CN105870453A - Electrolyte used for aluminum battery and preparation method thereof - Google Patents
Electrolyte used for aluminum battery and preparation method thereof Download PDFInfo
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- CN105870453A CN105870453A CN201610374615.XA CN201610374615A CN105870453A CN 105870453 A CN105870453 A CN 105870453A CN 201610374615 A CN201610374615 A CN 201610374615A CN 105870453 A CN105870453 A CN 105870453A
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- aluminum
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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 provides an electrolyte used for an aluminum battery and a preparation method thereof. The electrolyte contains 85-90 parts of ionic liquid, 1-3 parts of a dendritic crystal inhibitor, 8.5-11 parts of viscosity modifier, and 0.5-1 part of a corrosion inhibitor. The prepared electrolyte has the characteristics of good high-low-temperature cycling, good heat stability and good electrical conductivity, and the like, meanwhile can be used for simultaneously inhibiting the formation of aluminum dendritic crystal, and is low in cost and suitable for industrial large-scale production.
Description
Technical field
The invention belongs to aluminum cell technical field, more particularly, to a kind of aluminum cell electrolyte and preparation method thereof.
Background technology
Aluminum secondary battery is the electrochmical power source of new generation after lead-acid battery, nickel-cadmium cell, Ni-MH battery and lithium secondary battery.
Aluminum secondary battery compared with other secondary cell systems, have that energy is bigger, cost is lower, weight is lighter, volume is less,
Stable, cost performance more high more environmentally friendly, safer, is the renewable new forms of energy meeting and recycling sustainable development, can
The problem not enough to improve current vapour Vehicular dynamic battery performance.
But owing to aluminum is a kind of active metal, reduction potential is more negative than hydrogen, it is to cannot be carried out charging reduction instead at aluminum saline solution
Should, therefore want to realize the chargeable of aluminum cell, be necessary for solving aluminum cell electrolyte problem, and the composition of electrolyte is also
The cycle performance of aluminum cell, stability, safety are largely fixed it.Aluminum current battery electrolyte includes that aluminium salt is organic
Dissolvent electrolytic solution and aluminum room temperature fused salt system.Wherein aluminum room temperature fused salt is widely studied owing to having more advantages.Aluminum room temperature
Fused salt is to be made up of specific cation and anion, the molten salt system being in a liquid state under room temperature or room temperature condition, the most also by
It is referred to as ionic liquid, has and conduct electricity very well, do not contain the performances such as water, specific heat are big.
Chinese patent CN 104078705B secondary aluminium cell and electrolyte thereof, disclose a kind of non-aqueous containing aluminium electrolyte,
This electrolyte contains anhydrous aluminium salt, ionic liquid and organic solvent, it is achieved that the recharging of aluminum cell, but uses this electrolysis
Secondary aluminium cell cycle performance prepared by matter is poor, and after circulating 50 times, discharge capacity only remains about 50%.
Chinese patent CN101764256B rechargeable aluminum battery and preparation method thereof, discloses a kind of halogen aluminic acid ion
Liquid, this ionic liquid, as aluminum cell electrolyte, improves the capacity of battery, cycle performance and safety, it is achieved that aluminum
The Rechargeability of battery.But the aluminum cell prepared with this electrolyte, after circulating 50 times, capacity have dropped about 20%, as
Using as power aluminum cell, battery capacity is the most not enough.
As the secondary aluminium cell of electrokinetic cell, form aluminum dendrite at higher current densities and easily, can be to the peace of aluminum cell
Quan Xing, cycle life, capacity bring considerable influence, two above patent not to suggest that solution.
Summary of the invention
Present invention is primarily targeted at offer electrolyte that can be used for aluminum cell and preparation method thereof, the aluminum cell electrolysis of preparation
Liquid has that high/low temperature cyclicity is good, Heat stability is good, and the features such as electric conductivity is good can suppress the formation of aluminum dendrite simultaneously, become
Basis is the lowest is suitable to industrialization large-scale production.
For reaching object above, the technical solution used in the present invention is:
The present invention provides a kind of aluminum cell electrolyte, consists of the following composition: ionic liquid 85-90 weight portion, dendrite press down
Preparation 1-3 weight portion, viscosity-controlling agent 8.5-11 weight portion, corrosion inhibiter 0.5-1 weight portion.
Preferably, described ionic liquid is made up of with aluminum halide 3-fluoro-N-alkyl pyridine hydrochlorate, wherein alkyl be isobutyl group,
One in neopentyl, aluminum halide is the one in aluminum chloride, aluminium bromide, 3-fluoro-N-alkyl pyridine hydrochlorate and aluminum halide
Mol ratio is 1:2.3.
