CN103311529A - Legume-shaped carbon-coated manganese oxide core-shell structure composite material and preparation method and application thereof - Google Patents
Legume-shaped carbon-coated manganese oxide core-shell structure composite material and preparation method and application thereof Download PDFInfo
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical group [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 239000011258 core-shell material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 17
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229960003638 dopamine Drugs 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 16
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method 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
- 230000011218 segmentation Effects 0.000 claims description 4
- 238000005255 carburizing Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 7
- -1 polyethylene Polymers 0.000 abstract description 6
- 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
- 238000000840 electrochemical analysis Methods 0.000 abstract description 3
- 239000002070 nanowire Substances 0.000 abstract description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 abstract description 2
- 239000004698 Polyethylene Substances 0.000 abstract description 2
- 239000010406 cathode material Substances 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract description 2
- 229920001690 polydopamine Polymers 0.000 abstract description 2
- 229920000573 polyethylene Polymers 0.000 abstract description 2
- 229920000428 triblock copolymer Polymers 0.000 abstract description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 abstract 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 abstract 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 2
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 abstract 1
- 239000004743 Polypropylene Substances 0.000 abstract 1
- 238000010000 carbonizing Methods 0.000 abstract 1
- 229920001155 polypropylene 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
- 238000012360 testing method Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 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
- 239000006183 anode active material 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
- 230000009286 beneficial effect Effects 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
- 238000004891 communication Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient 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
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010408 film Substances 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
- 238000012423 maintenance Methods 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 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
- 239000010409 thin film Substances 0.000 description 1
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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 legume-shaped carbon-coated manganese oxide core-shell structure composite material and a preparation method and application thereof. The preparation method comprises the following steps: firstly, with a triblock copolymer polyethylene oxide-polypropylene oxide-polyethylene oxide PEO-PPO-PEO (P123) and polyvinyl pyrrolidone (PVP) as surfactants and potassium permanganate as a manganese source, carrying out hydrothermal reaction so as to obtain a precursor nano wire of manganese; then with dopamine as a carbon source, uniformly wrapping a layer of thin polydopamine on the surface of the precursor, and carbonizing for a certain period at a high temperature so as to prepare the legume-shaped carbon-coated manganese oxide core-shell structure composite material. Due to the wrapping of the carbon layer, the electron conductivity of the manganese oxide is improved; due to the large space among the manganese oxide active material, the volume expansion in the repeated charging and discharging process is effectively buffered; and the electrochemical test result shows that the material serving as a lithium ion battery cathode material has excellent multiplying power and circulation property, and the material is expected to be widely applied to the field of lithium ion batteries.
Description
Technical field
The invention belongs to the new energy materials field, relate to a kind of lithium ion battery electrode material and its preparation method and application, be specifically related to a kind of pod-like carbon coated manganese oxide nucleocapsid combination electrode material that has.
Background technology
Sony corporation of Japan was released first business-like lithium ion battery first to market in 1991, because it has bigger energy density, and long advantages such as 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, people also have higher requirement to the performance of energy storage device lithium ion battery.Electrode material is one of lithium ion battery key issue that need solve, the update of anode material for lithium-ion batteries is very frequent, from initial cobalt acid lithium, the LiFePO4 that nickle cobalt lithium manganate uses up till now, spinel lithium manganate, the performance of material is become better and better.Yet the negative material of commercial lithium ion battery is 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 begin restricting the development of entire lithium ion battery.The researcher when improving the material with carbon element performance as possible, also begin to develop new, can be used as material lithium ion battery negative, that performance is more superior.
In recent years, because the manganese oxide material has high theoretical capacity, wide electromotive force window, cheap and good advantages such as fail safe as lithium ion battery negative material, become the focus of research.But it also exists first, and irreversible capacity is higher, cyclical stability and the relatively poor problem of high rate performance.Carry out improved method at the manganese oxide material at present and mainly contain pattern control and carbon coating, as document (X.Q.Yu, Y.He, J.P.Sun, et al.Nanocrystalline MnO Thin Film Anode for Lithium Ion Batteries with Low Overpotential Electrochemistry Communications.2009,11:791～794) prepare nanoscale MnO film with the method for pulsed laser deposition, the removal lithium embedded capacity of MnO membrane electrode is 472mAhg under the system that discharges and recharges of 0.125C
-1, circulating, capacity still can remain on more than 90% after 25 times.Document (K.Zhong, X.Xia, B.Zhang, et al.MnO Powder as Anode Active Materials for Lithium Ion Batteries.Journal of Power Sources.2010,195:3300～3308) with after commercial MnO and the sucrose mechanical mixture, obtain the MnO/C composite material of carbon coated by high temperature sintering.The charge/discharge capacity of this composite material can reach 650mAhg
-1, the cycle performance of MnO is significantly improved after the carbon coated.But first charge-discharge efficiency is lower than 65%, and the current potential platform difference of removal lithium embedded is excessive when discharging and recharging, and also needs further to improve its performance.So here we have proposed a kind of pod-like carbon coated manganese oxide nucleocapsid composite material and preparation method thereof, this material has been showed outstanding multiplying power and cycle performance as lithium ion battery negative material.
