CN117374238A - High-conductivity nano composite positive electrode material for aluminum ion battery - Google Patents
High-conductivity nano composite positive electrode material for aluminum ion battery Download PDFInfo
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- CN117374238A CN117374238A CN202311185867.4A CN202311185867A CN117374238A CN 117374238 A CN117374238 A CN 117374238A CN 202311185867 A CN202311185867 A CN 202311185867A CN 117374238 A CN117374238 A CN 117374238A
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- ion battery
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 54
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 53
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 31
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 64
- 239000002052 molecular layer Substances 0.000 claims abstract description 22
- 239000010405 anode material Substances 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 5
- -1 aluminum ion Chemical class 0.000 claims description 44
- 239000002238 carbon nanotube film Substances 0.000 claims description 37
- 238000004070 electrodeposition Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910001437 manganese ion Inorganic materials 0.000 claims description 7
- 150000002696 manganese Chemical class 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000012827 research and development Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229940071125 manganese acetate Drugs 0.000 description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 3
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007785 strong electrolyte Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- FQERWQCDIIMLHB-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CC[NH+]1CN(C)C=C1 FQERWQCDIIMLHB-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910003174 MnOOH Inorganic materials 0.000 description 1
- GQCYCMFGFVGYJT-UHFFFAOYSA-N [AlH3].[S] Chemical compound [AlH3].[S] GQCYCMFGFVGYJT-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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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
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
-
- 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
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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 relates to a high-conductivity nano composite positive electrode material for an aluminum ion battery, and belongs to the technical field of aluminum ion batteries. The high-conductivity nano composite anode material is a composite anode material consisting of a high-conductivity nano composite film and a manganese oxide nano layer loaded on the high-conductivity nano composite film. The high-conductivity nano composite positive electrode material is applied to an aluminum ion battery, can realize higher charge-discharge capacity and better cycle performance of the aluminum ion battery, has simple preparation method operation and easily controlled reaction conditions, is easy for large-scale production, and is beneficial to promoting the further research and development of the aluminum ion battery.
Description
Technical Field
The invention relates to a high-conductivity nano composite positive electrode material for an aluminum ion battery, and belongs to the technical field of aluminum ion batteries.
Background
The theoretical capacity of aluminum is high, the content in the crust is rich, and the rechargeable aluminum battery is an ideal choice for future electrochemical energy storage systems. The aluminum ion battery can provide three-electron electrochemical reaction, so that the lithium ion battery has ultrahigh theoretical capacity and energy density, and the theoretical volumetric energy density of the aluminum ion battery is even higher than that of the lithium ion battery. The advantages of light weight, low price, high theoretical capacity and energy density and the like lead the aluminum ion battery to have great development potential, and the development of the aluminum ion battery technology has important significance for effectively utilizing renewable energy sources.
Suitable positive electrode materials have a critical role in the development of aluminum ion batteries. The currently commonly used positive electrode materials of aluminum ion batteries include carbon materials, transition metal oxides, transition metal sulfides, and prussian blue analogues. The carbon material has good cycle reversibility, and is used as an anode material of the aluminum ion battery, so that the anode material has good cycle performance, but the specific capacity of the carbon material is low due to limited containing capacity of the carbon material, and the specific capacity after stable cycle is only about 30mAh/g; sulfide has highest reversible capacity, but when the sulfide is used as a positive electrode material of an aluminum ion battery, serious aluminum dissolution phenomenon exists, so that the capacity retention rate is poor, the capacity decays to less than 10% after more than 20 weeks of circulation, and the discharge voltage is low due to the fact that aluminum is weaker than alkali metals or alkaline earth metals such as lithium, sodium, magnesium and the like, and the specific energy and specific power of the aluminum sulfur battery are low; the surface capacities of the transition metal oxide and the transition metal sulfide are also higher, for example, the first-week capacity of nickel sulfide is close to 300mAh/g, but the capacity attenuation is quite obvious, namely, the capacity attenuation is obviously reduced to less than 100mAh/g after 10 weeks, and the discharge voltage of the aluminum secondary battery with the sulfide as the positive electrode material is lower due to lower potential difference between the sulfide and aluminum metal, and the specific energy and the specific power are both lower. It is found that the above-mentioned positive electrode materials for aluminum ion batteries are all deficient. Therefore, it is necessary to develop an aluminum ion battery positive electrode material with higher capacity and good cycle performance, which is important for further developing an aluminum ion battery.
