CN108232371A - A kind of additive and application for being used to improve aluminium-air cell particle size - Google Patents
A kind of additive and application for being used to improve aluminium-air cell particle size Download PDFInfo
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- CN108232371A CN108232371A CN201611133611.9A CN201611133611A CN108232371A CN 108232371 A CN108232371 A CN 108232371A CN 201611133611 A CN201611133611 A CN 201611133611A CN 108232371 A CN108232371 A CN 108232371A
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- aluminium
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/02—Details
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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
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Abstract
The invention discloses a kind of for improving additive and the application of aluminium-air cell particle size, the additive is made of nano aluminium oxide, polyethylene glycol (PEG) and low-carbon alcohols.The polyethylene glycol is made of the polyethylene glycol mixture that the degree of polymerization is 400,600,2000, one or more of 4000, and the low-carbon alcohols are the mixture of one or more of methanol, ethyl alcohol, propyl alcohol.The present invention for improving the additive of aluminium-air cell particle size, have it is of low cost, it is safe, it is environmentally protective the advantages that, and do not influence aluminium-air cell discharge performance.The grain size of the aluminium hydroxide of generation is compared, in the polymer good dispersion as fire retardant with big grain size fire retardant in Nano grade, and mechanical performance is high, and compatibility is good, and flame retardant effect is more excellent.To reducing the raw material and use cost of aluminium-air cell, realize that waste utilization is of great significance.
Description
Technical field
The invention belongs to material preparations, a kind of aluminium-air cell product additive are related in particular to, for improving battery
The grain size of discharging product aluminium hydroxide.
Background technology
Aluminium-sky aluminium hydroxide have it is fire-retardant, eliminate smoke and filling three zones, when burning do not generate pernicious gas, therefore wide
It is general to be applied in the plastics and rubber such as electric wire, daily necessities construction material, transport.However aluminium hydroxide must be in high filler loading capacity
It can be only achieved preferable flame retardant effect when (more than 40%), but make the processing fluidity and physics of high molecular material after a large amount of fillings
Mechanical performance declines.Solve the problems, such as this, most efficient method is exactly to reduce grain size, prepares ultra micro of the grain size below 1 μm
Thin aluminium hydroxide to improve its dispersibility in high molecular material, improves mechanical performance.
In discharge process, with the gradual saturation of aluminate ion concentration in solution, a large amount of hydrogen can be precipitated in aluminium-air cell
Precipitation of alumina, the generation of precipitation can all adversely affect battery electrolyte management and battery performance, so as to constrain aluminium-
The commercial applications of air cell.
By adding in precipitation additives, improve the grain size for the precipitation that aluminium-air cell discharge process generates, and in time will be heavy
Shallow lake is separated, and can not only keep the good discharge performance of battery, and the precipitation of generation also has a vast market application, favorably
In reducing aluminium-air cell raw material and use cost, refuse reclamation is realized.Therefore research significance of the present invention is great.
Invention content
The purpose of the present invention is to provide a kind of aluminium-air cell product additives, it is intended to improve product aluminium hydroxide
Grain size reaches Nano grade, to meet market application, reduces battery cost.Wherein nano aluminium oxide rises as crystal seed
To the effect for promoting aluminum hydroxide precipitation.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of additive for being used to improve aluminium-air cell particle size, including nano aluminium oxide, polyethylene glycol and low-carbon
Alcohol；The low-carbon alcohols are the mixed alcohol of one or more of methanol, ethyl alcohol, propyl alcohol；It is nano oxidized in the additive
The mass ratio of aluminium, polyethylene glycol and low-carbon alcohols is (0.01~0.1):(0.1~15):(10~25).
The mass ratio of nano aluminium oxide, polyethylene glycol and low-carbon alcohols is (0.01~0.05) in the additive:(0.5-
5):(12~21).
The grain size of the aluminium oxide is 30nm-100nm；The degree of polymerization of the polyethylene glycol is 400-4000.
Addition manner of the additive in aluminium-air cell electrolyte for aluminium-air cell electric discharge before, discharge process
In or electric discharge after one or more.
Mass content of the nano aluminium oxide in electrolyte is 0.01~0.1% in the additive, and polyethylene glycol is in electricity
It is 0.1%~15% to solve the mass content in liquid, and mass content of the low-carbon alcohols in electrolyte is 10%~25%.
