CN103236540A - Positive material for magnesium cell, preparation method of positive material and magnesium cell - Google Patents
Positive material for magnesium cell, preparation method of positive material and magnesium cell Download PDFInfo
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- CN103236540A CN103236540A CN2013101837856A CN201310183785A CN103236540A CN 103236540 A CN103236540 A CN 103236540A CN 2013101837856 A CN2013101837856 A CN 2013101837856A CN 201310183785 A CN201310183785 A CN 201310183785A CN 103236540 A CN103236540 A CN 103236540A
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Abstract
The invention relates to a positive material for a magnesium cell, a preparation method of the positive material, and a magnesium cell. The positive material for the magnesium cell comprises ferric oxide and a carbon source with a mass fraction ratio of (80:20) to (95:5). The preparation method comprises preparing materials according to the ratio, and mixing uniformly; adding the mixed material into a corundum agate jar with a ball-to-material ratio of 5:1; adding absolute ethanol as a dispersing agent; carrying out ball milling by a planetary ball mill at a speed of 300 to 500 rotations per minute for 4 to 6 hours to obtain a slurry mixture; drying the slurry mixture; and grinding the mixture into fine powder by the ball mill at a speed of 300 to 500 rotations per minute. The positive material is made into a positive electrode of the magnesium cell; a pure magnesium or magnesium alloy material is made into a negative electrode; and an electrolyte contains one or more of magnesium perchlorate, nitrates or acetates. The positive material has the advantages of abundant sources, no pollution to the environment, and low cost; and the prepared magnesium cell not only is low in cost and environment-friendly, but also has stable discharge and high specific discharge capacity.
Description
Skill
Technical field
The present invention relates to the battery technology field, particularly magnesium primary cell, being specifically related to di-iron trioxide is the magnesium primary cell of positive electrode.
Background technology
Dry cell is born in mid-term in 19th century, 1860, the thunder Crane scholar (George Leclanche) of France has invented carbon zinc battery, and the electrolyte with the glutinous similar paste of turbid shape has replaced the electrolyte of moist water-based first, so " doing " property battery in the container just occurred being contained in.Along with science and technology development, dry cell has developed into extended familys, and up to the present kind more than 100 has been arranged approximately.Common have common zinc-maganese dioxide dry cell, alkaline zinc-manganese dioxide dry cell, magnesium-manganese dry cell, zinc-air battery, zinc-mercuric oxide cell, zinc-silver oxide battery, a lithium-manganese cell etc.The most frequently used in these batteries is zinc-manganese dioxide dry cell, and the electromotive force of this battery is 1.5V, but produces NH in the discharge process meeting of battery
3, NH
3Be adsorbed on and cause on the graphite that cell emf descends comparatively fast.In order to address this problem, people replace NH with the pasty state KOH of high conduction
4Cl, positive electrode is used steel cylinder instead, and the Mn layer is made alkaline zinc-manganese dioxide cell near steel cylinder, and because cell reaction does not have gas to produce, interior resistance is lower, and electromotive force is 1.5V, and is more stable.This battery claims the carbon battery again, is the most common on the market, and the most cheap is a kind of.But the discharge capacity of this battery is low, is not suitable for the occasion of big electric current and longer-term continuous operation, and waste of raw materials is very big in addition, and the price of zinc is higher, and electrolyte causes irremediable destruction to environment.
Compare with zinc-manganese dioxide dry cell, the magnesium primary cell all has its unique characteristic.Magnesium metal aboundresources, cheap, environmental friendliness have that density is little, electrode potential is negative, theoretical specific capacity big (2205mAhg-1), and are the profuse light-weight metal elements of reserves on the earth.Magnesium cell is as a kind of novel green chemical power source, also has high specific energy, safety, characteristics such as pollution-free, is considered to one of following desirable regeneration product that substitutes conventional batteries.Existing magnesium primary cell is by MnO
2As positive pole, but use MnO
2As the positive pole of magnesium primary cell, not only can make the production cost of this magnesium cell higher, but also can cause certain pollution to environment.
Summary of the invention
Above-mentioned deficiency at existing magnesium cell has an object of the present invention is to provide a kind of environmental protection, and the positive electrode used of the low magnesium cell of production cost.
