CN106558693B - A kind of aluminium ion battery and preparation method thereof based on the anode containing iodine - Google Patents
A kind of aluminium ion battery and preparation method thereof based on the anode containing iodine Download PDFInfo
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- CN106558693B CN106558693B CN201610972497.2A CN201610972497A CN106558693B CN 106558693 B CN106558693 B CN 106558693B CN 201610972497 A CN201610972497 A CN 201610972497A CN 106558693 B CN106558693 B CN 106558693B
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- ion battery
- aluminium ion
- iodine
- anode
- containing iodine
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- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 20
- 239000011630 iodine Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- 239000002585 base Substances 0.000 claims abstract description 13
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002608 ionic liquid Substances 0.000 claims abstract description 12
- FQERWQCDIIMLHB-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CC[NH+]1CN(C)C=C1 FQERWQCDIIMLHB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011888 foil Substances 0.000 claims abstract description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 24
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 239000004020 conductor Substances 0.000 claims description 15
- OKJPEAGHQZHRQV-UHFFFAOYSA-N iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 15
- 239000007774 positive electrode material Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000006245 Carbon black Super-P Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 235000012149 noodles Nutrition 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- 239000006230 acetylene black Substances 0.000 claims 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims 1
- 239000002657 fibrous material Substances 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 230000002441 reversible effect Effects 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000003780 insertion Methods 0.000 abstract description 3
- 230000037431 insertion Effects 0.000 abstract description 3
- 239000011229 interlayer Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000007600 charging Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical group 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229940035535 iodophors Drugs 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of aluminium ion battery and preparation method thereof based on the anode containing iodine, the battery includes anode, cathode, ionic liquid base electrolyte, diaphragm, the described just extremely iodine substance, cathode is high-purity aluminum foil, and ionic liquid base electrolyte is mixed by anhydrous aluminum chloride and 1- ethyl-3-methylimidazole chloride.Reversible chemical reaction can occur in the aluminium ion battery, it is essentially different with the aluminium ion battery that reversible insertion and abjection type occurs in positive electrode interlayer using aluminium ion, used in battery positive electrode is simple and easy to get, only need conventional equipment i.e. implementable, so that the aluminium ion battery can be widely used for all kinds of energy devices.
Description
Technical field
The invention belongs to secondary cell and its preparation fields, are related to the technology of preparing of aluminium ion battery, in particular to a kind of
Aluminium ion battery based on the anode containing iodine and preparation method thereof, the battery are reversible based on aluminium ion and positive active material generation
The secondary ion battery of chemical reaction.
Background technique
As the mankind are increasingly dependent on the various equipment of driven by energy, the rapid reduction of fossil fuel and increasingly serious
Environmental problem, people increasingly pay attention to the exploitation of energy stores and conversion system, and sight is locked lithium ion battery by most people,
Although large-scale commercial applies a very long time to lithium battery, energy density, the power density of lithium ion battery
Etc. performances need to be improved, currently, in terms of the power battery of electric car develop, however, the limitation of lithium resource hinders
Its large-scale application, safety issue limit the further development of lithium ion battery, rise in by the end of August, 2016, Samsung Note7
Nearly 40 explosion accidents occur in the whole world, cell safety problem causes the concern of people again, and development resource is abundant, low in cost
Novel rechargeable battery system, have biggish realistic meaning.
Compared with lithium, aluminium is the most abundant metallic element of content in the earth's crust, at low cost, cheap, in electrochemistry charge and discharge
In electricity reaction, the electron number of transfer is 3, and compared with the lithium ion of single electron, the theoretical specific capacity of aluminium reaches 2980mAh/g,
Second is occupied in all metallic elements, is only second to lithium (3870mAh/g), volume and capacity ratio 8050mAh/cm3, it is current
It is highest in all metal electrode materials, it is used as cell negative electrode material, there are other unrivaled advantages of metal negative electrode material.
On April 6th, 2015, Nature have delivered paper " An of the Dai Hongjie team, Stanford University about aluminium ion battery
The ultrafast rechargeablealuminium-ion battery " team uses grapheme foam as aluminium ion battery
Positive electrode, charging/discharging voltage platform is higher, and close to 2V, cycle performance is excellent, and cycle-index is up to 7500 times, battery tool
The characteristic and overlength cycle life for having fast charging and discharging are however, its actual specific capacity is lower, only 70mAh/g, also, graphite
The preparation process of alkene foam is comparatively laborious, and general laboratory can not meet, and is even more a relatively difficult thing by its industrialization
Feelings.
