CN105118692A - Method for preparing SnO2-MnO2-Fe3O4 ternary composite capacitive material - Google Patents
Method for preparing SnO2-MnO2-Fe3O4 ternary composite capacitive material Download PDFInfo
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- CN105118692A CN105118692A CN201510589123.8A CN201510589123A CN105118692A CN 105118692 A CN105118692 A CN 105118692A CN 201510589123 A CN201510589123 A CN 201510589123A CN 105118692 A CN105118692 A CN 105118692A
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- 239000000463 material Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 10
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title abstract 7
- 239000011206 ternary composite Substances 0.000 title abstract 3
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- 230000002459 sustained effect Effects 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 235000014121 butter Nutrition 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 239000011218 binary composite Substances 0.000 abstract description 13
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002052 molecular layer Substances 0.000 abstract 2
- 238000005253 cladding Methods 0.000 abstract 1
- 239000004005 microsphere Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 38
- 239000011135 tin Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 10
- 230000008859 change Effects 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- 229910002551 Fe-Mn Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013066 combination product Substances 0.000 description 2
- 229940127555 combination product Drugs 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000004098 selected area electron diffraction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a method for preparing the spherical SnO2-MnO2-Fe3O4 ternary composite capacitive material, which solves the problem in the prior art that oxide materials are poor in electrical conductivity and low in specific surface area at the same time. According to the method, firstly, with the assistance of ultrasonic waves, Fe2+ are guided to grow at an accelerated speed to form the MnO2-Fe3O4 binary composite material of a spherical porous structure, wherein Fe3O4 nanoparticles are doped inside MnO2 microspheres. After that, an electrically conductive SnO2 nano layer grows on the surface of the MnO2-Fe3O4 binary composite material through the hydrothermal process. The electrical conductivity of the composite material is improved and the composite material is ensured to be higher in specific surface area at the same time through adjusting the cladding amount of the SnO2 nano layer. Finally, the SnO2-MnO2-Fe3O4 ternary composite capacitive material of excellent capacitive performance is prepared. In particular, the content ratio of three oxides in the composite material can be effectively controlled based on the concentrations of reactants. In addition, the method is simple in device, easy to operate, low in cost, good in reproducibility and easy in large-scale preparation.
Description
Technical field
The present invention relates to a kind of preparation method of electrode material for super capacitor, especially a kind of novel spherical SnO
2-MnO
2-Fe
3o
4the preparation method of tri compound capacitance material.MnO
2for the material of main part of whole composite balls, Fe
3o
4ball inside is entrained in, SnO with the form of nano particle
2nano particle coating layer is defined on ball surface.
Background technology
Ultracapacitor is regarded as very potential energy storage device owing to having the advantages such as fast charging and discharging, high power density and service life cycle length.The preparation of exploration excellent performance electrode material is study hotspot in recent years always.Wherein, transition metal oxide (as manganese oxide, cobalt oxide, nickel oxide, ruthenium-oxide and iron oxide etc.) is subject to extensive research because it has higher theoretical ratio capacitance.But the electric conductivity poor due to self and low specific surface area, oxide material ubiquity actual capacitance is all well below the problem of theoretical value.By in conjunction with multiple capacitance material advantage, design high-specific surface area structure and utilize the dimensional effect of nano unit and cooperative effect to be one of effective way addressed this problem.At present, the research about manganese dioxide as capacitance material is a lot, but the new electrode materials three kinds of transition metal oxides being carried out compound preparation unique seldom has report.
The present invention is with MnO
2for material of main part, carry out size, structural compound by adding other transition metal oxides with it, the dimensional effect of nanometer and micron is strengthened; There is in its superficial growth the nanometer layer of conductivity again.Under ultrasonic wave added, Fe2+ guides and accelerates growth rate thus generate the MnO of spherical porous structure
2-Fe
3o
4binary composite (Fe
3o
4mnO is entrained in the form of nano particle
2the inside of micron ball), recycling hydro thermal method, while guaranteeing spherical porous structure, carries out coated enhancing monolithic conductive at its superficial growth tin oxide nanoparticles, final obtained spherical SnO
2-MnO
2-Fe
3o
4tri compound capacitance material.Content particularly in composite material between three kinds of oxides is than controling effectively by reactant concentration.
