CN108232371B - A kind of additive and application for improving aluminium-air cell particle size - Google Patents

A kind of additive and application for improving aluminium-air cell particle size Download PDF

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CN108232371B
CN108232371B CN201611133611.9A CN201611133611A CN108232371B CN 108232371 B CN108232371 B CN 108232371B CN 201611133611 A CN201611133611 A CN 201611133611A CN 108232371 B CN108232371 B CN 108232371B
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aluminium
additive
air cell
electrolyte
low
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CN108232371A (en
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王二东
聂玉娟
孙公权
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • 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
    • 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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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hybrid Cells (AREA)
  • Inert Electrodes (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The additive and application, the additive that the invention discloses a kind of for improving aluminium-air cell particle size are 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 one or more of 400,600,2000,4000, and the low-carbon alcohols are the mixture of one or more of methanol, ethyl alcohol, propyl alcohol.It is of the invention for improving the additive of aluminium-air cell particle size, have it is low in cost, it is highly-safe, it is environmentally protective the advantages that, and do not influence aluminium-air cell discharge performance.The partial size of the aluminium hydroxide of generation is compared in Nano grade, as fire retardant with big partial size fire retardant, in the polymer good dispersion, and mechanical performance is high, and compatibility is good, and flame retardant effect is more excellent.To the raw material and use cost for reducing aluminium-air cell, realize that waste utilization is of great significance.

