CN109319845A - A kind of spherical porous LiMn2O4 and the preparation method and application thereof - Google Patents
A kind of spherical porous LiMn2O4 and the preparation method and application thereof Download PDFInfo
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- CN109319845A CN109319845A CN201811087833.0A CN201811087833A CN109319845A CN 109319845 A CN109319845 A CN 109319845A CN 201811087833 A CN201811087833 A CN 201811087833A CN 109319845 A CN109319845 A CN 109319845A
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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
- C01G45/12—Manganates manganites or permanganates
- C01G45/1207—Permanganates ([MnO]4-) or manganates ([MnO4]2-)
- C01G45/1214—Permanganates ([MnO]4-) or manganates ([MnO4]2-) containing alkali metals
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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
- H01M4/36—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
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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 a kind of spherical porous LiMn2O4s and the preparation method and application thereof, include the following steps: 1) to be added to manganese source and organic ligand in solvent according to setting ratio, it is uniformly mixed, reaction obtains the organic double compound of manganese, and the organic ligand is the mixture of one or more of trimesic acid, trimellitic acid, terephthalic acid (TPA), M-phthalic acid, benzoic acid, methylimidazole, polyvinylpyrrolidone；2) after mixing by the organic double compound of the manganese after separation, drying and lithium source, calcining obtains spherical porous LiMn2O4.The preparation process of LiMn2O4 of the invention is mild, environmentally protective controllable, is suitable for large-scale production, and the raw material type of manganese source and lithium source is more.
Description
Technical field
The present invention relates to chemical cell fields more particularly to a kind of spherical porous LiMn2O4 and the preparation method and application thereof.
Background technique
Lithium ion battery be a new generation green high-capacity battery, have operating voltage is high, light-weight, energy density per unit volume is high,
The advantages that non-environmental-pollution is modern communication, IT and portable electronic product (desirable chemical power supply, and the following electronic vapour
The preferred electrical source of power of vehicle has broad application prospects and huge economic benefit.
In the composition of lithium ion battery, positive electrode is to determine its security performance, chemical property and future development
An important factor for direction.In the lithium ion battery being commercialized at present, positive electrode mainly uses or cobalt acid lithium has portion concurrently
Divide lithium nickelate and LiMn2O4 and a small amount of ternary material.Cobalt acid lithium is expensive, and security performance is not high；Lithium nickelate preparation is difficult,
Voltage is low；And LiMn2O4 is resourceful, and it is cheap, and safety is good, non-environmental-pollution, it is lithium ion cell positive at this stage
Material optimal selection.
Although LiMn2O4 has many advantages, such as, but also have self-defect, i.e., capacity attenuation is serious in cyclic process.This is asked
Topic is mainly reflected in following three aspects: (1) LiMn2O4It is easily soluble in electrolyte；(2) there is Jiang Taile effect when LiMn2O4 discharges
It answers, changes its spinel structure, influence capacity and cycle performance；(3) electrolyte easily decomposes and easily forms passivation in electrode surface
Film generates self-discharge phenomenon.Regarding to the issue above one, it can mutually be mixed using body, metal cation M is added, and (it has than Mn3+
Radius is small can be bigger than Mn in conjunction with oxygen, such as Al, Co, Li, Ni, B) serve and stablizes structure cell, to inhibit jahn teller effect；For
The above problem two and three, because it is all with electrolyte close relation, solution is mostly to use special electrolyte, is not easy it point
Solution reduces manganese ion dissolution not with electrode reaction.But the modified product capacity as obtained by these methods is still differed with theoretical value
It is very big, and the improvement degree of cycle performance is also very limited.