Nano aluminium oxide mass content in electrolyte is preferably 0.01%~0.05% in the additive, polyethylene glycol
Mass content in electrolyte is preferably 0.5%~5%, and mass content of the low-carbon alcohols in electrolyte be preferably 12%~
21%.
Nano aluminium oxide too high levels can influence the content of aluminium hydroxide, and cause particle agglomeration phenomenon；Nano aluminium oxide
The too low effect for not having crystal seed of content.The too high levels of polyethylene glycol can cause solution viscosity to increase, and precipitate bad dispersibility；It is poly-
Ethylene glycol content is too low, does not have the effect for improving particle size.And if low-carbon alcohols too high levels, solution conductivity can be reduced
Rate influences heavy-current discharge performance；Content is too low, then does not have the effect for improving grain size.Nano aluminium oxide in the additive
Mass content in the electrolytic solution is preferably 0.01%~0.05%, and the mass content of polyethylene glycol is preferably 0.5%~5%,
The mass content of low-carbon alcohols is preferably 12%~21%.
The electrolyte solution is 4M NaOH sodium hydrate aqueous solutions before battery discharge；The addition side of the additive
Formula is before aluminium-air cell electric discharge, the one or more in discharge process or after electric discharge.
The preparation method of the aluminium-air cell additive, includes the following steps,
(1) nano aluminium oxide, polyethylene glycol and low-carbon alcohols are uniformly mixed obtained additive by certain mass ratio.
(2) additive obtained by step (1) is added in alkaline electrolyte solution so that the quality of nano aluminium oxide accounts for electrolysis
The 0.01~0.1% of liquid quality；The quality of polyethylene glycol accounts for the 0.1~15% of electrolyte quality；The mass content of low-carbon alcohols accounts for
The 10%~25% of electrolyte quality.
Aluminium-air cell is by high-purity aluminium anodes, air cathode, alkaline electrolyte, cell reaction room, electrolyte storage tank group
Into.
In the aluminium-air cell discharge process, electrolyte is driven by peristaltic pump and carries out electrolyte cycle, the purpose of cycle
It is：
(1) promote scattering and disappearing for discharge process heat, prevent reaction indoor temperature excessively high, irreversible damage is caused to cathode；
(2) ensure that temperature keeps stablizing in battery discharge procedure.
Start aluminium-air cell to discharge, electric discharge products therefrom is aluminium hydroxide, and grain size is between 100-300nm.
The products therefrom that discharges is neutrality to its cleaning solution pH by way of vacuum pump suction filtration, is placed in 80 DEG C of vacuum condition dryings
48h is obtained.Drying time is too short, does not have the effect being completely dried；Drying time is long, and product grain is easily reunited, and leads to grain
Diameter is unevenly distributed.
In conclusion beneficial effects of the present invention include：
The additive for being used to improve aluminium-air cell particle size of the present invention, is conducive to the grain for making product aluminium hydroxide
Diameter is evenly distributed, tiny, and purity is higher, has high purity aluminium hydroxide market application potential.It is studied, is expected to by this item purpose
Aluminium/air cell product economic value added is significantly increased from full industrial chain angle, reduces battery use cost, opens up aluminium/air
The completely new business application pattern of fuel cell.Thus with great research significance and application value.
Description of the drawings
Fig. 1 is aluminium-air cell structure diagram；
1 is electrolyte outlet in cell reaction room in figure, and 5 is click also import in reative cell, 3 be electrolyte storage tank, and 4 are
Storage tank electrolyte inside exports, and 2 be the air cathode that Ag is catalyst, flat with high-purity aluminium anodes 6 respectively on reative cell side wall
Row is placed.
Fig. 2 is aluminium-air cell structure schematic cross-sectional view；
Electrolyte is flowed out from 1 hole in discharge process in figure, and high-purity aluminium anodes 6 carries out oxidation reaction, and oxygen passes through in air
2 diffusion layer of air cathode enters reative cell, and reduction reaction is carried out in oxygen, electrolyte, catalyst three phase boundary.
Fig. 3 is the particle size distribution figure of products therefrom aluminium hydroxide in embodiment 1.
Fig. 4 is the particle size distribution figure of products therefrom aluminium hydroxide in embodiment 2.