Another object of the present invention provides the preparation method of the positive electrode that a kind of magnesium cell simple to operate uses.
Also purpose of the present invention is a kind of environmental protection, and storage life is long, discharge stability, the magnesium cell that production cost is low.
For achieving the above object, the technical solution used in the present invention is: the positive electrode that a kind of magnesium cell is used, comprise di-iron trioxide and conduction carbon source, and the ratio of quality and the number of copies of described di-iron trioxide and carbon source is: 80:20 ~ 95:5.
The optimization of the positive electrode of using as magnesium cell, described carbon source is one or more in acetylene black, aquadag, graphite or the amorphous carbon conductive carbon.
The preparation method of the positive electrode that a kind of magnesium cell is used specifically comprises the steps:
S1: the quality percentage portion rate according to di-iron trioxide described in the claim 1 and conduction carbon source is prepared material, evenly mixes then;
S2: the mixture in the step S1 is that the ratio of 5:1 is put into the corundum ball grinder with the ratio of grinding media to material, with the 30ml absolute ethyl alcohol as dispersant, then on planetary ball mill with 300-500r/min batch (-type) ball milling 4-6h;
S3: will through the paste mixture that obtains behind the step S2 40-70 ℃ down oven dry make the presoma of the positive electrode that described magnesium cell uses;
S4, the presoma that step S3 is obtained speed with 300-500r/min on ball mill is levigate then, namely gets the positive electrode that magnesium cell is used.
A kind of magnesium cell comprises positive pole, negative pole and electrolyte, and described positive pole is by the positive electrode described in the technique scheme
Constitute, described negative pole is a kind of formation in pure magnesium, AZ31, AZ21, AZ61, AZ11, calcium-magnesium alloy or the manganese alloy, described electrolyte is magnesium perchlorate, in nitrate or the acetate one or more mix formation, and the concentration of electrolyte is 1mol/L, when electrolyte is that several materials mix when constituting, the mole between each material is used than being 1:1.
As the optimization of magnesium cell, described nitrate comprises in magnesium nitrate, lithium nitrate or the sodium nitrate one or more mixing.
As the optimization of magnesium cell, described acetate comprises in magnesium acetate, calcium acetate, the potassium acetate one or more mixing.
Compared to existing technology, the present invention has following beneficial effect:
1, the di-iron trioxide that adopts of the positive electrode used of magnesium cell of the present invention, stable in properties, wide material sources, price are than two
Manganese oxide more cheaply is easy to get, the cost of producing battery material is reduced, the safer environmental protection of comparing with manganese sesquioxide managnic oxide, and the content of ferro element in the earth's crust quite enriches, even after discarded, active material almost is zero pollution to environment, is reusable edible through recovery, has alleviated the problem of shortage of resources.Simultaneously, this material also is very useful for human body.
2, magnesium cell provided by the invention can more expensive magnesium perchlorate be electrolyte with traditional price not only, also can use
Price is than protonitrate and acetate, perhaps the mixed solution of magnesium perchlorate and these several salt is as electrolyte, reduced cost greatly, to be used to complete nearly all be zero to pollute to this magnesium cell from producing to simultaneously, more meets the green of modern society, the aim of environmental protection.
3, Mg-Fe provided by the invention
2O
3Battery, its charge and discharge platform are steadily, voltage is higher relatively, specific discharge capacity can
Reach 290 mAh/g.
?
Description of drawings
Fig. 1 is the pure magnesium of Mg()-Fe
2O
3Battery, electrolyte are the magnesium acetate of 1mol/L, the discharge image under the electric current of 0.3mA.
Fig. 2 is the Mg(manganese alloy)-Fe
2O
3Battery, electrolyte are the discharge image of magnesium acetate under the electric current of 0.3mA of 1mol/l.
Embodiment
The present invention is described in further detail with embodiment with reference to the accompanying drawings.
Embodiment 1:Take by weighing di-iron trioxide 9.0075g, acetylene black 0.5004g, graphite 0.5021g, the ratio that with the ratio of grinding media to material is 5:1 is put into the corundum ball grinder, as dispersant, on planetary ball mill, with the rotating speed batch (-type) ball milling 4h of 400r/min, then the paste mixture behind the ball milling is dried the presoma that makes the positive electrode that magnesium cell uses in 60 ℃ baking oven with the 30ml absolute ethyl alcohol, speed with 300-500r/min is levigate on ball mill again, makes magnesium cell anode material.