Spheroidization mangaic acid lithiumation can not only improve the mobility of material slurry in electrode preparation, and can be improved electricity
The cyclicity in pond, from whole the single battery even quality of battery pack of improving.To sum up, the LiMn2O4 of spherical porousization is explored especially
It is important.102267726 A of patent CN reports a kind of preparation method of spherical lithium manganate, includes the following steps: lithium
Saline solution and manganese salt solution are uniformly mixed to prepare the colloidal solution of gust solution or the steady state that is situated between, spray-dried later to be made
Then spheroidal particle presoma is carried out dynamic roasting heat treatment by spheroidal particle presoma.LiMn2O4 obtained in this way
And it is non-porous, chemical property is general.A kind of manganate cathode material for lithium of porous spherical structure of patent CN102931393B and
Preparation method needs that manganese carbonate powder calcination is first obtained porous spherical manganese trioxide presoma, then presoma and hydroxide
Lithium after mixing, then is calcined and can just obtain porous spherical LiMn2O4, and this method needs to calcine twice, complex process, and to manganese
Salt and lithium salts limitation are more stringent；The preparation method of patent CN104409719B porous spherical manganate cathode material for lithium, wherein adopting
Manganese salt is precipitated with sodium carbonate and sodium hydrate aqueous solution, then sediment is mixed with lithium carbonate, and roasting obtains porous mangaic acid
Lithium material is easy the method use highly basic there are security risk, and lithium salts can only use lithium carbonate, more single.
So researching and developing, one kind is easy to operate, raw material sources are extensive, the preparation of the spherical porous LiMn2O4 function admirable of preparation
Method is particularly important.
Summary of the invention
For above-mentioned the technical problems existing in the prior art, the purpose of the present invention is to provide a kind of spherical porous mangaic acids
The preparation method of lithium, by the way that LiMn2O4 spherical porousization is obtained anode material for lithium-ion batteries, it is intended to accelerate in cyclic process
In ion transmission speed, and improve LiMn2O4 electrode preparation when slurry mobility, thus effectively improve LiMn2O4 work
For the chemical property of positive electrode.
In order to solve the above technical problems, the technical solution of the present invention is as follows:
A kind of preparation method of spherical porous LiMn2O4, includes the following steps:
1) manganese source and organic ligand are added in solvent according to setting ratio, are uniformly mixed, reaction obtains the organic of manganese
Compound, the organic ligand are trimesic acid, trimellitic acid, terephthalic acid (TPA), M-phthalic acid, benzoic acid, methyl
The mixture of one or more of imidazoles, polyvinylpyrrolidone；
2) after mixing by the organic double compound of the manganese after separation, drying and lithium source, calcining obtains spherical porous mangaic acid
Lithium.
The pattern of the organic double compound of manganese is spherical.
Preferably, in step 1), the manganese source is manganese nitrate, protochloride manganese, manganese sulfate, manganese acetate, one in manganese chloride
Kind or two or more mixtures.
Preferably, in step 1), the molar ratio of manganese source and organic ligand is 1:0.5-4.
Preferably, in step 1), the solvent is the mixed solvent of water and ethyl alcohol.
Preferably, in step 1), the temperature of reaction is 10-60 DEG C, and the time of reaction is 1-24h.
It is further preferred that the temperature of reaction is 25-30 DEG C in step 1), the time of reaction is 10-20h.
Preferably, in step 2), the lithium source is lithium carbonate, lithium chloride, lithium sulfate, lithium nitrate, lithium acetate, hydroxide
The mixture of one or more of lithium, lithia, lithium fluoride, carbonic acid dihydro lithium, lithium oxalate.
Preferably, in step 2), the molar ratio of lithium and manganese is 1:2-2:1 in the organic double compound of lithium source and manganese.
Preferably, in step 2), uniformly mixed mode is ball milling.
Preferably, in step 2), the temperature of calcining is 500-1000 DEG C, and the time of calcining is 5-20h.
It is further preferred that the temperature of calcining is 700-900 DEG C in step 2), the time of calcining is 10-15h.
Secondly, the present invention also provides the spherical porous LiMn2O4s using the preparation of above-mentioned preparation method.
Finally, the invention also discloses above-mentioned preparation method preparation spherical porous LiMn2O4 as lithium ion battery just
Application in the active material of pole material, further in lithium ion battery, electric car, electric bicycle or energy storage material
Application.
The invention has the benefit that
1) preparation process of LiMn2O4 of the invention is mild, environmentally protective controllable, is suitable for large-scale production, and manganese source and lithium
The raw material type in source is more.
2) present invention can control the size of the particle of the organic double compound of manganese by adjusting time and temperature, and then control
System control LiMn2O4 porosity and granule size, to obtain the LiMn2O4 of best performance.
3) partial size of LiMn2O4 prepared by the present invention is 100-200nm, and particle is tiny, pore size 200-300nm, is fitted
The transmission of lithium ion in cyclic process.
