CN104103806A - WS2 nano tile/graphene electrochemical lithium storage composite electrode and preparation method - Google Patents
WS2 nano tile/graphene electrochemical lithium storage composite electrode and preparation method Download PDFInfo
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- CN104103806A CN104103806A CN201410339858.0A CN201410339858A CN104103806A CN 104103806 A CN104103806 A CN 104103806A CN 201410339858 A CN201410339858 A CN 201410339858A CN 104103806 A CN104103806 A CN 104103806A
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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 WS2 nano tile/graphene electrochemical lithium storage composite electrode and a preparation method thereof. An electrochemical lithium storage active substance of the composite electrode adopts a WS2 nano tile/graphene composite nanomaterial, a substance ratio of the WS2 nano tiles to graphene is 1:2, a few layers of the WS2 nano tiles are provided, the average layer number is four, and the composite electrode comprises components in percentage by mass as follows: 80%-85% of the WS2 nano tile/graphene composite nanomaterial, 5%-10% of acetylene black and 10% of polyvinylidene fluoride. The preparation method comprises the steps as follows: the WS2 nano tile/graphene composite nanomaterial is prepared firstly, the prepared WS2 nano tile/graphene composite nanomaterial, acetylene black and polyvinylidene fluoride are prepared into paste, copper foil is coated with the paste, and the electrode is obtained through rolling. The prepared electrochemical lithium storage composite electrode has high electrochemical lithium storage capacity, excellent cycle performance and enhanced magnification characteristic.
Description
Technical field
The present invention relates to electrochemistry storage lithium electrode and preparation method thereof, relate in particular to WS
2nanometer watt/Graphene electrochemistry storage lithium method for preparing composite electrode, belongs to new energy materials and application thereof.
Background technology
Lithium ion battery has the excellent properties such as high specific energy, memory-less effect, environmental friendliness, in the Portable movable such as mobile phone and notebook computer electrical equipment, is widely used.As electrokinetic cell, lithium ion battery is also with a wide range of applications at aspects such as electric bicycle, electric automobile and intelligent grids.The negative material of lithium ion battery mainly adopts graphite material (as: graphite microspheres, natural modified graphite and Delanium etc.) at present, these graphite materials have good stable circulation performance, but its capacity is lower, the theoretical capacity of graphite is 372 mAh/g.Capacity and the stable circulation performance of a new generation's lithium ion battery to electrode material had higher requirement, the performance of lithium ion battery depends on the project of electrode material to a great extent, especially the performance of negative material, not only require negative material to there is high electrochemistry storage lithium specific capacity, and there is excellent stable circulation performance and high magnification characteristic.
two-dimensional nano material has the characteristic of numerous excellences with its unique pattern, its research has caused people's very big interest.Graphene is most typical two-dimensional nano material, and its unique two-dimensional nano chip architecture makes the performances such as physics, chemistry and the mechanics of its numerous uniquenesses, has important scientific research meaning and technology application prospect widely.Graphene has high specific area, high conduction and heat conductivility, high charge mobility, excellent mechanical property, these excellent characteristics make Graphene be with a wide range of applications at aspects such as micro-nano electronic device, energy storage material and novel catalyst carriers, and Graphene and material thereof have obtained people's very big concern as the application of electrochemistry storage lithium recently.
WS
2having and layer structure like graphite-like, is the S-Mo-S of very strong covalent bonds in its layer, is weak Van der Waals force between layers.WS
2weak interlaminar action power and larger interlamellar spacing allow to be reacted at its interlayer and introduced external atom or molecule by insertion.Such characteristic makes WS
2material can be used as the material of main part that inserts reaction.Therefore, WS
2it is the electrode material of a kind of rising electrochemical lithium storage and electrochemistry storage magnesium.
