CN102456939A - Improved large-capacity magnesium air battery - Google Patents
Improved large-capacity magnesium air battery Download PDFInfo
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- CN102456939A CN102456939A CN2011100017920A CN201110001792A CN102456939A CN 102456939 A CN102456939 A CN 102456939A CN 2011100017920 A CN2011100017920 A CN 2011100017920A CN 201110001792 A CN201110001792 A CN 201110001792A CN 102456939 A CN102456939 A CN 102456939A
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- electrolyte
- battery
- air battery
- cathode
- storage tank
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 35
- 239000011777 magnesium Substances 0.000 title claims abstract description 35
- 239000003792 electrolyte Substances 0.000 claims abstract description 72
- 238000001816 cooling Methods 0.000 claims abstract description 9
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 5
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 239000002893 slag Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 239000000446 fuel Substances 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 description 8
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 7
- 239000000347 magnesium hydroxide Substances 0.000 description 7
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910000861 Mg alloy Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003818 cinder Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 phthalocyanine transition metal Chemical class 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 241000251729 Elasmobranchii Species 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Y02E60/128—
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- Hybrid Cells (AREA)
Abstract
The invention relates to an improved high-capacity magnesium air battery, which belongs to the technical field of fuel cells and comprises a cathode, an anode and electrolyte, and is characterized in that the cathode is a polymerized phthalocyanine transition metal ion complex cathode, an external circulating electrolyte circulation pipeline is arranged corresponding to the electrolyte, a circulating power pump, a cooling heat exchanger and a purifier are arranged on the electrolyte circulation pipeline, an electrolyte storage tank is also connected on the electrolyte circulation pipeline, and a power pump is additionally arranged on a connecting pipeline between an inlet and an outlet of the electrolyte storage tank. Not only solves the problem of precipitation in the electrolyte, but also solves the problem of temperature rise in the use process of the battery, and is economic and safe.
Description
Technical Field
The invention relates to an improved large-capacity magnesium air battery, belonging to the technical field of fuel cells.
Background
In the present day that the environmental protection consciousness is increasingly enhanced and the sustainable development is more and more emphasized, the electric automobile is emphasized by people for its cleanness and environmental protection. However, since the development of power batteries is delayed, the power batteries become the bottleneck of the development of electric vehicles, and the research of metal air batteries as vehicle batteries is regarded as important [ maozong et al, power technology, 1996,20 (6): 252-266]. In addition, when a disaster occurs in a local area, for example, a natural disaster such as an earthquake, storm, frost, flood, etc., power is interrupted, and a high-power emergency power supply is required. Therefore, the development and research of the high-power magnesium air battery not only can drive the development of the battery industry, but also can drive the development of the industries such as electric vehicles, electronic products and the like, and generate good economic benefits, and has important significance on environmental protection, emergency and disaster relief, communication, military, civil use and other national strategic requirements [ populus, humble and the like, power technology, 2005, 29 (3): 182-186].
The magnesium alloy air fuel cell (magnesium air cell for short) is an electrochemical power generation device which can directly and continuously convert the chemical energy in magnesium alloy and oxygen (from air) into electric energy, and has the characteristics of high specific energy, rich raw material sources, low cost, safe and convenient use, no pollution and the like. As a high-energy chemical power supply, the power supply can be used for power supplies for electric vehicles, power supplies for movable electronic equipment, power supplies for autonomous submerging devices, emergency standby power supplies and the like. It can replace traditional power sources such as zinc-manganese battery, lead-acid battery, cadmium-nickel battery, etc. and can meet the requirement of power source in the process of research and development of electric vehicles.
The structure of a common magnesium air battery is that an anode adopts magnesium alloy, an electrolyte adopts NaCl solution, a cathode adopts a gas diffusion electrode, an oxygen reduction reaction part is a gas-solid-liquid three-phase system on the surface of a catalyst, and a smooth gas transmission channel, an electron transmission channel and a hydroxyl ion transmission channel are required. The whole gas diffusion electrode is required to be waterproof and breathable. The problem that the prior disposable batteries such as torpedoes and the like need to be considered is relatively simple. The non-disposable battery, the ordinary magnesium air battery, requires to change the electrolyte after the discharge is completed, and to clean the electrode to remove the flocculent precipitate of the product magnesium hydroxide of the electrode reaction, which brings inconvenience to the operator of the battery and is not beneficial to recycling the product magnesium hydroxide and causes environmental pollution. In addition, the temperature of the battery is increased when the battery discharges at high power for a long time, the corrosion action of the anode is enhanced due to the increase of the temperature of the battery, the hydrogen evolution reaction is intensified, the utilization rate of the magnesium alloy of the anode is influenced, and potential safety hazards are caused by the hydrogen evolved by the anode. Therefore, the above problems of the magnesium air battery are key technical problems which must be solved for the magnesium air battery for electric vehicles or large capacity.