Chinese patent CN104701541A discloses a kind of WS2Do the aluminium ion battery and preparation method thereof of anode, battery
The WS of use2Layered Structural Positive Electrode Materials show stable cycle performance, and electrochemical window is wider, battery use temperature range
Wider, but its specific discharge capacity is too low, initial discharge specific capacity is the highest specific capacity in cyclic process, and only 20mAh/g.
Chinese patent CN105449271A discloses the aluminium ion secondary cell and its preparation process that a kind of CuS is anode,
CuS is readily synthesized, at low cost, nontoxic, and using CuS material, its first discharge specific capacity is up to 275mAh/g, discharge platform
Up to 1.5V, but entire battery system capacity attenuation is serious, after 16 circulations, capacity attenuation 160mAh/g, capacity is possessed
Rate is only 57%.
Research for room temperature aluminum secondary battery positive electrode, most of is the research of the material based on layer structure, benefit
The insertion and abjection that make aluminium ion reversible in interlayer with its layer structure, but since multivalence aluminium ion is in intercalation/deintercalation
Dynamics is poor, so that reversible charge and discharge become relatively difficult.Therefore, it researches and develops based on the aluminium ion electricity that reversible chemical reaction occurs
Pond has a very important significance the commercial applications for realizing aluminium ion battery.
Summary of the invention
It is an object of the invention to aiming at the shortcomings in the prior art, provide a kind of aluminium ion battery based on the anode containing iodine
And preparation method thereof, which uses the novel anode material that reversible chemical reaction occurs with aluminium ion, realizes aluminium ion battery
High capacity charge and discharge, the preparation process of positive electrode is simple, only needs conventional equipment i.e. implementable, raw materials used cheap and easy to get.
Technical solution: to achieve the above object, the present invention the following technical schemes are provided:
A kind of aluminium ion battery based on the anode containing iodine, include anode, cathode, ionic liquid base electrolyte, diaphragm,
In, described just extremely povidon iodine or iodoform, cathode are high-purity aluminum foil, and ionic liquid base electrolyte is by anhydrous chlorine
Change aluminium and 1- ethyl-3-methylimidazole chloride mixes.
In above-mentioned technical proposal, anhydrous aluminum chloride and 1- ethyl-3-methylimidazole in the ionic liquid base electrolyte
The molar ratio of chloride is 1:1-10:1.
Active material in anode contains iodine, and anode is prepared using load method.
The anode for rolling the acquisition of piece method, raw material containing iodine used are povidon iodine (PVPI), iodoform
(CHI3), one of poly N-vinyl carbazole, the anode raw material containing iodine used of the load method preparation is all kinds of Iodophors.
The Iodophor be povidon iodine, polyglycol iodine, nonylphenol polyoxyethylene ether iodine, polyalcohol ether iodine,
One or more of chlorhexidinium iodine.
Povidon iodine (PVPI) described above is brownish red or yellowish-brown powder, and wherein content of iodine is 9%-
12%, preferably, content of iodine is 10%.
Positive electrode is prepared using load method, specifically includes the following steps:
(1) positive active material, conductive material, binder are weighed respectively；The positive active material is polyethylene pyrrole
Pyrrolidone iodine (PVPI), iodoform (CHI3), one of poly N-vinyl carbazole；The conductive material is super-P, acetylene
One or more of black, Li Qinhei, the binder are polytetrafluoroethylene (PTFE) (PTFE) or the high molecular derivatives with carboxyl
Object, the polymeric derivative with carboxyl are sodium carboxymethylcellulose (CMC), Kynoar (PVDF) or butylbenzene rubber
Glue (SBR)；
(2) mode by weighed positive active material and conductive material grinding or ball milling is uniformly mixed；
(3) on the basis of step (2), the binder of weighing is added, grinds repeatedly, be sufficiently mixed three uniformly, obtain
To flaky material；
(4) by step (3) resulting flaky material, tabletting is carried out with noodle press, pole piece is made；
(5) it is used to be assembled into aluminium ion battery for above-mentioned pole piece as positive electrode.