?the immense success that the discovery of Graphene and research thereof obtain has excited the very big interest of people to other inorganic two-dimensional nano investigations of materials, as the transition metal dichalcogenide of individual layer or few number of plies etc.Recently, Graphene concept has expanded to the inorganic compound of other layer structures from material with carbon element, namely for the inorganic material of layer structure, in the time that its number of plies reduces (below 8 layers), especially while reducing to individual layer, its electronic property or band structure can produce obvious variation, thereby cause it to show the physics and chemistry characteristic different from corresponding body phase material.Except Graphene, research shows as body phase WS
2reduce to few number of plies when individual layer (especially), shown and the visibly different physics of body phase material, chemistry and electronics property.Studies have reported that the WS of individual layer or few number of plies
2there is better electrochemistry storage lithium performance.But as the electrode material of electrochemistry storage lithium, WS
2low electric conductivity between layers affected the performance of its application.
Due to WS
2nanometer sheet and Graphene have similar two-dimensional nano sheet pattern, and both have good similitude on microscopic appearance and crystal structure.If by WS
2the composite material of nanometer sheet and the compound preparation of Graphene, the high conduction performance of graphene nanometer sheet can further improve the electric conductivity of composite material, strengthen the electronics transmission in electrochemistry storage lithium electrode course of reaction, can further improve the electrochemistry storage lithium performance of composite material.With common WS
2nanometer sheet comparison, the WS of little nanometer watt shape pattern
2not only there is more edge, more short lithium ion diffusion admittance can be provided, and load on Graphene, there is more contact area with electrolyte.Therefore WS
2the composite nano materials of nanometer watt/Graphene can show the electrochemistry storage lithium performance of remarkable enhancing.
?but, up to the present, use WS
2nanometer watt/Graphene composite nano materials have not been reported as electrochemistry storage lithium combination electrode and the preparation thereof of electroactive substance.First the present invention is raw material with graphene oxide and sulfo-ammonium tungstate, and the hydrothermal method of assisting by Gemini surface active agent and heat treatment subsequently, prepared WS
2the composite nano materials of nanometer watt/Graphene, then uses WS
2the composite nano materials of nanometer watt/Graphene, as the active material of electrochemistry storage lithium, has been prepared the combination electrode of electrochemistry storage lithium.This preparation WS
2the method of nanometer watt/Graphene composite nano materials electrochemistry storage lithium combination electrode has simply, facilitates and be easy to expand industrial applications a little.
Summary of the invention
The object of the present invention is to provide a kind of WS
2nanometer watt/Graphene electrochemistry storage lithium combination electrode and preparation method thereof, the electrochemistry storage lithium active material of this combination electrode is WS
2-the composite nano materials of nanometer watt/Graphene, WS in composite nano materials
2the ratio of the amount of substance of nanometer watt/Graphene is 1:2, described WS
2the nanometer watt layer structure for few number of plies, the component of combination electrode and mass percentage content thereof are: WS
2nanometer watt/Graphene composite nano materials 80-85%, acetylene black 5-10%, Kynoar 5-10%.
In technique scheme, the layer structure of few number of plies refers to the layer structure of the number of plies below 6 layers or 6 layers, described WS
2the average number of plies of nanometer watt is 4 layers.
Above-mentioned WS
2the preparation method of nanometer watt/Graphene electrochemistry storage lithium combination electrode carries out according to the following steps:
(1) be dispersed in deionized water ultrasonic graphene oxide, add the two ammonium bromides (seeing accompanying drawing 1) of Gemini surface active agent N-dodecyl trimethylene diamine, and fully stir, then add successively Cys and sulfo-ammonium tungstate, and constantly stir Cys and sulfo-ammonium tungstate are dissolved completely, the ratio of the amount of substance of Cys and sulfo-ammonium tungstate consumption is 5:1, and sulfo-ammonium tungstate is 1:2 with the ratio of the amount of substance of graphene oxide;
(2) mixed dispersion step (1) being obtained is transferred in hydrothermal reaction kettle, and add deionized water to adjust volume to 80% of hydrothermal reaction kettle nominal volume, the concentration of the two ammonium bromides of Gemini surface active agent N-dodecyl trimethylene diamine is 0.01 ~ 0.02 mol/L, the content of graphene oxide is 31.25-62.0 mmol/L, this reactor is put in constant temperature oven, at 230-250 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation collection hydro-thermal solid product, and fully wash with deionized water, vacuumize at 100 DEG C, by the hydro-thermal solid product obtaining in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2 h, in mist, hydrogen volume mark is 10%, finally prepare WS
2the composite nano materials of nanometer watt/Graphene,
(3) by the WS of above-mentioned preparation
2nanometer watt/Graphene composite nano materials is as the electrochemistry storage lithium active material of electrode, under agitation fully mix the uniform pastel of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass fraction 5%, each constituent mass percentage is: WS
2nanometer watt/Graphene composite nano materials 80-85%, acetylene black 5-10%, Kynoar 10%, is coated onto this pastel on the Copper Foil of collector equably, and dry, roll extrusion obtains electrode.
