CN104143623B - A kind of anode of magnesium ion battery material and preparation method thereof - Google Patents
A kind of anode of magnesium ion battery material and preparation method thereof Download PDFInfo
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- CN104143623B CN104143623B CN201410324285.4A CN201410324285A CN104143623B CN 104143623 B CN104143623 B CN 104143623B CN 201410324285 A CN201410324285 A CN 201410324285A CN 104143623 B CN104143623 B CN 104143623B
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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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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 present invention relates to a kind of anode of magnesium ion battery material and preparation method thereof, molecular formula is Mg1‑xSrxZnyFe1‑ySiO4, wherein 0 < x≤0.05,0 < y≤0.3；Preparation: by magnesium source compound, strontium source compound, zinc source compound, Fe source compound and silicon source compound, add ethanol, ball milling, drying; then under argon shield, it is warming up to 350 500 DEG C, is incubated 1 2h; it is continuously heating to 800 1200 DEG C, is incubated 2 8h, to obtain final product.Preparation technology of the present invention is simple to operate, easily controllable, be advantageously implemented large-scale industrial produces；The anode of magnesium ion battery material of preparation has bigger reversible capacity and stronger high rate during charging-discharging.
Description
Technical field
The invention belongs to electrode material and preparation field thereof, particularly to a kind of anode of magnesium ion battery material and preparation method thereof.
Background technology
Lithium ion battery is considered as the most promising energy storage at present and power electrochmical power source.But, whole world lithium resource is the most rich,
Elemental lithium is only 0.006% at crustal abundance, and the poor and high price of resource becomes the melancholy of following lithium ion battery large-scale application
Suffer from.Meanwhile, the safety issue of lithium ion battery self, also bring certain difficulty for practical.Therefore, it is badly in need of developing next
The energy storage excellent for comprehensive effectiveness and electrokinetic cell new system.For comparing lithium resource, magnesium reserves are the abundantest, and crustal abundance is
440 times of lithium, and each magnesium atom can store 2 electric charges, substitutes lithium exploitation Magnesium ion battery with magnesium and has boundless
Application prospect.
The at present research in terms of rechargeable magnesium cell anode material focus primarily upon transient metal sulfide (such as disulphide and
Chevrel phase sulfide etc.) and transition metal oxide (as barium oxide, spinel-type can be inserted into oxide etc.).Transition
Metal sulfide magnesium cell anode material is the rechargeable magnesium cell anode material studying comparative maturity at present, have more excellent embedding magnesium/
De-magging performance, but their thermodynamic property is unstable, and preparation condition is harsh, and the non-oxidizability of material is poor, and voltage is put down
Platform is the highest, and the energy density causing material is relatively low.The preparation of transition metal oxide positive electrode is easier to, and cost is relatively low, chemistry
Good stability, but the universal reversible capacity of such material is the highest, and under the conditions of high current charge-discharge, capacity attenuation is quickly.These lack
Point limits their application.
Polyanionic silicate anode of magnesium ion battery material has bigger three dimensions and stable frame structure, and formation can
The space occupied for other high coordination of metal ion, has the crystalline phase knot different from transient metal sulfide and metal oxide materials
Structure, shows higher storage magnesium capacity and preferable reversible stability.But the shortcoming of such positive electrode is electronic conductivity ratio
Relatively low, the heavy-current discharge performance of material is poor.
Summary of the invention
The technical problem to be solved is to provide a kind of anode of magnesium ion battery material and preparation method thereof, the system of this invention
Standby technological operation is simple, easily controllable, is advantageously implemented large-scale industrial and produces；The anode of magnesium ion battery material of preparation has relatively
Big reversible capacity and stronger high rate during charging-discharging.
A kind of anode of magnesium ion battery material of the present invention, the molecular formula of described positive electrode is Mg1-xSrxZnyFe1-ySiO4, its
In 0 < x≤0.05,0 < y≤0.3.
A kind of preparation method of the anode of magnesium ion battery material of the present invention, including:
By magnesium source compound, strontium source compound, zinc source compound, Fe source compound and silicon source compound, add ethanol, ball milling,
Dry, then under argon shield, be warming up to 350-500 DEG C, be incubated 1-2h, be continuously heating to 800-1200 DEG C, be incubated 2-8h,
Obtain anode of magnesium ion battery material Mg1-xSrxZnyFe1-ySiO4。
Described magnesium source compound is one or more in magnesium oxide, magnesium hydroxide, magnesium carbonate, organic acid magnesium salt.
Described strontium source compound is one or more in strontium oxide, Strontium hydrate., strontium carbonate, strontium acetate, strontium oxalate.
Described zinc source compound is one or more in zinc oxide, zinc hydroxide, zinc carbonate, zinc salts of organic acid.
Described Fe source compound is ferro-compound.
Described ferro-compound is one or more in ferrous oxide, Ferrox..
Described silicon source compound is tetravalence silicon compound.
Described tetravalence silicon compound is one or more in silicon dioxide, silicic acid, organo-silicon compound.
Described ball milling is ball mill ball milling 2-4h；Dry temperature and be 120-140 DEG C.
