CN103236540B - 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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- CN103236540B CN103236540B CN201310183785.6A CN201310183785A CN103236540B CN 103236540 B CN103236540 B CN 103236540B CN 201310183785 A CN201310183785 A CN 201310183785A CN 103236540 B CN103236540 B CN 103236540B
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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 cell art, particularly magnesium primary cell, be specifically related to the magnesium primary cell that di-iron trioxide is positive electrode.
Background technology
Mid-term in 19th century is born in by dry cell, 1860, the thunder Crane scholar (George Leclanche) of France has invented carbon zinc battery, instead of the electrolyte of moist water-based first, so just there is " doing " property battery be contained in container with the electrolyte of the glutinous similar paste of turbid shape.Along with the development of science and technology, dry cell has developed into extended familys, up to the present about has kind more than 100.Common are 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, 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
3being adsorbed on graphite causes cell emf to decline comparatively fast.In order to address this problem, the pasty state KOH of people's high connductivity replaces NH
4cl, positive electrode uses steel cylinder instead, and Mn layer makes 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, more stable.This battery, also known as carbon battery, is the most common on market, the most cheap one.But the discharge capacity of this battery is low, be not suitable for the occasion of big current and longer-term continuous operation, waste of raw materials is very large in addition, and the price of zinc is higher, and electrolyte causes irremediable destruction to environment.
Compared with zinc-manganese dioxide dry cell, magnesium primary cell all has the characteristic of its uniqueness.Magnesium metal aboundresources, cheap, environmental friendliness, have that density is little, electrode potential be negative, theoretical specific capacity large (2205mAhg-1), and be the light-weight metal element that on the earth, reserves enrich very much.Magnesium cell, as a kind of novel green chemical power source, also has high specific energy, safety, the feature such as pollution-free, is considered to following and substitutes one of desirable regeneration product of conventional batteries.Existing magnesium primary cell is by MnO
2as positive pole, but use MnO
2as the positive pole of magnesium primary cell, the production cost of this magnesium cell not only can be made higher, but also certain pollution can be caused to environment.
Summary of the invention
For the above-mentioned deficiency that existing magnesium cell has, an object of the present invention is to provide a kind of environmental protection, and the positive electrode of the low magnesium cell of production cost.
Another object of the present invention is to provide a kind of preparation method of positive electrode of magnesium cell simple to operate.
An also object 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: a kind of positive electrode of magnesium cell, and 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.
As the optimization of the positive electrode of magnesium cell, described carbon source is one or more in acetylene black, aquadag, graphite or amorphous carbon conductive carbon.
A preparation method for the positive electrode of magnesium cell, specifically comprises the steps:
S1: prepare material, then Homogeneous phase mixing according to the percent mass portion rate of di-iron trioxide described in claim 1 and conduction carbon source;
S2: the ratio taking ratio of grinding media to material as 5:1 to the mixture in step S1 puts into corundum ball grinder, with 30ml absolute ethyl alcohol as dispersant, then on planetary ball mill with 300-500r/min batch (-type) ball milling 4-6h;
S3: the presoma of the paste mixture obtained after step S2 being dried at 40-70 DEG C the positive electrode of obtained described magnesium cell;
S4, the speed of the presoma then obtained by step S3 with 300-500r/min on ball mill is levigate, obtains the positive electrode of magnesium cell.
A kind of magnesium cell, comprise positive pole, negative pole and electrolyte, described positive pole is by the positive electrode described in technique scheme
Form, described negative pole is that the one in pure magnesium, AZ31, AZ21, AZ61, AZ11, calcium-magnesium alloy or manganese alloy is formed, described electrolyte is magnesium perchlorate, one or more mixing in nitrate or acetate are formed, and the concentration of electrolyte is 1mol/L, when electrolyte be the mixing of several material form time, between each material mole with than being 1:1.
As the optimization of magnesium cell, described nitrate to comprise in magnesium nitrate, lithium nitrate or sodium nitrate one or more mixing.
As the optimization of magnesium cell, described acetate to comprise in magnesium acetate, calcium acetate, potassium acetate one or more mixing.
Compared to existing technology, the present invention has following beneficial effect:
1, the di-iron trioxide of the positive electrode employing of magnesium cell of the present invention, stable in properties, wide material sources, cost ratio two
Manganese oxide is more cheaply easy to get, the cost of production battery material is reduced, safer environmental protection compared with manganese sesquioxide managnic oxide, and the content of ferro element in the earth's crust quite enriches, even if after discarded, active material is almost no pollution to environment, through recovery and reusable edible, alleviates the problem of shortage of resources.Meanwhile, this material is also very useful for human body.
2, the magnesium perchlorate that magnesium cell provided by the invention not only can be more expensive by traditional price is electrolyte, also can use
Price is protonitrate and acetate comparatively, or the mixed solution of magnesium perchlorate and this several salt is as electrolyte, greatly reduce cost, from producing to, to be used to complete be nearly all no pollution to this magnesium cell 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 steadily, voltage is relatively high, specific discharge capacity can
Reach 290 mAh/g.