4) LiMn2O4 stable structure prepared by the present invention has good chemical property.
5) manganese source of the invention and lithium source are simple and easy to get, easy to operate, and existing equipment can be used and directly produced.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is the XRD diagram of the organic double compound of manganese in embodiment 1.
Fig. 2 is the XRD diagram of LiMn2O4 (b) in the LiMn2O4 (a) and embodiment 1 of purchase.
Fig. 3 is the SEM figure of the organic double compound of the manganese in embodiment 1.
Fig. 4 is the SEM figure of the LiMn2O4 of purchase.
Fig. 5 is the SEM figure of LiMn2O4 in embodiment 1.
Fig. 6 is the circulation figure of the LiMn2O4 of purchase.
Fig. 7 is the circulation figure of LiMn2O4 in embodiment 1.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
Embodiment 1:
Solution A: 0.49g manganese acetate and 3g polyvinylpyrrolidone are dissolved in the mixing of 50mL deionized water and 50ml ethyl alcohol
In solvent, stirring to solution is clarified.B solution: 1.65g trimesic acid is dissolved in the mixing of 50mL deionized water and 50ml ethyl alcohol
In solvent, stirring to solution is clarified.Then B solution is added in solution A, is reacted at room temperature for 24 hours, be then centrifuged for separating,
Drying, can be obtained the organic double compound of manganese.2g lithium hydroxide is taken to be added in the organic double compound of manganese, ball milling, 500
5h is heated at DEG C, and spherical porous LiMn2O4 can be obtained.
Fig. 1 is the XRD diagram of the organic double compound of manganese in embodiment 1.It can be seen from the figure that without miscellaneous peak, surface success
The substance is synthesized.
Fig. 2 is that the LiMn2O4 of purchase (buys from the rich electrochemical material of match) LiMn2O4 (b) prepared in (a) and embodiment 1
XRD diagram.The position at peak does not change in the XRD of LiMn2O4 done in the embodiment 1 and XRD for the LiMn2O4 bought, and illustrates to implement
LiMn2O4 is successfully synthesized in example 1.
Fig. 3 is the SEM figure of the organic double compound of the manganese prepared in embodiment 1.It can be seen that the organic double compound of manganese be it is spherical,
It is porous, and particle is smaller, partial size 50-70nm, and this structure is conducive to synthesize the LiMn2O4 of porous spherical.
Fig. 4 is the SEM figure of the LiMn2O4 of purchase.The lithium manganate particle is larger, uneven, and not porous structure.
Fig. 5 is the SEM figure of LiMn2O4 in embodiment 1.The LiMn2O4 is porous structure, is reunited by each spherical little particle
This porous structure, particle size 100-150nm are formed, pore size 200-300nm is conducive to the transmission of lithium ion.
Fig. 6 is the circulation figure of the LiMn2O4 of purchase.The chart is bright, and the LiMn2O4 bought capacity after circulation 90 weeks is only remaining
90mAh g-1, cyclicity is poor, this causes its cycle poor possibly due to particle is larger.
Fig. 7 is the circulation figure of the LiMn2O4 prepared in embodiment 1.The chart is bright, and the LiMn2O4 of spherical porousization is recycling
Capacity keeps 95mAh g after 800 weeks-1, relative to the LiMn2O4 of purchase, the cycle of the LiMn2O4 has great raising, perhaps
It is since the LiMn2O4 of porous is conducive to the transmission of lithium ion.