Preferably, described dendrite inhibitor is the one in potassium nitrate, thionyl chloride.
Preferably, the one during described viscosity-controlling agent is halogen acid amide.
Preferably, the one during described corrosion inhibiter is fluoro-alkyl ammonium.
Accordingly, the present invention also provides for the preparation method of a kind of aluminum cell electrolyte, comprises the following steps: (1) is lazy
Property gas shield under aluminum halide is slowly added in 3-fluoro-N-alkyl pyridine hydrochlorate according to mol ratio 2.3:1, simultaneously quickly
Stirring, prepares ionic liquid；(2) 8.5-11 weight portion viscosity-controlling agent is added in ionic liquid, depend on after stirring fully
Secondary addition 1-3 weight portion dendrite inhibitor, 0.5-1 weight portion corrosion inhibiter, mix homogeneously, obtain the electrolysis of described aluminum cell
Liquid.
Beneficial effect:
The present invention provides a kind of aluminum cell electrolyte and preparation method thereof, and compared with prior art, the present invention is with the fluoro-N of 3-
Alkyl pyridine hydrochlorate-aluminum halide system ionic liquid is electrolyte main body, has that viscosity is low, fusing point is low, Heat stability is good
Advantage；Add dendrite inhibitor, it is possible to reduce the generation of aluminum dendrite under high current density, improve the circulation of aluminum cell
Performance；Viscosity-controlling agent can regulate the viscosity of electrolyte, is that electrolyte has suitable electrical conductivity；Corrosion inhibiter can be protected
Aluminum electrode, reduces the electrolyte corrosion to aluminum electrode.The aluminum cell electrolyte high/low temperature cyclicity that therefore prepared by the present invention is good,
Heat stability is good, the features such as electric conductivity is good, the formation of aluminum dendrite can be suppressed simultaneously, low cost is suitable to industrialization and gives birth on a large scale
Produce.
Detailed description of the invention
Hereinafter describe and be used for disclosing the present invention so that those skilled in the art are capable of the present invention.Preferred reality in below describing
Execute example and be only used as citing, it may occur to persons skilled in the art that other obvious modification.
The present invention provides a kind of aluminum cell electrolyte, consists of the following composition: ionic liquid 85-90 weight portion, dendrite press down
Preparation 1-3 weight portion, viscosity-controlling agent 8.5-11 weight portion, corrosion inhibiter 0.5-1 weight portion.
Described ionic liquid is made up of with aluminum halide 3-fluoro-N-alkyl pyridine hydrochlorate, and wherein alkyl is isobutyl group, neopentyl
In one, aluminum halide is the one in chlorination, aluminium bromide, and 3-fluoro-N-alkyl pyridine hydrochlorate with aluminum halide mol ratio is
1:2.3.N-alkyl pyridine after fluorine replaces can reduce interionic active force, reduces viscosity and the fusing point of ionic liquid.
Described dendrite inhibitor is the one in potassium nitrate, thionyl chloride, and dendrite inhibitor can destroy aluminum dendritic growth point,
Thus suppress aluminum dendrite to produce, more excellent is chosen as thionyl chloride.
Described viscosity-controlling agent is the one in halogen acid amide, and electrolyte can be made to have certain viscosity, makes ion motion speed
Degree improves, and improves the conductivity of electrolyte, and more excellent is chosen as acetbromamide.
Described corrosion inhibiter is the one in fluoro-alkyl ammonium, hinders electrolyte to aluminum electrode by forming attachment on aluminium electroloysis surface
Corrosion, more excellent is chosen as the fluoro-propylamine of 2-.
Accordingly, the present invention also provides for the preparation method of a kind of aluminum cell electrolyte, comprises the following steps: (1) is lazy
Property gas shield under aluminum halide is slowly added in 3-fluoro-N-alkyl pyridine hydrochlorate according to mol ratio 2.3:1, simultaneously quickly
Stirring, prepares ionic liquid；(2) 8.5-11 weight portion viscosity-controlling agent is added in ionic liquid, depend on after stirring fully
Secondary addition 1-3 weight portion dendrite inhibitor, 0.5-1 weight portion corrosion inhibiter, mix homogeneously, obtain the electrolysis of described aluminum cell
Liquid.
In order to be further appreciated by the present invention, the technical scheme provided the present invention below in conjunction with embodiment is described in detail, this
The protection domain of invention is not limited by the following examples.
Embodiment 1
Various raw material is weighed: ionic liquid 85 weight portion, dendrite inhibitor thionyl chloride according to hereinafter described mass fraction ratio
3 weight portions, viscosity-controlling agent acetbromamide 11 weight portion, corrosion inhibiter 2-fluoro-propylamine 1 weight portion.
