CN105140506A - Three-dimensional porous MnO/C-N nano-composite material based on rape pollen, preparing method thereof and application thereof - Google Patents
Three-dimensional porous MnO/C-N nano-composite material based on rape pollen, preparing method thereof and application thereof Download PDFInfo
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- CN105140506A CN105140506A CN201510641977.6A CN201510641977A CN105140506A CN 105140506 A CN105140506 A CN 105140506A CN 201510641977 A CN201510641977 A CN 201510641977A CN 105140506 A CN105140506 A CN 105140506A
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
Abstract
The invention provides a three-dimensional porous MnO/C-N nano-composite material based on rape pollen, a preparing method thereof and an application thereof. In other words, MnO nanometer micro crystals are assembled in a C-N frame provided by the rape pollen. The preparing method includes the steps that the rape pollen is scattered into a KMnO4 solution, and stirring is carried out at the normal temperature; then filtering, washing and vacuum drying are carried out, high-temperature calcination is carried out, and the nano-composite material is obtained. According to the MnO/C-N nano-composite material, the rape pollen low in price and easy to get serves as raw materials, stirring, soaking and calcination are carried out, the preparing method is simple, and popularization is easy; a lithium ion battery prepared from the MnO/C-N nano-composite material is low in cost, good in lithium ion storage performance and circularity and high in stability, and has the characteristics such as the high rate, and therefore the large application potential is achieved.
Description
Technical field
The present invention relates to the research field of lithium ion battery negative material, particularly a kind of MnO/C-N and its preparation method and application of three-dimensional porous nano structure.
Background technology
Recently, lithium battery is regarded as the first-selection of portable set and electric automobile power source, and the performance of lithium battery is mainly fixed against its electrode material, and therefore the electrode material of development of new causes very large concern.And now, graphite/carbon is by widely with being negative material, but that blemish in an otherwise perfect thing is its lower theoretical capacity (372mAhg
-1) and be not suitable for the lithium battery of high-energy-density of new generation.Therefore, in its evolution, most critical be exactly look for out low cost, Large Copacity, long-life Novel anode material.
Current, the transition metal oxide of high theoretical specific capacity is fully developed, in these oxides, manganese monoxide (MnO) is due to its good environment compatibility, low Transformation Potential, the stagnant ring of low-voltage (being less than 0.7 volt), high density (5.43 grams every cubic centimetre) and high theoretical capacity (756mAhg
-1) cause concern.But, the same with other metal oxide negative poles, MnO negative pole is also because lithium ion (Li in the circulating cycle
+) diffusion, low conductivity and serious stereomutation cause the problem unstable, multiplying power is lower that circulates.Up to now, found a variety of method and gone to alleviate above problem, wherein reduction particle size mixes carbon is again a kind of well method, and this technology improves lithium ion conductivity, adjusted volume change and then enhancing chemical property.But this method still has circumscribed at raising lithium deintercalation aspect of performance.
Summary of the invention
In order to solve the problem, the object of the invention is to provide lithium cell cathode material that a kind of stable capacity is large, the life-span is long and its preparation method and application.
To achieve these goals, the present invention adopts following technical scheme:
The present invention provide firstly a kind of three-dimensional porous MnO/C-N nano composite material based on rape pollen, and it is assembled with MnO nano microcrystalline in the C-N framework provided by rape pollen.
Further, the invention provides the preparation method of above-mentioned nano composite material, is that rape pollen is dispersed in KMnO
4in solution, stirring at normal temperature, then filters, washs, vacuumize, and final high temperature is calcined, and namely obtains three-dimensional porous MnO/C-N nano composite material.
Preferably, described KMnO
4kMnO in solution
4concentration be 0.225mol/L.
Preferably, described rape pollen quality and KMnO
4the proportioning of liquor capacity is: 4g/250.0mL.
Preferably, the time of described stirring at normal temperature is 8h.
Preferably, the temperature of described high-temperature calcination is 500 DEG C, and the time is 15.0 hours, and heating rate is 2.0 DEG C of min
-1; Calcination atmosphere is the argon gas atmosphere containing 5.0vol.% hydrogen.