The present invention carries out Effective Doping by strontium, zinc element to magnesium position and the ferrum position of polyanionic silicic acid iron salt, improves material
Electronic conductivity and magnesium ion migration rate, improve its reversible capacity and heavy-current discharge performance, this preparation technology is simple to operate,
Easily controllable, be advantageously implemented large-scale industrial produce.
Beneficial effect
The preparation technology of the present invention is simple to operate, easily controllable, be advantageously implemented large-scale industrial produces；The magnesium ion electricity of preparation
Pond positive electrode has bigger reversible capacity and stronger high rate during charging-discharging.
Accompanying drawing explanation
Fig. 1 is the anode of magnesium ion battery material Mg of embodiment 1 synthesis0.98Sr0.02Zn0.1Fe0.9SiO4The first two week charging and discharging curve；
Fig. 2 is the anode of magnesium ion battery material Mg of the 2-in-1 one-tenth of embodiment0.96Sr0.04Zn0.13Fe0.87SiO4Charging and discharging currents at 0.1C
The first two discharge capacity curve of ten weeks lower；
Fig. 3 is the anode of magnesium ion battery material Mg of the 2-in-1 one-tenth of embodiment0.96Sr0.04Zn0.13Fe0.87SiO4Charging and discharging currents at 0.5C
The first two discharge capacity curve of ten weeks lower.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments be merely to illustrate the present invention and not
For limiting the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, those skilled in the art can
To make various changes or modifications the present invention, these equivalent form of values fall within the application appended claims limited range equally.
Embodiment 1
Accurately weigh 0.098molMgO, 0.002mol Sr (CH3COO)2、0.010mol ZnO、0.090molFeC2O4·2H2O
With 0.1mol Si (CH3CH2O)4, put in the Achates tank of planetary ball mill after mix homogeneously, add dehydrated alcohol as mix grinding
Medium, with the abundant ball milling of Achates abrading-ball 4 hours, after drying at 120 DEG C, is placed in powder body in tube furnace and protects at high pure nitrogen
Under be heated to 400 DEG C with the heating rate of 5 DEG C/min, be incubated 1 hour, continue to be warmed up to 1000 DEG C, be incubated 6 hours,
To anode of magnesium ion battery material Mg0.98Sr0.02Zn0.1Fe0.9SiO4。
Anode of magnesium ion battery material Mg by synthesis0.98Sr0.02Zn0.1Fe0.9SiO4With acetylene black, politef by about 75:
The quality of 15:10, than mix homogeneously, is pressed into, with film laminator, the thin film that thickness is about 1mm, is placed in baking oven and fills in 100 DEG C
Dividing and dry, intercepting surface area is 1cm2Circular membrane, be compressed on copper mesh, make Electrode.Using Electrode as just
Pole, with metal magnesium rod as negative pole, Entek PE film is barrier film, with the Mg (AlCl of 0.25mol/L2BuEt)2/ THF is electrolyte,
CR2032 type button cell it is assembled in the glove box of full argon.Button cell is placed on battery test system and tests it
Room temperature charge-discharge performance, charging and discharging currents is 0.1C, and charging/discharging voltage scope is 0.5V to 2.1V (vs.Mg).First may be used
Inverse specific discharge capacity is 143mAh/g, and after 20 times circulate, discharge capacity is 136mAh/g.Big electric current at 0.5C fills
Under discharging condition, after 20 times circulate, discharge capacity is 98mAh/g.
Embodiment 2
Accurately weigh 0.096molMg (OH)2, 0.004molSrO, 0.013mol ZnO, 0.087molFeO and 0.1mol
Si(CH3CH2O)4, put in the Achates tank of planetary ball mill after mix homogeneously, add dehydrated alcohol as mix grinding medium, use
The abundant ball milling of Achates abrading-ball 3 hours, after drying at 120 DEG C, is placed in powder body in tube furnace under high pure nitrogen is protected with 4 DEG C/min
Heating rate be heated to 350 DEG C, be incubated 2 hours, continue to be warmed up to 1100 DEG C, be incubated 4 hours, obtain Magnesium ion battery
Positive electrode Mg0.96Sr0.04Zn0.13Fe0.87SiO4。
Anode of magnesium ion battery material Mg by synthesis0.96Sr0.04Zn0.13Fe0.87SiO4With acetylene black, politef by about 75:
The quality of 15:10, than mix homogeneously, is pressed into, with film laminator, the thin film that thickness is about 1mm, is placed in baking oven and fills in 100 DEG C
Dividing and dry, intercepting surface area is 1cm2Circular membrane, be compressed on copper mesh, make Electrode.Using Electrode as just
Pole, with metal magnesium rod as negative pole, Entek PE film is barrier film, with the Mg (AlCl of 0.25mol/L2BuEt)2/ THF is electrolyte,
CR2032 type button cell it is assembled in the glove box of full argon.Button cell is placed on battery test system and tests it
Room temperature charge-discharge performance, charging and discharging currents is 0.1C, and charging/discharging voltage scope is 0.5V to 2.1V (vs.Mg).First may be used
Inverse specific discharge capacity is 132mAh/g, and after 20 times circulate, discharge capacity is 129mAh/g.Big electric current at 0.5C fills
Under discharging condition, after 20 times circulate, discharge capacity is 101mAh/g.