Disclosure of Invention
The invention aims to provide an improved large-capacity magnesium air battery, which not only solves the problem of precipitation in electrolyte, but also solves the problem of temperature rise in the using process of the battery, and is economical and safe.
The improved high-capacity magnesium air battery comprises a cathode, an anode and electrolyte, and is characterized in that the cathode is a polymerized phthalocyanine transition metal ion complex cathode, an external circulating electrolyte circulating pipeline is arranged corresponding to the electrolyte, and a circulating power pump, a cooling heat exchanger and a purifier are arranged on the electrolyte circulating pipeline.
An electrolyte storage tank is connected to the electrolyte circulation pipeline, and a power pump is additionally arranged on a connecting pipeline between the inlet and the outlet of the electrolyte storage tank.
The clarifier can be the flocculator, at this moment, can connect the settlement equipment in the low reaches of flocculator, and the bottom of settling equipment is equipped with row cinder notch, and the export of settling equipment communicates the electrolyte holding vessel.
The purifier may also be an adsorption filter.
The cooling heat exchanger, the flocculator, the settling device, the electrolyte storage tank, the adsorption filter and the circulating power pump are all common devices or devices in the existing industry, the power pump and the circulating power pump can be different or the same, and the names are different and are convenient for description.
Compared with the prior art, the invention has the following beneficial effects:
(1) Through the setting of electrolyte extrinsic cycle, can be used to getting rid of the positive pole deposit and the regeneration of magnesium, solved the positive pole deposit and adsorbed electrode surface, or formed the flocculus in electrolyte, increased the demand of battery to water, influenced the problem of battery performance. In addition, the recycling of the anode electrode sediment and the regeneration of magnesium not only can solve the problem of environmental pollution, but also can recycle magnesium resources, thereby solving the problem of reasonable utilization of the resources, and being economic and environment-friendly.
(2) And the water in the electrolyte is timely replenished through the electrolyte storage tank, so that the water management problem of the battery system is solved.
(3) The electrolyte cools the heat exchanger, can adjust the temperature of the battery, solve the problem that the anode hydrogen evolution is accelerated due to the rise of the temperature of the battery in the long-time operation process of the battery, the use efficiency of the anode is influenced, the potential safety hazard caused by a large amount of hydrogen evolution is avoided, and the corrosion of the anode material is aggravated when the temperature of the battery rises. The battery is safe and environment-friendly, and the problem of thermal management in the long-term operation process of the battery is solved.
(4) When the battery is not used for a long time, the electrolyte in the battery can be pumped into the electrolyte storage tank, so that the battery can be prevented from automatically discharging or anode corrosion. The service life of the battery can be prolonged. When the battery is started, the electrolyte can be added into the battery by opening the valve, and the battery can start to work, so that the operation is convenient.
(5) The polymerized phthalocyanine transition metal complex has the advantages of simple synthesis process, easily obtained raw materials, low cost, high catalytic activity, good selectivity and long service life. The cathode adopts the polymerized phthalocyanine transition metal complex, so that the performance of the battery can be improved, and the cost can be reduced.
Drawings
Fig. 1 is a schematic structural diagram of embodiment 1 of the present invention.
Fig. 2 is a schematic structural diagram of embodiment 2 of the present invention.
In the figure: 1. the device comprises a magnesium air battery 2, a cooling heat exchanger 3, a flocculator 4, a settling device 5, an electrolyte storage tank 6, an adsorption filter A, an anode B, a cathode a, a circulating power pump B and a power pump.
Detailed Description
The invention is further explained below with reference to the drawings of the embodiments.
As shown in fig. 1, the improved high-capacity magnesium air battery of the present invention comprises a cathode B, an anode a and an electrolyte, wherein the cathode B is a polymeric phthalocyanine transition metal ion complex cathode, an external circulation electrolyte circulation pipeline is arranged corresponding to the electrolyte, and a circulation power pump a, a cooling heat exchanger 2 and a purifier are arranged on the electrolyte circulation pipeline.
An electrolyte storage tank 5 is further connected to the electrolyte circulation pipeline, and a power pump b is additionally arranged on a connecting pipeline between an inlet and an outlet of the electrolyte storage tank 5.
