CN107055631A - A kind of porous C o3O4The preparation method and application of cuboid - Google Patents
A kind of porous C o3O4The preparation method and application of cuboid Download PDFInfo
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Abstract
The invention discloses a kind of porous C o3O4The preparation method of cuboid, comprises the following steps:By the mixed solution of the ethanol of the trimesic acid containing scheduled volume and water be added dropwise to same volume containing in the water cobalt acetate of scheduled volume four and the ethanol of polyvinylpyrrolidone and the mixed solution of water, stood after stirring;It is centrifugally separating to obtain Co BTC cuboids;Gained Co BTC cuboids are placed in Muffle furnace, is calcined in air atmosphere the scheduled time, porous C o is obtained after calcining3O4Cuboid.The invention also discloses a kind of porous C o3O4The application of cuboid.The advantage of the invention is that:Be simple and convenient to operate there is provided a kind of technique, cost it is low, and the porous C o of superperformance can be obtained3O4The preparation method and application of cuboid;Porous C o3O4Rectangular preparation process is simple, and pattern is homogeneous, more larger than surface, has very big application potential in terms of lithium ion battery, electrochemical energy storage and catalysis.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, more particularly to a kind of preparation method of porous C o3O4 cuboids
And application.
Background technology
Because lithium battery has the advantages that higher energy density and power density, it is widely used in electric automobile and electricity
The mobile energy storage device of sub- product.With traditional lithium cell cathode material graphite-phase ratio, metal oxide (such as MnO, Fe3O4、
Mn2O3And Co3O4) there is higher specific capacity, by the extensive concern of researcher.In numerous transition metal oxides, Co3O4
Rich reserves on earth, are a kind of excellent lithium cell cathode materials.2011, Britain《Chemical communication》Magazine
(Chem.Commun., volume 47, page 12280 in 2011) report Co3O4With higher theoretical specific capacity (890mAhg-1), it is the lithium cell cathode material graphite (372mAhg commercially used at present-1) twice, and think that it is a kind of potential
Lithium ion battery negative material.However, the U.S. in 2014《ACS applied chemistries interface》Magazine (ACS
Appl.Mater.Interfaces, volume 6, page 7117 in 2014) report Co3O4Easily hold in charge and discharge process
Amount decay.Because Co3O4Volumetric expansion easily occurs in charge and discharge process, so that cause its lattice to collapse,
Structure receives destruction.Britain in 2014《Materials chemistry》Magazine (J.Mater.Chem.A, volume 2, page 17408 in 2014)
Report the Co with loose structure3O4It is possible to prevente effectively from its Volumetric expansion in charge and discharge process, also, it is this
Loose structure is conducive to electrolyte and electronics in its internal transmission.But, report that the preparation method of synthesizing porous structure is complicated,
It is costly, it is unfavorable for commercialization and promotes.
Therefore, be badly in need of at present a kind of technique be simple and convenient to operate, cost it is low, and the porous C O of superperformance can be obtained3O4
The preparation method of cuboid, being desirably to obtain hollow-core construction, there is provided the performance improved when it is used as lithium ion battery negative material.
The content of the invention
Be simple and convenient to operate it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of technique, cost
It is low, and the porous C o of superperformance can be obtained3O4The preparation method and application of cuboid.
The present invention is achieved by the following technical solutions:A kind of porous C o3O4The preparation method of cuboid, including it is as follows
Step:
(1) under room temperature environment, the mixed solution of the 9-11mL ethanol for containing 85-95mg trimesic acids and water is added dropwise to
The four water cobalt acetates containing 44-54mg and the ethanol and the mixed solution of water of 0.2-0.4g polyvinylpyrrolidones of same volume
In, stand 22-26 hours after stirring;
(2) above-mentioned mixed solution is centrifuged, pink precursor C o-BTC cuboids, i.e. cobalt and trimesic acid is obtained
The complex of formation;
(3) the pink precursor C o-BTC cuboids of gained are placed in Muffle furnace, in atmosphere with 8-12 DEG C/min
Speed be warming up to 500 DEG C;Calcine 0.5-1.5 hours at this temperature again, naturally cool to after room temperature, obtain porous C o3O4It is long
Cube.
