CN102339987A - Method for preparing anode of magnesium ion battery - Google Patents
Method for preparing anode of magnesium ion battery Download PDFInfo
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- CN102339987A CN102339987A CN2011103407035A CN201110340703A CN102339987A CN 102339987 A CN102339987 A CN 102339987A CN 2011103407035 A CN2011103407035 A CN 2011103407035A CN 201110340703 A CN201110340703 A CN 201110340703A CN 102339987 A CN102339987 A CN 102339987A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a method for preparing an anode of a magnesium ion battery, and the method comprises the following steps: uniformly mixing and stirring conductive ink (mass percent: 73.5-80.9%), manganese salt (mass percent: 2.3-3.2%) and magnesium powder (mass percent: 15.9-24.2%) so as to obtain a raw material mixture; and filling the raw material mixture into a reaction kettle, and then heating the raw material mixture in one of the following two modes: a) heating the raw material mixture to 100-200 DEG C and then carrying out heat preservation for 1-3 hours under a pressure condition of no less than three barometric pressures, then under the same pressure condition, rapidly raising the temperature to 300-400 DEG C and then carrying out heat preservation for 10-30 minutes, or b) rapidly raising the temperature to 200-300 DEG C under a vacuum condition and then carrying out heat preservation for 10-20 minutes; and then, rapidly cooling and drying the obtained raw material mixture so as to obtain an anode material for the magnesium ion battery. The anode material for the magnesium ion battery prepared by using the method disclosed by the invention is large in specific capacity (160 MAh/g), high in operating voltage (2.2 V), and excellent in cycle performance (after a deep drawing-discharge cycle is performed 50 times, more than 95% of capacity still can be maintained).
Description
Technical field
The invention belongs to the battery electrode preparing technical field, relate to the preparation method of electrode for secondary battery, particularly adopt the battery electrode preparation method of the synthetic new material of high temperature.
Background technology
Magnesium is in the lower right corner of lithium on the periodic table of elements, the most approaching with lithium in nature.Lithium rechargeable battery has obtained extensive use on the removable power supply that low capacity requires, and is requiring under the situation of big capacity power source, and the fail safe of lithium ion battery is relatively poor, and cost is higher, and resource reserve is lower.The relative stable in properties of magnesium, cost is lower, all nontoxic or low toxicity of the compound of most magnesium, and magnesium resource is abundant.Therefore, the magnesium ion battery comes into one's own as a kind of very potential big load battery gradually.
Compare with lithium ion battery, magnesium is as electrode material, and theoretical specific capacity is big (2205mAh/g); Can provide than high energy densities that manys such as lead-acid battery, nickel-cadmium cells, think be applicable to more need more powerful electric motor car etc. green storage battery, but because magnesium ion charge density is big; Polarization is strong; Often embed in the positive electrode with the solvation form, therefore, a lot of than lithium ion insert material difficulty; In addition, magnesium all can form passivating film in most electrolyte, cause magnesium ion to pass, thereby can't deposit smoothly and dissolve, but the magnesium ion battery mainly is exactly to launch corresponding to positive pole insert material and two problem points of electrolyte.
At present, to the research of magnesium ion positive electrode, main still mixing with reference to some positive electrodes of lithium ion, such as transition metal oxide, sulfide etc., and all is very thin layer of active material, need be attached on other auxiliary electrical pole plate; To electrolyte, the main at present still ethereal solution of liquid organic-magnesium aluminum complex, polymer dielectric and ionic liquid etc. also has research, but does not still find suitable anodal insert material and nonaqueous electrolyte, so its development has received obstruction.
Summary of the invention
The objective of the invention is deficiency, a kind of preparation method of magnesium ion anode is provided, make anodal itself becoming one, reduced electrode resistance with active material to present magnesium ion cell positive material, but to improve active material utilization and loading.
Electrode preparation method of the present invention is to prepare according to following steps:
1) according to electrically conductive ink 73.5～80.9%, Mazhev salt 2.3～3.2%, the mass percent of magnesium powder 15.9～24.2% with electrically conductive ink, Mazhev salt and magnesium powder mixing and stirring, obtains raw mix;
2) raw mix is filled in the agitated reactor, with a kind of heating the in following two kinds of methods:
A) be heated to 100～200 ℃ of insulation 1～3h under 3 atmospheric pressure in being not less than, 300～400 ℃ of insulation 10～30min that are rapidly heated that keep-up pressure,
B) be rapidly heated under the vacuum condition 200～300 ℃ the insulation 10～20min;
3) cooling back drying obtains the magnesium ion cell positive material fast.
Wherein, can electrically conductive ink, Mazhev salt and magnesium powder be mixed together stirring, also can be earlier with electrically conductive ink and Mazhev salt mixing and stirring, add the magnesium powder again and stir and obtain raw mix.
