CN110492178A - A kind of aluminium ion battery electrolyte, battery and application - Google Patents
A kind of aluminium ion battery electrolyte, battery and application Download PDFInfo
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- CN110492178A CN110492178A CN201910783990.3A CN201910783990A CN110492178A CN 110492178 A CN110492178 A CN 110492178A CN 201910783990 A CN201910783990 A CN 201910783990A CN 110492178 A CN110492178 A CN 110492178A
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- ion battery
- electrolyte
- aluminium ion
- cln
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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
-
- 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
- H01M10/0568—Liquid materials characterised by the solutes
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The disclosure belongs to aluminium ion battery technology field, specifically discloses a kind of aluminium ion battery electrolyte, battery and application.Aluminium ion battery is due to having many advantages, such as the favor of good charge-discharge performance, safety in utilization by researcher.It has been recognised by the inventors that aluminium ion battery electrolyte price disclosed in the prior art is costly, and capacitance is lower.In view of the foregoing drawbacks, present disclose provides a kind of aluminium ion battery electrolytes, with AlCl3/C13H22ClN is as electrolyte, and battery is in 25A g‑1Under, charge and discharge can be completed within 13 seconds.Present disclose provides C13H22The research direction of aluminium ion battery exploitation has been expanded in application of the ClN as aluminium ion battery electrolyte.The battery has good charge-discharge performance, and cheap, and more conducively industrial expanded production has good dissemination.
Description
Technical field
The disclosure belongs to aluminium ion battery technology field, and in particular to a kind of aluminium ion battery electrolyte, battery and application.
Background technique
The information for disclosing the background technology part is merely intended to increase the understanding to the general background of the disclosure, without certainty
It is considered as recognizing or implying in any form that information composition has become existing skill well known to persons skilled in the art
Art.
With the raising of social engineering degree, environmental problem is more serious.Such as air pollution, energy consumption, organic
The persistent problems such as pollution, greenhouse effects, the health for seriously hampering social progress, threatening the mankind.In order to cope with above-mentioned ring
Border problem, new energy and energy storage device are increasingly valued by people.Currently, lithium ion battery, Magnesium ion battery, sodium
Ion battery and kalium ion battery etc. are the more deep electrochemical energy storage devices of research in the art.Wherein, due to aluminium reserves
It is abundant, and aluminium ion battery safety is good, cycle performance is superior, three electron redox of high reversible can occur
Reaction, can realize quick charge at higher current densities, be more in line with the modernization demand of people and favored.
Dai Hongjie team has delivered entitled " An ultrafast rechargeable aluminium- on " nature "
Ion battery " research achievement, the battery using foamy graphite as anode, metallic aluminium as cathode, glass fibre as every
Film, electrolyte use AlCl3/ [EMIm] Cl, above-mentioned battery can realize 7500 circle charge and discharge, and one minute fully charged, have good
Charge-discharge performance.It has been recognised by the inventors that above-mentioned aluminium ion battery electrolyte system (AlCl3/ [EMIm] Cl) price costly,
Industrial expanded production higher cost, in addition, also having the shortcomings that battery capacity is low etc..
Summary of the invention
For the studies above background, inventor thinks to develop that a kind of price is cheap and the aluminium ion battery electricity of better performances
Solution liquid has great importance for industrial expanded production.Present disclose provides a kind of aluminium ion battery electrolyte, the electrolysis
Liquid price is cheap, cycle performance of battery is preferable, at higher current densities can preferable charge and discharge, and realize charge and discharge in 13 seconds.
Effect in view of the above technology, the disclosure the following technical schemes are provided:
The disclosure is in a first aspect, provide C13H22ClN (triethyl benzyl ammonia chloride) answering in aluminium ion battery electrolyte
With.
Disclosure second aspect, provides AlCl3/C13H22Application of the ClN as aluminium ion battery electrolyte.
The disclosure third aspect, provides a kind of aluminium ion battery, and the aluminium ion battery includes anode, cathode, electrolyte；
The raw material of the anode includes graphite, PVDF, carbon black；The electrolyte is AlCl3/C13H22ClN；The cathode is 98%-
The aluminium of 99.999% purity.
Preferably, it is described anode the preparation method is as follows: by graphite, PVDF, carbon black mix after be added solvent make its mixing
Slurry uniformly is obtained, on a current collector by slurry coating, obtains anode after dry solvent.