Above-mentioned graphene oxide adopts improved Hummers method preparation.
Hydrothermal method with the two ammonium bromides assistance of Gemini surface active agent N-dodecyl trimethylene diamine of the present invention is prepared WS
2the method of nanometer watt/Graphene composite nano materials has the following advantages: graphene oxide surface and edge with a lot of oxygen-containing functional groups (as hydroxyl, carbonyl, carboxyl), these oxygen-containing functional groups are more easily dispersed in water or organic liquid graphene oxide, but these oxygen-containing functional groups make graphene oxide surface with negative electrical charge, make graphene oxide and the WS with negative electrical charge
4 2-ion is incompatible, and the present invention is first adsorbed onto graphene oxide surface by two Gemini surface active agent N-dodecyl trimethylene diamine ammonium bromides by electrostatic interaction, makes it with part positive charge, due to electrostatic interaction, and WS
4 2-ion is just easy to interact and combine with the graphene oxide that has adsorbed Gemini surface active agent.The more important thing is, compared with common single cationic surfactant, in the two ammonium bromides of Gemini surface active agent N-dodecyl trimethylene diamine, there are 2 positively charged quaternary ammonium hydrophilic radicals, there is enough hydrophilies, and between electronegative graphene oxide, there is stronger mutual electrostatic interaction; The two ammonium bromides of N-dodecyl trimethylene diamine also have 2 hydrophobic long alkyl chain groups (seeing accompanying drawing 1), and its hydrophobicity is stronger.The two ammonium bromides of N-dodecyl trimethylene diamine are adsorbed on Graphene surface, and its hydrophobic grouping exists (seeing accompanying drawing 2) with irregular " brush head " form of bending, and this version has caused water-heat process and the heat treatment back loading WS on Graphene surface
2there is the pattern of nanometer watt.This undersized WS
2nanometer watt has more edge, as electrochemistry Lithium storage materials, can provide more short lithium ion diffusion admittance, contributes to strengthen its electrochemistry storage lithium performance; In addition, WS
2nanometer watt/graphene composite material can increase the contact area of itself and electrolyte, can further contribute to improve its chemical property.Therefore the present invention WS
2the electrochemistry storage lithium electrode that nanometer watt/graphene composite material is prepared as electroactive substance has high electrochemistry storage lithium capacity, excellent cycle performance and significantly strengthen large current density electrical characteristics.
Brief description of the drawings
The two ammonium bromide structural representations of Fig. 1 Gemini surface active agent N-dodecyl trimethylene diamine.
Fig. 2 Gemini surface active agent is adsorbed on the schematic diagram on graphene oxide surface.
The WS that Fig. 3 embodiment 1 prepares
2the XRD (a) of nanometer watt/Graphene composite nano materials, SEM shape appearance figure (b) and transmission electron microscope photo (c, d).
WS prepared by Fig. 4 comparative example
2the TEM of nanometer sheet and Graphene composite nano materials and HRTEM photo.
Embodiment
Further illustrate the present invention below in conjunction with embodiment.
Graphene oxide in following example adopts improved Hummers method preparation: 0
ounder C ice bath, by 10.0 mmol (0.12 g) graphite powder dispersed with stirring in the 50 mL concentrated sulfuric acids, under constantly stirring, slowly add KMnO
4, institute adds KMnO
4quality be 4 times of graphite powder, stir 50 minutes, in the time of temperature rise to 35 DEG C, slowly add 50 mL deionized waters, then stir 30 minutes, add the H of 15 mL mass fractions 30%
2o
2, stir 30 minutes, through centrifugation, after HCl solution, deionized water and the acetone cyclic washing with mass fraction 5%, obtain graphene oxide successively.
