CN103915611A - Water-based aluminum ion battery positive electrode material and preparation method thereof - Google Patents
Water-based aluminum ion battery positive electrode material and preparation method thereof Download PDFInfo
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- CN103915611A CN103915611A CN201410136400.5A CN201410136400A CN103915611A CN 103915611 A CN103915611 A CN 103915611A CN 201410136400 A CN201410136400 A CN 201410136400A CN 103915611 A CN103915611 A CN 103915611A
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- ion battery
- leaf
- anode material
- water system
- aluminium ion
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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 water-based aluminum ion battery positive electrode material and a preparation method thereof. The material consists of titanium dioxide nano-leaves, the chemical composition of the titanium dioxide nano-leaves is TiO1.976(NH)0.024, and the titanium dioxide nano-leaves are 50 nanometers in average length, 10 nanometers in widths and 314.2 m<2>/g in specific surface areas. The method comprises the following steps: using a TALH aqueous solution a precursor under the induction of an inducer Brij-30; synthesizing black anatase TiO2 through a liquid phase plasma method; performing electrochemical performance testing on the prepared titanium dioxide nano-leaves serving as the water-based aluminum ion battery positive electrode material. The water-based aluminum ion battery positive electrode material has the advantages of easiness in preparation, high charging and discharging performance, stable cyclic voltammetry and the like, and titanium dioxide nano-leaf is an excellent aluminum ion battery positive electrode material which shows extremely high energy storage performance. Meanwhile, a novel low-cost aluminum ion battery system which has greater competitive advantage than commercial lithium ion batteries is provided. Moreover, black anatase TiO2 can be widely applied to the aspects of adsorbents, catalysts, sensors and the like.
Description
Technical field
The invention belongs to battery material field, relate in particular to a kind of water system aluminium ion battery anode material and preparation method thereof.
Background technology
Along with economy is advanced by leaps and bounds, energy crisis and environmental pollution increasingly sharpen.Battery system, as a kind of energy storage device, has greatly caused people's research interest.Common battery system has: lithium ion battery, Ni-MH battery and lead ion battery, wherein to have circulation timei long because of it for lithium ion battery, the advantages such as high rate capability, thereby be widely used in many fields, for example mobile phone, notebook computer, miniature camera etc., and increasing country by this battery applications in military use, but the huge market demand has caused again the shortage of lithium resource.Simultaneously current most of battery system adopts organic substance as electrolyte, battery system using organic substance as electrolyte unavoidably all can be used strong toxicity, inflammable and explosive organic substance as solvent, all can bring danger and injury to user if there is improper operations such as overcharged and short circuits.Report about organic type lithium ion battery accident is of common occurrence, and major part is all fire and explosion accident.Thereby start to substitute the electrolytic medium of organic substance as battery system with the aqueous solution nontoxic, that be easy to get, but the electric capacity of water system battery, charge rate and cyclical stability are all not so good as organic phase lithium ion battery, can not meet the demand of practical application far away, be difficult to attract investment person's sight, make it produce strong interest and investment hope.
In order to solve lithium resource shortage and the poor problem of water system battery system electrical property, find novel water system battery system imperative.Because aluminum oxidation reduction electricity in charge discharge reaction is to relating to three electron transfer process, compared with the lithium ion battery shifting with Single Electron, aluminium ion battery has larger storage volume.Therefore water system rechargeable aluminium ion battery is potential sustainable energy storage device.As everyone knows, the nanostructure of electrode material has a great impact its energy storage performance, and the ability of different nanostructure storage power is also different.Studies show that: black anatase titanium dioxide is a kind of high magnification electrode material of excellence in lithium-ion battery systems, there is electronic conduction ability Ti to contain
3+the black anatase titanium dioxide of ion has good using value and prospect as the electrode material of aluminium ion battery.
Summary of the invention
The object of the present invention is to provide a kind of water system aluminium ion battery anode material and preparation method thereof, be intended to solve current lithium resource shortage and the poor problem of water system battery system electrical property.
Necessary technology scheme:
The present invention is achieved in that a kind of water system aluminium ion battery anode material, and this material is made up of nano titania leaf, and the chemical composition of nano titania leaf is TiO
1.976(NH)
0.024, average length is 50nm, and width is 10nm, and specific area is 314.2m
2/ g.
