CN107369825A - A kind of nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell and preparation method and application - Google Patents

A kind of nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell and preparation method and application Download PDF

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CN107369825A
CN107369825A CN201710620295.6A CN201710620295A CN107369825A CN 107369825 A CN107369825 A CN 107369825A CN 201710620295 A CN201710620295 A CN 201710620295A CN 107369825 A CN107369825 A CN 107369825A
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manganese
lithium ion
manganese oxide
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nitrogen
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CN107369825B (en
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蒋仲杰
秦艳敏
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South China University of Technology SCUT
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • 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 discloses a kind of nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell and preparation method and application, the composite is combined by nanoscale manganese and dopamine, and wherein manganese oxide is spherical in shape.This method is to be mixed the spherical manganese oxide nano granule of preparation with Dopamine hydrochloride, filtration washing, obtains manganese oxide and the compound of poly-dopamine after drying；Then polymer layer is converted into the carbon-coating of N doping by high temperature cabonization；Nitrogen-doped carbon coated manganese oxide prepared by the present invention（MnO@NC）Composite cathode material for lithium ion cell Stability Analysis of Structures, conducts electricity very well, and has excellent high rate performance and stable circulation performance as lithium ion battery negative material；The polymerization of dopamine only needs to complete under room temperature and weak basic condition, so cost is cheap, energy consumption is relatively low, easy to control, environment-friendly, is adapted to lithium ion battery practical application, can realize industrial-scale production.

Description

A kind of nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell and its preparation Method and application
Technical field
The invention belongs to electrochemical field, and in particular to a kind of nitrogen-doped carbon coated manganese oxide lithium ion battery composite cathode Material and preparation method and application.
Background technology
Three big themes of 21st century scientific technological advance are the energy, environment and information, wherein the scarcity of the energy and Serious problem of environmental pollution has become two hang-ups urgently to be resolved hurrily.In order to tackle the hang-up of the above two, people are directed to Develop the new green clean energy resourcies such as solar energy, wind energy and tide energy, so as to gradually substitute non-renewable and cause ring The fossil class A fuel A of border pollution.But most of clean energy resource through utilizing all be it is non-controllable, and intermittent, this Energy storage and the cost of management are added, so as to promote people largely to study energy storage material.
Traditional energy storage device has lead-acid battery, chromium nickel-based battery, wherein, the energy density of lead-acid battery and chromium nickel-based battery compared with It is low, it can also cause environmental pollution, can not meet the needs of people.Lithium ion battery has high voltage, usage time length, held The advantages that measuring big, small volume, memory-less effect and having a safety feature, just gradually substitutes lead-acid battery and chromium nickel-based battery, it has also become Focus of concern.With the rapid popularization of portable electric appts and the fast development of electric automobile, commercial natural stone Black negative material and requirement of the electrical equipment to energy density and power density can not be met, therefore there is an urgent need to high performance Ion cathode material lithium.Therefore, it is extremely urgent to develop lithium ion battery negative material of new generation.
Transition metal oxide is widely studied because it has high specific capacity in field of lithium ion battery.In crowd In more transition metal oxides, manganese oxide is and environment-friendly low with cost etc. excellent due to higher initial specific capacities Point, become potential lithium ion battery negative material of new generation.But the electronic conduction of most metal oxide Rate and ionic conductivity are all poor, so as to cause its high rate performance poor.Meanwhile in the charge and discharge process repeated, metal The larger Volume Changes of oxide can reduce the cyclical stability of material.Therefore, the electronic conduction of metal oxide how is improved Property and cyclical stability, are the huge challenges to researcher.At present, particle size, cladding or doping conductive materials are reduced It is the Main Means for improving material electrochemical performance.
The present invention using nature polymerization by manganese oxide with Dopamine hydrochloride is compound prepares nitrogen-doped carbon coated manganese oxide （MnO@NC）Composite, up to now untill, also not by spherical manganese oxide and the compound relevant report of poly-dopamine.
The content of the invention
It is poor for transition metal oxide lithium ion battery negative material electric conductivity and cyclical stability traditional at present The shortcomings of, the present invention provides a kind of nitrogen-doped carbon coated manganese oxide（MnO@NC）Lithium ion battery negative material and preparation method thereof With application, this method can improve the electric conductivity and structural stability of material, so as to improve the chemical property of negative material.Separately Outside, nitrogen-doped carbon coated manganese oxide provided by the invention（MnO@NC）Preparation method it is simple, cost is relatively low, environment-friendly, energy Enough promote the development of scale lithium ion battery negative material, be expected to large-scale industrialization application.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell, comprises the following steps：
1）By manganese source and ammonium bicarbonate solubility in a solvent, then continue at the laggard water-filling heat of polytetrafluoroethyllining lining autoclave Reason, then centrifuge washing, dry, obtain manganese carbonate nanosphere；
2）Manganese carbonate nanosphere is dissolved in cushioning liquid with Dopamine hydrochloride and reacted, then by reaction product separation of solid and liquid, is washed Solid is washed, dries, obtains manganese carbonate/poly-dopamine composite；
3）By step 2）Gained manganese carbonate/poly-dopamine composite carries out calcination processing in a nitrogen atmosphere, obtains N doping Carbon coating manganese oxide composite cathode material for lithium ion cell.