Take by weighing the aforementioned magnesium cell anode material of 0.1507g at electronic balance and be attached on the stainless steel collector positive pole as magnesium cell, the sodium nitrate of configuration 1mol/L is as electrolyte, pure magnesium is the negative pole collector of holding concurrently, and the centre is alkaline barrier film in addition, splashes into electrolyte and is assembled into the magnesium primary cell.With the 0.3mA discharge, its discharge capacity is 270mAh/g.
Embodiment 2:Take by weighing di-iron trioxide 9.0025g, acetylene black 0.5064g, graphite 0.5023g, the ratio that with the ratio of grinding media to material is 5:1 is put into the corundum ball grinder, as dispersant, on planetary ball mill, with the rotating speed batch (-type) ball milling 4h of 400r/min, then the paste mixture behind the ball milling is dried the presoma that makes the positive electrode that magnesium cell uses in 40 ℃ baking oven with the 30ml absolute ethyl alcohol, speed with 300-500r/min is levigate on ball mill again, makes magnesium cell anode material.
Take by weighing the aforementioned magnesium cell anode material of 0.1521g at electronic balance and be attached on the stainless steel collector positive pole as magnesium cell, the magnesium acetate of configuration 1mol/L is as electrolyte, pure magnesium is the negative pole collector of holding concurrently, and the centre is alkaline barrier film in addition, splashes into electrolyte and is assembled into the magnesium primary cell.With the 0.3mA discharge, its discharge capacity is 220mAh/g, as shown in Figure 1.
Embodiment 3:Take by weighing di-iron trioxide 8.5065g, acetylene black 0.5014g, graphite 0.5003g, manganese dioxide 0.5021g, the ratio that with the ratio of grinding media to material is 5:1 is put into the corundum ball grinder, with the 30ml absolute ethyl alcohol as dispersant, on planetary ball mill with the rotating speed batch (-type) ball milling 4h of 400r/min, then the paste mixture behind the ball milling is dried the presoma that makes the positive electrode that magnesium cell uses in 60 ℃ baking oven, speed with 300-500r/min is levigate on ball mill again, makes magnesium cell anode material.
Take by weighing the aforementioned magnesium cell anode material of 0.1221g at electronic balance and be attached on the stainless steel collector positive pole as magnesium cell, the magnesium acetate of configuration 1mol/L is as electrolyte, pure magnesium is the negative pole collector of holding concurrently, and the centre is alkaline barrier film in addition, splashes into electrolyte and is assembled into the magnesium primary cell.With the 1mA discharge, its discharge capacity is 190mAh/g.
Embodiment 4:Take by weighing di-iron trioxide 9.5120g, acetylene black 0.2530g, graphite 0.2517g, the ratio that with the ratio of grinding media to material is 5:1 is put into the corundum ball grinder, as dispersant, on planetary ball mill, with the rotating speed batch (-type) ball milling 4h of 400r/min, then the paste mixture behind the ball milling is dried the presoma that makes the positive electrode that magnesium cell uses in 70 ℃ baking oven with the 30ml absolute ethyl alcohol, speed with 300-500r/min is levigate on ball mill again, makes magnesium cell anode material.
Taking by weighing the aforementioned magnesium cell anode material of 0.1074g at electronic balance and be attached on the stainless steel collector positive pole as battery, is that proportional arrangement 1mol/L magnesium nitrate, the magnesium perchlorate mixed liquor of 1:1 is electrolyte with the mol ratio.AZ31 is the battery cathode collector of holding concurrently, and the centre is alkaline barrier film in addition, splashes into electrolyte and is assembled into the magnesium primary cell.With the 0.3mA discharge, its discharge capacity is 178 mAh/g.