Further, nano titania leaf contains many nano-pores, is Al
3+storage enough spaces are provided.
Further, nano titania leaf has larger surface area, and enough electrode/electrolyte interface are provided, and is beneficial to Al
3+adsorb, promote the carrying out of charge transfer reaction simultaneously.
Further, in nano titania leaf, contain the Ti with conductivity
3+, increased electronic conductivity; TiO
2nanometer leaf crystal formation is good, Stability Analysis of Structures.
The present invention is achieved in that a kind of preparation method of water system aluminium ion battery anode material, and the step of the method comprises:
Step 1, under the induction of derivant Brij-30, with the TALH aqueous solution as presoma;
Step 2, by liquid phase plasma body method synthesizing black Detitanium-ore-type TiO
2;
Step 3, using the nano titania leaf of preparing as water system aluminium ion battery anode material, it is carried out to electrochemical property test.
Further, the specific implementation process of the liquid phase plasma body method in step 2 is, the solution after derivant Brij-30 and the TALH aqueous solution are mixed is transferred in plasma device, carries out plasma treatment certain hour; After reaction, by sample separation out, use respectively distilled water and absolute ethanol washing.
Further, the electrochemical property test carrying out in step 3 can be charge/discharge curve and the cyclic voltammetry curve of nano titania leaf electrode.
Water system aluminium ion anode material of a kind of better performances provided by the invention and preparation method thereof, this material possesses that preparation is simple, charge-discharge performance is good and cyclic voltammetric such as stablizes at the advantage.The nano titania leaf chemical composition of preparation is TiO
1.976(NH)
0.024, average length is 50nm, and width is 10nm, and specific area is 314.2m
2/ g.This nano titania leaf or a kind of very excellent aluminium ion anode material, show very high energy-storage property.As the anode material of aluminium ion battery, at 1.0MAl (NO
3)
3in the aqueous solution, nano titania leaf shows super excellent performance, outstanding rate capability, stable cycle characteristics.When current density is up to 2.0Ag
-1time, still can observe 141.3mAhg
-1capacity.Our result of study shows: the nano titania leaf of preparation is a kind of very excellent aluminium ion anode material at present, show very high energy-storage property, simultaneously to we provide one new than commercial li-ion battery have more competitive advantage, low cost aluminium ion battery system.In addition this black Detitanium-ore-type TiO,
2very likely, at adsorbent, are used widely in catalyst and sensor aspect.
Accompanying drawing explanation
Fig. 1 is the preparation method's of the water system aluminium ion battery anode material that provides of the embodiment of the present invention flow chart.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention is achieved in that a kind of preparation method of water system aluminium ion battery anode material, i.e. the preparation of black anatase titanium dioxide nanometer leaf:
Measure and get 10mLTALH aqueous solution presoma and 40mL0.5MBrij-30 solution mixes;
Subsequently the solution after mixing is transferred in plasma device, carried out plasma treatment certain hour;
After reaction, by sample separation out, use respectively distilled water and absolute ethanol washing;
In baking oven, dry, grind and obtain TiO2 nanometer leaf.
The preparation process of the required work electrode of electrochemistry experiment:
By TiO
2nanometer leaf (80%) adds in polyvinylidene difluoride (10%) and acetylene black (10%) and grinds, and then with supersonic cleaning machine, it is well dispersed in 1-METHYLPYRROLIDONE, stirs into pasty state.
The compound making is above evenly coated on the Pt disc electrode that diameter is 2mm, is then put in 100 ℃ of dry for standby in baking oven.Total 3mg active material on final work electrode.
Electrochemical property test:
Adopt traditional three-electrode cell to carry out the chemical property of test electrode, conduct is to electrode and reference electrode respectively for Pt disk and a saturated calomel electrode, and electrolyte is 1.0M Al (NO
3)
3solution.What electrochemical measurement used is μ-Autolab potentiostat that Holland produces, TypeIII, FRA2.The parameter of impedance measurement is: frequency 500kHz-5mHz, and alternating voltage amplitude 10mV, the sampling interval is 5s.