When raw mix is filled into agitated reactor, preferably raw mix is filled up agitated reactor, do not interspace.The agitated reactor that require to use can the above intensity of anti-3 atmospheric pressure, and agitated reactor has pressure-reducing valve.
When adopting a) method heating, the raw mix in the agitated reactor when 100～200 ℃ holding temperature is carried out secondary temperature elevation, should be rapidly heated raw mix to 300～400 ℃ from 100～200 ℃ with the programming rate of 30 ℃/min.
Electrically conductive ink, Mazhev salt and magnesium powder are key reaction raw materials of the present invention, and wherein, electrically conductive ink comprises that mainly gold is that electrically conductive ink, copper are electrically conductive ink and carbon series conductive printing ink, all is gel state under the low temperature; Mazhev salt is for analyzing pure level; Magnesium powder degree 200～250 μ m.
In above-mentioned reaction raw materials, both as the basic framework of electrode, as the carrier of magnesium powder embedding, manganese in the Mazhev salt and hydrogen phosphate helped the embedding of magnesium powder to electrically conductive ink again.In the high temperature building-up process, the solvent evaporates of electrically conductive ink, partial liquefaction has improved the dispersiveness of magnesium powder and Mazhev salt, promote Mazhev salt and magnesium powder at high temperature with electrically conductive ink generation certain reaction.Simultaneously, the back cooling fast that is rapidly heated, purpose is to guarantee that the structure that at high temperature forms can be able to preserve.
The magnesium ion cell positive material that above-mentioned preparation method is obtained cuts into the thin slice of definite shape and thickness as required, has promptly obtained a complete magnesium ion anode.
The present invention prepares electrode material with electrically conductive ink, Mazhev salt and magnesium powder as reaction mass, and electrode size can be controlled arbitrarily, directly uses, and need not be coated on other electrode holder.Because it is less that electrically conductive ink solidifies back resistance, can effectively reduce the internal resistance of battery.
Compare with the Mg secondary cell preparation method who has reported; Magnesium ion cell positive material preparation method of the present invention has high synthesis temperature (the highest 300 ℃); Bigger specific capacity (160MAh/g); Higher operating voltage (2.2V) and good cycle advantages such as (after 50 deep-draw-discharge cycles, still can keep the capacity more than 95%).
Description of drawings
Fig. 1 is embodiment 1 a simulated battery charging and discharging curve.
Fig. 2 is the charging and discharging curve of embodiment 1 simulated battery device through 2～4 weeks.
Fig. 3 is the specific capacity curve chart of embodiment 1 simulated battery device through 50 cycle charge-discharges.
Embodiment
Embodiment 1
With 390 gram gold is after electrically conductive ink, 14 gram Mazhev salts are put into mixer stir about 30min, slowly to add 120 gram magnesium powder (particle mean size≤200～250 μ m) again, continues to stir 1h; Taking-up is filled in the agitated reactor, and sealing is under 5 atmospheric pressure; Be heated to 180 ℃ earlier; The insulation 1h, keep-uping pressure afterwards be rapidly heated 300 ℃ the insulation 15min after, together put into cold water together with agitated reactor and cool off fast; Can obtain the anodal block materials of magnesium ion battery, put into vacuum desiccator and preserve.
Magnesium metal with through sanding and polishing is made negative pole and reference electrode respectively, saturated Mg (AlBu
2Cl
2)
2/ THF solution is made electrolyte, and the magnesium ion block materials of above-mentioned preparation is assembled into simulated battery as positive pole in the glove box of anhydrous inert gas.
Analog result shows, at the Mg of 0.30mol/L (AlBu
2Cl
2)
2In/THF the electrolyte; 0.1C under the discharge rate; In the circulation first time of simulated battery, discharge platform (is seen accompanying drawing 1) about 2.2V, and magnesium ion embedding ratio capacity can reach 160mAh/g; Simulated battery can carry out reversible discharging and recharging, and the charge/discharge capacity of 2～4 all batteries is kept basically constant (seeing accompanying drawing 2).After 50 deep-draw-discharge cycles, still can keep the capacity more than 98%, be 157mAh/g (seeing accompanying drawing 3).
Embodiment 2
With 365 gram copper is after electrically conductive ink, 12 gram Mazhev salts are put into mixer stir about 30min, slowly to add 110 gram magnesium powder again, continues to stir 2h, takes out and fills in the agitated reactor; Sealing under 7 atmospheric pressure, is heated to 100 ℃ earlier; Insulation 1.5h, keep-uping pressure afterwards is rapidly heated behind 350 ℃ of insulation 30min, takes out; Together put into cold water together with agitated reactor and cool off fast, can obtain the anodal block materials of magnesium ion battery, put into vacuum desiccator and preserve.