Disclosure of Invention
Aiming at the problem that the discharge specific capacity and the cycle performance of the current aluminum ion battery cathode material cannot be well considered, the invention provides the high-conductivity nano composite cathode material for the aluminum ion battery.
The aim of the invention is achieved by the following technical scheme.
A high-conductivity nano composite anode material for an aluminum ion battery is a composite anode material composed of a high-conductivity nano composite film and a manganese oxide nano layer loaded on the high-conductivity nano composite film.
Further, the manganese oxide nano-layer is loaded on the high-conductivity nano-composite film in a three-electrode electrolytic cell by an electrochemical deposition method. It should be noted that there is no particular limitation on the counter electrode and the reference electrode in the three electrodes, for example, a platinum wire or a platinum metal sheet may be used as the counter electrode, and an Ag/AgCl reference electrode may be used as the reference electrode.
Further, the thickness of the high-conductivity nano composite film is 7-150 μm.
Further, the high-conductivity nano composite film is a carbon nano tube film.
Further, the thickness of the manganese oxide nano layer is 0.5-2 mu m.
Further, when the manganese oxide nano layer is deposited on the high-conductivity nano composite film, the high-conductivity nano composite film is treated by utilizing a mixed acid solution of dilute hydrochloric acid and dilute nitric acid. More preferably, the hydrochloric acid and nitric acid concentrations in the mixed acid solution are both 0.02 to 1mol/L, and accordingly, the high-conductivity nanocomposite membrane is preferably sonicated in the mixed acid solution for 10 to 40 minutes.
Further, when the manganese oxide nano layer is prepared by adopting an electrochemical deposition method, a mixed aqueous solution of sodium salt and manganese salt is adopted as an electrodeposition liquid, wherein the molar ratio of manganese ions to sodium ions is 0.2-20:1. More preferably, the molar ratio of manganese ions to sodium ions is 0.5 to 1:1.
Further, the concentration of manganese ions in the electrodeposition bath is 0.05 to 1mol/L, more preferably 0.1 to 0.2mol/L.
Further, manganese salt adopts manganese acetate tetrahydrate, and sodium salt adopts sodium sulfate.
Further, the electrodeposition potential is controlled to be-2.0 to-1.5V.
The beneficial effects are that:
(1) In the composite positive electrode material, the manganese oxide is a nano lamellar substance, has a larger specific surface area, is beneficial to the transmission of aluminum ions in the material, and is beneficial to the reduction of electrode polarization in the electrochemical reaction process. MnO (MnO) x The nanoparticles are electrochemically oxidized to form Birnesite MnO with low crystallinity 2 Birnesite type MnO with low crystallinity in discharge process 2 First converted into monoclinic phase MnOOH, after further discharge the intermediate phase is reduced to Mn 2+ Dissolving into electrolyte. Reversible Mn 2+ /Mn 4+ The energy density of the battery is improved through the double-electron oxidation-reduction reaction; meanwhile, the manganese oxide is loaded on the surface of the high-conductivity nano composite film, so that the electron conductivity of the high-conductivity nano composite film can be fully utilized, and meanwhile, the electrode material can work in electrolyte for a long time stably, so that the high-conductivity nano composite film and the manganese oxide nano layer are composited together to be applied to an aluminum ion battery, and the higher charge-discharge capacity and better cycle performance of the aluminum ion battery can be realized.
(2) The content of active substances in the electrode determines the capacity and energy density which can be output by the battery pack, and the high-conductivity nano composite film directly overlaps the electrode with larger manganese oxide composition thickness, which means that higher energy output can be realized. However, increasing the thickness of the electrode has some adverse effects, and in practical applications, the thickness is relatively highThe large electrode is easy to cause the positive electrode to crack and fall off in the drying process, meanwhile, the thickness of the electrode is increased, al + /e - Extended transmission distance (high curvature Al + /e - Transmission channel), meaning that the internal impedance increases.
(3) The electrodeposition method has the advantages of mild condition, simple operation, less time consumption and low energy consumption, and the morphology of the deposition product can be regulated by changing the composition of the electrolyte, the voltage/current and the deposition time. The electrodeposition method is also more suitable for mass production, which has great significance in promoting the commercialization process of the electrochemical energy conversion system.