Nano titania leaf electrode cyclic voltammetry curve test experiments result proves: TiO
2the peak intensity of nanometer leaf electrode and peak area are all better than commercial white titanium dioxide, and this illustrates that it has higher capacity.In lasting afterwards circulation, both CV curves almost do not change, and this shows that electrochemical reaction is stable with reversible.
Nano titania leaf electrode charge and discharge performance test experimental result is found: be-1.4～-0.4V at voltage, current density is 0.05A/g, after 100 circulations, the capacity that nano titania leaf shows a completely reversibility is that 254.6mAhg-1 is (with Al
0.25tiO
2unanimously), even after 300 circulations, its capacity attenuation only only has 8.4%.
Sample is 0.1-2.0Ag in current density
-1rate capability under condition.Current density is 0.1Ag
-1time, the reversible capacity of leaf shape nano titanium oxide electrode is 259.7mAhg
-1; When current density becomes 2.0Ag
-1time, corresponding reversible capacity reaches 40mAhg
-1.
Carry out the chemical property of assess sample by dual electrode cell system, battery system adopts titanium dioxide as negative electrode, and Al is as anode.In three-electrode cell, black anatase titania nanometer leaf electrode shows excellent chemical property, and fidelity factor is high.
The invention provides a kind of water system aluminium ion battery anode material, this material is made up of nano titania leaf, and the chemical composition of nano titania leaf is TiO
1.976(NH)
0.024, average length is 50nm, and width is 10nm, and specific area is 314.2m
2/ g.Nano titania leaf contains many nano-pores, is Al
3+storage enough spaces are provided.Nano titania leaf has larger surface area, and enough electrode/electrolyte interface are provided, and is beneficial to Al
3+adsorb, promote the carrying out of charge transfer reaction simultaneously.In nano titania leaf, contain the Ti with conductivity
3+, increased electronic conductivity; TiO
2nanometer leaf crystal formation is good, Stability Analysis of Structures.
The present invention also provides a kind of preparation method of water system aluminium ion battery anode material, and the step of the method comprises: under the induction of derivant Brij-30, use the TALH aqueous solution as presoma; By liquid phase plasma body method synthesizing black Detitanium-ore-type TiO
2; Using the nano titania leaf of preparing as water system aluminium ion battery anode material, it is carried out to electrochemical property test.The specific implementation process of the liquid phase plasma body method in step 2 is, the solution after derivant Brij-30 and the TALH aqueous solution are mixed is transferred in plasma device, carries out plasma treatment certain hour; After reaction, by sample separation out, use respectively distilled water and absolute ethanol washing.The electrochemical property test carrying out in step 3 can be charge/discharge curve and the cyclic voltammetry curve of nano titania leaf electrode.
The water system aluminium ion anode material of a kind of better performances provided by the invention, this material will possess that preparation is simple, charge-discharge performance is good and cyclic voltammetric such as stablizes at the advantage.The nano titania leaf chemical composition of preparation is TiO
1.976(NH)
0.024, average length is 50nm, and width is 10nm, and specific area is 314.2m
2/ g.This nano titania leaf or a kind of very excellent aluminium ion anode material, show very high energy-storage property.As the anode material of aluminium ion battery, at 1.0MAl (NO
3)
3in the aqueous solution, nano titania leaf shows super excellent performance, outstanding rate capability, stable cycle characteristics.When current density is up to 2.0Ag
-1time, still can observe 141.3mAhg
-1capacity.Our result of study shows: the nano titania leaf of preparation is a kind of very excellent aluminium ion anode material at present, show very high energy-storage property, simultaneously to we provide one new than commercial li-ion battery have more competitive advantage, low cost aluminium ion battery system.In addition this black Detitanium-ore-type TiO,
2very likely, at adsorbent, are used widely in catalyst and sensor aspect.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (7)
1. a water system aluminium ion battery anode material, is characterized in that, this material is made up of nano titania leaf, and the chemical composition of nano titania leaf is TiO
1.976(NH)
0.024, average length is 50nm, and width is 10nm, and specific area is 314.2m
2/ g.
2. water system aluminium ion battery anode material as claimed in claim 1, is characterized in that, nano titania leaf contains many nano-pores, is Al
3+storage enough spaces are provided.
