CN106328919A - Lithium ion battery cathode material microgranitic trimanganese tetroxide, and preparation method and application thereof - Google Patents
Lithium ion battery cathode material microgranitic trimanganese tetroxide, and preparation method and application thereof Download PDFInfo
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- CN106328919A CN106328919A CN201610849244.6A CN201610849244A CN106328919A CN 106328919 A CN106328919 A CN 106328919A CN 201610849244 A CN201610849244 A CN 201610849244A CN 106328919 A CN106328919 A CN 106328919A
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- manganic oxide
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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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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- 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 lithium ion battery cathode material microgranitic trimanganese tetroxide, and a preparation method and application thereof. An organic solvent N, N-dimethylformamide, 2-thiophene carboxylic acid, surface active agent hexadecyltrimethyl ammonium bromide, and manganese source manganese acetate are adopted as raw materials. By adopting a solvent heat treatment method, the prepared microgranitic Mn3O4 formed by nanosheets has the size being 10 micrometers, and the thickness of each nanosheet is dozens of nanometers, so that compared with Mn3O4 nanoparticles, the microgranitic Mn3O4 has better cycling stability. The process is simple, the repeatability is good, the yield is high, the synthesis condition is moderate, and the cost is low.
Description
Technical field
The invention belongs to cell negative electrode material preparation field, be specifically related to a kind of lithium ion battery negative material nanometer sheet structure
The micro-flower-shaped mangano-manganic oxide built and preparation method and application.
Background technology
Along with increasingly exhausted, global warming and the environmental pollution of fossil energy, develop renewable clear energy sources and
Reduce the discharge of greenhouse gases, cause the great attention of whole world scientist.Automobile with lithium battery as power source is not
But zero-emission, but also can be the ideal source of electric vehicle with petroleum replacing and reduce greenhouse gas emission, to slow
Solve energy crisis tool to be of great significance.Power and hybrid power electric car require that the positive and negative pole material of lithium ion battery to have
There is higher specific capacity.And the theoretical capacity of business-like negative material graphite also only has 372mAhg-1.Simultaneously, however it remains electricity
Pond energy density is little and high in cost of production problem.Thus, it is found that the both positive and negative polarity of the lithium ion battery of stable circulation and high-energy-density
Material, significant.In terms of environment, economy and energy angle, there is the lithium ion cell electrode material of potential application foreground
The preparation of material answers environmental protection, technique simple and low cost.
Mangano-manganic oxide has rich reserves, height ratio capacity, cheap and advantages of environment protection, thus extremely closes
Note.But because of poorly conductive and weak lithiumation, causing cyclical stability poor, capacity is easily decayed.Up to the present, mainly micro-by preparing
Mangano-manganic oxide or the trimanganese tetroxide nano composite of micro-nano structure improve its cyclical stability.The nano-scale of cystose
The initial discharge specific capacity of mangano-manganic oxide reaches 869mA h/g, circulates the specific discharge capacity after 40 times and can reach 800mA h/g
[J.Gao,M.A.Lowe,H.D.Chem.Mater.23(2011)3223.].Trimanganese tetroxide nano granule and graphite
The specific discharge capacity of alkene nano composite material may be up to 900mA h/g, has good rate charge-discharge performance and stable circulation
Property [H.L.Wang, L.F.Cui, Y.Yang, H.S.Casalongue, J.K.Robinson, Y.Y.Liang, Y.Cui,
H.J.Dai,J.Am.Chem.Soc.132(2010),13978.].Etching Mn5Fe5The Mn that the nanometer sheet that Al obtains is constructed3O4/
Fe3O4Micro-flower is at 1500mAg-1Discharge current density under, represent preferable cyclical stability [D.Y.Zhao, Q.Hao,
C.X.Xu,D.Y.Zhao,Electrochim.Acta 180(2015)493.].Mn/Al in the basic conditions, goes alloy to convert
MnO and Mn become3O4The porous microsphere of nano-particle composition, at 500mA g-1Discharge current density, circulate the electric discharge of 100 times
Specific capacity can reach 757mAh g-1[X.J.Jiang,Y.Y.Wang,L.Yang,D.W.Li,H.Y.Xu,Y.Ding,J.Power
Sources 274(2015)862.].Recently, the Mn that nanometer rods is constructed3O4Micro-flower can be with cetyl trimethylammonium bromide, carbamide
It is raw material with manganese sulfate, then high-temperature roasting synthesis [M.Wang, L.M.Cheng, G.B.Li, Z.W.Chen, S.L.Wang,
Phys.Chem.Chem.Phys.,16(2014)21742.].But what synthesis nanometer sheet was piled under cryogenic is pure mutually micro-
Flower-shaped Mn3O4 report is few, is rarely applied to the negative material of lithium ion battery.