It is further preferred that the graphite, PVDF, carbon black are 7~10:0.8~1.2:0.8~1.2 according to mass ratio
It is mixed.
It is further preferred that the collector is nickel, molybdenum foil；More preferably molybdenum foil.
In some specific embodiments, the molybdenum foil is with a thickness of 12~18 μm.
Preferably, the electrolyte is r=AlCl3/C13H22ClN, wherein r is AlCl3And C13H22The molar ratio of ClN,
And 2.2≤r≤2.6.
The disclosure is studies have shown that AlCl in electrolyte3And C13H22It, can be to battery when the ratio of ClN is adjusted
Performance is adjusted.In above-mentioned molar ratio, the conductivity of the battery can be adjusted within the scope of 450~540 μ S/cm
Section.
Preferably, the electrolyte the preparation method is as follows: by AlCl3And C13H22ClN is placed in atmosphere of inert gases and mixes
It is heated after conjunction, agitated, standing obtains ionic liquid again.
It is further preferred that the heating temperature is 130~150 DEG C.
It is further preferred that the heating time is 0.8~1.2h.
Disclosure fourth aspect provides a kind of button cell, is followed successively by just from anode to cathode direction inside button cell
Pole shell, supporting element, cathode, diaphragm, anode and negative electrode casing.
Preferably, the diaphragm is Whatman glass fibre；It further, is Whatman-934 glass fibre.
Preferably, the anode cover, negative electrode casing material are stainless steel material.
Preferably, the electrolyte content is no less than 15 μ L.
Preferably, the supporting element is spring leaf and steel disc, and the spring leaf is placed in close to negative electrode casing side.
It is further preferred that button cell the preparation method comprises the following steps: anode is placed on negative electrode casing, dripped on positive electrode
Add electrolyte, then is sequentially placed into diaphragm, aluminium foil, steel disc, spring leaf and anode cover, repressed formation button cell.
Compared with prior art, the beneficial effect of the disclosure is:
Present disclose provides a kind of aluminium ion battery electrolytes of function admirable, provide C for the first time13H22ClN is in aluminium ion
Application in battery electrolyte.By adjusting AlCl3/C13H22The ratio of two kinds of ingredients, may be implemented to battery performance in ClN
Adjustment.The electrolyte price is cheap, cycle performance of battery is preferable, can realize charge and discharge in 13 seconds at higher current densities.
Detailed description of the invention
The Figure of description for constituting a part of this disclosure is used to provide further understanding of the disclosure, and the disclosure is shown
Meaning property embodiment and its explanation do not constitute the improper restriction to the disclosure for explaining the disclosure.
Fig. 1 is that the SEM of cell cathode graphite schemes；
Fig. 2 is the Raman spectrum analysis result figure of prepared electrolyte in embodiment 1-3；
Wherein, the Raman spectrum of molar ratio r=2.2 electrolyte is 1. represented.2. representing molar ratio r=2.4 electrolyte
Raman spectrum.3. representing the Raman spectrum of molar ratio r=2.6 electrolyte.
Fig. 3 is the XRD diagram of positive (cathode) material in embodiment 4；
Fig. 4 is the CV curve graph of aluminum cell in embodiment 7；
Fig. 5 is the cyclic curve of aluminum cell；
Fig. 6 is charge and discharge time graph of the aluminum cell under a current density.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the disclosure.Unless another
It indicates, all technical and scientific terms used herein has usual with disclosure person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the disclosure.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
As background technique is introduced, aluminium ion battery has the characteristics that safe and efficient to be favored.In the prior art
Aluminium ion battery cost costly, and battery capacity is lower, is unfavorable for industrial expanded production.Present disclose provides one
Kind aluminium ion battery electrolyte and corresponding aluminium ion battery have cheap and good charge-discharge performance.
In order to enable those skilled in the art can clearly understand the technical solution of the disclosure, below with reference to tool
The technical solution of the disclosure is described in detail in the embodiment and comparative example of body.