3. water system aluminium ion battery anode material as claimed in claim 1, is characterized in that, nano titania leaf has larger surface area, and enough electrode/electrolyte interface are provided, and is beneficial to A1
3+adsorb, promote the carrying out of charge transfer reaction simultaneously.
4. water system aluminium ion battery anode material as claimed in claim 1, is characterized in that, contains the Ti with conductivity in nano titania leaf
3+, increased electronic conductivity; TiO
2nanometer leaf crystal formation is good, Stability Analysis of Structures.
5. a preparation method for water system aluminium ion battery anode material, is characterized in that, the step of the method comprises:
Step 1, under the induction of derivant Brij-30, with the TALH aqueous solution as presoma;
Step 2, by liquid phase plasma body method synthesizing black Detitanium-ore-type TiO
2;
Step 3, using the nano titania leaf of preparing as water system aluminium ion battery anode material, it is carried out to electrochemical property test.
6. the preparation method of water system aluminium ion battery anode material as claimed in claim 5, it is characterized in that, the specific implementation process of the liquid phase plasma body method in step 2 is, solution after derivant Brij-30 and the TALH aqueous solution are mixed is transferred in plasma device, carries out plasma treatment certain hour; After reaction, by sample separation out, use respectively distilled water and absolute ethanol washing.
7. the preparation method of water system aluminium ion battery anode material as claimed in claim 5, is characterized in that, the electrochemical property test carrying out in step 3 can be charge/discharge curve and the cyclic voltammetry curve of nano titania leaf electrode.
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| CN201410136400.5A CN103915611A (en) | 2014-04-08 | 2014-04-08 | Water-based aluminum ion battery positive electrode material and preparation method thereof |
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| CN201410136400.5A CN103915611A (en) | 2014-04-08 | 2014-04-08 | Water-based aluminum ion battery positive electrode material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108539190A (en) * | 2018-03-30 | 2018-09-14 | 华南理工大学 | The molybdenum trioxide of a kind of oxygen-containing vacancy and using it as the water system aluminium ion battery of negative electrode active material and their preparation method |
| US10418663B2 (en) | 2016-05-17 | 2019-09-17 | Industrial Technology Research Institute | Metal-ion battery |
| CN114006129A (en) * | 2015-10-08 | 2022-02-01 | 艾沃伦24公司 | Chargeable aluminium ion battery |
| US11296329B2 (en) | 2016-12-16 | 2022-04-05 | Industrial Technology Research Institute | Metal-ion battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569761A (en) * | 2010-12-08 | 2012-07-11 | 中国科学院金属研究所 | Titanium dioxide/graphene nanocomposite material and preparation method and application thereof |
-
2014
- 2014-04-08 CN CN201410136400.5A patent/CN103915611A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569761A (en) * | 2010-12-08 | 2012-07-11 | 中国科学院金属研究所 | Titanium dioxide/graphene nanocomposite material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| YING JUAN HE等: "Black mesoporous anatase TiO2 nanoleaves: a high capacity and high rate anode for aqueous Al-ion batteries", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114006129A (en) * | 2015-10-08 | 2022-02-01 | 艾沃伦24公司 | Chargeable aluminium ion battery |
| US10418663B2 (en) | 2016-05-17 | 2019-09-17 | Industrial Technology Research Institute | Metal-ion battery |
| US11296329B2 (en) | 2016-12-16 | 2022-04-05 | Industrial Technology Research Institute | Metal-ion battery |
| CN108539190A (en) * | 2018-03-30 | 2018-09-14 | 华南理工大学 | The molybdenum trioxide of a kind of oxygen-containing vacancy and using it as the water system aluminium ion battery of negative electrode active material and their preparation method |
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Effective date of registration: 20150119 Address after: Three road 610059 Sichuan city of Chengdu province Chenghua District Erxian Qiaodong No. 1 Applicant after: Chengdu University of Technology Address before: Three road 610041 Sichuan city of Chengdu province Chenghua District Erxian Qiaodong No. 1 Chengdu University of Technology and College of chemistry and chemical engineering Applicant before: Tong Dongge |
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Application publication date: 20140709 |