Summary of the invention
Object of the present invention: propose a kind of novel spherical SnO
2-MnO
2-Fe
3o
4the preparation method of tri compound capacitance material.With MnO
2for material of main part, carry out size, structural compound by adding other transition metal oxides with it, the dimensional effect of nanometer and micron is strengthened; By having the nanometer layer of conductivity in its superficial growth, regulate and control while its covering amount reaches raising material conductivity and guarantee the specific area that composite material is higher.This technology solves oxide material poorly conductive and the little problem of specific surface simultaneously.This preparation method has the advantages such as reaction condition gentleness, cost be low and reproducible.
1, technical scheme of the present invention is: first prepare spherical porous Fe
3o
4-MnO
2binary composite, is dissolved into a certain amount of manganese sulfate, ammonium persulfate and ferrous sulfate successively in 50ml deionized water, in water bath with thermostatic control, carries out ultrasonic reaction, by freeze drying again after product centrifugation, repeatedly cleaning; Then SnO
2surface coating, by appropriate Fe
3o
4-MnO
2be made into suspension in ball ultrasonic disperse to deionized water, add a certain amount of butter of tin, magnetic agitation 10min, then add appropriate NaOH; Mixed liquor is proceeded in 50ml reactor, sustained response 6h at 180 DEG C; By suspended matter with the centrifugal 5min of the rotating speed of 8000r/min, repeatedly clean 3-5 time with absolute ethyl alcohol, freeze drying 12h, obtain final trielement composite material.
In sonochemistry reaction preparation process, solution system remains in 40 ~ 80 DEG C of waters bath with thermostatic control; The ultrasonic duration controls at 0.5 ~ 3h, and ultrasonic wave plays the spontaneous assembling that adds fast particle and avoids a large amount of gathering and homodisperse double action.
Preparation Fe
3o
4-MnO
2during binary composite suspension, need by ul-trasonic irradiation, make it be dispersed in water.
Optimum condition, for obtaining uniform SnO
2nanometer coating layer, gets 40ml mixed liquor and is transferred in 50ml reactor, sustained response 6h at 180 DEG C.
Product deionized water carries out cleaning-and the step of centrifugation redispersion carries out repeatedly wash cycles.
Porous Fe
3o
4-MnO
2with final SnO
2-MnO
2-Fe
3o
4tri compound product needs dry 12h in freeze drier.
Other method is compared, and the method that the present invention proposes can obtain porous, uniform trielement composite material, and component and size controlled; Without the need to any additive or template, the time is shorter, is conducive to saving preparation cost.In addition, the method device simply, easily operates, controllability is good, easily realize scale prepares fast.
Beneficial effect of the present invention:
(1) propose one and prepare SnO
2-MnO
2-Fe
3o
4the new method of tri compound capacitance material.
(2) preparation process relies on hyperacoustic double action to realize the control of spherical composite material pattern and component, simple to operate.
(3) in addition, compared with other method, this preparation method also has following particular advantages:
1. experimental provision, experiment condition and preparation process are very simple, easily operate;
2. controllability is good, by the generation and the size that regulate the concentration of reactant, reaction time and reaction temperature etc. to control product;
3. with low cost, there is good industrial applications prospect;
4. applicability is strong, extends to the controlled synthesis of other kind multi-element composite material.
Accompanying drawing explanation
Fig. 1 (a) embodiment 1 first step obtains Fe
3o
4-MnO
2the high power SEM figure of product; B () embodiment 1 obtains end product SnO
2-MnO
2-Fe
3o
4high power SEM and (c) low power SEM schemes; Each distribution diagram of element in (d) individual particle; (e) and (f) EDS collection of illustrative plates.
Fig. 2 (a) embodiment 1 first step obtains Fe
3o
4-MnO
2the TEM figure of product; B () embodiment 1 obtains end product SnO
2-MnO
2-Fe
3o
4high power TEM (c) low power TEM and (d) HRTEM picture.
The different Sn of Fig. 3 embodiment 2-5
4+(a) 0.1mM under concentration; (b) 1.0mM; C () 1.5mM obtains the energy spectrogram of product; (d) Sn
4+concentration and SnO
2-MnO
2-Fe
3o
4the graph of a relation of particle diameter; SnO in trielement composite material
2the contrast of mass fraction theory and practice value.
The ratio capacitance value of Fig. 4 (a) different Fe-Mn atomic ratio binary composite; B () embodiment 1 obtains SnO
2-MnO
2-Fe
3o
4product is scan round figure under different scanning rates; Charging and discharging curve under (c) different constant current charge-discharge; SnO in (d) trielement composite material
2mass fraction and capacitance variation graph of a relation.