In above scheme, by weight, positive active material dosage is 50-80 parts, and conductive material dosage is 10-20
Part, consumption of binder is 10-25 parts.
In above-mentioned aluminium ion battery, existing between diaphragm with being additionally provided with water proof type carbon paper, thickness between positive electrode
Between 0.1-0.3mm.
The diaphragm is used with ion passability, is not reacted with positive and negative anodes, the good glass fibers of electrochemical stability
Tie up material.
The cathode aluminium foil need to be polished with sand paper, remove the passivation layer on surface, and surface is made to become smooth.
Positive electrode, including following preparation step are prepared using load method:
(1) Iodophor of aimed concn, targeted species is prepared.
(2) quality of carbon cloth is weighed, and impregnates carbon cloth, soaking time 0.5h-48h with above-mentioned Iodophor.
(3) it is weighed again after being drained by the carbon cloth drying after immersion or with the transitional storehouse of glove box, positive electrode is made.
Ready positive electrode, cathode aluminium foil, ionic liquid base electrolyte, diaphragm material, battery case etc. are assembled into aluminium ion electricity
Pond.
Beneficial effects of the present invention: the present invention uses iodine substance as positive electrode, and high-purity aluminum foil is as cathode, ion
Liquid constitutes a kind of aluminium ion battery based on generation reversible chemical reaction as electrolyte, with utilization aluminium ion in anode
The aluminium ion battery that reversible insertion and abjection occur for material interlayer is essentially different, used in battery positive electrode material letter
It is singly easy to get, only needs conventional equipment i.e. implementable, and battery performance is excellent, especially the positive material of povidon iodine (PVPI)
Material higher specific capacity is shown in lasting charge-discharge test, for the first time discharge capacity close to theoretical capacity one third,
Also, as the cycle progresses, the completion of activation process, specific discharge capacity increased, and see attached drawing 2, by adjusting voltage model
The method activated is enclosed, so that specific discharge capacity is up to 194.8mAh/g, coulombic efficiency is maintained at 75% or so, sees attached
Fig. 3.Therefore, can be used for respectively in following development designed by the present invention based on the aluminium ion battery that reversible chemical reaction occurs
Kind energy device.
Detailed description of the invention
Fig. 1 is the cyclic voltammetry curve of aluminium ion battery prepared by embodiment 1；
Fig. 2 is that aluminium ion battery the 4th, 9,14 prepared by embodiment 2 encloses charge-discharge test curve；
Fig. 3 is the cycle performance curve of aluminium ion battery prepared by embodiment 3.
Specific embodiment
Below in conjunction with embodiment, the present invention is described in more detail, it should be understood that specific reality described herein
Example is used only for explaining that the present invention, protection scope of the present invention are not limited to these embodiments.
Embodiment 1
Positive active material is PVPI, and conductive material Li Qinhei, binder is polytetrafluoroethylene (PTFE) (PTFE), is first weighed
0.5gPVPI, 0.2g conductive material are added in ball grinder, and ball grinder is put into high-performance ball mill, in 600r/min revolving speed
The good mixture of ball milling is put into inside mortar, weighs the polytetrafluoroethylene (PTFE) (PTFE) of 0.25g, ground by lower ball milling 2h
Processing, finally, being cut off it from centre with scissors, with pestle by sheet block pestle not of uniform size at an entirety by 2 parts
It is individually placed to carry out compressing tablet process on noodle press, then, puts on a glass, carried out rolling piece with glass bar, until its thickness exists
0.1mm or so is cut into sizeable with scissors, the positive electrode as battery.Cathode is using 0.03mm thickness
High-purity aluminum foil after being sliced with the punching pin that diameter is 13mm, is used as negative electrode material after carrying out grinding process with fine sandpaper.Ion
The electrolyte of liquid base is mixed by anhydrous aluminum chloride and 1- ethyl-3-methylimidazole chloride according to molar ratio 1.5:1.With
Glass fiber filter paper (GF/D, Whatman) is diaphragm.After material required for being ready to, battery is assembled into glove box, it is quiet
It only after half an hour, is carried out cyclic voltammetry (CV) with 1470E type electrochemical workstation, scanning voltage range is 0.5-
1.25V, sweep speed 0.1mV/s, passes through cyclic voltammetry, it is determined that the electrode material charging/discharging voltage range is 0.6-
1.1V is shown in attached drawing 1.