Summary of the invention
It is an object of the invention to provide the four micro-flower-shaped oxygen that a kind of lithium ion battery negative material nanometer sheet is piled into
Change three manganese and preparation method and technique.Present invention process is simple, reproducible, and productivity is high；Synthesis condition is gentle, low cost；Institute
The electrode material specific capacity of preparation is high.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of micro-flower-shaped mangano-manganic oxide of lithium ion battery negative material, is to live with organic solvent, 2-thiophenic acid, surface
Property agent and manganese source be raw material, use solvent-thermal process method, obtain micro-flower-shaped mangano-manganic oxide, particle diameter in 10 microns,
The thickness of nanometer sheet is in tens nanometers, and its chemical formula is: Mn3O4。
The preparation method of the micro-flower-shaped mangano-manganic oxide of lithium ion battery negative material of the present invention, including following step
Rapid:
(1) surfactant and 2-thiophenic acid are dissolved in the mixed solvent of organic solvent and water, obtain mixed solution,
The volume ratio of described organic solvent and water is 1:4-5；
(2) under magnetic agitation, manganese source is joined in the mixed solution of step (1), continue stirring 1.5-2.5h；Described manganese
The mol ratio of source and 2-thiophenic acid is 1:2-2.5；
(3) solution step (2) obtained moves in reactor, seals, and reacts 2-200h, filter at 120-200 DEG C,
After deionized water and absolute ethanol washing, 50-60 DEG C of dry 12-15h, obtain micro-flower-shaped four oxidations three of nanometer sheet composition
Manganese.
Described organic solvent is DMF, and described surfactant is cetyl trimethylammonium bromide,
Described manganese source is the manganese source of manganese acetate or other form.
Micro-flower-shaped mangano-manganic oxide is as the active component of the negative material of lithium ion battery, and conductive agent is acetylene black,
Binding agent is Kynoar；Electrolyte is containing 1mol/L LiPF6Ethylene carbonate, Ethyl methyl carbonate and carbonic acid diformazan
The mixed liquor of ester；Battery case is CR2025 model, and collector is copper sheet, and barrier film is Celgard2400；Lithium metal as positive pole,
Battery is completed under argon shield.
Further, the mass ratio of described mangano-manganic oxide work, acetylene black and Kynoar is 6-7:1.5-2:1；Described
Volume ratio 1:1-1.5:1-1.5 of ethylene carbonate, Ethyl methyl carbonate and dimethyl carbonate in electrolyte.
Preferably, the mass ratio of described mangano-manganic oxide work, acetylene black and Kynoar is 7:2:1；Described electrolyte
Volume ratio 1:1:1 of middle ethylene carbonate, Ethyl methyl carbonate and dimethyl carbonate.
The remarkable advantage of the present invention is: the present invention uses the raw material of low cost, environmentally friendly, simple, productivity
Height, size is uniform, good dispersion, favorable reproducibility, it is easy to large-scale production.Mangano-manganic oxide prepared by the present invention is as lithium ion
The negative material of battery, micro-secondary specific discharge capacity of flower-shaped mangano-manganic oxide can reach 870.2mAhg-1, stable circulation
The specific discharge capacity of 20 times reaches 392.8mAhg-1。
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the mangano-manganic oxide of the embodiment of the present invention 1.
Fig. 2 is the XRD figure of the mangano-manganic oxide of the embodiment of the present invention 1.
Fig. 3 is charging and discharging curve (a) and the circulation of the first with 1st circulation of the mangano-manganic oxide of the embodiment of the present invention 1
Performance map (b).
Fig. 4 is the scanning electron microscope (SEM) photograph of the mangano-manganic oxide of the embodiment of the present invention 2.
Fig. 5 is the scanning electron microscope (SEM) photograph of the mangano-manganic oxide of the embodiment of the present invention 3.
Detailed description of the invention
With manganese acetate, 2-thiophenic acid and cetyl trimethylammonium bromide as raw material, use solvent-thermal process method, prepare
Mangano-manganic oxide.Typical case's pattern is micro-flower, microplate and nano-particle.