Embodiment 5:Take by weighing di-iron trioxide 8.0180g, acetylene black 1.501g, aquadag 0.5078g, the ratio that with the ratio of grinding media to material is 5:1 is put into the corundum ball grinder, as dispersant, on planetary ball mill, with the rotating speed batch (-type) ball milling 4h of 400r/min, then the paste mixture behind the ball milling is dried the presoma that makes the positive electrode that magnesium cell uses in 70 ℃ baking oven with the 30ml absolute ethyl alcohol, speed with 300-500r/min is levigate on ball mill again, makes magnesium cell anode material.
Take by weighing the aforementioned magnesium cell anode material of 0.1410g at electronic balance and be attached on the stainless steel collector positive pole as battery, the magnesium acetate of configuration 1mol/L is as electrolyte, manganese alloy is the battery cathode collector of holding concurrently, and the centre is alkaline barrier film in addition, splashes into electrolyte and is assembled into the magnesium primary cell.With the 0.3mA discharge, its discharge capacity is 278mAh/g, as shown in Figure 2.
Embodiment 6:Take by weighing di-iron trioxide 8.0180g, acetylene black 1.500g, aquadag 0.5078g, the ratio that with the ratio of grinding media to material is 5:1 is put into the corundum ball grinder, as dispersant, on planetary ball mill, with the rotating speed batch (-type) ball milling 4h of 400r/min, then the paste mixture behind the ball milling is dried the presoma that makes the positive electrode that magnesium cell uses in 60 ℃ baking oven with the 30ml absolute ethyl alcohol, speed with 300-500r/min is levigate on ball mill again, makes magnesium cell anode material.
Take by weighing the aforementioned magnesium cell anode material of 0.1000g at electronic balance and be attached on the stainless steel collector positive pole as battery, the magnesium acetate of configuration 1mol/L is as electrolyte, calcium-magnesium alloy is the battery cathode collector of holding concurrently, and the centre is alkaline barrier film in addition, splashes into electrolyte and is assembled into the magnesium primary cell.With the 0.3mA discharge, its discharge capacity is 288mAh/g.
Embodiment 7:Take by weighing di-iron trioxide 9.0025g, acetylene black 1.5012g, the ratio that with the ratio of grinding media to material is 5:1 is put into the corundum ball grinder, with the 30ml absolute ethyl alcohol as dispersant, on planetary ball mill with the rotating speed batch (-type) ball milling 4h of 400r/min, then the paste mixture behind the ball milling is dried the presoma that makes the positive electrode that magnesium cell uses in 60 ℃ baking oven, the speed with 300-500r/min is levigate on ball mill again, makes magnesium cell anode material.
Take by weighing the aforementioned magnesium cell anode material of 0.1000g at electronic balance and be attached on the stainless steel collector positive pole as battery, the calcium acetate of configuration 1mol/L is as electrolyte, AZ31 is the battery cathode collector of holding concurrently, and the centre is alkaline barrier film in addition, splashes into electrolyte and is assembled into the magnesium primary cell.With the 0.3mA discharge, its discharge capacity is 226mAh/g.
Embodiment 8:Take by weighing di-iron trioxide 9.0012g, acetylene black 0.5006g, aquadag, 0.50021g, be that the ratio of 5:1 is put into the corundum ball grinder with the ratio of grinding media to material, with the 30ml absolute ethyl alcohol as dispersant, on planetary ball mill with the rotating speed batch (-type) ball milling 4h of 400r/min, then the paste mixture behind the ball milling is dried the presoma that makes the positive electrode that magnesium cell uses in 60 ℃ baking oven, the speed with 300-500r/min is levigate on ball mill again, makes magnesium cell anode material.
Take by weighing the aforementioned magnesium cell anode material of 0.1517g at electronic balance and be attached on the stainless steel collector positive pole as battery, be that the mixed solution of 1:1 configuration 1mol/L is electrolyte with the mol ratio of magnesium acetate and magnesium nitrate, AZ31 is the battery cathode collector of holding concurrently, the centre is alkaline barrier film in addition, splashes into electrolyte and is assembled into the magnesium primary cell.With the 0.3mA discharge, its discharge capacity is 229mAh/g.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although with reference to preferred embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (6)
1. positive electrode that magnesium cell is used is characterized in that: comprise di-iron trioxide and conduction carbon source, the ratio of quality and the number of copies of described di-iron trioxide and carbon source is: 80:20 ~ 95:5.