Embodiment 2:
Solution A: 0.6g manganese chloride and 3g polyvinylpyrrolidone are dissolved in the mixing of 50mL deionized water and 50ml ethyl alcohol
In solvent, stirring to solution is clarified.B solution: 2.13g terephthalic acid (TPA) is dissolved in the mixing of 50mL deionized water and 50ml ethyl alcohol
In solvent, stirring to solution is clarified.Then B solution is added in solution A, reacts 10h at room temperature, be then centrifuged for separating,
Drying, can be obtained the organic double compound of manganese.1.4g lithium carbonate is taken to be added in the organic double compound of manganese, ball milling, 700
10h is heated at DEG C, and spherical porous LiMn2O4 can be obtained.The particle diameter of the LiMn2O4 of preparation is 110-160nm, aperture diameter
Range is 250-300nm.The LiMn2O4 of spherical porousization capacity after circulation 100 weeks keeps 102mAh g-1。
Embodiment 3:
Solution A: 0.69g manganese nitrate and 3g polyvinylpyrrolidone are dissolved in the mixing of 50mL deionized water and 50ml ethyl alcohol
In solvent, stirring to solution is clarified.B solution: 1.65g trimellitic acid is dissolved in the mixing of 50mL deionized water and 50ml ethyl alcohol
In solvent, stirring to solution is clarified.Then B solution is added in solution A, reacts 1h at room temperature, be then centrifuged for separating, dried
It is dry, the organic double compound of manganese can be obtained.1.2g lithium sulfate is taken to be added in the organic double compound of manganese, ball milling, at 900 DEG C
Lower heating 5h, can be obtained spherical porous LiMn2O4.The particle diameter of the LiMn2O4 of preparation is 150-180nm, aperture diameter model
It encloses for 200-300nm.The LiMn2O4 of spherical porousization capacity after circulation 100 weeks keeps 99mAh g-1。
Embodiment 4:
Solution A: 0.3g manganese sulfate and 3g polyvinylpyrrolidone are dissolved in the mixing of 50mL deionized water and 50ml ethyl alcohol
In solvent, stirring to solution is clarified.B solution: the mixing that 4g terephthalic acid (TPA) is dissolved in 50mL deionized water and 50ml ethyl alcohol is molten
In agent, stirring to solution is clarified.Then B solution is added in solution A, is reacted at room temperature for 24 hours, be then centrifuged for separating, dried
It is dry, the organic double compound of manganese can be obtained.2.4g lithium oxalate is taken to be added in the organic double compound of manganese, ball milling, at 800 DEG C
Lower heating 10h, can be obtained spherical porous LiMn2O4.The particle diameter of the LiMn2O4 of preparation is 120-170nm, aperture diameter model
It encloses for 200-250nm.The LiMn2O4 of spherical porousization capacity after circulation 100 weeks keeps 100mAh g-1。
Embodiment 5:
Solution A: 0.5g manganese acetate and 3g polyvinylpyrrolidone are dissolved in the mixing of 50mL deionized water and 50ml ethyl alcohol
In solvent, stirring to solution is clarified.B solution: 1.65g trimesic acid is dissolved in the mixing of 50mL deionized water and 50ml ethyl alcohol
In solvent, stirring to solution is clarified.Then B solution is added in solution A, is reacted at room temperature for 24 hours, be then centrifuged for separating,
Drying, can be obtained the organic double compound of manganese.2g lithium hydroxide is taken to be added in the organic double compound of manganese, ball milling, 500
5h is heated at DEG C, and spherical porous LiMn2O4 can be obtained.The particle diameter of the LiMn2O4 of preparation is 140-200nm, aperture diameter
Range is 230-300nm.The LiMn2O4 of spherical porousization capacity after circulation 100 weeks keeps 97mAh g-1。
Embodiment 6:
Solution A: 0.36g manganese chloride and 3g polyvinylpyrrolidone are dissolved in the mixing of 50mL deionized water and 50ml ethyl alcohol
In solvent, stirring to solution is clarified.B solution: 1.65g trimesic acid is dissolved in the mixing of 50mL deionized water and 50ml ethyl alcohol
In solvent, stirring to solution is clarified.Then B solution is added in solution A, is reacted at room temperature for 24 hours, be then centrifuged for separating,
Drying, can be obtained the organic double compound of manganese.2g lithium hydroxide is taken to be added in the organic double compound of manganese, ball milling, 500
5h is heated at DEG C, and spherical porous LiMn2O4 can be obtained.The particle diameter of the LiMn2O4 of preparation is 100-160nm, aperture diameter
Range is 150-250nm.The LiMn2O4 of spherical porousization capacity after circulation 100 weeks keeps 105mAh g-1。
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (10)
1. a kind of preparation method of spherical porous LiMn2O4, characterized by the following steps:
1) manganese source and organic ligand are added in solvent according to setting ratio, are uniformly mixed, reaction obtains the organic composite of manganese
Object, the organic ligand be trimesic acid, trimellitic acid, terephthalic acid (TPA), M-phthalic acid, benzoic acid, methylimidazole,
The mixture of one or more of polyvinylpyrrolidone；
2) after mixing by the organic double compound of the manganese after separation, drying and lithium source, calcining obtains spherical porous LiMn2O4.