Embodiment 1
1) be dispersed in 60 mL deionized waters ultrasonic 2.5 mmol graphene oxides, add again the two ammonium bromides of 0.8 mmol Gemini surface active agent N-dodecyl trimethylene diamine, and fully stir, then add successively 0.76g (6.25 mmol) Cys and 1.25 mmol sulfo-ammonium tungstates, and constantly stir Cys and sulfo-ammonium tungstate are dissolved completely, with extremely approximately 80 mL of deionized water adjustment volume;
2) obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, this reactor is put in constant temperature oven, at 230 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash with deionized water, vacuumize at 100 DEG C, by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2h, in mist, the volume fraction of hydrogen is 10%, prepares WS
2the composite nano materials of nanometer watt/Graphene, WS in composite nano materials
2with the ratio of Graphene amount of substance be 1:2, with XRD, SEM and TEM are to the prepared WS that obtains
2the composite nano materials of nanometer watt/Graphene characterizes.XRD analysis result (seeing accompanying drawing 3 (a)) shows WS in composite nano materials
2for the layer structure of few number of plies, the average number of plies is 4 layers, and SEM pattern (seeing accompanying drawing 3 (b)) and TEM photo (seeing accompanying drawing 3 (c), (d)) have also shown the WS loading on Graphene
2have little nanometer watt pattern, its number of plies is at 3-6 layer, and most numbers of plies are 4 layers, consistent with XRD analysis;
3) by the WS of above-mentioned preparation
2nanometer watt/Graphene composite nano materials is as the electrode active material of electrochemistry storage lithium, under agitation fully mix the uniform pastel of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass fraction 5%, this pastel is coated onto equably on the Copper Foil of collector, vacuumize at 110 DEG C, then roll extrusion obtains WS
2nanometer watt/Graphene electrochemistry storage lithium combination electrode, in combination electrode, each constituent mass percentage is: WS
2nanometer watt/Graphene composite nano materials 80%, acetylene black 10%, Kynoar 10%.
?electrochemistry storage lithium performance test: as to electrode, electrolyte is 1.0 M LiPF with lithium sheet
6eC/DMC solution (1:1 volume ratio), barrier film is polypropylene screen (Celguard-2300), in the suitcase that is full of argon gas, be assembled into two electrode test batteries, the test of battery constant current charge-discharge is carried out on programme controlled auto charge and discharge instrument, charging and discharging currents density 100 mA/g, voltage range 0.005 ~ 3.00 V; The test of high-rate charge-discharge capability: test its electrochemistry storage lithium specific capacity in the time that charging and discharging currents is 1000 mA/g, as measuring of its high power charging-discharging characteristic.
?electrochemical results shows: WS
2the initial reversible capacity of electrochemistry storage lithium of nanometer watt/graphene combination electrode is 1233 mAh/g, and after 50 and 100 circulations, reversible capacity is 1196 and 1150 mAh/g, has shown high specific capacity and excellent stable circulation performance; In the time of high current charge-discharge (charging and discharging currents is 1000 mA/g), its capacity is 875 mAh/g, is much higher than the theoretical capacity (372 mA/g) of graphite material, has shown the high power charging-discharging characteristic of its enhancing.