2. the positive electrode used of magnesium cell as claimed in claim 1, it is characterized in that: described carbon source is one or more in acetylene black, aquadag, graphite or the amorphous carbon conductive carbon.
3. the preparation method of the positive electrode used of a magnesium cell is characterized in that: specifically comprise the steps:
S1: the quality percentage portion rate according to di-iron trioxide described in the claim 1 and conduction carbon source is prepared material, evenly mixes then;
S2: the mixture in the step S1 is that the ratio of 5:1 is put into the corundum ball grinder with the ratio of grinding media to material, with the 30ml absolute ethyl alcohol as dispersant, then on planetary ball mill with 300-500r/min batch (-type) ball milling 4-6h;
S3: will through the paste mixture that obtains behind the step S2 40-70 ℃ down oven dry make the presoma of the positive electrode that described magnesium cell uses;
S4, the presoma that step S3 is obtained speed with 300-500r/min on ball mill is levigate then, namely gets the positive electrode that magnesium cell is used.
4. magnesium cell, comprise positive pole, negative pole and electrolyte, it is characterized in that: the described positive electrode of described just very claim 1 constitutes, described negative pole is a kind of formation in pure magnesium, AZ31, AZ21, AZ61, AZ11, calcium-magnesium alloy or the manganese alloy, described electrolyte is magnesium perchlorate, and one or more in nitrate or the acetate mix formation, and the concentration of electrolyte is 1mol/L, when electrolyte is that several materials mix when constituting, the mole between each material is used than being 1:1.
5. magnesium cell as claimed in claim 4 is characterized in that: described nitrate comprises in magnesium nitrate, lithium nitrate or the sodium nitrate one or more mixing.
6. magnesium cell as claimed in claim 4 is characterized in that: described acetate comprises in magnesium acetate, calcium acetate, the potassium acetate one or more mixing.
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|---|---|---|---|
| CN201310183785.6A CN103236540B (en) | 2013-05-17 | 2013-05-17 | Positive material for magnesium cell, preparation method of positive material and magnesium cell |
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| CN103236540B CN103236540B (en) | 2015-06-10 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103545578A (en) * | 2013-09-30 | 2014-01-29 | 刘甲祥 | Electrolyte of magnesium air battery |
| CN106410231A (en) * | 2016-10-10 | 2017-02-15 | 重庆大学 | Novel composite electrolyte suitable for magnesium-manganese dry battery |
| CN112501640A (en) * | 2020-12-10 | 2021-03-16 | 东莞理工学院 | Battery system for converting nitrate wastewater into ammonia |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3719530A (en) * | 1968-08-09 | 1973-03-06 | Magnesium Elektron Ltd | Electric batteries and alloys therefor |
| CN101355151A (en) * | 2007-07-25 | 2009-01-28 | 比亚迪股份有限公司 | Battery anode and primary cell as well as preparation method thereof |
| CN102306758A (en) * | 2011-08-08 | 2012-01-04 | 嘉兴中科亚美合金技术有限责任公司 | Magnesium dry battery |
-
2013
- 2013-05-17 CN CN201310183785.6A patent/CN103236540B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3719530A (en) * | 1968-08-09 | 1973-03-06 | Magnesium Elektron Ltd | Electric batteries and alloys therefor |
| CN101355151A (en) * | 2007-07-25 | 2009-01-28 | 比亚迪股份有限公司 | Battery anode and primary cell as well as preparation method thereof |
| CN102306758A (en) * | 2011-08-08 | 2012-01-04 | 嘉兴中科亚美合金技术有限责任公司 | Magnesium dry battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103545578A (en) * | 2013-09-30 | 2014-01-29 | 刘甲祥 | Electrolyte of magnesium air battery |
| CN103545578B (en) * | 2013-09-30 | 2016-03-02 | 刘甲祥 | A kind of electrolyte of magnesium air cell |
| CN106410231A (en) * | 2016-10-10 | 2017-02-15 | 重庆大学 | Novel composite electrolyte suitable for magnesium-manganese dry battery |
| CN112501640A (en) * | 2020-12-10 | 2021-03-16 | 东莞理工学院 | Battery system for converting nitrate wastewater into ammonia |
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| CN103236540B (en) | 2015-06-10 |
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