Preferably, step 1）The manganese source is the one or more in manganese acetate, manganese nitrate, manganese sulfate and manganese chloride.
Preferably, step 1）The solvent is the one or more in ethylene glycol, water and absolute ethyl alcohol.
Preferably, step 1）The hydro-thermal process is carried out in air dry oven.
Preferably, step 1）The temperature of the hydro-thermal process is 150-200 DEG C, time 10-15h.
Preferably, step 1）The washing is washed 3-5 times respectively with water and absolute ethyl alcohol.
Preferably, step 1）The drying is to be dried in vacuum drying chamber at 80 DEG C.
Preferably, step 2）Manganese carbonate/poly-dopamine nanosphere in the manganese carbonate/poly-dopamine composite Particle diameter is 400 ~ 600 nm.
Preferably, step 2）The manganese oxide nanosphere adds mass ratio control 1 with Dopamine hydrochloride:（1~1.5）.
Preferably, step 2）The reaction is to carry out at room temperature.
Preferably, step 2）The time of the reaction is 10-48h.
Preferably, step 3）The washing is washed 3-5 times respectively with water and absolute ethyl alcohol.
Preferably, step 3）The drying is to be dried in vacuum drying chamber at 80 DEG C.
Preferably, step 4）The calcination processing is that 3-8h is first calcined at 600 ~ 800 DEG C, is then cooled to 300- 500 DEG C of calcining 1-3h.
A kind of nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell as made from the process described above, should Nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell uniformly wraps up nano manganese oxide particle by stratiform carbon-coating and formed； The particle diameter of described carbon coating manganese oxide is 400 ~ 600 nm；Described carbon coating manganese oxide is that Dopamine hydrochloride is aggregated in oxidation Manganese surface forms.
A kind of above-described nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell is preparing lithium-ion electric Application in pond.
Compared with prior art, the invention has the advantages that：
1）Because the carbon-coating of cladding has good electric conductivity, the conductance of material can be increased so that nitrogen-doped carbon of the present invention Coated manganese oxide composite cathode material for lithium ion cell has preferable high rate performance in charge and discharge process；Meanwhile carbon-coating may be used also Volume Changes as cushion, can effectively alleviate material in charge and discharge process so that material have it is preferably steady It is qualitative.
2）Have the doping of nitrogen in the composite, the carbon material of N doping can also improve material cycle performance and High rate performance.
3）The polymerization of dopamine of the present invention is very simple, it is only necessary to is carried out under room temperature and weak basic condition, therefore Synthesis cost is cheap, and energy consumption is relatively low, environment-friendly, is adapted to lithium ion battery practical application, can realize industrial-scale production.
Brief description of the drawings
Fig. 1 is the XRD of gained nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell in the embodiment of the present invention 1 Figure.
Fig. 2 is the drawing of gained nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell in the embodiment of the present invention 1 Graceful spectrogram.
Fig. 3 is the SEM of gained nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell in the embodiment of the present invention 1 Figure.
Fig. 4 is the TEM of gained nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell in the embodiment of the present invention 1 Figure.
Fig. 5 is gained nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell conduct in the embodiment of the present invention 1 The constant current charge-discharge performance map of lithium ion battery negative material.
Fig. 6 is gained nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell conduct in the embodiment of the present invention 1 Lithium ion battery negative material circulate 50 weeks after constant current charge-discharge performance map.
Fig. 7 is gained nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell conduct in the embodiment of the present invention 1 The high rate performance figure of lithium ion battery negative material.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is further illustrated, but embodiments of the present invention are not limited to This.