The preparation of 1 electrolyte of embodiment
By aluminum trichloride (anhydrous) (AlCl3) and triethyl benzyl ammonia chloride (C13H22ClN) and required glassware (weighs
Bottle, glass bar, soupspoon) it is dried 12 hours at 60 DEG C before the experiments, it is transferred in argon gas glove box later.According to one
Certainty ratio weighs AlCl3And C13H22ClN is mixed in weighing bottle, r=2.4.Weighing bottle is placed in heating plate, heating plate setting
It is 140 DEG C, weighing bottle is placed on magnetic stirring apparatus at the uniform velocity stirs 5min later, removes by heated at constant temperature 1h, stands and arrives room
Temperature obtains curried color shape ionic liquid.
The preparation of 2 electrolyte of embodiment
By aluminum trichloride (anhydrous) (AlCl3) and triethyl benzyl ammonia chloride (C13H22ClN) and some glasswares (weigh
Bottle, glass bar, soupspoon) it is dried 12 hours at 60 DEG C before the experiments, it is transferred in argon gas glove box later.According to one
Certainty ratio weighs AlCl3And C13H22ClN is mixed in weighing bottle, r=2.2.Weighing bottle is placed in heating plate, heating plate setting
It is 130 DEG C, weighing bottle is placed on magnetic stirring apparatus at the uniform velocity stirs 5min later, removes by heated at constant temperature 1.2h, stands and arrives room
Temperature obtains curried color shape ionic liquid.
The preparation of 3 electrolyte of embodiment
By aluminum trichloride (anhydrous) (AlCl3) and triethyl benzyl ammonia chloride (C13H22ClN) and some glasswares (weigh
Bottle, glass bar, soupspoon) it is dried 12 hours at 60 DEG C before the experiments, it is transferred in argon gas glove box later.According to one
Certainty ratio weighs AlCl3And C13H22ClN is mixed in weighing bottle, r=2.6.Weighing bottle is placed in heating plate, heating plate setting
It is 150 DEG C, weighing bottle is placed on magnetic stirring apparatus at the uniform velocity stirs 5min later, removes by heated at constant temperature 0.8h, stands and arrives room
Temperature obtains curried color shape ionic liquid.
By electrolyte in Raman spectrum analysis embodiment 1-3, as a result as shown in Fig. 2, it can be seen from the figure that above-mentioned reality
Apply electrolyte AlCl in example3/C13H22There are anion AlCl in ClN4 -And Al2Cl7 -, and in molar ratio r=2.4, yin
The maximum intensity of ion.
By adjusting AlCl3And C13H22The molar ratio of ClN, the performance for testing electrolyte are as shown in table 1 below.
1 different mol ratio electrolyte property table of table
The preparation of 4 positive electrode of embodiment
Graphite, PVDF and carbon black are mixed according to the ratio of mass ratio 8:1:1, NMP is added dropwise as solvent, stirs 24 hours
It is uniformly mixed slurry, slurry is coated on molybdenum foil (99%, 15 μ m-thicks), 60 DEG C keep the temperature 12 hours, sweep away on Lamination mould
The disk of diameter 14mm is as aluminium ion anode.
As shown in figure 3, as can be seen that being compared with initial cathode sheets, the yin that charge and discharge second are enclosed from the XRD diagram of the material
The peak intensity variation of pole piece illustrates the AlCl in charge and discharge process4 -Insertion and deintercalation cause the structure change of graphite cathode,
To demonstrate aluminum cell with AlCl3/C13H22Mechanism of electrochemical behaviors of anhydrous when ClN is electrolyte charge and discharge.
The preparation of 5 positive electrode of embodiment
Graphite, PVDF and carbon black are mixed according to the ratio of mass ratio 7:0.8:0.8, NMP is added dropwise as solvent, stirring 24
Hour is uniformly mixed slurry, and slurry is coated on molybdenum foil (99%, 12 μ m-thicks), and 55 DEG C keep the temperature 10 hours, on Lamination mould
The disk of diameter 14mm is swept away as aluminium ion anode.
The preparation of 6 positive electrode of embodiment
Graphite, PVDF and carbon black are mixed according to the ratio of mass ratio 10:1.2:1.2, NMP is added dropwise as solvent, stirring
It is uniformly mixed slurry, slurry is coated on molybdenum foil (99%, 18 μ m-thicks), 65 DEG C keep the temperature 14 hours, in Lamination mould
On sweep away the disk of diameter 14mm as aluminium ion anode.