(4) The acid washing treatment of the high-conductivity nano composite film can remove impurities and oxides on the surface, and improve the purity and quality of the high-conductivity nano composite film, so that the performance and application effect of the high-conductivity nano composite film are improved, and meanwhile, the loading of the manganese oxide nano layer on the surface of the high-conductivity nano composite film is facilitated.
(5) The higher the concentration of manganese salt in the electrodepositing solution, the faster the diffusion mass transfer speed, the smaller the concentration polarization, and the faster the electrodeposition is allowed to be performed with the higher the cathode current density. However, the deposition is too fast, which leads to rough deposition layer, poor binding force and easy falling. The sodium salt which is used as the conductive salt in the electrodeposition liquid is an inert strong electrolyte added for improving the conductivity of the deposition liquid, and almost one hundred percent of the inert strong electrolyte is ionized into positive ions and negative ions in the deposition liquid. The conductivity of the plating solution is improved after the conductive salt is added, the dispersion capability is better, and the thickness distribution of the deposition layer on the material is more uniform; when the total current (current intensity) is the same, the better the conductivity of the deposition solution, the lower the voltage, the more power-saving. However, if the conductivity of the solution is too high, the conductivity of the solution may be lowered, and a side effect "salting-out" may occur.
(6) The composite positive electrode material provided by the invention has higher charge-discharge capacity and better cycle performance when being applied to an aluminum ion battery, and the preparation method is simple to operate, easy to control reaction conditions, easy to realize large-scale production and beneficial to promoting the further research and development of the aluminum ion battery.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of a carbon nanotube film used in the embodiment.
Fig. 2 is a Transmission Electron Microscope (TEM) image of a carbon nanotube film used in the present embodiment.
Fig. 3 is an X-ray diffraction (XRD) pattern of a carbon nanotube film used in the embodiment.
Fig. 4 is SEM images of the high-conductivity nanocomposite positive electrode material for aluminum ion batteries prepared in example 1 at various magnifications.
Fig. 5 is an elemental analysis mapping graph and an EDX graph of the high-conductivity nanocomposite positive electrode material for an aluminum ion battery prepared in example 1.
Fig. 6 is a graph showing the results of cycle performance test of a battery assembled using the high-conductivity nanocomposite positive electrode material for an aluminum ion battery prepared in example 1.
Fig. 7 is a graph showing the results of cycle performance test of a battery assembled using the high-conductivity nanocomposite positive electrode material for an aluminum ion battery prepared in example 2.
Fig. 8 is a graph showing the results of the cycle performance test of the battery assembled using the carbon nanotube film of comparative example 1.
Fig. 9 is a graph showing the results of cycle performance test of a battery assembled using the manganese oxide powder-loaded carbon nanotube film prepared in comparative example 2.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and detailed description, wherein the process is a conventional process unless otherwise specified, and wherein the starting materials are commercially available from the public sources.
In the following examples:
assembling a battery: the commercial aluminum plastic film obtained by Kolu is taken as a battery shell, the high-conductivity nano composite film of the electrodeposited manganese oxide nano layer is taken as a battery anode, the aluminum foil (Kolu) is taken as a battery cathode, the commercial pure polytetrafluoroethylene is taken as a battery diaphragm, the electrolyte is a mixed solution of 1-ethyl-3 methyl imidazole chloride and anhydrous aluminum chloride in a molar ratio of 1:1.3, and the soft-package battery is assembled in an Ar glove box. The assembled cell was then subjected to electrochemical performance testing, wherein 1.2mA was charged to greater than 2.3V at a constant current and 1.2mA was discharged to less than 0.4V at a test temperature of 25 ℃.
Example 1
(1) Uniformly mixing dilute hydrochloric acid and dilute nitric acid to form a mixed acid solution, wherein the concentration of the hydrochloric acid and the nitric acid in the mixed acid solution is 0.1mol/L; placing a conventional multi-wall carbon nano tube film with the length, width and thickness of 5cm, 5cm and 10 mu m in 200mL of prepared mixed acid solution, ultrasonically cleaning for 30min at 30 ℃, then flushing for three times by deionized water, and then placing the film at 100 ℃ for vacuum drying for 120min to obtain an acid-treated carbon nano tube film;
(2) 7.84g of manganese acetate tetrahydrate and 4.54g of sodium sulfate were dissolved in 200mL of deionized water to obtain a mixed aqueous solution containing 0.16mol/L manganese acetate and 0.16mol/L sodium sulfate; in a three-electrode electrolytic cell, the prepared mixed aqueous solution containing 0.16mol/L manganese acetate and 0.16mol/L sodium sulfate is used as electrodepositing liquid, an acid-treated carbon nanotube film is used as a working electrode, a platinum metal sheet is used as a counter electrode, an Ag/AgCl reference electrode is used as a reference electrode, the electrodepositing potential is controlled at-1.8V, and the electrodepositing is carried out for 20min, so that a manganese oxide nano layer with the thickness of 0.5-2 mu m is formed on the carbon nanotube film used as the working electrode, then the carbon nanotube film loaded with the manganese oxide nano layer is cleaned by deionized water, and then the carbon nanotube film is dried in vacuum at 100 ℃ for 120min, thereby obtaining the high-conductivity nano composite anode material for the aluminum ion battery.