Embodiment 2
Positive active material is PVPI, and conductive material Super-P, binder is polytetrafluoroethylene (PTFE) (PTFE), is first weighed
0.5gPVPI, 0.2g conductive material Super-P, are added in ball grinder, and ball grinder is put into high-performance ball mill,
The good mixture of ball milling is put into inside mortar, weighs the polytetrafluoroethylene (PTFE) of 0.25g by ball milling 2h under 600r/min revolving speed
(PTFE), be ground, finally with pestle by sheet block pestle not of uniform size at an entirety, with scissors by it therefrom
Between cut off, 2 parts are individually placed to carry out compressing tablet process on noodle press, then, puts on a glass, is rolled with glass bar
Piece, until its thickness in 0.1mm or so, is cut into sizeable with scissors, the positive electrode as battery.Cathode
Using the high-purity aluminum foil of 0.03mm thickness, after being sliced with the punching pin that diameter is 13mm, used after carrying out grinding process with fine sandpaper
Make negative electrode material.The electrolyte of ionic liquid base is by anhydrous aluminum chloride and 1- ethyl-3-methylimidazole chloride according to molar ratio
1.1:1 mixing.With glass fiber filter paper (GF/D, Whatman) for diaphragm.After material required for being ready to, in gloves
Battery is assembled into case, after static half an hour, use 8 fill enamel electric battery test system (model specification: CT2001A5V10MA) into
Row charge-discharge test, charging/discharging voltage range are 0.6V-1.1V, and coulombic efficiency is maintained at 80% or so, the 4th specific discharge capacity
For 109.3mAh/g, close to the half of theoretical capacity, with the progress of cyclic process, charging and discharging capacity is gradually increased,
See attached drawing 2.
Embodiment 3
Positive active material is PVPI, and conductive material Super-P, binder is polytetrafluoroethylene (PTFE) (PTFE), is first weighed
0.5gPVPI, 0.2g conductive material Super-P, are added in ball grinder, and ball grinder is put into high-performance ball mill,
The good mixture of ball milling is put into inside mortar, weighs the polytetrafluoroethylene (PTFE) of 0.25g by ball milling 2h under 600r/min revolving speed
(PTFE), be ground, finally with pestle by sheet block pestle not of uniform size at an entirety, with scissors by it therefrom
Between cut off, 2 parts are individually placed to carry out compressing tablet process on noodle press, then, puts on a glass, is rolled with glass bar
Piece, until its thickness in 0.1mm or so, is cut into sizeable with scissors, the positive electrode as battery.Cathode
Using the high-purity aluminum foil of 0.03mm thickness, after being sliced with the punching pin that diameter is 13mm, used after carrying out grinding process with fine sandpaper
Make negative electrode material.The electrolyte of ionic liquid base is by anhydrous aluminum chloride and 1- ethyl-3-methylimidazole chloride according to molar ratio
2:1 is mixed.With glass fiber filter paper (GF/D, Whatman) for diaphragm.After material required for being ready to, in glove box
In be assembled into battery, after static half an hour, carried out with 8 electric battery test systems (model specification: CT2001A5V10MA) of filling enamel
Charge voltage range is first set as 0.6-1.05V by charge-discharge test, is activated, and voltage range is set as 0.6-1.1V later,
With the change of upper voltage limit, coulombic efficiency variation less, maintains essentially in 75% or so, but its specific discharge capacity has substantially
Increase, maintains 180mAh/g, be specifically shown in attached drawing 3.