Embodiment 1
（1）1mmol manganese acetate and 10mmol ammonium bicarbonate solubility are weighed into 30mL ethylene glycol, is stirred at room temperature After 30min, well mixed solution is obtained；Solution obtained above is transferred in 50mL reactor, carried out at 180 DEG C Hydro-thermal reaction 12h；Hydro-thermal reaction product is centrifuged, after washing 4 times with water and absolute ethyl alcohol, done in 80 DEG C of vacuum Dried in dry case, obtain presoma nanosphere manganese carbonate particle；Then, the cladding of dopamine is carried out, process is as follows：Respectively 100mg nanosphere manganese carbonate and 100mg Dopamine hydrochlorides is weighed, is dissolved in 50 mL Tris cushioning liquid（pH=8.5）In, 24h is stirred at room temperature, with absolute ethyl alcohol centrifuge washing 4 times, is dried, is obtained manganese carbonate@poly-dopamine compounds.It will finally obtain Manganese carbonate@poly-dopamine compounds be put into porcelain boat and be placed in tube furnace, under nitrogen atmosphere protection, 700 DEG C of reaction 5h, with After cool to 500 DEG C, then sustained response 2h, be finally cooled to room temperature, obtain nitrogen-doped carbon coated manganese oxide particle, i.e. N doping Carbon coating manganese oxide composite cathode material for lithium ion cell.X-ray powder diffraction（XRD）Product obtained by analysis shows is pure oxygen Change manganese, do not find dephasign, illustrate that purity is higher（As shown in Figure 1）.It can be seen that, G peaks appear in from Raman spectrograms 1350cm-1Left and right, D peaks appear in 1600cm-1Left and right, the carbon for illustrating to have in the product obtained by the present invention is with amorphous carbon Based on（As shown in Figure 2）.From SEM（SEM）And transmission electron microscope（TEM）It can be seen from the figure that carbon-coating uniformly wraps Wrap up in spherical manganese oxide particle surface, particle diameter 400-600nm（As shown in Figure 3,4）.
（2）By step（1）Obtained nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell is as active material Material, acetylene black is conductive agent, and Kynoar is binding agent, and according to active material：Conductive agent：Binding agent=7：2：1 quality Than inserting in 5 mL cillin bottle, the N-methyl pyrrolidones that 0.5 mL is then added dropwise stirs pulp after 4 h, and slurry is uniform It is applied on copper foil, is then put into 80 DEG C of thermostatic drying chamber and dries 12 h, gone out after being dried to constant weight using sheet-punching machine as 12 Mm sequin is working electrode, and sequin is put into the glove box full of argon gas in the case of guarantee is anhydrous, purchase Lithium piece is used as to electrode and reference electrode, and the type barrier films of Celgard 2400 used, electrolyte is 1 mol L-1LiPF6With carbon Vinyl acetate（EC）, dimethyl carbonate（DMC）（EC：DMC=1：2, ν/ν）Mixed liquor, model is finally assembled into glove box CR2025 button cell, the glove box in whole process must keep oxygen and water vapour content to be respectively less than 1 ppm.25 DEG C of temperature Under degree, so that during progress constant current charge-discharge test, discharge capacity is 2312 mAh/g first for it, first under 100 mA/g current density Secondary charging capacity reaches 1444 mAh/g（As shown in Figure 5）.At a temperature of 25 DEG C, constant current is carried out under 100 mA/g current density During charge-discharge test, after circulating 50 weeks, its reversible capacity is 1126 mAh/g（As shown in Figure 6）.At a temperature of 25 DEG C, different electric currents High rate performance under density as shown in fig. 6, under 5000mA/g high current density, still with about 330 mAh/g can Inverse capacity, has preferable high rate performance（As shown in Figure 7）.
Embodiment 2
（1）1mmol manganese nitrate and 5 mmol ammonium bicarbonate solubility are weighed into 30mL absolute ethyl alcohol, is stirred at room temperature After 30min, well mixed solution is obtained；Solution obtained above is transferred in 50mL reactor, carried out at 150 DEG C Hydro-thermal reaction 10h；Hydro-thermal reaction product is centrifuged, after washing 4 times with water and absolute ethyl alcohol, done in 80 DEG C of vacuum Dried in dry case, obtain presoma nanosphere manganese carbonate particle；Then, the cladding of dopamine is carried out, process is as follows：Respectively 100mg nanosphere manganese carbonate and 150mg Dopamine hydrochlorides is weighed, is dissolved in 50 mL Tris cushioning liquid（pH=8.5）In, 24h is stirred at room temperature, with absolute ethyl alcohol centrifuge washing 4 times, is dried, is obtained product manganese carbonate@poly-dopamine compounds.Finally will Obtained manganese carbonate@poly-dopamine compounds, which are put into porcelain boat, to be placed in tube furnace, under nitrogen atmosphere protection, 800 DEG C of reactions 3h, 500 DEG C, then sustained response 2h are then cooled to, is finally cooled to room temperature, obtain nitrogen-doped carbon coated manganese oxide particle, i.e., Nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell.
（2）Button half-cell is assembled into using nitrogen-doped carbon coated manganese oxide manufactured in the present embodiment and lithium piece, method with As in embodiment 1.At a temperature of 25 DEG C, so that during progress constant current charge-discharge test, it is first under 100 mA/g current density Discharge capacity is 2002 mAh/g, and initial charge capacity reaches 1204 mAh/g.It is close in 100 mA/g electric current at a temperature of 25 DEG C When constant current charge-discharge test is carried out under degree, after circulating 50 weeks, its reversible capacity is 1008 mAh/g.At a temperature of 25 DEG C, Under 5000mA/g high current density, still there is about 300 mAh/g reversible capacity, there is preferable high rate performance.