2. preparation method according to claim 1, it is characterised in that: in step 1), the manganese source is manganese nitrate, protochloride
The mixture of one or more of manganese, manganese sulfate, manganese acetate, manganese chloride.
3. preparation method according to claim 1, it is characterised in that: in step 1), the molar ratio of manganese source and organic ligand
For 1:0.5-4.
4. preparation method according to claim 1, it is characterised in that: in step 1), the solvent is the mixed of water and ethyl alcohol
Bonding solvent.
5. preparation method according to claim 1, it is characterised in that: in step 1), the temperature of reaction is 10-60 DEG C, instead
The time answered is 1-24h；
Preferably, in step 1), the temperature of reaction is 25-30 DEG C, and the time of reaction is 10-20h.
6. preparation method according to claim 1, it is characterised in that: 2) in, the lithium source is lithium carbonate, lithium chloride, sulphur
One or more of sour lithium, lithium nitrate, lithium acetate, lithium hydroxide, lithia, lithium fluoride, carbonic acid dihydro lithium, lithium oxalate
Mixture.
7. preparation method according to claim 1, it is characterised in that: in step 2), in the organic double compound of lithium source and manganese
The molar ratio of lithium and manganese is 1:2-2:1.
8. preparation method according to claim 1, it is characterised in that: in step 2), the temperature of calcining is 500-1000 DEG C,
The time of calcining is 5-20h；
Preferably, the temperature of calcining is 700-900 DEG C, and the time of calcining is 10-15h.
9. the spherical porous LiMn2O4 of -8 any preparation method preparations according to claim 1.
10. the spherical porous LiMn2O4 of preparation method preparation as claimed in claim 9 is as anode material for lithium-ion batteries
Application in active material, the further application in lithium ion battery, electric car, electric bicycle or energy storage material.
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| CN111600003A (en) * | 2020-06-01 | 2020-08-28 | 哈尔滨工业大学（威海） | Three-dimensional porous lithium nickel manganese oxide and preparation method thereof |
| CN111606359A (en) * | 2020-06-02 | 2020-09-01 | 山东大学 | Preparation method and application of porous lithium cobalt oxide positive electrode material |
| CN112538692A (en) * | 2020-11-05 | 2021-03-23 | 中国地质大学（北京） | Co-Mn bimetallic organic framework derived porous carbon fiber and preparation method and application thereof |
| CN113896244A (en) * | 2021-09-09 | 2022-01-07 | 江苏大学 | Porous disc-shaped lithium manganate electrode for extracting lithium from salt lake and preparation method thereof |
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| CN102931393A (en) * | 2012-11-15 | 2013-02-13 | 北京工业大学 | Lithium manganate anode material with porous spherical structure and preparation method of lithium manganate anode material |
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| CN102437324A (en) * | 2011-12-12 | 2012-05-02 | 中国科学技术大学 | Preparation method of cobalt-manganese composite oxide nanoparticles and cobalt-manganese composite oxide nanoparticles prepared by adopting same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111600003A (en) * | 2020-06-01 | 2020-08-28 | 哈尔滨工业大学（威海） | Three-dimensional porous lithium nickel manganese oxide and preparation method thereof |
| CN111600003B (en) * | 2020-06-01 | 2022-05-31 | 哈尔滨工业大学（威海） | Three-dimensional porous lithium nickel manganese oxide and preparation method thereof |
| CN111606359A (en) * | 2020-06-02 | 2020-09-01 | 山东大学 | Preparation method and application of porous lithium cobalt oxide positive electrode material |
| CN112538692A (en) * | 2020-11-05 | 2021-03-23 | 中国地质大学（北京） | Co-Mn bimetallic organic framework derived porous carbon fiber and preparation method and application thereof |
| CN113896244A (en) * | 2021-09-09 | 2022-01-07 | 江苏大学 | Porous disc-shaped lithium manganate electrode for extracting lithium from salt lake and preparation method thereof |
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