In addition, present invention also offers the application of above-mentioned three-dimensional porous MnO/C-N nano composite material in electrochemistry, it is for as lithium cell cathode material.
Further, the invention provides a kind of lithium battery, it comprises electrode, barrier film, electrolyte, auxiliary electrode.
Wherein, electrode is by MnO/C-N nano composite material, acetylene black and polyvinylidene fluoride as negative material, in mass ratio for 8:1:1 is dissolved in METHYLPYRROLIDONE, then spreads on Copper Foil, vacuumize, rolls, cuts, and namely forms electrode.
Barrier film is glass fibre, and auxiliary electrode is metallic lithium foil, and electrolyte is 1.0MLiPF for containing concentration
6ethylene carbonate, dimethyl carbonate and diethyl carbonate mixed liquor, and the mass percent of ethylene carbonate, dimethyl carbonate and diethyl carbonate is 1:1:1.
Beneficial effect of the present invention is as follows:
MnO/C-N nano composite material provided by the invention, with rape pollen cheap and easy to get for raw material, carry out stirring and soak-calcining, preparation method is simple, is easy to promote; So that the lithium ion battery that MnO/C-N nano composite material of the present invention is obtained is with low cost, lithium ion memory property is good, cyclicity is good, stability is high, has the characteristics such as high magnification, has very large application potential.
Accompanying drawing explanation
Fig. 1 is the phenogram in the embodiment of the present invention 1: the high-resolution-ration transmission electric-lens figure that (a) is rape pollen; The scanning electron microscope (SEM) photograph of (b) MnO/C-N sample; C scanning electron microscope (SEM) photograph that () amplifies for figure (b) selected zone; D () is the transmission electron microscope picture of MnO/C-N sample; The transmission electron microscope picture of (e)-(i) for MnO/C-N sample and the distribution diagram of element of MnO/C-N: (e) is typical transmission Electronic Speculum figure and the element distribution image of corresponding (f) C element, (g) N element, (h) Mn element, (i) O element.
Fig. 2 is xps energy spectrum figure, XRD collection of illustrative plates of sample in the embodiment of the present invention 1, Raman spectrogram and adsorption/desorption isotherms; Wherein, (a)-(c) the xps energy spectrum figure that is MnO/C-N: the high-resolution power spectrum of (a) institute test specification, (b) Mn3s and (c) N1s; D XRD collection of illustrative plates that () is MnO/C-N; The Raman spectrogram of (e) MnO/C-N nano composite material and pyrolysis pollen (ρ-R-pollen); F () is N in MnO/C-N
2adsorption/desorption isotherms (illustration: corresponding pore size distribution curve figure).
Fig. 3 is the XRD collection of illustrative plates of the sample MnO/C-N-8-400-15 in the embodiment of the present invention 1.
Fig. 4 is the XRD collection of illustrative plates of the sample MnO/C-N-8-500-12 in the embodiment of the present invention 1.
Fig. 5 is the scanning electron microscope diagram of the sample MnO/C-N-10-500-15 in the embodiment of the present invention 1.
Fig. 6 is the performance map of each battery of assembling in the embodiment of the present invention 2: the cycle characteristics curve chart of (a) each battery; (b) current density 300mAg
-1the charging and discharging curve of lower MnO/C-N under different cycle periods; (c) electric capacity hold facility of MnO/C-N under different current density; (d) in current density from 100 to 2000mAg
-1the charging and discharging curve of lower MnO/C-N; The volt-ampere cycle characteristics curve of (e) MnO/C-N electrode; F () current density is 300mAg
-1the Nyquist diagram (illustration: magnification region) of the MnO/C-N after different charging-discharging cycle.
Fig. 7 is the negative material formed by MnO/C-N in the embodiment of the present invention 2: (a) scanning electron microscope diagram before charge and discharge cycles and (b) transmission electron microscope picture; 300mAg
-1the distribution diagram of element of (c) scanning electron microscope diagram, (d) transmission electron microscope picture, (e) high power transmission electron microscope picture and corresponding element (f) C element after lower discharge and recharge 400 times, (g) N element, (h) Mn element, (i) O element.