Accompanying drawing explanation
Fig. 1 is the pure magnesium of Mg()-Fe
2o
3battery, electrolyte is the magnesium acetate of 1mol/L, the electric discharge image under the electric current of 0.3mA.
Fig. 2 is Mg(manganese alloy)-Fe
2o
3battery, electrolyte is the electric 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 di-iron trioxide 9.0075g, acetylene black 0.5004g, graphite 0.5021g, be that the ratio of 5:1 puts into corundum ball grinder with ratio of grinding media to material, with 30ml absolute ethyl alcohol as dispersant, with the rotating speed batch (-type) ball milling 4h of 400r/min on planetary ball mill, then the paste mixture after ball milling is dried in the baking oven of 60 DEG C the presoma of the positive electrode of obtained magnesium cell, speed again with 300-500r/min on ball mill is levigate, obtained magnesium cell anode material.
Electronic balance takes the aforementioned magnesium cell anode material of 0.1507g and is attached to positive pole as magnesium cell on stainless steel collector, the sodium nitrate of configuration 1mol/L is as electrolyte, pure magnesium is that negative pole is held concurrently collector, and centre in addition alkaline separators, instillation electrolyte is assembled into magnesium primary cell.With 0.3mA electric discharge, its discharge capacity is 270mAh/g.
embodiment 2:take di-iron trioxide 9.0025g, acetylene black 0.5064g, graphite 0.5023g, be that the ratio of 5:1 puts into corundum ball grinder with ratio of grinding media to material, with 30ml absolute ethyl alcohol as dispersant, with the rotating speed batch (-type) ball milling 4h of 400r/min on planetary ball mill, then the paste mixture after ball milling is dried in the baking oven of 40 DEG C the presoma of the positive electrode of obtained magnesium cell, speed again with 300-500r/min on ball mill is levigate, obtained magnesium cell anode material.
Electronic balance takes the aforementioned magnesium cell anode material of 0.1521g and is attached to positive pole as magnesium cell on stainless steel collector, the magnesium acetate of configuration 1mol/L is as electrolyte, pure magnesium is that negative pole is held concurrently collector, and centre in addition alkaline separators, instillation electrolyte is assembled into magnesium primary cell.With 0.3mA electric discharge, its discharge capacity is 220mAh/g, as shown in Figure 1.
embodiment 3:take di-iron trioxide 8.5065g, acetylene black 0.5014g, graphite 0.5003g, manganese dioxide 0.5021g, be that the ratio of 5:1 puts into corundum ball grinder with ratio of grinding media to material, with 30ml absolute ethyl alcohol as dispersant, with the rotating speed batch (-type) ball milling 4h of 400r/min on planetary ball mill, then the paste mixture after ball milling is dried in the baking oven of 60 DEG C the presoma of the positive electrode of obtained magnesium cell, speed again with 300-500r/min on ball mill is levigate, obtained magnesium cell anode material.
Electronic balance takes the aforementioned magnesium cell anode material of 0.1221g and is attached to positive pole as magnesium cell on stainless steel collector, the magnesium acetate of configuration 1mol/L is as electrolyte, pure magnesium is that negative pole is held concurrently collector, and centre in addition alkaline separators, instillation electrolyte is assembled into magnesium primary cell.With 1mA electric discharge, its discharge capacity is 190mAh/g.
embodiment 4:take di-iron trioxide 9.5120g, acetylene black 0.2530g, graphite 0.2517g, be that the ratio of 5:1 puts into corundum ball grinder with ratio of grinding media to material, with 30ml absolute ethyl alcohol as dispersant, with the rotating speed batch (-type) ball milling 4h of 400r/min on planetary ball mill, then the paste mixture after ball milling is dried in the baking oven of 70 DEG C the presoma of the positive electrode of obtained magnesium cell, speed again with 300-500r/min on ball mill is levigate, obtained magnesium cell anode material.
Electronic balance takes the aforementioned magnesium cell anode material of 0.1074g and is attached to positive pole as battery on stainless steel collector, take mol ratio as the proportional arrangement 1mol/L magnesium nitrate of 1:1, magnesium perchlorate mixed liquor is electrolyte.AZ31 is that battery cathode is held concurrently collector, and centre in addition alkaline separators, instillation electrolyte is assembled into magnesium primary cell.With 0.3mA electric discharge, its discharge capacity is 178 mAh/g.
embodiment 5:take di-iron trioxide 8.0180g, acetylene black 1.501g, aquadag 0.5078g, be that the ratio of 5:1 puts into corundum ball grinder with ratio of grinding media to material, with 30ml absolute ethyl alcohol as dispersant, with the rotating speed batch (-type) ball milling 4h of 400r/min on planetary ball mill, then the paste mixture after ball milling is dried in the baking oven of 70 DEG C the presoma of the positive electrode of obtained magnesium cell, speed again with 300-500r/min on ball mill is levigate, obtained magnesium cell anode material.