Summary of the invention
The purpose 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 defective that above-mentioned existing electrode material exists.Mentality of designing is as follows:
The manganese presoma nano wire synthetic with hydro thermal method is template, be carbon source with the dopamine, be coated on the surface of nano wire uniformly by dopamine auto polymerization under the effect of dissolved oxygen, high temperature cabonization again, volume contraction when inner manganese presoma is converted into manganese oxide, cause to produce big space between the manganese oxide particle, thereby form the pod-like pattern.In the prepared composite material, carbon-coating is coated with and is beneficial to the electrical conductivity performance that improves manganese oxide, can effectively improve the high rate performance of this material; Big space between the manganese oxide active material, the high cyclical stability of composite material is guaranteed in the effectively volumetric expansion that produces in the repeated charge process of padded coaming.
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: the manganese oxide nano granule segmentation is filled in the tube chamber of carbon nano-tube, forms pod-like core-shell nano structure; Long 2～8 μ m of described composite material, diameter is 50～150nm, it is 10～20nm that carbon-coating coats thickness.
A kind of preparation method of pod-like carbon coated manganese oxide composite material of core-shell structure comprises the steps:
(1) with 50～200mg P123(poly(ethylene oxide)-PPOX-poly(ethylene oxide) triblock copolymer) be dissolved in the water back and add 30～80mgPVP(polyethylene than pyrrolidone) stir to clarify, add the 0.1M KMnO of 5～20ml again
4Solution stirs, and carries out hydro-thermal reaction 6～12h under 150～180 ℃, is cooled to after the room temperature to clean and collecting reaction product;
(2) 0.2～0.6g P123 is dissolved in 200～600ml water, add the stirring of 0.25～0.75g tromethamine then and obtain cushioning liquid, again products therefrom in the step (1) is scattered in the described cushioning liquid of 40～200ml cool to room temperature behind ultrasonic 30～90min;
(3) in the product of step (2), add 10～80mg dopamine while stirring, 10～40 ℃ of following stirring reaction 3～24h, filtration washing collecting reaction product;
(4) with the product that obtains in (3) in inert atmosphere in 600～900 ℃ of following carburizing reagent 2～4h, can obtain described pod-like carbon coated manganese oxide composite material of core-shell structure, wherein, the manganese oxide nano granule segmentation is filled in the tube chamber of carbon nano-tube, forms pod-like core-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 namely, is applied to lithium ion battery as negative material.
By above technical scheme and implementation method as can be known, the prepared pod-like carbon coated manganese oxide nucleocapsid composite material of the present invention can show outstanding chemical property as lithium ion battery negative material.Carbon-coating is conducive to improve the electrical conductivity performance of manganese oxide, can effectively improve the high rate performance of this material; Space between the manganese oxide active material, the high cyclical stability of composite material is guaranteed in the effectively volumetric expansion that produces in the repeated charge process of padded coaming.
Description of drawings
Fig. 1 is the XRD curve of embodiment 1 product;
Fig. 2 is the transmission electron microscope photo of embodiment 1 product;
Fig. 3 is that prepared to have pod-like carbon coated manganese oxide nucleocapsid composite material be the electrochemical property test result of lithium cell cathode material for embodiment 1.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Add 50mgPVP after being dissolved in 50mg P123 in the water and stir to clarify, add 0.1M KMnO again
4Solution 6ml stirs, and carries out hydro-thermal reaction 8h at 150 ℃, is cooled to after the room temperature to clean and collecting reaction product.0.2g P123 is dissolved in the 200ml water, adds the stirring of 0.25g tromethamine then and obtain cushioning liquid, more above-mentioned products therefrom is scattered among the described cushioning liquid 100ml cool to room temperature behind the ultrasonic 30min.In above-mentioned solution, add the 20mg dopamine while stirring, stirring reaction 5h under the room temperature, filtration washing collecting reaction product.Then with the product that obtains in argon gas atmosphere 850 ℃ carry out high temperature cabonization 2h, obtain pod-like carbon coated manganese oxide nucleocapsid composite material, the XRD curve of product as shown in Figure 1, the transmission electron microscope photo of product as shown in Figure 2.Adopt CR2016 type button cell 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 slower, illustrates that this material has rate charge-discharge performance preferably.And the maintenance of the circulation volume several times under each multiplying power is stable, and when current density was returned low range, capacity can well recover, and proved that this material has good cyclical stability.