One of preferred embodiment as the present invention, ethanol and water mixed solution containing trimesic acid in the step (1)
In ethanol and water volume ratio be 1:1.
As one of preferred embodiment of the present invention, containing four water cobalt acetates and polyvinylpyrrolidone in the step (1)
Ethanol is 1 with the ethanol and the volume ratio of water in water mixed solution:1.
The porous C o of gained in one of preferred embodiment as the present invention, the step (3)3O4Cuboid has porous knot
Structure, specific surface area is 10.44m2/g。
A kind of porous C o of use the claims3O4Porous C o obtained by the preparation method preparation of cuboid3O4Should
With.
One of preferred embodiment as the present invention, by the porous C o obtained by above-mentioned preparation method3O4Cuboid is used as lithium ion
Cell negative electrode material prepares test battery, comprises the following specific steps that:
(1) the porous C o that will be obtained under calcining heat under heating rate is 8-12 DEG C/min3O4Cuboid and acetylene black and
Kynoar is mixed and made into muddy material, the muddy material is evenly coated on copper foil, in 75-85 DEG C of baking oven
After drying, copper foil is cut into a diameter of 12-16mm circular electric pole piece;
(2) to be loaded with porous C o3O4The electrode slice of cuboid is positive pole, with a diameter of 12-16mm circular metal lithium piece
For negative pole, using the mixed solution that is mixed by ethylene carbonate, diethyl carbonate and containing lithium hexafluoro phosphate as electrolyte, with straight
The circular polypropylene film that footpath is 14-18mm is barrier film, and button cell is assembled into the glove box that argon atmosphere is protected, as
Test battery.
One of preferred embodiment as the present invention, porous C o in the muddy material3O4Cuboid, acetylene black and poly- inclined
The mass ratio of PVF is (6-9):1:1.
One of preferred embodiment as the present invention, the mass ratio of sour ethyl and diethyl carbonate is 1 in the electrolyte:
1。
One of preferred embodiment as the present invention, the concentration of lithium hexafluoro phosphate is 1mol/L in the electrolyte.
One of preferred embodiment as the present invention, after the completion of prepared by the test battery, charge-discharge performance survey is carried out to it
Examination;In the case where current density is 100mA/g, after having circulated 55-65 times, discharge capacity is maintained at 886mAh/g;Test battery point
Not when being tested under the conditions of current density is 100mA/g, 200mA/g, 400mA/g, 800mA/g and 1600mA/g, its is corresponding
Average size is 590mAh/g, 486mAh/g, 386mAh/g, 260mAh/g and 163mAh/g.
The advantage of the present invention compared with prior art is:
(1) at present, people prepare porous oxide frequently with two-step method or multistep processes, i.e., with the silica prepared in advance
Or then carbon material removes template by the method for acid corrosion or calcining again as template;The preparation method not only technique
Complexity, and it is very time-consuming, increase the commercialization cost of porous oxide;And the present invention can pass through dinectly bruning metal in atmosphere
Organic frame compound prepares porous Co3O4Cuboid, is effectively prevented from template and is preparing porous C o3O4During cuboid
Application;
(2) during the present invention drives thing (Co-BTC) before calcination, have substantial amounts of carbon dioxide and hydrone overflow,
Cause the Co finally given3O4Cuboid has loose structure;Loose structure is conducive to lithium ion and electrolyte to pass in and out electrode material
Material, increases Co3O4With the contact area of electrolyte, shorten the diffusion length of lithium ion and electrolyte;This feature makes porous C o3O4
Cuboid has very high capacity and good cyclical stability as negative material;
(3) present invention prepares porous C o3O4The technique of cuboid is simply efficient, and safety is easy, and synthesis cycle is short, is expected to
To popularization and industrialization production.