Embodiment 4
Positive active material is CHI3, conductive material Li Qinhei, binder SBR first weigh 0.8g CHI3, 0.2g leads
Electric material is added in ball grinder, and ball grinder is put into high-performance ball mill, the ball milling 2h under 600r/min revolving speed, by ball milling
Good mixture is put into inside mortar, is weighed the SBR of 0.1g, is ground, finally, with pestle by piece not of uniform size
Shape block pestle cuts off it from centre at an entirety, with scissors, and 2 parts are individually placed to carry out compressing tablet process on noodle press,
Then, it puts on a glass, is carried out rolling piece with glass bar, until its thickness in 0.1mm or so, is cut into size with scissors
Suitable piece, the positive electrode as battery.Cathode uses the high-purity aluminum foil of 0.03mm thickness, is carried out with the punching pin that diameter is 13mm
After slice, negative electrode material is used as after carrying out grinding process with fine sandpaper.The electrolyte of ionic liquid base is by anhydrous aluminum chloride and 1-
Ethyl-3-methylimidazole chloride is mixed according to molar ratio 2:1.With glass fiber filter paper (GF/D, Whatman) be every
Film.After material required for being ready to, battery is assembled into glove box, between diaphragm with being additionally provided with thickness between positive electrode
The water proof type carbon paper in 0.1-0.3mm is spent, aluminium ion battery is obtained.
Claims (7)
1. a kind of aluminium ion battery based on the anode containing iodine, which is characterized in that comprising anode, cathode, ionic liquid base electrolyte,
Diaphragm, wherein described just extremely povidon iodine or iodoform, cathode are high-purity aluminum foil, ionic liquid base electrolyte
It is mixed by anhydrous aluminum chloride and 1- ethyl-3-methylimidazole chloride.
2. the aluminium ion battery according to claim 1 based on the anode containing iodine, which is characterized in that the ionic liquid base
The molar ratio of anhydrous aluminum chloride and 1- ethyl-3-methylimidazole chloride is 1:1-10:1 in electrolyte.
3. the aluminium ion battery according to claim 1 based on the anode containing iodine, which is characterized in that the polyvinyl pyrrole
Content of iodine is 10% in alkanone iodine (PVPI).
4. a kind of aluminium ion battery based on the anode containing iodine as described in claim 1, which is characterized in that the anode uses
Load method is made, specifically includes the following steps:
(1) positive active material, conductive material, binder are weighed respectively；The positive active material is polyvinylpyrrolidine
Ketone iodine (PVPI), iodoform (CHI3), one of poly N-vinyl carbazole；The conductive material be super-P, acetylene black,
One or more of Li Qinhei, the binder be polytetrafluoroethylene (PTFE) (PTFE) or the polymeric derivative with carboxyl,
The polymeric derivative with carboxyl is sodium carboxymethylcellulose (CMC), Kynoar (PVDF) or butadiene-styrene rubber
(SBR)；
(2) mode by weighed positive active material and conductive material grinding or ball milling is uniformly mixed；
(3) on the basis of step (2), the binder of weighing is added, grinds repeatedly, be sufficiently mixed three uniformly, obtain piece
Shape material；
(4) by step (3) resulting flaky material, tabletting is carried out with noodle press, pole piece is made；
(5) it is used to be assembled into aluminium ion battery for above-mentioned pole piece as positive electrode.
5. the aluminium ion battery according to claim 4 based on the anode containing iodine, which is characterized in that by weight, anode
Amount of active mass is 50-80 parts, and conductive material dosage is 10-20 parts, and consumption of binder is 10-25 parts.
6. the aluminium ion battery according to claim 1 based on the anode containing iodine, which is characterized in that between diaphragm with anode
Water proof type carbon paper is additionally provided between material, thickness is between 0.1-0.3mm.
7. the aluminium ion battery according to claim 1 based on the anode containing iodine, which is characterized in that the diaphragm uses glass
Glass fibrous material.
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| CN1808744A (en) * | 2005-12-09 | 2006-07-26 | 水新国 | Chemical cell with aluminum alloy as negative electrode material |
| CN103140962A (en) * | 2010-09-22 | 2013-06-05 | 安维亚系统公司 | Metal halide coatings on lithium ion battery positive electrode materials and corresponding batteries |
| CN104810544A (en) * | 2015-04-20 | 2015-07-29 | 北京科技大学 | Rechargeable aluminum ion battery and preparation method thereof |
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| CN1808744A (en) * | 2005-12-09 | 2006-07-26 | 水新国 | Chemical cell with aluminum alloy as negative electrode material |
| CN103140962A (en) * | 2010-09-22 | 2013-06-05 | 安维亚系统公司 | Metal halide coatings on lithium ion battery positive electrode materials and corresponding batteries |
| CN104810544A (en) * | 2015-04-20 | 2015-07-29 | 北京科技大学 | Rechargeable aluminum ion battery and preparation method thereof |
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