Embodiment 3
（1）1mmol manganese sulfate and 15mmol ammonium bicarbonate solubility are weighed into 30mL deionized water, is stirred at room temperature After 30min, well mixed solution is obtained；Solution obtained above is transferred in 50mL reactor, carried out at 200 DEG C Hydro-thermal reaction 15h；Hydro-thermal reaction product is centrifuged, after respectively being washed 4 times with deionized water and absolute ethyl alcohol, at 80 DEG C Vacuum drying chamber in dried, obtain presoma nanosphere manganese carbonate particle；Then, the cladding of dopamine, process are carried out It is as follows：100mg nanosphere manganese carbonate and 125mg Dopamine hydrochlorides is weighed respectively, is dissolved in 50 mL Tris cushioning liquid （pH=8.5）In, 24h is stirred at room temperature, with absolute ethyl alcohol centrifuge washing 4 times, is dried, is obtained product manganese carbonate@poly-dopamines and answer Compound.Finally obtained manganese carbonate@poly-dopamine compounds are put into porcelain boat and are placed in tube furnace, are protected in nitrogen atmosphere Under, 600 DEG C of reaction 8h, 500 DEG C, then sustained response 2h are then cooled to, is finally cooled to room temperature, obtain nitrogen-doped carbon cladding oxygen Change manganese particle, i.e. nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell.
（2）Button half-cell is assembled into using nitrogen-doped carbon coated manganese oxide manufactured in the present embodiment and lithium piece, method with As in embodiment 1.At a temperature of 25 DEG C, so that during progress constant current charge-discharge test, it is first under 100 mA/g current density Discharge capacity is 1908 mAh/g, and initial charge capacity reaches 1054 mAh/g.It is close in 100 mA/g electric current at a temperature of 25 DEG C When constant current charge-discharge test is carried out under degree, after circulating 50 weeks, its reversible capacity is 1038 mAh/g.At a temperature of 25 DEG C, Under 5000mA/g high current density, still there is about 310 mAh/g reversible capacity, there is preferable high rate performance.

Claims (10)

  1. A kind of 1. preparation method of nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell, it is characterised in that including Following steps：
    1）By manganese source and ammonium bicarbonate solubility in a solvent, then continue at the laggard water-filling heat of polytetrafluoroethyllining lining autoclave Reason, then centrifuge washing, dry, obtain manganese carbonate nanosphere；
    2）Manganese carbonate nanosphere is dissolved in cushioning liquid with Dopamine hydrochloride and reacted, then by reaction product separation of solid and liquid, is washed Solid is washed, dries, obtains manganese carbonate/poly-dopamine composite；
    3）By step 2）Gained manganese carbonate/poly-dopamine composite carries out calcination processing in a nitrogen atmosphere, obtains N doping Carbon coating manganese oxide composite cathode material for lithium ion cell.
  2. 2. preparation method according to claim 1, it is characterised in that step 1）The manganese source be manganese acetate, manganese nitrate, One or more in manganese sulfate and manganese chloride；The manganese source and the mol ratio of ammonium hydrogen carbonate are 1：（5 -15）.
  3. 3. preparation method according to claim 1, it is characterised in that step 1）The solvent is ethylene glycol, water and anhydrous One or more in ethanol.
  4. 4. preparation method according to claim 1, it is characterised in that step 1）The temperature of the hydro-thermal process be 150 DEG C- 200 DEG C, the time of hydro-thermal process is 10-15h.
  5. 5. preparation method according to claim 1, it is characterised in that step 2）The manganese carbonate/poly-dopamine composite wood The particle diameter of manganese carbonate/poly-dopamine nanosphere in material is 400 ~ 600 nm.
  6. 6. preparation method according to claim 1, it is characterised in that step 2）The manganese carbonate nanosphere and hydrochloric acid DOPA Amine adds mass ratio control 1:（1~1.5）.
  7. 7. preparation method according to claim 1, it is characterised in that step 2）The time of the reaction is 10-48h.
  8. 8. preparation method according to claim 1, it is characterised in that step 3）The calcination processing is first 600 ~ 800 3-8h is calcined at DEG C, is then cooled to 300-500 DEG C of calcining 1-3h.
  9. 9. a kind of nitrogen-doped carbon coated manganese oxide lithium ion battery is compound as made from the method described in claim any one of 1-8 Negative material.
  10. 10. a kind of nitrogen-doped carbon coated manganese oxide composite cathode material for lithium ion cell described in claim 9 prepare lithium from Application in sub- battery.
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