Brief description of the drawings
Fig. 1 is a kind of porous C o in embodiment 33O4The X of the precursor C o-BTC cuboids of the preparation method of cuboid is penetrated
Ray diffraction diagram;
Fig. 2 is a kind of porous C o in embodiment 33O4The precursor C o-BTC cuboids of the preparation method of cuboid are swept
Retouch electron microscope;
Fig. 3 is a kind of porous C o in embodiment 33O4The heat of the precursor C o-BTC cuboids of the preparation method of cuboid
Weight curve map;
Fig. 4 is a kind of porous C o in embodiment 33O4The porous C o of the preparation method of cuboid3O4The X-ray of cuboid
Diffraction pattern;
Fig. 5 is a kind of porous C o in embodiment 33O4The porous C o of the preparation method of cuboid3O4The scanning electricity of cuboid
Mirror figure (Fig. 5 a) and transmission electron microscope picture (Fig. 5 b and Fig. 5 c);
Fig. 6 is a kind of porous C o in embodiment 33O4The porous C o of the preparation method of cuboid3O4The nitrogen of cuboid is inhaled
Attached-desorption curve figure;
Fig. 7 is a kind of porous C o in embodiment 63O4The gained half-cell of the application of cuboid is in current density
Discharge capacity and cycle-index curve map during 100mA/g;
Fig. 8 is a kind of porous C o in embodiment 63O4The gained half-cell of the application of cuboid is close in different discharge currents
Discharge capacity and cycle-index curve map under degree.
Embodiment
Embodiments of the invention are elaborated below, the present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementations
Example.
Embodiment 1
A kind of porous C o of the present embodiment3O4The preparation method of cuboid, comprises the following steps:
(1) under room temperature environment, 9mL is contained to the molten (body of ethanol and water of mixing of the ethanol and water of 85mg trimesic acids
Product compares 1:1) liquid is added dropwise to the mixed of the four water cobalt acetates containing 44mg of same volume and the ethanol of 0.2 polyvinylpyrrolidone and water
Close the solution (volume ratio 1 of ethanol and water:1) in, 22 hours are stood after stirring;
(2) above-mentioned mixed solution is centrifuged, pink precursor C o-BTC cuboids, i.e. cobalt and trimesic acid is obtained
The complex of formation;
(3) the pink precursor C o-BTC cuboids of gained are placed in Muffle furnace, in atmosphere with 8 DEG C/min speed
Rate is warming up to 500 DEG C;Calcine 0.5 hour at this temperature again, naturally cool to after room temperature, obtain porous C o3O4Cuboid;Institute
Obtain porous Co3O4Cuboid has loose structure, and specific surface area is 10.44m2/g。
Embodiment 2
A kind of porous C o of the present embodiment3O4The preparation method of cuboid, comprises the following steps:
(1) under room temperature environment, 11mL is contained to the molten (body of ethanol and water of mixing of the ethanol and water of 95mg trimesic acids
Product compares 1:1) liquid is added dropwise to the four water cobalt acetates containing 54mg of same volume and the ethanol of 0.4g polyvinylpyrrolidones and water
Mixed solution (the volume ratio 1 of ethanol and water:1) in, 26 hours are stood after stirring;
(2) above-mentioned mixed solution is centrifuged, pink precursor C o-BTC cuboids, i.e. cobalt and trimesic acid is obtained
The complex of formation;
(3) the pink precursor C o-BTC cuboids of gained are placed in Muffle furnace, in atmosphere with 12 DEG C/min's
Speed is warming up to 500 DEG C;Calcine 1.5 hours at this temperature again, naturally cool to after room temperature, obtain porous C o3O4Cuboid;
Gained porous C o3O4Cuboid has loose structure, and specific surface area is 10.44m2/g。
Embodiment 3
A kind of porous C o of the present embodiment3O4The preparation method of cuboid, comprises the following steps:
(1) under room temperature environment, 10mL is contained to the molten (body of ethanol and water of mixing of the ethanol and water of 90mg trimesic acids
Product compares 1:1) liquid is added dropwise to the four water cobalt acetates containing 49mg of same volume and the ethanol of 0.3g polyvinylpyrrolidones and water