Embodiment
In order to further illustrate technical scheme of the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The Bee Pollen of Anhui the best's bee product Co., Ltd is adopted to be raw material in following embodiment, adopt the ESEM of ZeissSupra40, the CHI760D electrochemical workstation adopting Shanghai Chen Hua company to produce, the chemical property of Wuhan Lan electricity Electronics Co., Ltd. to electrochemical capacitor detect.
In addition, the experimental technique used in following embodiment if no special instructions, is conventional method, the reagent used, inert gas, if no special instructions, all can obtain from commercial channels.
Embodiment 1
The present embodiment prepares MnO/C-N nano composite material as follows:
At room temperature, quantitative KMnO is taken
4, add 250.0mL deionized water to dissolve, obtaining concentration is the KMnO of 0.225mol/L
4solution; 4g rapeseed pollen is dispersed in KMnO
4in solution, stir 8 hours at normal temperatures.Then product is filtered, once clean with deionized water and ethanol, then carry out drying at 80 DEG C, vacuum; Last 500 DEG C of high-temperature calcinations 15.0 under the argon gas atmosphere of 5% hydrogen, obtain product MnO/C-N nano composite material, are labeled as MnO/C-N.
For contrast mixing time, high-temperature calcination temperature and high-temperature calcination time are on the impact of product, by method same as described above preparation contrast sample, and contrast sample is labeled as MnO/C-N-x-y-z, wherein x, the value of y, z is respectively stirring at normal temperature time of this contrast sample, high-temperature calcination temperature and high-temperature calcination time.The contrast sample prepared in the present embodiment is respectively MnO/C-N-8-400-15, MnO/C-N-8-500-12 and MnO/C-N-10-500-15.
Fig. 1 (a) is the high resolution TEM figure of the raw materials used rape pollen of the present embodiment, can find out that it has three-dimensional porous nanostructure.
The scanning electron microscope (SEM) photograph of the sample MnO/C-N of Fig. 1 (b) prepared by the present embodiment, (c) is its partial enlarged drawing, can find out that it is the same with rape pollen, is the nanostructure containing large number of orifices.
The transmission electron microscope picture of the sample MnO/C-N of Fig. 1 (d) prepared by the present embodiment, the nanocrystalline diameter of known MnO is 8-10nm.And, can find out that from this illustration the crystallinity of MnO is fine.
The transmission electron microscope picture of Fig. 1 (e)-(i) for MnO/C-N sample and the distribution diagram of element of MnO/C-N: (e) is typical transmission Electronic Speculum figure and the element distribution image of corresponding (f) C element, (g) N element, (h) Mn element, (i) O element, can find out that in sample MnO/C-N, Mn and O element is dispersed in C-N framework.
The xps energy spectrum figure that Fig. 2 (a)-(c) is sample MnO/C-N.Can find out that the essential element contained by sample is C, Mn, O and N from 2 (a).As shown in Fig. 2 (b), sample MnO/C-N contains the spin separation energy of 5.77ev, and the diformazan oxidation state containing manganese is described, illustrates that MnO is the part of final sample simultaneously.As shown in Fig. 2 (c), in sample MnO/C-NXPS power spectrum, be divided into two peaks, in conjunction with at 398.15eV and 399.70eV, the existence of pyrimidine Type-N and pyrroles's type-N being correspond to respectively.
As shown in Fig. 2 (d), can find out from the XRD figure of MnO/C-N sample in the sample to which exist cube MnO, the grain size can deriving MnO nano particle from Scherrer formula is about 22.1nm.
As shown in Fig. 2 (e), sample is at 490.5-694.9cm
-1the broad peak at place illustrates to there is MnO in the sample to which, is being about 1352.0cm
-1and 1588.8cm
-1peak correspond to D key and the G key of carbon respectively.Can contrast from the Raman collection of illustrative plates of the rape pollen (p-R-pollen) of MnO/C-N and 500 DEG C cracking, the ratio of D key to G key obviously increases in the sample to which, illustrates to there is more defect and non-graphitized carbon in sample carbon framework.
As shown in Fig. 2 (f), can draw in sample to there is meso-hole structure from isothermal chart, specific area is 15.54m
2g
-1.