The clarifier is flocculator 3, and the downstream of flocculator 3 is connected and is subsided equipment 4, and the bottom of subsiding equipment 4 is equipped with row cinder notch, and the export of subsiding equipment 4 communicates electrolyte holding vessel 5.
The scheme constitutes a flocculation and sedimentation method. The process is as follows:
in the magnesium air battery 1, after the electrolyte containing the magnesium hydroxide flocculent precipitate is reacted for a period of time and is cooled in the cooling heat exchanger 2 through the circulating power pump a, the electrolyte enters the flocculator 3, flocculent precipitate particles in the flocculator 3 are enlarged, then the electrolyte enters the settling equipment 4, solid particles are settled and separated from the electrolyte, the precipitate is discharged through a slag discharge port at the bottom of the settling equipment 4, and supernatant is pumped into the magnesium air battery 1 through the power pump b. If a shortage of electrolyte is found, it can be replenished through the electrolyte storage tank 5. If the battery is not used for a long time, the electrolyte in the magnesium air battery 1 can be pumped into the electrolyte storage tank 5 by the circulating power pump a for storage, so that the automatic discharge of the battery or the anode corrosion can be prevented, and the service life of the battery is prolonged. When the battery needs to work, the electrolyte in the electrolyte storage tank 5 is added into the magnesium air battery 1.
The advantages are that: the operation is simple, and professional operation is not needed.
The disadvantages are as follows: the removal effect of the magnesium hydroxide precipitate is slightly poor, and the electrolyte is partially lost and needs to be supplemented.
The magnesium air battery is suitable for occasions such as power supplies, movable power supplies and the like, and has good effect on the actual running condition of the magnesium air battery.
As shown in fig. 2, the improved high-capacity magnesium air battery of the present invention includes a cathode B, an anode a and an electrolyte, wherein the cathode B is a polymerized phthalocyanine transition metal ion complex cathode, an external circulation electrolyte circulation pipeline is provided corresponding to the electrolyte, and a circulation power pump a, a cooling heat exchanger 2 and a purifier are provided on the electrolyte circulation pipeline.
An electrolyte storage tank 5 is further connected to the electrolyte circulation pipeline, and a power pump b is additionally arranged on a connecting pipeline between an inlet and an outlet of the electrolyte storage tank 5.
The purifier is an adsorption filter 6.
The scheme forms an adsorption and filtration method, and the flow is as follows:
in the magnesium air battery 1, after the electrolyte which reacts for a period of time and contains flocculent magnesium hydroxide precipitate is cooled by a cooling heat exchanger 2 through a circulating power pump a, the magnesium hydroxide precipitate is removed through an adsorption filter F, and clear liquid is pumped into the magnesium air battery 1 through a power pump b. If a shortage of electrolyte is found, it can be replenished through the electrolyte storage tank 5. If the battery is not used for a long time, the electrolyte in the magnesium air battery can be pumped into the electrolyte storage tank 5 through the power pump a for storage, and when the battery needs to work, the electrolyte is added into the magnesium air battery 1.
The advantages are that: the precipitation removal effect is good, and the electrolyte loss is less.
The disadvantages are that: the magnesium hydroxide precipitate collection is slightly complex, the adsorption material needs to be regenerated, and the operator needs to have certain professional level.
The device is suitable for a fixed power supply, and the actual operation condition of the magnesium air battery has the best effect.
According to the schemes shown in fig. 1 and fig. 2, the operation experiment is performed by using a 5W magnesium air battery, and after the magnesium air battery which is respectively adopting the schemes shown in fig. 1 and fig. 2 and is not added with the electrolyte circulation condition runs for 10 hours, the temperature change and the battery performance stability condition of the magnesium air battery are detected as follows:
1) The embodiment 1 shown in fig. 1 has the battery performance reduced by 12% compared with the initial start-up period while the battery temperature is kept constant.
2) The embodiment 2 as shown in fig. 2, the battery temperature is kept unchanged, and the battery performance is reduced by 5.5% compared with the initial start-up.
3) Without electrolyte circulating system, the temperature of the battery is respectively increased by 12 ℃, and the performance of the battery is reduced by 33.1 percent compared with the initial starting stage.
Claims (4)
1. An improved high-capacity magnesium air battery comprises a cathode, an anode and electrolyte, and is characterized in that the cathode is a polymerized phthalocyanine transition metal ion complex cathode, an external circulating electrolyte circulating pipeline is arranged corresponding to the electrolyte, and a circulating power pump, a cooling heat exchanger and a purifier are arranged on the electrolyte circulating pipeline.