Mixed solution (the volume ratio 1 of ethanol and water:1) in, 24 hours are stood after stirring;
(2) above-mentioned mixed solution is centrifuged, pink precursor C o-BTC cuboids, i.e. cobalt and trimesic acid is obtained
The complex of formation;Fig. 1 is the X-ray diffraction of precursor C o-BTC in the present embodimentFigure, can from Fig. 1
To find out itself and the U.S. in 1996《American Chemical Society's proceedings》(J.Am.Chem.Soc., volume 118, page 9096 in 1996) are reported
The Co-BTC in road X-ray diffractogram is consistent;Fig. 2 is precursor C o-BTC ESEM (SEM) figure, can from Fig. 2
Going out precursor C o-BTC is present with rectangular parallelepiped form;Fig. 3 is the thermogravimetric curves of precursor C o-BTC under air, from curve
As can be seen that the weightless platform below 150 DEG C is caused by some solvent molecules adsorbed as precursor C o-BTC, and second
Secondary weightless platform is due to that caused by precursor C o-BTC decomposition, therefore, the gross weight that precursor C o-BTC loses twice reaches
To 73.2%;
(3) the pink precursor C o-BTC cuboids of gained are placed in Muffle furnace, in atmosphere with 10 DEG C/min's
Speed is warming up to 500 DEG C;Calcine 1 hour at this temperature again, naturally cool to after room temperature, obtain porous C o3O4Cuboid;Forge
The chemical composition of product can be determined by X-ray diffraction after burning, and Fig. 4 is the X-ray diffraction of products therefrom in the present embodimentFigure, it can be seen that the X-ray diffraction peak of products therefrom and standard JCPDS cards No.42-
1462 is consistent, and it is Co to illustrate obtained sample3O4;Fig. 5 is the ESEM (SEM) and transmission electron microscope (TEM) figure of product, such as
Shown in Fig. 5 a and Fig. 5 b, product can still keep the profile of precursor cuboid after calcining, simultaneously because calcined
The effusion of internal gas in journey, generates fluffy loose structure, the surface of cuboid becomes coarse, as shown in Figure 5 c, in height
The lattice fringe that spacing of lattice is 0.24nm can be recognized under resolved transmittance microscope, Co is correspond to3O4(311) crystal face;Figure
6 be nitrogen adsorption-desorption curve, as can be seen from the figure prepared Co3O4Cuboid has loose structure, is than surface
10.44m2/g。
Embodiment 4
A kind of porous C o of use above-described embodiment of the present embodiment3O4It is porous obtained by the preparation method preparation of cuboid
Co3O4Application, by the porous C o3O4Cuboid prepares test battery, including following tool as lithium ion battery negative material
Body step:
(1) the porous C o that will be obtained under calcining heat under heating rate is 8 DEG C/min3O4Cuboid and acetylene black and poly-
Vinylidene is 6 in mass ratio:1:1 is mixed and made into muddy material, the muddy material is evenly coated on copper foil, 75
DEG C baking oven in dry after, copper foil is cut into a diameter of 12mm circular electric pole piece;
(2) to be loaded with porous C o3O4The electrode slice of cuboid be positive pole, using a diameter of 12mm circular metal lithium piece as
Negative pole, with by ethylene carbonate and diethyl carbonate in mass ratio 1:1 constitute and the lithium hexafluoro phosphates of 1mol/L containing concentration it is mixed
Conjunction solution is electrolyte, and the circular polypropylene film using a diameter of 14mm is barrier film, the group in the glove box that argon atmosphere is protected
Button cell is dressed up, test battery is used as;
(3) after the completion of prepared by test battery, charge-discharge performance test is carried out to it;In the case where current density is 100mA/g,
Circulate after 55 times, discharge capacity is maintained at 886mAh/g;Test battery respectively current density be 100mA/g, 200mA/g,
When being tested under the conditions of 400mA/g, 800mA/g and 1600mA/g, its corresponding average size be 590mAh/g, 486mAh/g,
386mAh/g, 260mAh/g and 163mAh/g.