The simulated battery device is identical with embodiment 1.
Analog result shows, at the Mg of 0.450mol/L (AlBu
2Cl
2)
2In/THF the electrolyte, under the 0.2C discharge rate, in the circulation first time of simulated battery; Discharge platform is about 1.8V; Magnesium ion embedding ratio capacity can reach 150mAh/g, and simulated battery can carry out reversible discharging and recharging, and the charge/discharge capacity of 2～4 all batteries is kept constant basically.After 50 deep-draw-discharge cycles, still can keep the capacity more than 97%, be 146mAh/g.
Embodiment 3
404 gram carbon series conductive printing ink (filler is a graphite), 15 gram Mazhev salts, 75 gram magnesium powder are put into mixer and continued to stir 2.5h; Taking-up is filled in the agitated reactor, sealing, and 230 ℃ of insulation 20min afterwards are rapidly heated under vacuum condition; Take out; Together put into cold water together with agitated reactor and cool off fast, can obtain the anodal block materials of magnesium ion battery, put into vacuum desiccator and preserve.
The simulated battery device is with identical with embodiment 1.
Analog result shows, at the Mg of 0.20mol/L (AlBu
2Cl
2)
2In/THF the electrolyte, under the 0.4C discharge rate, in the circulation first time of simulated battery; Discharge platform is about 2.0V; Magnesium ion embedding ratio capacity can reach 152mAh/g, and simulated battery can carry out reversible discharging and recharging, and the charge/discharge capacity of 2～4 all batteries is kept constant basically.After 50 deep-draw-discharge cycles, still can keep the capacity more than 97%, be 148mAh/g.
Claims (6)
1. the preparation method of a magnesium ion anode is to prepare according to following steps:
1) according to electrically conductive ink 73.5～80.9%, Mazhev salt 2.3～3.2%, the mass percent of magnesium powder 15.9～24.2% with electrically conductive ink, Mazhev salt and magnesium powder mixing and stirring, obtains raw mix;
2) raw mix is filled in the agitated reactor, with a kind of heating the in following two kinds of methods:
A) be heated to 100～200 ℃ of insulation 1～3h under 3 atmospheric pressure in being not less than, 300～400 ℃ of insulation 10～30min that are rapidly heated keep-up pressure;
B) be rapidly heated under the vacuum condition 200～300 ℃ the insulation 10～20min;
3) cooling back drying obtains the magnesium ion cell positive material fast.
2. the preparation method of magnesium ion anode according to claim 1 is characterized in that earlier electrically conductive ink and Mazhev salt mixing and stirring, adds the magnesium powder again and stirs and obtain raw mix.
3. the preparation method of magnesium ion anode according to claim 1 is characterized in that described raw mix fills up agitated reactor, does not interspace.
4. the preparation method of magnesium ion anode according to claim 1, the granularity that it is characterized in that the magnesium powder are 200～250 μ m.
5. the preparation method of magnesium ion anode according to claim 1 is characterized in that when adopting a) method heating, with the programming rate of 30 ℃/min raw mix is rapidly heated to 300～400 ℃ from 100～200 ℃.
6. the magnesium ion cell positive material for preparing with the preparation method of claim 1 magnesium ion anode.
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| CN2011103407035A CN102339987B (en) | 2011-11-02 | 2011-11-02 | Method for preparing anode of magnesium ion battery |
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| CN2011103407035A CN102339987B (en) | 2011-11-02 | 2011-11-02 | Method for preparing anode of magnesium ion battery |
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| CN102339987B CN102339987B (en) | 2013-10-30 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1837033A (en) * | 2006-03-24 | 2006-09-27 | 山东科技大学 | Process for synthesizing LiFePO4 as positive electrode materials of lithium ion cell |
| CN101217194A (en) * | 2007-12-27 | 2008-07-09 | 上海交通大学 | A magnesium secondary battery anode material and the corresponding preparation method |
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2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1837033A (en) * | 2006-03-24 | 2006-09-27 | 山东科技大学 | Process for synthesizing LiFePO4 as positive electrode materials of lithium ion cell |
| CN101217194A (en) * | 2007-12-27 | 2008-07-09 | 上海交通大学 | A magnesium secondary battery anode material and the corresponding preparation method |
Non-Patent Citations (2)
| Title |
|---|
| HUATANG YUAN ET AL: "Development of Magnesium-Insertion Positive Electrode for Rechargeable Magnesium Batteries", 《JOURNAL OF MATERIAL SCIENCE AND TECHNOLOGY》 * |
| KOJI MAKINO ET AL: "Electrochemical insertion of magnesium to Mg0.5Ti2(PO4)3", 《JOURNAL OF POWER SOURCES》 * |
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