2. The improved magnesium-air battery with large capacity as claimed in claim 1, wherein the electrolyte circulation pipeline is further connected with an electrolyte storage tank, and a power pump is additionally arranged on a connecting pipeline between the inlet and the outlet of the electrolyte storage tank.
3. The improved high-capacity magnesium air battery as claimed in claim 1 or 2, wherein the purifier is a flocculator, a settling device is connected downstream of the flocculator, a slag discharge port is arranged at the bottom of the settling device, and an outlet of the settling device is communicated with the electrolyte storage tank.
4. The improved large capacity magnesium air battery as claimed in claim 1 or 2, wherein the purifier is an adsorption filter.
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CN102456939B CN102456939B (en) | 2013-12-11 |
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Cited By (22)
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CN103296338A (en) * | 2013-06-20 | 2013-09-11 | 北京西区码头商贸有限公司 | Aluminum air fuel cell system |
CN103390771A (en) * | 2013-07-30 | 2013-11-13 | 东莞市杉杉电池材料有限公司 | Battery electrolyte blending system |
CN103855446A (en) * | 2012-11-29 | 2014-06-11 | 中国科学院大连化学物理研究所 | Electrolyte storage box for metal-air cell system |
CN104577033A (en) * | 2014-10-31 | 2015-04-29 | 浙江吉利控股集团有限公司 | Electrolyte filling device of metal fuel battery and filling method thereof |
CN105161796A (en) * | 2015-09-12 | 2015-12-16 | 哈尔滨工业大学 | Aluminum air battery circulating and filtering system and method |
CN106340698A (en) * | 2015-07-08 | 2017-01-18 | 三星电子株式会社 | Metal air battery system and method for operating the same |
CN107017415A (en) * | 2017-03-09 | 2017-08-04 | 桂林恒泰环保科技发展有限公司 | A kind of reaction electricity generation system of water and metal |
CN107836052A (en) * | 2015-05-06 | 2018-03-23 | 阿札咨询有限责任公司 | Zinc-air battery with airlift pump |
CN108075212A (en) * | 2017-12-09 | 2018-05-25 | 合肥伏雷科技有限公司 | A kind of single battery and cell apparatus |
CN108091911A (en) * | 2017-12-09 | 2018-05-29 | 合肥伏雷科技有限公司 | A kind of metal air fuel flow battery with circulated filter system |
CN108110299A (en) * | 2017-12-14 | 2018-06-01 | 中国科学院宁波材料技术与工程研究所 | Metal-air battery device and its temprature control method, metal-air battery system |
CN108106470A (en) * | 2017-11-24 | 2018-06-01 | 上海华普汽车有限公司 | A kind of cooling device and aluminium-air cell |
CN108140920A (en) * | 2015-10-27 | 2018-06-08 | 住友化学株式会社 | Magnesium air electrode for cell and magnesium air battery and aromatic compound and metal complex |
CN108365282A (en) * | 2018-04-25 | 2018-08-03 | 上海交通大学 | Aluminium-air cell recycles and precipitation retracting device |
CN108417835A (en) * | 2018-01-30 | 2018-08-17 | 江西理工大学 | A kind of sandwich layer structure negative material of rare earth phthalocyanine and preparation method thereof |
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CN103296338A (en) * | 2013-06-20 | 2013-09-11 | 北京西区码头商贸有限公司 | Aluminum air fuel cell system |
CN103390771A (en) * | 2013-07-30 | 2013-11-13 | 东莞市杉杉电池材料有限公司 | Battery electrolyte blending system |
CN104577033B (en) * | 2014-10-31 | 2017-09-29 | 浙江吉利控股集团有限公司 | Metal fuel battery electrolyte charging method |
CN104577033A (en) * | 2014-10-31 | 2015-04-29 | 浙江吉利控股集团有限公司 | Electrolyte filling device of metal fuel battery and filling method thereof |
CN107836052A (en) * | 2015-05-06 | 2018-03-23 | 阿札咨询有限责任公司 | Zinc-air battery with airlift pump |
CN106340698A (en) * | 2015-07-08 | 2017-01-18 | 三星电子株式会社 | Metal air battery system and method for operating the same |
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CN108140920A (en) * | 2015-10-27 | 2018-06-08 | 住友化学株式会社 | Magnesium air electrode for cell and magnesium air battery and aromatic compound and metal complex |
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