Embodiment
The spherical SnO of one that the present invention proposes
2-MnO
2-Fe
3o
4the preparation method of trielement composite material, embodiment is as follows:
Embodiment 1
SnO
2-MnO
2-Fe
3o
4the preparation of trielement composite material: first prepare spherical porous Fe
3o
4-MnO
2binary composite, is dissolved into a certain amount of manganese sulfate, ammonium persulfate and ferrous sulfate successively in 50ml deionized water, in water bath with thermostatic control, carries out ultrasonic reaction, by product centrifugation, repeatedly cleaning after through freeze drying; Then SnO is carried out
2surface coating, by appropriate Fe
3o
4-MnO
2composite balls ultrasonic disperse, in deionized water, adds a certain amount of butter of tin, magnetic agitation 10min, then adds appropriate NaOH; Mixed liquor is proceeded in 50ml reactor, sustained response 6h at 180 DEG C; By suspended matter with the centrifugal 5min of the rotating speed of 8000r/min, repeatedly clean 3-5 time with absolute ethyl alcohol, freeze drying 12h, obtains end product.
Fig. 1 a is embodiment 1 first step gained Fe
3o
n-MnO
2the SEM figure of binary combination product, can find out that binary composite is spherical porous structure, particle size is homogeneous.Fig. 1 b is embodiment 1 second step SnO
2product S EM figure after Surface coating, can see, binary Fe
3o
4-MnO
2porous nanometer structure by SnO
2coated.
Fig. 1 c is SnO
2-MnO
2-Fe
3o
4the low power SEM figure of trielement composite material.The pattern that product presents is spherical porous micron particles, and particle size size is homogeneous, and relatively independently between particle and particle does not reunite.
Fig. 1 d is the SnO that embodiment 1 second step obtains
2-MnO
2-Fe
3o
4the EDS energy spectrogram of trielement composite material, Mn, O element dominate, Fe, Sn element is detected equally, shows the existence of three kinds of metal oxides.In the line sweep figure of single micron ball (see Fig. 1 e), according to the linear distribution track situation of Mn, Fe, Sn tri-kinds of elements, can find out that Sn is positioned at the surface of micron ball.Fig. 1 f is the EDS-mapping figure of single micron ball, according to Mn, Fe, Sn tri-kinds of elements concrete distribution situation in spheroid, further demonstrates SnO
2be coated on the surface of micron ball.
Fig. 2 a is embodiment 1 first step gained Fe
3o
4-MnO
2binary combination product TEM schemes, and intuitively can find out that this binary composite is microns Particle size, its structure is porous spherical.Fig. 2 b-c is the SnO that embodiment 1 second step obtains
2-MnO
2-Fe
3o
4trielement composite material different amplification TEM schemes.Known SnO
2nano particle is coated on Fe
3o
4-MnO
2the surface of binary composite sphere.Fig. 2 d is the HRTEM figure of trielement composite material, according to interplanar distance size, confirms that product is by MnO
2, Fe
3o
4and SnO
2formed; Illustration is its selected area electron diffraction figure, proves that product is polycrystalline state.
Embodiment 2
Change Sn
4+concentration be 0.1mM, other conditions are identical with embodiment 1.
Embodiment 3
Change Sn
4+concentration be 1.0mM, other conditions are identical with embodiment 1.
Embodiment 4
Change Sn
4+concentration be 1.5mM, other conditions are identical with embodiment 1.
Embodiment 5
Change Sn
4+concentration be 2.0mM, other conditions are identical with embodiment 1.
Fig. 3 a-c is different Sn
4+obtained Fe under concentration
3o
4-MnO
2-SnO
2the EDS collection of illustrative plates of trielement composite material.Because nano-pore structure determines specific area, thus affect the chemical property of material, therefore SnO
2need thickness be controlled time coated, ensure porousness and the high-specific surface area of material.Fig. 3 d is Sn
4+concentration and SnO
2-MnO
2-Fe
3o
4particle diameter graph of a relation and SnO
2the comparison diagram of mass fraction theory and practice value.Can see, by changing Sn
4+concentration can control the content ratio between three kinds of oxides.