The assembling of 7 battery of embodiment
Assemble 2025 model button cells in argon gas glove box, button cell internal structure from anode to cathode direction according to
Secondary is anode cover, spring leaf, steel disc, aluminium foil, diaphragm (Whatman-934), anode and negative electrode casing.Anode is placed in cathode
On shell, the electrolyte of 15 μ L is added dropwise on positive electrode, then is sequentially placed into diaphragm, aluminium foil, steel disc, spring leaf and anode cover, In
Compression moulding on mold.
As shown in figure 4, wherein the CV curve of molybdenum collector is horizontal line, without redox peaks, illustrate that aluminum cell is filling
In discharge process, molybdenum is not involved in reaction, illustrates that molybdenum is suitable as the collector of aluminum cell.The CV curve of aluminum cell is it can be concluded that two
A oxidation peak (1.53-2.08V, 2.21-2.40V) and corresponding two reduction peaks (1.15-1.53V, 1.71-2.01V).
As shown in figure 5, in current density 5A g-1Under, with AlCl3/C13H22ClN is that the aluminum cell of electrolyte can obtain
117mA h g-1Specific capacity.
As shown in fig. 6, battery is in 25A g-1Under, charge and discharge can be completed within 13 seconds.
The foregoing is merely preferred embodiment of the present disclosure, are not limited to the disclosure, for the skill of this field
For art personnel, the disclosure can have various modifications and variations.It is all within the spirit and principle of the disclosure, it is made any to repair
Change, equivalent replacement, improvement etc., should be included within the protection scope of the disclosure.
Claims (10)
1.C13H22Application of the ClN in aluminium ion battery electrolyte.
2.AlCl3/C13H22Application of the ClN as aluminium ion battery electrolyte.
3. a kind of aluminium ion battery, which is characterized in that the aluminium ion battery includes anode, cathode, electrolyte；The anode
Raw material includes graphite, PVDF, carbon black, NMP；The electrolyte is AlCl3/C13H22ClN。
4. aluminium ion battery as claimed in claim 3, which is characterized in that it is described anode the preparation method is as follows: by graphite,
PVDF, carbon black mixing after be added NMP make its be uniformly mixed obtain slurry, by the slurry coating on metal foil, keep the temperature one section
Time obtains the positive electrode；Preferably, the graphite, PVDF, carbon black are 7~10:0.8~1.2 than ratio according to quality:
0.8~1.2 is mixed.
5. aluminium ion battery as claimed in claim 4, which is characterized in that the metal foil is molybdenum foil；Preferably, the molybdenum foil is thick
Degree is 12~18 μm.
6. aluminium ion battery as claimed in claim 3, which is characterized in that the cathode is aluminium.
7. aluminium ion battery as claimed in claim 3, which is characterized in that the electrolyte is r=AlCl3/C13H22ClN, wherein r
It is AlCl3And C13H22The molar ratio of ClN, and 2.2≤r≤2.5.
8. aluminium ion battery as claimed in claim 3, which is characterized in that the electrolyte the preparation method is as follows: by AlCl3With
C13H22ClN is heated after being placed in the interior mixing of atmosphere of inert gases, agitated, standing obtains ionic liquid again.
9. a kind of button cell, which is characterized in that be followed successively by anode cover, support inside button cell from anode to cathode direction
Part, cathode, diaphragm, anode and negative electrode casing.
10. button cell as claimed in claim 9, which is characterized in that the diaphragm is Whatman glass fibre；Or it is described
Anode cover, negative electrode casing material are stainless steel material；Or the electrolyte content is no less than 15 μ L；The supporting element is spring leaf and steel
Piece, the spring leaf are placed in close to negative electrode casing side, further, button cell the preparation method comprises the following steps: anode is placed in
On negative electrode casing, electrolyte is added dropwise on positive electrode, then is sequentially placed into diaphragm, aluminium foil, steel disc, spring leaf and anode cover, through pressing
System forms button cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201910783990.3A CN110492178B (en) | 2019-08-23 | 2019-08-23 | Aluminum ion battery electrolyte, battery and application |
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| CN201910783990.3A CN110492178B (en) | 2019-08-23 | 2019-08-23 | Aluminum ion battery electrolyte, battery and application |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111463414A (en) * | 2020-04-09 | 2020-07-28 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Interlayer material and preparation method and application thereof |
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| CN111463414A (en) * | 2020-04-09 | 2020-07-28 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Interlayer material and preparation method and application thereof |
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