Fig. 5 is the particle size distribution figure of products therefrom in comparative example.
Fig. 6 is the XRD spectra of 1 products therefrom aluminium hydroxide of embodiment.
Specific embodiment
The present invention will be further described below in conjunction with the accompanying drawings.
Embodiment 1：
70mL 4M NaOH solutions are taken as electrolyte, add in quantitative nothing before aluminium-air cell exoelectrical reaction at room temperature
Machine nano aluminium oxide, PEG400 and ethyl alcohol are simultaneously uniformly mixed, and the mass fraction for making inorganic nano aluminium oxide in electrolyte is
The mass fraction of 0.1%, PEG400 are 1%, and the mass fraction of ethyl alcohol is for 10% to get electrolyte used in battery discharge.Aluminium-sky
Pneumoelectric pond connection peristaltic pump carries out electrolyte cycle, starts aluminium-air cell and carries out constant current discharge, battery discharge current density
For 100mA/cm2, electrolyte temperature maintains 33 ± 2 DEG C in discharge process, after electric discharge at the sealing ageing of gained electrolyte
Reason, vacuum pump filter to obtain white precipitate, and 80 DEG C of vacuum drying 48h are up to product aluminium hydroxide.It will be appreciated from fig. 6 that product is single
Aluminium hydroxide, purity are higher.Compared with comparative example granularity, it is known that product characteristics are largely improved, and average particle size is less than
Originally 1/3, particle size distribution is also more uniform.Understand that additive therefor is conducive to the improvement of product particle size.
Comparative example：
70mL 4M NaOH solutions are taken as electrolyte, aluminium-air cell connection peristaltic pump carries out electrolyte cycle, starts
Aluminium-air cell carries out constant current discharge, and battery discharge current density is 100mA/cm2, electrolyte temperature is tieed up in discharge process
It holds at 33 ± 2 DEG C, gained electrolyte sealing ripening, vacuum pump filter to obtain white precipitate after electric discharge, and 80 DEG C of vacuum are done
Dry 48h is up to product aluminium hydroxide.As shown in Figure 5, in the case of no additive, product particle size is larger and is unevenly distributed
It is even.
Embodiment 2：
70mL 4M NaOH solutions are taken as electrolyte, add in quantitative nothing before aluminium-air cell exoelectrical reaction at room temperature
Machine nano aluminium oxide, PEG400 and ethyl alcohol are simultaneously uniformly mixed, and the mass fraction for making inorganic nano aluminium oxide in electrolyte is
The mass fraction of 0.05%, PEG600 are 0.1%, and the mass fraction of ethyl alcohol is for 5% to get electrolyte used in battery discharge.Aluminium-
Air cell connection peristaltic pump carries out electrolyte cycle, starts aluminium-air cell and carries out constant current discharge, battery discharge current is close
It spends for 100mA/cm2, electrolyte temperature maintains 33 ± 2 DEG C in discharge process, gained electrolyte sealing ageing after electric discharge
Processing, vacuum pump filter to obtain white precipitate, and 80 DEG C of vacuum drying 48h are up to product aluminium hydroxide.Compared with comparative example granularity, add
Add the presence of agent product particle size is made largely to be improved, average particle size becomes original 1/3 or so, particle size distribution
More uniformly.
Embodiment 3：
70mL 4M NaOH solutions are taken as electrolyte, add in quantitative nothing before aluminium-air cell exoelectrical reaction at room temperature
Machine nano aluminium oxide, PEG2000 and ethyl alcohol are simultaneously uniformly mixed, and the mass fraction for making inorganic nano aluminium oxide in electrolyte is
The mass fraction of 0.08%, PEG2000 are 10%, and the mass fraction of ethyl alcohol is for 10% to get electrolyte used in battery discharge.
Aluminium-air cell connection peristaltic pump carries out electrolyte cycle, starts aluminium-air cell and carries out constant current discharge, battery discharge electricity
Current density is 100mA/cm2, electrolyte temperature maintains 33 ± 2 DEG C in discharge process, gained electrolyte sealing after electric discharge
Ripening, vacuum pump filter to obtain white precipitate, and 80 DEG C of vacuum drying 48h are up to product aluminium hydroxide.The result shows that additive
Presence so that product particle size is smaller, particle size distribution also more uniformly.