As shown in Figure 3, Figure 4, there is Mn in sample MnO/C-N-8-400-15 and sample MnO/C-N-8-500-12
3o
4.As shown in Figure 5, in sample MnO/C-N-10-500-15, the Mn nanocrystal that a large amount of particles is larger is had.So the reaction condition of selective redox of the present invention is 500 DEG C, 15.0 hours.
Embodiment 2
Sample prepared by embodiment 1 is used for assembling lithium battery by the present embodiment as follows:
The each sample that embodiment 1 is prepared and pyrolysis pollen (p-R-pollen) respectively with acetylene black, polyvinylidene fluoride in mass ratio 8:1:1 be dissolved in n-N-methyl-2-2-pyrrolidone N-, then spread on Copper Foil and form electrode.By electrode 80 DEG C of dryings 12.0 hours under vacuum, more above-mentioned electrode is rolled, cut into the circle that diameter is 1.0 centimetres, put into pure argon glove box.Be auxiliary electrode with metallic lithium foil, take glass fibre as barrier film and mass percent be 1:1:1 be 1.0MLiPF containing concentration
6ethylene carbonate, dimethyl carbonate, diethyl carbonate electrolyte be material, in glove box, assemble button cell.
As shown in Fig. 6 (a), compared to the battery assembled by sample MnO/C-N-8-400-15, sample MnO/C-N-8-500-12 and sample MnO/C-N-10-500-15, and compared to the battery assembled by pyrolysis pollen (p-R-pollen), the battery assembled by sample MnO/C-N has better cycle characteristics, is 300mAg in 400 primary current density
-1after charge and discharge cycles, still have 513.0mAhg
-1high power capacity, be initial 539.1mAhg
-195.16%.
As shown in Fig. 6 (b), in initial constant voltage discharge process, sample has the voltage platform of a section very long being about 0.27V place, due to Mn
2+to Mn
0complete reduction slowly drops to 0.01V afterwards.In original charge process, be have downslide between 1.0V to 1.5V in voltage range, this is due to Mn
0be oxidized to Mn
2+.Fig. 6 (b) also illustrates, and the battery initial discharge capacity assembled by sample MnO/C-N is about 1045.8mAhg
-1, discharge capacity is about 539.1mAhg
-1.
As Fig. 6 (c) illustrates the high rate performance of the battery assembled by sample MnO/C-N, the battery assembled by sample MnO/C-N current density be 100,200,500,1000, and2000mAg
-1discharge capacity is 756.5,604.9,467.7,358.2 and 240.9mAhg
-1, rise to 5000mAg in current density from 100
-1, the charge/discharge capacity of sample becomes stable, and reduces gradually along with the raising of speed.
As shown in Fig. 6 (d), at higher current densities, capacity rapidly disappears sample, and voltage delay increases gradually, but the capacity that to circulate under different current density after 64 times is at 100mAg
-1under can return to 681.27mAhg
-1, prove that sample specific capacity is maintainable in different current density circulation.
As shown in Fig. 6 (e), positive pole peak at about 0.13V, 0.75V, 1.58V place, corresponding Mn
2+revert to Mn
0, observe peak 1.32V at negative pole place, be related to formation and the Li of MnO
2the decomposition of O.
As shown in Fig. 6 (f), it is very similar that the Nyquist diagram of sample MnO/C-N is recycled to the 400th circulation from the 1st time, and indicating electrode material has stable electric conductivity in the circulating cycle.
As shown in Fig. 7 (a), 7 (b), negative material is before carrying out charge and discharge cycles, and the acetylene black that the MnO nanocrystal exposed in active material MnO/C-N is added surrounded.
As shown in Fig. 7 (c), negative material is 300mAg in condition
-1under carry out 400 charge and discharge cycles after, the global shape of three-dimensional MnO/C-N still exists.
As shown in Fig. 7 (d), negative material is 300mAg in condition
-1under carry out 400 charge and discharge cycles after, initial MnO nanocrystal is broken down into some very tiny MnO nanoparticles.