Embodiment 5
A kind of porous C o of use above-described embodiment of the present embodiment3O4It is porous obtained by the preparation method preparation of cuboid
Co3O4Application, by the porous C o3O4Cuboid prepares test battery, including following tool as lithium ion battery negative material
Body step:
(1) the porous C o that will be obtained under calcining heat under heating rate is 12 DEG C/min3O4Cuboid and acetylene black and poly-
Vinylidene is 9 in mass ratio:1:1 is mixed and made into muddy material, the muddy material is evenly coated on copper foil, 85
DEG C baking oven in dry after, copper foil is cut into a diameter of 16mm circular electric pole piece;
(2) to be loaded with porous C o3O4The electrode slice of cuboid be positive pole, using a diameter of 16mm circular metal lithium piece as
Negative pole, with by ethylene carbonate and diethyl carbonate in mass ratio 1:1 constitute and the lithium hexafluoro phosphates of 1mol/L containing concentration it is mixed
Conjunction solution is electrolyte, and the circular polypropylene film using a diameter of 18mm is barrier film, the group in the glove box that argon atmosphere is protected
Button cell is dressed up, test battery is used as;
(3) after the completion of prepared by test battery, charge-discharge performance test is carried out to it;In the case where current density is 100mA/g,
Circulate after 65 times, discharge capacity is maintained at 886mAh/g;Test battery respectively current density be 100mA/g, 200mA/g,
When being tested under the conditions of 400mA/g, 800mA/g and 1600mA/g, its corresponding average size be 590mAh/g, 486mAh/g,
386mAh/g, 260mAh/g and 163mAh/g.
Embodiment 6
A kind of porous C o of use above-described embodiment of the present embodiment3O4It is porous obtained by the preparation method preparation of cuboid
Co3O4Application, by the porous C o3O4Cuboid prepares test battery, including following tool as lithium ion battery negative material
Body step:
(1) the porous C o that will be obtained under calcining heat under heating rate is 10 DEG C/min3O4Cuboid and acetylene black and poly-
Vinylidene is 8 in mass ratio:1:1 is mixed and made into muddy material, the muddy material is evenly coated on copper foil, 80
DEG C baking oven in dry after, copper foil is cut into a diameter of 14mm circular electric pole piece;
(2) to be loaded with porous C o3O4The electrode slice of cuboid be positive pole, using a diameter of 14mm circular metal lithium piece as
Negative pole, with by ethylene carbonate and diethyl carbonate in mass ratio 1:1 constitute and the lithium hexafluoro phosphates of 1mol/L containing concentration it is mixed
Conjunction solution is electrolyte, and the circular polypropylene film using a diameter of 16mm is barrier film, the group in the glove box that argon atmosphere is protected
Button cell is dressed up, test battery is used as;
(3) after the completion of prepared by test battery, charge-discharge performance test is carried out to it;As shown in fig. 7, being in current density
Under 100mA/g, after having circulated 60 times, discharge capacity is maintained at 886mAh/g;Multiplying power test is also to weigh a battery stabilization
It is respectively 100mA/g, 200mA/ in current density that the half-cell prepared in one important parameter, the present embodiment tests battery respectively
When being tested under the conditions of g, 400mA/g, 800mA/g and 1600mA/g, its charge and discharge cycles curve is as shown in Figure 8;Can from Fig. 8
Go out, when being tested under conditions of current density is respectively 100mA/g, 200mA/g, 400mA/g, 800mA/g and 1600mA/g, its
Corresponding average size is 590mAh/g, 486mAh/g, 386mAh/g, 260mAh/g and 163mAh/g, and this result is shown, this
Half-cell in embodiment has preferable stability.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modifications, equivalent substitutions and improvements made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
1. a kind of porous C o3O4The preparation method of cuboid, it is characterised in that comprise the following steps:
(1) under room temperature environment, the mixed solution of the 9-11mL ethanol for containing 85-95mg trimesic acids and water is added dropwise to consubstantiality
In the long-pending four water cobalt acetates and the ethanol of 0.2-0.4g polyvinylpyrrolidones and the mixed solution of water containing 44-54mg, stir
Mix uniform rear standing 22-26 hours;
(2) above-mentioned mixed solution is centrifuged, pink precursor C o-BTC cuboids, i.e. cobalt is obtained and is formed with trimesic acid
Complex;
(3) the pink precursor C o-BTC cuboids of gained are placed in Muffle furnace, in atmosphere with 8-12 DEG C/min speed
Rate is warming up to 500 DEG C;Calcine 0.5-1.5 hours at this temperature again, naturally cool to after room temperature, obtain porous C o3O4It is rectangular
Body.
2. porous C o according to claim 13O4The preparation method and application of cuboid, it is characterised in that the step
(1) volume ratio of ethanol and water in ethanol and water mixed solution containing trimesic acid is 1:1.