Embodiment 4：
70mL 4M NaOH solutions are taken as electrolyte, add in quantitative nothing before aluminium-air cell exoelectrical reaction at room temperature
Machine nano aluminium oxide, PEG4000 and ethyl alcohol are simultaneously uniformly mixed, and the mass fraction for making inorganic nano aluminium oxide in electrolyte is
The mass fraction of 0.03%, PEG4000 are 5%, and the mass fraction of ethyl alcohol is for 15% to get electrolyte used in battery discharge.Aluminium-
Air cell connection peristaltic pump carries out electrolyte cycle, starts aluminium-air cell and carries out constant current discharge, battery discharge current is close
It spends for 100mA/cm2, electrolyte temperature maintains 33 ± 2 DEG C in discharge process, gained electrolyte sealing ageing after electric discharge
Processing, vacuum pump filter to obtain white precipitate, and 80 DEG C of vacuum drying 48h are up to product aluminium hydroxide.The result shows that additive is deposited
Causing product particle size smaller, particle size distribution is also more uniform.
Claims (6)
1. a kind of additive for being used to improve aluminium-air cell particle size, it is characterised in that：Including nano aluminium oxide, poly- second
Glycol and low-carbon alcohols；The low-carbon alcohols are the mixed alcohol of one or more of methanol, ethyl alcohol, propyl alcohol；The additive
The mass ratio of middle nano aluminium oxide, polyethylene glycol and low-carbon alcohols is (0.01~0.1):(0.1~15):(10~25).
2. additive as described in claim 1, it is characterised in that：Nano aluminium oxide, polyethylene glycol and low-carbon in the additive
The mass ratio of alcohol is (0.01~0.05):(0.5-5):(12~21).
3. additive as claimed in claim 1 or 2, it is characterised in that：The grain size of the aluminium oxide is 30nm-100nm；It is described poly-
The degree of polymerization of ethylene glycol is 400-4000.
4. a kind of application of any additives of claim 1-3 in aluminium-air cell, it is characterised in that：The addition
Addition manner of the agent in aluminium-air cell electrolyte is before aluminium-air cell electric discharge, in discharge process or after electric discharge
It is one or more kinds of.
5. application of the additive as claimed in claim 4 in aluminium-air cell, it is characterised in that：Nanometer in the additive
Mass content of the aluminium oxide in electrolyte is 0.01~0.1%, mass content of the polyethylene glycol in electrolyte for 0.1%~
15%, mass content of the low-carbon alcohols in electrolyte is 10%~25%.
6. application of the additive as claimed in claim 5 in aluminium-air cell, it is characterised in that：Nanometer in the additive
Aluminium oxide mass content in electrolyte is preferably 0.01%~0.05%, and mass content of the polyethylene glycol in electrolyte is preferred
It is 0.5%~5%, mass content of the low-carbon alcohols in electrolyte is preferably 12%~21%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611133611.9A CN108232371B (en) | 2016-12-10 | 2016-12-10 | A kind of additive and application for improving aluminium-air cell particle size |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611133611.9A CN108232371B (en) | 2016-12-10 | 2016-12-10 | A kind of additive and application for improving aluminium-air cell particle size |
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| CN108232371B CN108232371B (en) | 2019-10-11 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150143289A (en) * | 2014-06-13 | 2015-12-23 | 주식회사 엘지화학 | Separator for metal air battery, metal air battery including the same, manufacturing method of separator for metal air battery and manufacturing method of metal air battery |
| CN105720327A (en) * | 2016-02-16 | 2016-06-29 | 上海电力学院 | Aluminum-air battery electrolyte compound additive and aluminum-air battery electrolyte and preparation method of aluminum-air battery electrolyte |
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2016
- 2016-12-10 CN CN201611133611.9A patent/CN108232371B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150143289A (en) * | 2014-06-13 | 2015-12-23 | 주식회사 엘지화학 | Separator for metal air battery, metal air battery including the same, manufacturing method of separator for metal air battery and manufacturing method of metal air battery |
| CN105720327A (en) * | 2016-02-16 | 2016-06-29 | 上海电力学院 | Aluminum-air battery electrolyte compound additive and aluminum-air battery electrolyte and preparation method of aluminum-air battery electrolyte |
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