Description

A kind of additive and application for improving aluminium-air cell particle size
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 partial size of discharging product aluminium hydroxide.
Background technique
Aluminium-sky aluminium hydroxide have it is fire-retardant, eliminate smoke and filling three zones, when burning do not generate pernicious gas, therefore it is wide It is general to be applied in the plastics and rubber product 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 (40% or more), but make the processing fluidity and physics of high molecular material after a large amount of fillings Mechanical performance decline.This problem is solved, most efficient method is exactly to reduce partial size, prepares partial size in 1 μm of ultra micro below Thin aluminium hydroxide improves mechanical performance to improve its dispersibility in high molecular material.
Aluminium-air cell during discharge in solution aluminate ion concentration be gradually saturated, a large amount of hydrogen can be precipitated The generation of precipitation of alumina, precipitating can all adversely affect battery electrolyte management and battery performance, to constrain aluminium- The commercial applications of air cell.
By the way that precipitation additives are added, improve the partial size for the precipitating that aluminium-air cell discharge process generates, and will sink in time Shallow lake is separated, and the good discharge performance of battery can be not only kept, and the precipitating 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.
Summary of the invention
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 Partial 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:
It is a kind of for improving the additive of 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): (0.5- in the additive 5): (12~21).
The partial 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 be 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 Solving the mass content in liquid is 0.1%~15%, 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 will affect 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 will lead to solution viscosity increase, 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 partial 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 solution 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) additive is made than being uniformly mixed by certain mass in nano aluminium oxide, polyethylene glycol and low-carbon alcohols.
(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 At.
In the aluminium-air cell discharge process, electrolyte is driven by peristaltic pump and carries out electrolyte circulation, the purpose of circulation It is:
(1) promote scattering and disappearing for discharge process heat, prevent reaction room temperature excessively high, irreversible damage is caused to cathode；
(2) guarantee that temperature keeps stablizing in battery discharge procedure.
Starting aluminium-air cell discharges, and electric discharge products therefrom is aluminium hydroxide, and partial size is between 100-300nm.
The products therefrom that discharges is neutrality to its cleaning solution pH by way of vacuum pump suction filtration, and it is dry to be placed in 80 DEG C of vacuum conditions 48h is obtained.Drying time is too short, does not have the effect being completely dried；Drying time is too long, and product grain is easy to reunite, leads to grain Diameter is unevenly distributed.
In conclusion the beneficial effect comprise that
The additive for being used to improve aluminium-air cell particle size of the 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.By the research of this project, it is expected to Aluminium/air cell product economic value added is significantly increased from full industrial chain angle, reduces battery operating cost, opens up aluminium/air The completely new business application mode of fuel cell.Thus there is great research significance and application value.
Detailed description of the invention
Fig. 1 is aluminium-air cell structural schematic diagram；
1 is electrolyte outlet in cell reaction room in figure, and 5 is click also import in reaction chamber, 3 be electrolyte storage tank, and 4 are The outlet of storage tank electrolyte inside, 2 be the air cathode that Ag is catalyst, is located on reaction chamber side wall, flat with high-purity aluminium anodes 6 Row is placed.
Fig. 2 is aluminium-air cell schematic structural 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 reaction chamber, carries out reduction reaction 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 with reference to the accompanying drawing.
Embodiment 1:
Taking 70mL 4M NaOH solution is electrolyte, and quantitative nothing is added before aluminium-air cell exoelectrical reaction at room temperature Machine nano aluminium oxide, PEG400 and ethyl alcohol are simultaneously uniformly mixed, and make the mass fraction of inorganic nano aluminium oxide in electrolyte The mass fraction of 0.1%, PEG400 are 1%, and the mass fraction of ethyl alcohol is 10% to get electrolyte used in battery discharge.Aluminium-sky Pneumoelectric pond connects peristaltic pump and carries out electrolyte circulation, and starting aluminium-air cell 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.Know that additive therefor is conducive to the improvement of product particle size.
Comparative example:
Taking 70mL 4M NaOH solution is electrolyte, and aluminium-air cell connects peristaltic pump and carries out electrolyte circulation, starting Aluminium-air cell carries out constant current discharge, and battery discharge current density is 100mA/cm2, electrolyte temperature dimension in discharge process It holds at 33 ± 2 DEG C, gained electrolyte seals ripening after electric discharge, and vacuum pump filters to obtain white precipitate, and 80 DEG C of vacuum are dry Dry 48h is up to product aluminium hydroxide.As shown in Figure 5, in the case where no additive, product particle size is larger and is unevenly distributed It is even.
Embodiment 2:
Taking 70mL 4M NaOH solution is electrolyte, and quantitative nothing is added before aluminium-air cell exoelectrical reaction at room temperature Machine nano aluminium oxide, PEG400 and ethyl alcohol are simultaneously uniformly mixed, and make the mass fraction of inorganic nano aluminium oxide in electrolyte The mass fraction of 0.05%, PEG600 are 0.1%, and the mass fraction of ethyl alcohol is 5% to get electrolyte used in battery discharge.Aluminium- Air cell connects peristaltic pump and carries out electrolyte circulation, and starting aluminium-air cell carries out constant current discharge, and battery discharge current is close Degree is 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 Adding the presence of agent improves product particle size largely, and average particle size becomes original 1/3 or so, particle size distribution It is more uniform.
Embodiment 3:
Taking 70mL 4M NaOH solution is electrolyte, and quantitative nothing is added before aluminium-air cell exoelectrical reaction at room temperature Machine nano aluminium oxide, PEG2000 and ethyl alcohol are simultaneously uniformly mixed, and make the mass fraction of inorganic nano aluminium oxide in electrolyte The mass fraction of 0.08%, PEG2000 are 10%, and the mass fraction of ethyl alcohol is 10% to get electrolyte used in battery discharge. Aluminium-air cell connects peristaltic pump and carries out electrolyte circulation, and starting aluminium-air cell 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 make product particle size smaller, particle size distribution is also more uniform.
Embodiment 4:
Taking 70mL 4M NaOH solution is electrolyte, and quantitative nothing is added before aluminium-air cell exoelectrical reaction at room temperature Machine nano aluminium oxide, PEG4000 and ethyl alcohol are simultaneously uniformly mixed, and make the mass fraction of inorganic nano aluminium oxide in electrolyte The mass fraction of 0.03%, PEG4000 are 5%, and the mass fraction of ethyl alcohol is 15% to get electrolyte used in battery discharge.Aluminium- Air cell connects peristaltic pump and carries out electrolyte circulation, and starting aluminium-air cell carries out constant current discharge, and battery discharge current is close Degree is 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 Making product particle size smaller, particle size distribution is also more uniform.

Claims (6)

1. a kind of for improving the additive of aluminium-air cell particle size, it is characterised in that: including nano aluminium oxide, poly- second Two pure and mild 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 partial 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 additive 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 discharges, 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%, and mass content of the polyethylene glycol in electrolyte is 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 0.01% ~ 0.05%, and mass content of the polyethylene glycol in electrolyte is 0.5% ~ 5%, Mass content of the low-carbon alcohols in electrolyte is 12% ~ 21%.
CN201611133611.9A 2016-12-10 2016-12-10 A kind of additive and application for improving aluminium-air cell particle size Active CN108232371B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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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