Embodiment 2
Add 30mgPVP after being dissolved in 50mg P123 in the water and stir to clarify, add 0.1M KMnO again
4Solution 8ml stirs, and carries out hydro-thermal reaction 10h at 160 ℃, is cooled to after the room temperature to clean and collecting reaction product.0.4g P123 is dissolved in the 400ml water, adds the stirring of 0.5g tromethamine then and obtain cushioning liquid, more above-mentioned products therefrom is scattered among the described cushioning liquid 40ml cool to room temperature behind the ultrasonic 60min.In above-mentioned solution, add the 40mg dopamine while stirring, stirring reaction 10h under the room temperature, filtration washing collecting reaction product.Then with the product that obtains in argon gas atmosphere 750 ℃ carry out high temperature cabonization 4h, obtain pod-like carbon coated manganese oxide nucleocapsid composite material.Electro-chemical test part is with embodiment 1, and prepared material has been showed the experimental result almost identical with embodiment 1.
Embodiment 3
Add 80mgPVP after being dissolved in 50mg P123 in the water and stir to clarify, add 0.1M KMnO again
4Solution 20ml stirs, and carries out hydro-thermal reaction 12h at 180 ℃, is cooled to after the room temperature to clean and collecting reaction product.0.6g P123 is dissolved in the 500ml water, adds the stirring of 0.75g tromethamine then and obtain cushioning liquid, more above-mentioned products therefrom is scattered among the described cushioning liquid 200ml cool to room temperature behind the ultrasonic 90min.In above-mentioned solution, add the 80mg dopamine while stirring, stirring reaction 24h under the room temperature, filtration washing collecting reaction product.Then with the product that obtains in argon gas atmosphere 900 ℃ carry out high temperature cabonization 2h, obtain pod-like carbon coated manganese oxide nucleocapsid composite material.Electro-chemical test part is with embodiment 1, and prepared material has been showed the experimental result almost identical with embodiment 1.
Claims (4)
1. pod-like carbon coated manganese oxide composite material of core-shell structure, it is characterized in that described composite material has following structure: the manganese oxide nano granule segmentation is filled in the tube chamber of carbon nano-tube, forms pod-like core-shell nano structure; Long 2～8 μ m of described composite material, diameter is 50～150nm, it is 10～20nm that carbon-coating coats thickness.
2. the preparation method of a pod-like carbon coated manganese oxide composite material of core-shell structure is characterized in that, comprises the steps:
(1) adds 30～80mgPVP after 50～200mg P123 being dissolved in the water and stir to clarify, add the 0.1M KMnO of 5～20ml again
4Solution stirs, and carries out hydro-thermal reaction 6～12h under 150～180 ℃, is cooled to after the room temperature to clean and collecting reaction product;
(2) 0.2～0.6g P123 is dissolved in 200～600ml water, add the stirring of 0.25～0.75g tromethamine then and obtain cushioning liquid, again products therefrom in the step (1) is scattered in the described cushioning liquid of 40～200ml cool to room temperature behind ultrasonic 30～90min;
(3) in the product of step (2), add 10～80mg dopamine while stirring, 10～40 ℃ of following stirring reaction 3～24h, filtration washing collecting reaction product;
(4) with the product that obtains in (3) in inert atmosphere in 600～900 ℃ of following carburizing reagent 2～4h, can obtain described pod-like carbon coated manganese oxide composite material of core-shell structure, wherein, the manganese oxide nano granule segmentation is filled in the tube chamber of carbon nano-tube, forms pod-like core-shell nano structure.
3. preparation method according to claim 2 is characterized in that, described inert atmosphere is argon gas.
4. the application of claims 1 described pod-like carbon coated manganese oxide composite material of core-shell structure is characterized in that, described pod-like carbon coated manganese oxide composite material of core-shell structure is applied to lithium ion battery as negative material.
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| CN103618061A (en) * | 2013-11-04 | 2014-03-05 | 中国科学院化学研究所 | Method for carbon layer controllable coating to polyanion-type lithium ion batteries cathode materials |
| 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 |
| CN105633373A (en) * | 2015-11-06 | 2016-06-01 | 北京化工大学 | Carbon-coated porous manganese monoxide composite material and preparation method and application thereof |
| 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 |
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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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| 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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| CN103618061A (en) * | 2013-11-04 | 2014-03-05 | 中国科学院化学研究所 | Method for carbon layer controllable coating to polyanion-type lithium ion batteries cathode materials |
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| 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 |
| CN105633373A (en) * | 2015-11-06 | 2016-06-01 | 北京化工大学 | Carbon-coated porous manganese monoxide composite material and preparation method and application thereof |
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