3. porous C o according to claim 13O4The preparation method and application of cuboid, it is characterised in that the step
(1) volume ratio for containing the ethanol in the ethanol and water mixed solution of four water cobalt acetates and polyvinylpyrrolidone and water in is 1:1.
4. porous C o according to claim 13O4The preparation method and application of cuboid, it is characterised in that the step
(3) the porous C o of gained in3O4Cuboid has loose structure, and specific surface area is 10.44m2/g。
5. the porous C o described in a kind of use the claims any one of 1-43O4It is many obtained by the preparation method preparation of cuboid
Hole Co3O4Application.
6. porous C o according to claim 53O4The application of cuboid, it is characterised in that by obtained by above-mentioned preparation method
Porous C o3O4Cuboid prepares test battery as lithium ion battery negative material, comprises the following specific steps that:
(1) the porous C o that will be obtained under calcining heat under heating rate is 8-12 DEG C/min3O4Cuboid and acetylene black and poly- inclined
PVF is mixed and made into muddy material, and the muddy material is evenly coated on copper foil, is dried in 75-85 DEG C of baking oven
Afterwards, copper foil is cut into a diameter of 12-16mm circular electric pole piece;
(2) to be loaded with porous C o3O4The electrode slice of cuboid is positive pole, and the circular metal lithium piece using a diameter of 12-16mm is negative
Pole, using the mixed solution that is mixed by ethylene carbonate, diethyl carbonate and containing lithium hexafluoro phosphate as electrolyte, with a diameter of
14-18mm circular polypropylene film is barrier film, is assembled into button cell in the glove box that argon atmosphere is protected, is used as test
Battery.
7. porous C o according to claim 63O4The application of cuboid, it is characterised in that porous in the muddy material
Co3O4The mass ratio of cuboid, acetylene black and Kynoar is (6-9):1:1.
8. porous C o according to claim 63O4The application of cuboid, it is characterised in that sour ethyl in the electrolyte
Mass ratio with diethyl carbonate is 1:1.
9. porous C o according to claim 63O4The application of cuboid, it is characterised in that hexafluorophosphoric acid in the electrolyte
The concentration of lithium is 1mol/L.
10. porous C o according to claim 63O4The application of cuboid, it is characterised in that prepared by the test battery
Cheng Hou, charge-discharge performance test is carried out to it;In the case where current density is 100mA/g, after having circulated 55-65 times, discharge capacity
It is maintained at 886mAh/g;Test battery respectively current density be 100mA/g, 200mA/g, 400mA/g, 800mA/g and
When being tested under the conditions of 1600mA/g, its corresponding average size be 590mAh/g, 486mAh/g, 386mAh/g, 260mAh/g and
163mAh/g。
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CN109516507A (en) * | 2017-09-18 | 2019-03-26 | 浙江工业大学 | A kind of preparation method of porous cobaltosic oxide nano piece |
CN109516507B (en) * | 2017-09-18 | 2021-05-11 | 浙江工业大学 | Preparation method of porous cobaltosic oxide nanosheet |
CN110172158A (en) * | 2019-04-25 | 2019-08-27 | 武汉理工大学 | A kind of preparation method of classifying porous metal-organic framework materials MIL-101 (Cr) |
CN110172158B (en) * | 2019-04-25 | 2021-07-27 | 武汉理工大学 | Preparation method of hierarchical porous metal organic framework material MIL-101(Cr) |
CN110212194A (en) * | 2019-06-12 | 2019-09-06 | 合肥工业大学 | A kind of preparation method and applications of one-dimensional MOF@ZIF core-shell structure |
CN110212194B (en) * | 2019-06-12 | 2021-01-08 | 合肥工业大学 | Preparation method and application of one-dimensional MOF @ ZIF core-shell structure |
CN113346070A (en) * | 2021-08-05 | 2021-09-03 | 河南师范大学 | Preparation method of lantern-shaped metal-oxygen-carbon composite material and application of lantern-shaped metal-oxygen-carbon composite material in non-aqueous potassium ion battery |
CN113346070B (en) * | 2021-08-05 | 2021-11-09 | 河南师范大学 | Preparation method of lantern-shaped metal-oxygen-carbon composite material and application of lantern-shaped metal-oxygen-carbon composite material in non-aqueous potassium ion battery |
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