Fig. 1 is an SEM image of a carbon nanotube film, which is formed by randomly stacking and interlacing tubular wires, and has a relatively uniform internal structure, and a single fiber diameter size of about 10-40 nm.
Fig. 2 is a TEM photograph of a carbon nanotube film, from which it can be seen that the carbon nanotubes exhibit a multi-wall structure and have a highly graphitized typical two-dimensional layered structure.
FIG. 3 is a XRD spectrum of a carbon nanotube film, 1350cm -1 And 1580cm -1 The peaks at the positions respectively represent a D peak and a G peak, and the higher G peak also proves that the carbon nano tube film has the characteristic of high graphitization.
Fig. 4 is an SEM image of the high-conductivity nanocomposite positive electrode material for aluminum ion batteries prepared in example 1 under different magnifications, and the carbon nanotube film showed uniform characteristics under different magnifications, which is advantageous for rapid migration of aluminum ions.
As can be seen from the elemental analysis mapping diagram and the EDX (energy dispersion X-ray dispersion spectrum) diagram of FIG. 5, the Mn element has obvious energy spectrum peak positions, the element is uniformly distributed, and the mass ratio is about 1.57%, thereby proving that the manganese oxide is successfully electrodeposited on the carbon nano tube film.
The high-conductivity nanocomposite positive electrode material prepared in this example was assembled into a soft pack battery, and then the assembled battery was subjected to cycle performance test in an incubator (25 ℃). According to the test results of fig. 6, the performance of the battery reaches 45mAh/g in the charge-discharge cycle test, and compared with the performance of the common carbon nanotube film without the manganese oxide nano layer, the performance of the common carbon nanotube film is remarkably improved.
Example 2
(1) Uniformly mixing dilute hydrochloric acid and dilute nitric acid to form a mixed acid solution, wherein the concentration of the hydrochloric acid and the nitric acid in the mixed acid solution is 0.1mol/L; placing a carbon nano tube film with the length, width and thickness of 5cm, 5cm and 10 mu m in 200mL of prepared mixed acid solution, ultrasonically cleaning for 30min at 30 ℃, then flushing for three times by deionized water, and then placing the carbon nano tube film at 100 ℃ for vacuum drying for 120min to obtain an acid-treated carbon nano tube film;
(2) 9.8g of manganese acetate tetrahydrate and 2.84g of sodium sulfate were dissolved in 200mL of deionized water to obtain a mixed aqueous solution containing 0.2mol/L manganese acetate and 0.1mol/L sodium sulfate; in a three-electrode electrolytic cell, the prepared mixed aqueous solution containing 0.2mol/L manganese acetate and 0.1mol/L sodium sulfate is used as electrodepositing liquid, an acid-treated carbon nanotube film is used as a working electrode, a platinum metal sheet is used as a counter electrode, an Ag/AgCl reference electrode is used as a reference electrode, the electrodepositing potential is controlled at-1.6V, and the electrodepositing is carried out for 30min, so that a manganese oxide nano layer with the thickness of 0.5-2 mu m is formed on the carbon nanotube film used as the working electrode, then the carbon nanotube film loaded with the manganese oxide nano layer is cleaned by deionized water, and then the carbon nanotube film is dried in vacuum at 100 ℃ for 120min, thereby obtaining the high-conductivity nano composite anode material for the aluminum ion battery.
According to the test results of the elemental analysis mapping graph and the EDX graph, the Mn element energy spectrum peak position is obvious, the element distribution is uniform, the mass ratio is about 1.52%, and the successful electrodeposition of the manganese oxide on the carbon nano tube film is proved.