Claims (10)
1. an anode of magnesium ion battery material, it is characterised in that: the molecular formula of described positive electrode is Mg1-xSrxZnyFe1-ySiO4,
Wherein 0 < x≤0.05,0 < y≤0.3.
2. a preparation method for anode of magnesium ion battery material as claimed in claim 1, including:
By magnesium source compound, strontium source compound, zinc source compound, Fe source compound and silicon source compound, add ethanol, ball
Mill, drying, then under argon shield, be warming up to 350-500 DEG C, is incubated 1-2h, is continuously heating to 800-1200 DEG C,
Insulation 2-8h, obtains anode of magnesium ion battery material Mg1-xSrxZnyFe1-ySiO4。
The preparation method of a kind of anode of magnesium ion battery material the most according to claim 2, it is characterised in that: described magnesium source chemical combination
Thing is one or more in magnesium oxide, magnesium hydroxide, magnesium carbonate, organic acid magnesium salt.
The preparation method of a kind of anode of magnesium ion battery material the most according to claim 2, it is characterised in that: described strontium source chemical combination
Thing is one or more in strontium oxide, Strontium hydrate., strontium carbonate, strontium acetate, strontium oxalate.
The preparation method of a kind of anode of magnesium ion battery material the most according to claim 2, it is characterised in that: described zinc source chemical combination
Thing is one or more in zinc oxide, zinc hydroxide, zinc carbonate, zinc salts of organic acid.
The preparation method of a kind of anode of magnesium ion battery material the most according to claim 2, it is characterised in that: described source of iron chemical combination
Thing is ferro-compound.
The preparation method of a kind of anode of magnesium ion battery material the most according to claim 6, it is characterised in that: described ferrous iron
Compound is one or more in ferrous oxide, Ferrox..
The preparation method of a kind of anode of magnesium ion battery material the most according to claim 2, it is characterised in that: described silicon source chemical combination
Thing is tetravalence silicon compound.
The preparation method of a kind of anode of magnesium ion battery material the most according to claim 8, it is characterised in that: described tetravalence silication
Compound is one or more in silicon dioxide, silicic acid, organo-silicon compound.
The preparation method of a kind of anode of magnesium ion battery material the most according to claim 2, it is characterised in that: described ball milling is ball
Grinding machine ball milling 2-4h；Dry temperature and be 120-140 DEG C.
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| CN105390684B (en) * | 2015-12-21 | 2017-12-29 | 宁波高新区锦众信息科技有限公司 | A kind of preparation method of rechargeable magnesium cell composite positive pole |
| CN106981655B (en) * | 2017-03-30 | 2020-08-18 | 宁波职业技术学院 | Novel magnesium ion battery positive electrode material and preparation method thereof |
| CN107293747B (en) * | 2017-05-08 | 2020-08-18 | 宁波职业技术学院 | Magnesium-site-doped magnesium ion battery positive electrode material and preparation method thereof |
| CN109659536A (en) * | 2018-12-18 | 2019-04-19 | 中科廊坊过程工程研究院 | A kind of anode of magnesium ion battery material and its preparation method and application |
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| JP2009048981A (en) * | 2007-08-23 | 2009-03-05 | Sony Corp | Nonaqueous electrolyte secondary battery |
| CN101393982B (en) * | 2008-10-28 | 2010-08-25 | 南京海泰纳米材料有限公司 | Method for producing carbon coated nano stage lithium iron phosphate by precipitation |
| CN103155235A (en) * | 2010-05-25 | 2013-06-12 | 佩里昂技术公司 | Electrode materials for magnesium batteries |
| CN102723479A (en) * | 2011-03-30 | 2012-10-10 | 昭荣化学工业株式会社 | Positive active material for rechargeable magnesium battery and rechargeable magnesium battery |
| CN102280620B (en) * | 2011-07-05 | 2013-10-02 | 内蒙古科技大学 | Method for preparing magnesium secondary battery anode material of rare-earth-doped manganese magnesium silicate |
| CN102420329B (en) * | 2011-10-18 | 2014-10-29 | 新乡市中科科技有限公司 | High-tap-density composite modified cathode material of lithium ion battery and preparation method thereof |
| CN102364726B (en) * | 2011-10-21 | 2013-06-12 | 济宁市无界科技有限公司 | Method for producing iron lithium manganese phosphate composite positive electrode material used in lithium ion battery through carbon reduction |
| CN102856545B (en) * | 2012-09-11 | 2014-07-23 | 清华大学 | Preparation method of micro-nano-grade metal-ion-doped lithium iron phosphate anode material |
| CN102903919B (en) * | 2012-10-23 | 2015-09-30 | 中国科学院过程工程研究所 | A kind of lithium ionic cell positive electrode material vanadium lithium silicate, preparation method and its usage |
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