Comparative example:
Adopt DTAB cationic surfactant, prepared WS by above-mentioned similar approach
2nanometer sheet/Graphene electrochemistry storage lithium combination electrode, concrete preparation process is as follows:
Be dispersed in 60 mL deionized waters ultrasonic 2.5 mmol graphene oxides, add again 1.6 mmol DTAB cationic surfactants, and fully stir, then add successively 0.76 g (6.25 mmol) Cys and 1.25 mmol sulfo-ammonium tungstates, and constantly stir Cys and sulfo-ammonium tungstate are dissolved completely, with extremely approximately 80 mL of deionized water adjustment volume, obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, this reactor is put in constant temperature oven, at 230 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash with deionized water, vacuumize at 100 DEG C, by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2h, in mist, the volume fraction of hydrogen is 10%, prepare WS
2the nano composite material of nanometer sheet/Graphene, WS in composite nano materials
2with the ratio of the amount of substance of Graphene be 1:2.With XRD, SEM and TEM are to finally preparing WS
2the nano composite material of nanometer sheet/Graphene characterizes, and XRD analysis result shows WS in composite nano materials
2for layer structure, its average number of plies is 7 layers, and TEM and HRTEM photo (seeing accompanying drawing 4, is (a) TEM photo, is (b) HRTEM photo) have shown the WS loading on Graphene
2for nanometer sheet pattern, its thickness and plane sizes are not so good as WS above
2nanometer watt evenly, WS
2the number of plies of nanometer sheet is mainly at 6-9 layer, and the average number of plies is 7 layers, consistent with XRD analysis;
?by above-mentioned steps 3) process prepare WS
2nanometer sheet/Graphene electrochemistry storage lithium combination electrode.Electrochemical results shows: WS
2the initial reversible capacity of nanometer sheet/Graphene electrochemistry storage lithium combination electrode electrochemistry storage lithium is 925 mAh/g, and after 50 and 100 circulations, reversible capacity is 912 and 865 mAh/g; In the time of high current charge-discharge (charging and discharging currents is 1000 mA/g), its capacity is 532 mAh/g.
Claims (3)
1. a WS
2nanometer watt/Graphene electrochemistry storage lithium combination electrode, is characterized in that, the electrochemistry storage lithium active material of combination electrode is WS
2-the composite nano materials of nanometer watt/Graphene, WS in composite nano materials
2the ratio of the amount of substance of nanometer watt and Graphene is 1:2, described WS
2the nanometer watt layer structure for few number of plies, the component of combination electrode and mass percentage content thereof are: WS
2nanometer watt/Graphene composite nano materials 80-85%, acetylene black 5-10%, Kynoar 10%.
2. WS according to claim 1
2nanometer watt/Graphene electrochemistry storage lithium combination electrode, is characterized in that described WS
2the average number of plies of nanometer watt is 4 layers.
3. a preparation method for WS2 nanometer watt described in claim 1 or 2/Graphene electrochemistry storage lithium combination electrode, is characterized in that, its preparation method carries out according to the following steps:
(1) be dispersed in deionized water ultrasonic graphene oxide, add the two ammonium bromides of Gemini surface active agent N-dodecyl trimethylene diamine, and fully stir, then add successively Cys and sulfo-ammonium tungstate, and constantly stir Cys and sulfo-ammonium tungstate are dissolved completely, the ratio of the amount of substance of Cys and sulfo-ammonium tungstate consumption is 5:1, sulfo-ammonium tungstate with the ratio of the amount of substance of graphene oxide at 1:2;
(2) mixed dispersion step (1) being obtained is transferred in hydrothermal reaction kettle, and add deionized water to adjust volume to 80% of hydrothermal reaction kettle nominal volume, the concentration of the two ammonium bromides of Gemini surface active agent N-dodecyl trimethylene diamine is 0.01 ~ 0.02 mol/L, the content of graphene oxide is 31.25-62.0 mmol/L, this reactor is put in constant temperature oven, at 230 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation collection hydro-thermal solid product, and fully wash with deionized water, vacuumize at 100 DEG C, by the hydro-thermal solid product obtaining in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2 h, in mist, hydrogen volume mark is 10%, finally prepare WS
2the composite nano materials of nanometer watt/Graphene,
(3) by the WS of above-mentioned preparation
2nanometer watt/Graphene composite nano materials is as the electrochemistry storage lithium active material of electrode, under agitation fully mix the uniform pastel of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass fraction 5%, this pastel is coated onto equably on the Copper Foil of collector, dry, roll extrusion obtains electrode.
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| CN101420031A (en) * | 2008-12-11 | 2009-04-29 | 浙江大学 | Electrochemical magnesium ionic insertion/deinsertion electrode and production method thereof |
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