The high-conductivity nanocomposite positive electrode material prepared in this example was assembled into a soft pack battery, and then the assembled battery was subjected to cycle performance test in an incubator (25 ℃). According to the test results of fig. 7, the battery performance reaches 44mAh/g in the charge-discharge cycle test, and compared with the common carbon nanotube film performance without the manganese oxide nano layer, the performance of the common carbon nanotube film is remarkably improved.
Comparative example 1
The untreated carbon nanotube film was assembled as a positive electrode material into a soft pack battery, and then the assembled battery was subjected to cycle performance test in an incubator (25 ℃). As can be seen from the test results of FIG. 8, the battery performance in the charge-discharge cycle test is only 24mAh/g, and the battery has the capability of removing and embedding aluminum ions.
Comparative example 2
The molar number of manganese element in the physically mixed manganese oxide powder was kept unchanged as compared with that of electrodeposited manganese element in example 1, and 0.55mg MnO was taken 2 Powder according to MnO 2 : conductive carbon: and mixing the pvdf=7:2:1 to obtain slurry, coating the slurry on the carbon nanotube film by using a scraper, and drying to obtain the carbon nanotube film loaded with the manganese oxide powder.
And assembling the carbon nano tube film loaded with the manganese oxide powder into a soft package battery, and then carrying out cycle performance test on the assembled battery in a constant temperature box (25 ℃). According to the test results of fig. 9, the performance of the battery is 25mAh/g in the charge-discharge cycle test, and compared with the performance of the common carbon nanotube film without the manganese oxide nano layer, the performance of the common carbon nanotube film is not obviously changed, namely, the effect of improving the electrochemical performance of the manganese oxide powder loaded on the carbon nanotube film through physical mixing is not obvious.
In summary, the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A high-conductivity nano composite positive electrode material for an aluminum ion battery is characterized in that: is a composite anode material composed of a high-conductivity nano composite film and a manganese oxide nano layer loaded on the high-conductivity nano composite film.
2. The high-conductivity nanocomposite positive electrode material for an aluminum ion battery according to claim 1, wherein: the manganese oxide nano-layer is loaded on the high-conductivity nano-composite film in a three-electrode electrolytic cell by an electrochemical deposition method.
3. The high-conductivity nanocomposite positive electrode material for an aluminum ion battery according to claim 1, wherein: the thickness of the high-conductivity nano composite film is 7-150 mu m.
4. A high-conductivity nanocomposite positive electrode material for an aluminum ion battery according to any one of claims 1 to 3, characterized in that: the high-conductivity nano composite film is a carbon nano tube film.
5. A high-conductivity nanocomposite positive electrode material for an aluminum ion battery according to any one of claims 1 to 3, characterized in that: the thickness of the manganese oxide nano layer is 0.5-2 mu m.
6. The high-conductivity nanocomposite positive electrode material for an aluminum ion battery according to claim 2, wherein: when depositing a manganese oxide nano layer on the high-conductivity nano composite film, firstly treating the high-conductivity nano composite film by utilizing a mixed acid solution of dilute hydrochloric acid and dilute nitric acid; wherein the concentration of hydrochloric acid and nitric acid in the mixed acid solution is 0.02-1 mol/L.
7. The high-conductivity nanocomposite positive electrode material for an aluminum ion battery according to claim 2, wherein: when the manganese oxide nano layer is prepared by adopting an electrochemical deposition method, a mixed aqueous solution of sodium salt and manganese salt is adopted as an electrodeposition liquid, wherein the molar ratio of manganese ions to sodium ions is 0.2-20:1.
8. The high-conductivity nanocomposite positive electrode material for an aluminum ion battery according to claim 7, wherein: the concentration of manganese ions in the electrodeposition liquid is 0.05-1 mol/L.
9. The high-conductivity nanocomposite positive electrode material for an aluminum ion battery according to claim 2, wherein: when the manganese oxide nano layer is prepared by adopting an electrochemical deposition method, a mixed aqueous solution of sodium salt and manganese salt is adopted as an electrodeposition liquid, wherein the molar ratio of manganese ions to sodium ions is 0.5-1:1, and the concentration of manganese ions in the electrodeposition liquid is 0.1-0.2 mol/L.
10. A high-conductivity nanocomposite positive electrode material for an aluminum ion battery according to claim 2, 7, 8 or 9, characterized in that: the electrodeposition potential is controlled to be-2.0 to-1.5V.
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