Further describe inventive feature below by example, but the invention is not limited in following example.
Embodiment 1
The preparation method of the micro-flower-shaped mangano-manganic oxide of a kind of lithium ion battery negative material, comprises the following steps:
(1) 2-thiophenic acid and cetyl trimethylammonium bromide are dissolved in DMF and deionized water
In mixed solvent, mixed solution in；The volume ratio of N, N-dimethyl formyl and water is 1:5；
(2) under magnetic agitation, manganese acetate is joined in the mixed solution of step (1), continue stirring 2 hours；Described second
The mol ratio of acid manganese and 2-thiophenic acid is 1:2；
(3) solution in step (2) is moved in reactor, seal, at 160 DEG C, react 100h, filter, with going in a large number
After ionized water and absolute ethanol washing, 60 DEG C of dry 12h, obtain Mn3O4Micro-flower.
Mangano-manganic oxide is as the active component of the negative material of lithium ion battery, and conductive agent is acetylene black, and binding agent is
Kynoar, three's mass ratio is 7:2:1；Electrolyte is 1mol/L LiPF6Ethylene carbonate, Ethyl methyl carbonate and carbon
The mixed liquor of dimethyl phthalate (volume ratio 1:1:1)；Battery case is CR2025 model, and collector is copper sheet, and barrier film is
Celgard2400；Lithium metal is completed under argon shield as positive pole, battery.
Embodiment 2
Not adding cetyl trimethylammonium bromide, other conditions, with embodiment 1, obtain the Mn of lamellar3O4。
Embodiment 3
With embodiment 1, it is only molten with deionized water by DMF in step (1) and deionized changing into
Agent, does not adds cetyl trimethylammonium bromide, the same embodiment of other conditions, obtains Mn3O4Nano-particle.
Embodiment 4
A kind of micro-flower-shaped mangano-manganic oxide of lithium ion battery negative material, be with organic solvent DMF,
2-thiophenic acid, surfactant cetyl trimethylammonium bromide and manganese source manganese acetate are raw material, use solvent-thermal process method,
Obtain micro-flower-shaped mangano-manganic oxide, specifically include following steps:
(1) cetyl trimethyl bromination and 2-thiophenic acid are dissolved in the mixed solvent of N,N-dimethylformamide and water
In, obtaining mixed solution, the volume ratio of described DMF and water is 1:4；
(2) under magnetic agitation, manganese acetate is joined in the mixed solution of step (1), continue stirring 1.5h；
The mol ratio of institute's manganese acetate and 2-thiophenic acid is 1:2.5；
(3) solution that step (2) obtained moves in reactor, seals, and reacts 200h, filter at 120 DEG C, spend from
After sub-water and absolute ethanol washing, 50 DEG C of dry 15h, obtain the micro-flower-shaped mangano-manganic oxide of nanometer sheet composition.
Mangano-manganic oxide is as the active component of the negative material of lithium ion battery, and conductive agent is acetylene black, and binding agent is
Kynoar, three's mass ratio is 7:1.5:1；Electrolyte is 1mol/L LiPF6Ethylene carbonate, Ethyl methyl carbonate and
The mixed liquor of dimethyl carbonate (volume ratio 1:1.5:1)；Battery case is CR2025 model, and collector is copper sheet, and barrier film is
Celgard2400；Lithium metal is completed under argon shield as positive pole, battery.
Embodiment 5
A kind of micro-flower-shaped mangano-manganic oxide of lithium ion battery negative material, specifically includes following steps:
(1) cetyl trimethyl bromination and 2-thiophenic acid are dissolved in the mixed solvent of N,N-dimethylformamide and water
In, obtaining mixed solution, the volume ratio of described DMF and water is 1:5；
(2) under magnetic agitation, manganese acetate is joined in the mixed solution of step (1), continue stirring 2.5h；
The mol ratio of institute's manganese acetate and 2-thiophenic acid is 1:2；
(3) solution step (2) obtained moves in reactor, seals, and reacts 2h, filter, use deionization at 200 DEG C
After water and absolute ethanol washing, 60 DEG C of dry 12h, obtain the micro-flower-shaped mangano-manganic oxide of nanometer sheet composition.