Embodiment 6
The ratio capacitance value of Fig. 4 a different Fe-Mn atomic ratio binary composite, as seen from the figure, when Fe-Mn atomic ratio is 0.075, the capacitive property of binary composite reaches and is up to 0.67F/cm
2.Select this binary composite, then by the SnO that embodiment 1 second step is obtained
2-MnO
2-Fe
3o
4the scan round figure of trielement composite material under different scanning rates (Fig. 4 b), under the sweep speed of 5mV/s, its capacitance reaches 1.12F/cm
2.Can be found out by the symmetry of trielement composite material charging and discharging curve (Fig. 4 c) under different constant current, resulting materials shows good discharge and recharge behavior.Along with SnO
2the change of content, ratio capacitance also there occurs the trend first increasing and reduce afterwards.Work as SnO
2when mass fraction is 5.3%, ternary SnO
2-MnO
2-Fe
3o
4the ratio capacitance of composite material reaches maximum, as shown in figure 4d.
Claims (6)
1. a SnO
2-MnO
2-Fe
3o
4the preparation method of tri compound capacitance material, is characterized in that, process in two steps (1) first prepares spherical porous Fe
3o
4-MnO
2: a certain amount of manganese sulfate, ammonium persulfate and ferrous sulfate are dissolved into successively in 50ml deionized water, in water bath with thermostatic control, carry out ultrasonic reaction, by product centrifugation, repeatedly clean postlyophilization; (2) SnO
2surface coating: by appropriate Fe
3o
4-MnO
2be made into suspension in composite balls ultrasonic disperse to deionized water, then add a certain amount of butter of tin, magnetic agitation 10min, then add appropriate NaOH; Mixed liquor is proceeded in 50ml reactor, sustained response 6h at 180 DEG C; By suspended matter with the centrifugal 5min of the rotating speed of 8000r/min, repeatedly clean 3-5 time with absolute ethyl alcohol, freeze drying 12h, obtains end product.
2. preparation method according to claim 1, is characterized in that, prepares spherical porous Fe
3o
4-MnO
2optimal parameter be: its concentration of the solution that manganese sulfate and ammonium persulfate are made into all controls between 0.05 ~ 0.25M, and the concentration of ferrous sulfate controls at 0.5 ~ 2.5mM, 40 ~ 80 DEG C of waters bath with thermostatic control, and ultrasonic time is 0.5 ~ 3h.
3. preparation method according to claim 1, is characterized in that, SnO
2surface coated optimal parameter is: Fe
3o
4-MnO
2the concentration range of suspended particulate is 0.2 ~ 1.5g/l's, and butter of tin concentration range is the concentration range of 0.1 ~ 1.5mM, NaOH is 0.5 ~ 5.0mM.
4. preparation method according to claim 1, is characterized in that, is transferred to by the mixed reaction solution of 40ml in 50ml hydrothermal reaction kettle, sustained response 6h at 180 DEG C.
5. preparation method according to claim 1, is characterized in that, porous Fe
3o
4-MnO
2with final SnO
2-MnO
2-Fe
3o
4tri compound product, all after centrifugation, is placed in the dry 12h of freeze drier.
6. preparation method according to claim 1, is characterized in that, obtained SnO
2-MnO
2-Fe
3o
4in trielement composite material, MnO
2for the material of main part of whole composite balls, Fe
3o
4ball inside is entrained in, SnO with the form of nano particle
2nano particle coating layer is defined on ball surface; Content between three kinds of oxides is than controling effectively by reactant concentration.
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Cited By (3)
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CN105914358A (en) * | 2016-06-24 | 2016-08-31 | 扬州大学 | Preparation method of yolk-eggshell structured nitrogen-doped carbon-coated Fe3O4@SnO2 magnetic nanometer box |
CN106298272A (en) * | 2016-10-28 | 2017-01-04 | 南京工程学院 | A kind of electrochemical capacitance metal ion mixing flower-shaped MnO2 nanometer sheet and preparation method thereof |
CN114639799A (en) * | 2022-03-28 | 2022-06-17 | 广东技术师范大学 | Composite electrode for all-solid-state metal lithium battery and preparation method thereof |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105914358A (en) * | 2016-06-24 | 2016-08-31 | 扬州大学 | Preparation method of yolk-eggshell structured nitrogen-doped carbon-coated Fe3O4@SnO2 magnetic nanometer box |
CN106298272A (en) * | 2016-10-28 | 2017-01-04 | 南京工程学院 | A kind of electrochemical capacitance metal ion mixing flower-shaped MnO2 nanometer sheet and preparation method thereof |
CN114639799A (en) * | 2022-03-28 | 2022-06-17 | 广东技术师范大学 | Composite electrode for all-solid-state metal lithium battery and preparation method thereof |
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