Described a kind of aluminum cell preparation method of electrolyte is as follows: (1) under inert gas shielding by aluminum halide according to mol ratio
2.3:1 is slowly added in 3-fluoro-N-alkyl pyridine hydrochlorate, the most quickly stirring, prepares ionic liquid；(2) by 11
Weight portion viscosity-controlling agent adds in ionic liquid, is sequentially added into 3 weight portion dendrite inhibitor, 1 weight portion after stirring fully
Corrosion inhibiter, mix homogeneously, obtain described aluminum cell electrolyte.
Embodiment 2
Various raw material is weighed: ionic liquid 90 weight portion, dendrite inhibitor thionyl chloride according to hereinafter described mass fraction ratio
1 weight portion, viscosity-controlling agent acetbromamide 8.5 weight portion, corrosion inhibiter 2-fluoro-propylamine 0.5 weight portion.
Described a kind of aluminum cell preparation method of electrolyte is as follows: (1) under inert gas shielding by aluminum halide according to mole
It is slowly added in 3-fluoro-N-alkyl pyridine hydrochlorate than 2.3:1, the most quickly stirring, prepares ionic liquid；(2) will
8.5 weight portion viscosity-controlling agents add in ionic liquids, be sequentially added into after stirring fully 1 weight portion dendrite inhibitor, 0.5
Weight portion corrosion inhibiter, mix homogeneously, obtain described aluminum cell electrolyte.
Embodiment 3
Various raw material is weighed: ionic liquid 88 weight portion, dendrite inhibitor thionyl chloride according to hereinafter described mass fraction ratio
2 weight portions, viscosity-controlling agent acetbromamide 9.4 weight portion, corrosion inhibiter 2-fluoro-propylamine 0.6 weight portion.
Described a kind of aluminum cell preparation method of electrolyte is as follows: (1) under inert gas shielding by aluminum halide according to mole
It is slowly added in 3-fluoro-N-alkyl pyridine hydrochlorate than 2.3:1, the most quickly stirring, prepares ionic liquid；(2) will
9.4 weight portion viscosity-controlling agents add in ionic liquids, be sequentially added into after stirring fully 2 weight portion dendrite inhibitor, 0.6
Weight portion corrosion inhibiter, mix homogeneously, obtain described aluminum cell electrolyte.
Using graphene-nickel material is positive pole, alumal be negative pole, PE film be battery diaphragm, vacuum injects embodiment system
Standby electrolyte also encapsulates, and prepares aluminum cell test performance.With graphene-nickel material as positive pole, alumal be negative pole,
PE film is battery diaphragm, and conventional aluminium chlorate ionic liquid is electrolyte, prepared aluminum cell test performance as a comparison case.
Result is as shown in table 1, table 2.
Electrolyte prepared by table 1 embodiment of the present invention 1-3 and-20 DEG C of test results of comparative example performance
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example |
| Discharge-rate | 20C | 20C | 20C | 20C |
| Charging voltage | 4.2V | 4.2V | 4.2V | 4.2V |
| Cycle-index | 3000 times | 3000 times | 3000 times | 3000 times |
| Initial capacity | 1025Amh | 1136Amh | 1094Amh | 629Amh |
| Residual capacity | 1003Amh | 1085Amh | 1038Amh | 358Amh |
Electrolyte property prepared by table 2 embodiment of the present invention 1-3 and 60 DEG C of test results of comparative example
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example |
| Discharge-rate | 20C | 20C | 20C | 20C |
| Charging voltage | 4.2V | 4.2V | 4.2V | 4.2V |
| Cycle-index | 3000 times | 3000 times | 3000 times | 500 times |
| Initial capacity | 1256Amh | 1327Amh | 1284Amh | 684Amh |
| Residual capacity | 1237Amh | 1295Amh | 1261Amh | 371Amh |
From the test result of embodiment 1-3 and comparative example it can be seen that the aluminum cell electrolyte prepared than the present invention with comparative example
Under higher or lower ambient temperature, still there is bigger residual capacity after discharge and recharge 3000 times under high-discharge-rate, have
Preferably high/low temperature cycle performance and initial capacity is high, it is possible to be used as the power battery electrolytes such as electric automobile.
The ultimate principle of the present invention, principal character and advantages of the present invention have more than been shown and described.The technical staff of the industry
It should be appreciated that the present invention is not restricted to the described embodiments, the simply present invention's described in above-described embodiment and description is former
Reason, the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, these changes and improvements
Both fall within the range of claimed invention.The protection domain of application claims is by appending claims and equivalent thereof
Thing defines.
