 150 ~ 180 DEG C, carry out hydro-thermal reaction 6 ~ 12h, cleans and collecting reaction product after being cooled to room temperature;
(2) 0.2 ~ 0.6gP123 is dissolved in 200 ~ 600ml water, then add the stirring of 0.25 ~ 0.75g tromethamine and obtain cushioning liquid, again products therefrom in step (1) is scattered in the described cushioning liquid of 40 ~ 200ml, cool to room temperature after ultrasonic 30 ~ 90min;
(3) in the product of step (2), 10 ~ 80mg dopamine is added while stirring, stirring reaction 3 ~ 24h at 10 ~ 40 DEG C, filtration washing collecting reaction product;
(4) the product carburizing reagent 2 ~ 4h at 600 ~ 900 DEG C in an inert atmosphere will obtained in (3), described pod-like carbon coated manganese oxide composite material of core-shell structure can be obtained, wherein, manganese oxide nano granule subsection filling, in the tube chamber of carbon nano-tube, forms pod-like nanometer nuclear shell nano-structure.
2. preparation method according to claim 1, is characterized in that, described inert atmosphere is argon gas.
3. preparation method according to claim 1 and 2, it is characterized in that, described pod-like carbon coated manganese oxide composite material of core-shell structure has following structure: manganese oxide nano granule has space each other and is filled in the tube chamber of carbon nano-tube with segmented mode, forms pod-like nanometer nuclear shell nano-structure; Long 2 ~ 8 μm of described composite material, diameter is 50 ~ 150nm, and the coated thickness of carbon-coating is 10 ~ 20nm.
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| CN103618061B (en) * | 2013-11-04 | 2016-02-24 | 中国科学院化学研究所 | The controlled coated method of carbon-coating is carried out to polyanionic lithium ion battery anode material |
| CN104409727A (en) * | 2014-05-31 | 2015-03-11 | 福州大学 | Method for preparing lithium ion battery porous electrode based on 3D printing technology |
| CN104638257A (en) * | 2015-01-22 | 2015-05-20 | 南京工业大学 | Nano-scale manganous oxide-conductive carbon black composite material and synthetic method thereof |
| CN105633373B (en) * | 2015-11-06 | 2018-06-22 | 北京化工大学 | A kind of porous manganese monoxide composite material of carbon coating and its preparation method and application |
| CN105664936A (en) * | 2016-01-07 | 2016-06-15 | 上海工程技术大学 | Method for preparing nano composite material having core-shell structure with dopamine as carbon source |
| CN106099106B (en) * | 2016-08-22 | 2019-06-18 | 上海工程技术大学 | It is ultrafast to fill lithium ion battery negative material, preparation method and lithium ion battery |
| CN106129407A (en) * | 2016-08-29 | 2016-11-16 | 上海大学 | MoS2the synthetic method of@graphene composite nano material |
| CN107369825B (en) * | 2017-07-26 | 2020-01-10 | 华南理工大学 | Nitrogen-doped carbon-coated manganese oxide lithium ion battery composite negative electrode material and preparation method and application thereof |
| CN109817948A (en) * | 2019-03-04 | 2019-05-28 | 河南师范大学 | A kind of preparation method of lithium ion battery carbon coating MnO/ crystalline flake graphite combination electrode material |
| CN110177449B (en) * | 2019-05-17 | 2020-12-29 | 同济大学 | Carbon nanotube-based electromagnetic composite wave-absorbing material and preparation method and application thereof |
| CN112870378B (en) * | 2021-01-29 | 2022-09-30 | 曲阜师范大学 | Manganese dioxide nano drug delivery system and preparation method and application thereof |
| CN112940690B (en) * | 2021-02-05 | 2021-11-02 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | Phase change energy storage material with pod structure and preparation method and application thereof |
| CN113194703B (en) * | 2021-04-28 | 2022-05-31 | 复旦大学 | Microwave absorption nano material with yolk shell structure and preparation and application thereof |
| CN115663138A (en) * | 2022-10-28 | 2023-01-31 | 安徽科技学院 | Nitrogen-doped carbon film-wrapped manganese monoxide nanowire lithium battery material and preparation method thereof |
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| CN102810673A (en) * | 2012-08-16 | 2012-12-05 | 山东大学 | Method for preparing carbon-coated MnO coaxial nanowire cathode material for lithium ion batteries |
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