As shown in Fig. 7 (e)-(i), can find out from the corresponding distribution diagram of element of projection microscan Electronic Speculum figure and institute, be circulated throughout rear very tiny MnO nanoparticle for 400 times to be similarly fixed in carbon framework, so three-dimensional MnO/C-N electrode still has Large Copacity after the charge and discharge cycles continued.
Although the present invention is described in conjunction with above embodiment, but the present invention is not defined to above-described embodiment, and only by the restriction of claims, those of ordinary skill in the art can easily modify to it and change, but do not leave essential idea of the present invention and scope.
Claims (7)
1. based on a three-dimensional porous MnO/C-N nano composite material for rape pollen, it is characterized in that: described MnO/C-N nano composite material is assembled with MnO nano microcrystalline in the C-N framework provided by rape pollen.
2. a preparation method for three-dimensional porous MnO/C-N nano composite material according to claim 1, is characterized in that: be that rape pollen is scattered in KMnO
4in solution, stirring at normal temperature, then filters, washs, vacuumize, and final high temperature is calcined, and namely obtains three-dimensional porous MnO/C-N nano composite material.
3. preparation method according to claim 2, is characterized in that: described KMnO
4kMnO in solution
4concentration be 0.225mol/L.
4. the preparation method according to Claims 2 or 3, is characterized in that: described rape pollen quality and described KMnO
4the proportioning of liquor capacity is 4g:250.0mL.
5. preparation method according to claim 2, is characterized in that: the time of described stirring at normal temperature is 8h.
6. preparation method according to claim 2, is characterized in that: the temperature of described high-temperature calcination is 500 DEG C, and the time is 15.0 hours, and heating rate is 2.0 DEG C of min
-1; Calcination atmosphere is the argon gas atmosphere containing 5.0vol.% hydrogen.
7. the application of three-dimensional porous MnO/C-N nano composite material according to claim 1 in electrochemistry, is characterized in that: for as lithium cell cathode material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450226A (en) * | 2016-11-22 | 2017-02-22 | 华南师范大学 | Preparation method of natural pollen-based metal sulfide-carbon composite material and application thereof |
| CN108273496A (en) * | 2018-03-16 | 2018-07-13 | 西南大学 | A kind of preparation method and applications of the bionic enzyme based on bacteria cellulose |
| CN109599554A (en) * | 2018-12-03 | 2019-04-09 | 重庆文理学院 | A kind of preparation method of manganese monoxide negative electrode material |
| CN110611096A (en) * | 2019-09-19 | 2019-12-24 | 苏州科技大学 | MnO/C composite material, preparation method thereof and application of MnO/C composite material as lithium ion battery negative electrode material |
-
2015
- 2015-09-30 CN CN201510641977.6A patent/CN105140506A/en active Pending
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| Title |
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| TIAN QIU ET AL: ""Facile fabrication of Chinese lantern-like MnO@N–C: a high-performance anode material for lithium-ion batteries"", 《RSC ADVANCES》 * |
| 朱文均: ""过渡金属氧化物锂离子电池负极材料的纳米化构建及电化学性能"", 《硕士学位论文（万方数据库）》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450226A (en) * | 2016-11-22 | 2017-02-22 | 华南师范大学 | Preparation method of natural pollen-based metal sulfide-carbon composite material and application thereof |
| CN108273496A (en) * | 2018-03-16 | 2018-07-13 | 西南大学 | A kind of preparation method and applications of the bionic enzyme based on bacteria cellulose |
| CN109599554A (en) * | 2018-12-03 | 2019-04-09 | 重庆文理学院 | A kind of preparation method of manganese monoxide negative electrode material |
| CN109599554B (en) * | 2018-12-03 | 2021-06-22 | 重庆文理学院 | Preparation method of manganese monoxide negative electrode material |
| CN110611096A (en) * | 2019-09-19 | 2019-12-24 | 苏州科技大学 | MnO/C composite material, preparation method thereof and application of MnO/C composite material as lithium ion battery negative electrode material |
| CN110611096B (en) * | 2019-09-19 | 2022-04-19 | 苏州科技大学 | MnO/C composite material, preparation method thereof and application of MnO/C composite material as lithium ion battery negative electrode material |
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Application publication date: 20151209 |