Mangano-manganic oxide is as the active component of the negative material of lithium ion battery, and conductive agent is acetylene black, and binding agent is
Kynoar, three's mass ratio is 6:2:1；Electrolyte is 1mol/L LiPF6Ethylene carbonate, Ethyl methyl carbonate and carbon
The mixed liquor of dimethyl phthalate (volume ratio 1:1:1.5)；Battery case is CR2025 model, and collector is copper sheet, and barrier film is
Celgard2400；Lithium metal is completed under argon shield as positive pole, battery.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modify, all should belong to the covering scope of the present invention.
Claims (6)
1. the micro-flower-shaped mangano-manganic oxide of lithium ion battery negative material, it is characterised in that: it is with organic solvent, 2-thiophene first
Acid, surfactant and manganese source are raw material, prepare micro-flower-shaped mangano-manganic oxide by solvent heat treatment method, and its chemical formula is:
Mn3O4。
2. a preparation method for the micro-flower-shaped mangano-manganic oxide of lithium ion battery negative material as claimed in claim 1, it is special
Levy and be: it comprises the following steps:
(1) surfactant and 2-thiophenic acid are dissolved in the mixed solvent of organic solvent and water, obtain mixed solution, described
The volume ratio of organic solvent and water is 1:4-5；
(2) under magnetic agitation, manganese source is joined in the mixed solution of step (1), continue stirring 1.5-2.5h；
The mol ratio of described manganese source and 2-thiophenic acid is 1:2-2.5；
(3) solution step (2) obtained moves in reactor, seals, and reacts 2-200h, filter, spend at 120-200 DEG C
After ionized water and absolute ethanol washing, 50-60 DEG C of dry 12-15h, obtain the micro-flower-shaped mangano-manganic oxide of nanometer sheet composition.
The preparation method of the micro-flower-shaped mangano-manganic oxide of lithium ion battery negative material the most according to claim 2, its feature
Being: described organic solvent is DMF, described surfactant is cetyl trimethylammonium bromide, described
Manganese source is manganese acetate.
4. an application for the micro-flower-shaped mangano-manganic oxide of lithium ion battery negative material as claimed in claim 1, its feature exists
In: mangano-manganic oxide is as the active component of the negative material of lithium ion battery, and conductive agent is acetylene black, and binding agent is poly-inclined fluorine
Ethylene；Electrolyte is containing 1mol/L LiPF6The mixed liquor of ethylene carbonate, Ethyl methyl carbonate and dimethyl carbonate；Battery
Shell is CR2025 model, and collector is copper sheet, and barrier film is Celgard2400；Lithium metal is as positive pole, and battery is under argon shield
It is completed.
The application of the micro-flower-shaped mangano-manganic oxide of a kind of lithium ion battery negative material the most according to claim 4, its feature
It is: the mass ratio of described mangano-manganic oxide work, acetylene black and Kynoar is 6-7:1.5-2:1；Carbon in described electrolyte
Volume ratio 1:1-1.5:1-1.5 of vinyl acetate, Ethyl methyl carbonate and dimethyl carbonate.
The application of the micro-flower-shaped mangano-manganic oxide of a kind of lithium ion battery negative material the most according to claim 5, its feature
It is: the mass ratio of described mangano-manganic oxide work, acetylene black and Kynoar is 7:2:1；Ethylene carbonate in described electrolyte
Volume ratio 1:1:1 of ester, Ethyl methyl carbonate and dimethyl carbonate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110364708A (en) * | 2019-06-28 | 2019-10-22 | 陕西科技大学 | Mangano-manganic oxide-stannic oxide/cobaltosic oxide composite material preparation method |
| CN111508728A (en) * | 2020-04-29 | 2020-08-07 | 绍兴博捷智能科技有限公司 | Long-life manganese-based water system mixed zinc ion capacitor and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110364708A (en) * | 2019-06-28 | 2019-10-22 | 陕西科技大学 | Mangano-manganic oxide-stannic oxide/cobaltosic oxide composite material preparation method |
| CN111508728A (en) * | 2020-04-29 | 2020-08-07 | 绍兴博捷智能科技有限公司 | Long-life manganese-based water system mixed zinc ion capacitor and preparation method thereof |
| CN111508728B (en) * | 2020-04-29 | 2021-09-28 | 绍兴容辛能源技术有限公司 | Long-life manganese-based water system mixed zinc ion capacitor and preparation method thereof |
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Application publication date: 20170111 |