Electronic balance takes the aforementioned magnesium cell anode material of 0.1410g and is attached to positive pole as battery on stainless steel collector, the magnesium acetate of configuration 1mol/L is as electrolyte, manganese alloy is that battery cathode is held concurrently collector, and centre in addition alkaline separators, instillation electrolyte is assembled into magnesium primary cell.With 0.3mA electric discharge, its discharge capacity is 278mAh/g, as shown in Figure 2.
embodiment 6:take di-iron trioxide 8.0180g, acetylene black 1.500g, aquadag 0.5078g, be that the ratio of 5:1 puts into corundum ball grinder with ratio of grinding media to material, with 30ml absolute ethyl alcohol as dispersant, with the rotating speed batch (-type) ball milling 4h of 400r/min on planetary ball mill, then the paste mixture after ball milling is dried in the baking oven of 60 DEG C the presoma of the positive electrode of obtained magnesium cell, speed again with 300-500r/min on ball mill is levigate, obtained magnesium cell anode material.
Electronic balance takes the aforementioned magnesium cell anode material of 0.1000g and is attached to positive pole as battery on stainless steel collector, the magnesium acetate of configuration 1mol/L is as electrolyte, calcium-magnesium alloy is that battery cathode is held concurrently collector, and centre in addition alkaline separators, instillation electrolyte is assembled into magnesium primary cell.With 0.3mA electric discharge, its discharge capacity is 288mAh/g.
embodiment 7:take di-iron trioxide 9.0025g, acetylene black 1.5012g, be that the ratio of 5:1 puts into corundum ball grinder with ratio of grinding media to material, with 30ml absolute ethyl alcohol as dispersant, with the rotating speed batch (-type) ball milling 4h of 400r/min on planetary ball mill, then the paste mixture after ball milling is dried in the baking oven of 60 DEG C the presoma of the positive electrode of obtained magnesium cell, then speed with 300-500r/min on ball mill is levigate, obtained magnesium cell anode material.
Electronic balance takes the aforementioned magnesium cell anode material of 0.1000g and is attached to positive pole as battery on stainless steel collector, the calcium acetate of configuration 1mol/L is as electrolyte, AZ31 is that battery cathode is held concurrently collector, and centre in addition alkaline separators, instillation electrolyte is assembled into magnesium primary cell.With 0.3mA electric discharge, its discharge capacity is 226mAh/g.
embodiment 8:take di-iron trioxide 9.0012g, acetylene black 0.5006g, aquadag, 0.50021g is that the ratio of 5:1 puts into corundum ball grinder with ratio of grinding media to material, with 30ml absolute ethyl alcohol as dispersant, with the rotating speed batch (-type) ball milling 4h of 400r/min on planetary ball mill, then the paste mixture after ball milling is dried in the baking oven of 60 DEG C the presoma of the positive electrode of obtained magnesium cell, then speed with 300-500r/min on ball mill is levigate, obtained magnesium cell anode material.
Electronic balance takes the aforementioned magnesium cell anode material of 0.1517g and is attached to positive pole as battery on stainless steel collector, with the mol ratio of magnesium acetate and magnesium nitrate for 1:1 configures the mixed solution of 1mol/L for electrolyte, AZ31 is that battery cathode is held concurrently collector, centre in addition alkaline separators, instillation electrolyte is assembled into magnesium primary cell.With 0.3mA electric discharge, its discharge capacity is 229mAh/g.
What finally illustrate is, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (4)
1. a preparation method for the positive electrode of magnesium cell, is characterized in that: specifically comprise the steps:
S1: described positive electrode comprises di-iron trioxide and conduction carbon source, and described di-iron trioxide with the ratio of quality and the number of copies of conduction carbon source is: 80:20 ~ 95:5, and prepare material, then Homogeneous phase mixing according to the percent mass portion rate of di-iron trioxide and conduction carbon source;
Described conduction carbon source is one or more in acetylene black, graphite or amorphous carbon conductive carbon;
S2: the ratio taking ratio of grinding media to material as 5:1 to the mixture in step S1 puts into corundum ball grinder, with 30ml absolute ethyl alcohol as dispersant, then on planetary ball mill with 300-500r/min batch (-type) ball milling 4-6h;
S3: the presoma of the paste mixture obtained after step S2 being dried at 40-70 DEG C the positive electrode of obtained described magnesium cell;
S4, the speed of the presoma then obtained by step S3 with 300-500r/min on ball mill is levigate, obtains the positive electrode of magnesium cell.
2. a magnesium cell, comprise positive pole, negative pole and electrolyte, it is characterized in that: the positive electrode of described just very claim 1 preparation is formed, described negative pole is that the one in pure magnesium, AZ31, AZ21, AZ61, AZ11, calcium-magnesium alloy or manganese alloy is formed, described electrolyte is magnesium perchlorate, and one or more mixing in nitrate or acetate are formed, and the concentration of electrolyte is 1mol/L, when electrolyte is several material mixing formation, the mol ratio between each material is 1:1.
3. magnesium cell as claimed in claim 2, is characterized in that: described nitrate to comprise in magnesium nitrate, lithium nitrate or sodium nitrate one or more mixing.
4. magnesium cell as claimed in claim 2, is characterized in that: described acetate to comprise in magnesium acetate, calcium acetate, 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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|---|---|---|---|
| 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 true CN103236540B (en) | 2015-06-10 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN112501640B (en) * | 2020-12-10 | 2023-01-06 | 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 |
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