Claims (6)
1. an aluminum cell electrolyte, it is characterised in that consist of the following composition: ionic liquid 85-90 weight portion, dendrite inhibitor 1-3 weight portion, viscosity-controlling agent 8.5-11 weight portion, corrosion inhibiter 0.5-1 weight portion.
Aluminum cell electrolyte the most according to claim 1, it is characterized in that, described ionic liquid is made up of with aluminum halide 3-fluoro-N-alkyl pyridine hydrochlorate, one during wherein alkyl is isobutyl group, neopentyl, aluminum halide is the one in aluminum chloride, aluminium bromide, and 3-fluoro-N-alkyl pyridine hydrochlorate and aluminum halide mol ratio are 1:2.3.
Aluminum cell electrolyte the most according to claim 1, it is characterised in that described dendrite inhibitor is the one in potassium nitrate, thionyl chloride.
Aluminum cell electrolyte the most according to claim 1, it is characterised in that described viscosity-controlling agent is the one in halogen acid amide.
Aluminum cell electrolyte the most according to claim 1, it is characterised in that described corrosion inhibiter is the one in fluoro-alkyl ammonium.
6. a preparation method for aluminum cell electrolyte, comprises the following steps:
(1) under inert gas shielding, aluminum halide is slowly added in 3-fluoro-N-alkyl pyridine hydrochlorate according to mol ratio 2.3:1, the most quickly stirring, prepares ionic liquid；
(2) 8.5-11 weight portion viscosity-controlling agent is added in ionic liquid, be sequentially added into 1-3 weight portion dendrite inhibitor, 0.5-1 weight portion corrosion inhibiter, mix homogeneously after stirring fully, obtain described aluminum cell electrolyte.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610374615.XA CN105870453B (en) | 2016-05-26 | 2016-05-26 | A kind of aluminum cell electrolyte and preparation method thereof |
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| CN201610374615.XA CN105870453B (en) | 2016-05-26 | 2016-05-26 | A kind of aluminum cell electrolyte and preparation method thereof |
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| CN105870453A true CN105870453A (en) | 2016-08-17 |
| CN105870453B CN105870453B (en) | 2019-01-29 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109560250A (en) * | 2017-09-27 | 2019-04-02 | 财团法人工业技术研究院 | Electrode, method of manufacturing the same, and device including the same |
| CN110400970A (en) * | 2019-06-04 | 2019-11-01 | 江西力能新能源科技有限公司 | A kind of electrolyte and its application in High Temperature Lithium Cell |
| CN111261946A (en) * | 2018-11-30 | 2020-06-09 | 浙江大学 | Aluminum ion battery electrolyte solution and battery |
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| CN1973397A (en) * | 2004-04-20 | 2007-05-30 | 德古萨公司 | Electrolyte composition in addition to the use thereof as an electrolyte material for electrochemical energy storage systems |
| CN103633396A (en) * | 2013-07-31 | 2014-03-12 | 河南科技大学 | Electrolyte corrosion inhibitor for aluminum-air cell, electrolyte and preparation method |
| CN104078680A (en) * | 2014-05-23 | 2014-10-01 | 南京中储新能源有限公司 | Carbon-sulfur composite positive electrode and secondary aluminium-sulfur battery |
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2016
- 2016-05-26 CN CN201610374615.XA patent/CN105870453B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1973397A (en) * | 2004-04-20 | 2007-05-30 | 德古萨公司 | Electrolyte composition in addition to the use thereof as an electrolyte material for electrochemical energy storage systems |
| CN103633396A (en) * | 2013-07-31 | 2014-03-12 | 河南科技大学 | Electrolyte corrosion inhibitor for aluminum-air cell, electrolyte and preparation method |
| CN104078680A (en) * | 2014-05-23 | 2014-10-01 | 南京中储新能源有限公司 | Carbon-sulfur composite positive electrode and secondary aluminium-sulfur battery |
Non-Patent Citations (1)
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| 桂长清等: "《实用蓄电池手册》", 31 January 2011, 机械工业出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109560250A (en) * | 2017-09-27 | 2019-04-02 | 财团法人工业技术研究院 | Electrode, method of manufacturing the same, and device including the same |
| CN111261946A (en) * | 2018-11-30 | 2020-06-09 | 浙江大学 | Aluminum ion battery electrolyte solution and battery |
| CN111261946B (en) * | 2018-11-30 | 2021-08-06 | 浙江大学 | Aluminum ion battery electrolyte solution and battery |
| CN110400970A (en) * | 2019-06-04 | 2019-11-01 | 江西力能新能源科技有限公司 | A kind of electrolyte and its application in High Temperature Lithium Cell |
| CN110400970B (en) * | 2019-06-04 | 2023-09-05 | 江西力能新能源科技有限公司 | Electrolyte material and application thereof in high-temperature lithium battery |
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