CN104078680A - Carbon-sulfur composite positive electrode and secondary aluminium-sulfur battery - Google Patents
Carbon-sulfur composite positive electrode and secondary aluminium-sulfur battery Download PDFInfo
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- CN104078680A CN104078680A CN201410223624.XA CN201410223624A CN104078680A CN 104078680 A CN104078680 A CN 104078680A CN 201410223624 A CN201410223624 A CN 201410223624A CN 104078680 A CN104078680 A CN 104078680A
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- 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
- H01M4/606—Polymers containing aromatic main chain polymers
- H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
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Abstract
The invention discloses a novel secondary aluminium-sulfur battery which comprises electrochemical active sulfur-containing positive electrode, a negative electrode made of aluminium active material, and non-aqueous electrolyte. The active material of the positive electrode is made of a carbon/sulfide benzo heterocyclic compound composite material; the general formula of a carbon/sulfide benzo heterocyclic compound is as described in the formula I, wherein X represents for power supply groups such as amino, hydroxyl, alkoxy, ester group, aminoacyl, aminoaldehyde, and alkyl. The general formula I is as described in the specification.
Description
Technical field
The present invention relates to the secondary aluminium-sulfur battery taking " carbon/sulfuration Benzoheterocyclic compounds composite material " as positive electrode active materials with one, belong to electrochemistry and new forms of energy product scope.
Background technology
Compared with existing electrode material, the metallic element aluminium that earth's crust reserves are maximum has the advantages such as solid density is large, aboundresources, cheap, environmentally friendly, use is safe.Metallic aluminium theoretical energy density, up to 2980mAh/g, is only second to lithium metal (3682mAh/g), and volume and capacity ratio is 8050mAh/cm3, be about 4 times of lithium (2040Ah/cm3), and chemical activity is relatively stable, is desirable negative material; Elementary sulfur also has larger theoretical energy density (1670 mAh/g), is the positive electrode of known energy density maximum.Therefore, secondary aluminium-sulfur battery be all from every side a kind of cheap, energy density is high, use safe ideal battery.
The electrochemical reaction of secondary aluminium-sulfur battery based between aluminium and sulphur, in discharge process, the fracture of sulphur-sulfide linkage, the little molecular sulfur compound of generation is dissolved in electrolyte, moves to aluminium negative pole, and they can form undissolved product at that, make negative pole passivation.This high-dissolvability also causes active electrode mass loss, causes the self discharge of battery, increases electrolyte viscosity, affect active material distribution.Repeatedly after circulation, cause capacity to decay rapidly, cycle performance of battery is declined very soon.Many sulfuration anion can have influence on the efficiency of battery simultaneously.Therefore, for the research of aluminium-sulfur battery positive electrode, to improve its conductivity on the one hand, improve the utilance of positive active material; To keep on the other hand the stability of positive electrode structure, suppress the irreversible loss of capacity, to improve the cycle performance of battery.
Summary of the invention
(1) goal of the invention
In view of the defect that prior art exists, the object of the present invention is to provide a kind of novel cheap, energy density is high, use safe secondary aluminium cell.
The present invention also aims to provide a kind of secondary aluminium-sulfur battery taking " carbon/sulfuration Benzoheterocyclic compounds composite material " as positive electrode active materials, this secondary aluminium-sulfur battery can effectively reduce sulphur and dissolve, and improves cycle performance of battery.
Term " secondary aluminium cell " in the present invention for example comprises " aluminum secondary battery ", " rechargeable aluminium battery ", " aluminium storage battery ", " aluminium energy-storage battery " and similar concept.
(2) technical scheme
To achieve these goals, of the present inventionly provide a kind of secondary aluminium cell, having comprised: the positive pole that (a) comprises electro-chemical activity sulphur-containing substance; (b) containing the negative pole of aluminium active material; (c) nonaqueous electrolytic solution.
The description of the preferred negative pole of electrochemical cell of the present invention, positive pole, electrolyte below.
Anodal
The positive pole of battery of the present invention comprises the positive active material, conductive agent, binding agent and the collector that contain electro-chemical activity sulphur-containing substance.Wherein, term " electro-chemical activity sulphur-containing substance " refers to comprise the positive active material containing element sulphur here, and wherein, electro-chemical activity relates to fracture or the formation of sulphur-sulphur covalent bond.
Electro-chemical activity sulphur-containing substance described in scheme is carbon/sulfuration Benzoheterocyclic compounds composite material, and the general formula of sulfuration Benzoheterocyclic compounds is:
Wherein, X functional group is electron-donating group, comprises amino, hydroxyl, alkoxyl, ester group, aminoacyl, amine aldehyde radical, alkyl etc.
With respect to other similar compounds, sulfuration Benzoheterocyclic compounds great advantage is in its structure, there is a closed hexatomic ring that contains S-S key, in battery charge and discharge process, S-S the key that plays energy storage effect disconnects and the compound intramolecule that occurs over just, do not produce that other can dissolve by electrolyte containing the little molecule of S, thereby effectively stoped sulphur dissolving, reduced positive electrode capacity loss, lower negative pole passivation effect, improved cycle performance of battery.
The material with carbon element using in carbon/sulfuration Benzoheterocyclic compounds composite material described in scheme, preferably mesoporous carbon, carbon nano-tube, graphite, active carbon.
The preparation method of carbon/sulfuration Benzoheterocyclic compounds composite material described in scheme:
By the material with carbon element of processing, with sulfuration Benzoheterocyclic compounds after 1:1-10 mixes in mass ratio, 70-80 DEG C of heating 6h under inert conditions, obtains carbon/sulfuration Benzoheterocyclic compounds composite material after cooling.
Conductive agent described in scheme includes but not limited to graphite-based material, carbon-based material and conducting polymer.Graphite-based material comprises electrically conductive graphite KS6, and carbon-based material comprises that Super P, Ketjen are black, acetylene black or carbon black.Conducting polymer comprises polyaniline, polypyrrole, polythiophene, polyacetylene, or their mixture.
Adhesive described in scheme is polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), Kynoar (PVDF), polystyrene butadiene copolymer (SBR), Viton and polyurethane, PVP, polyethyl acrylate, polyvinyl chloride, polyacrylonitrile, polycaprolactam, polybutadiene, polyisoprene, polyacrylic acid, and derivative, mixture or copolymer.
Collector includes but not limited to stainless steel, copper, nickel, titanium, aluminium.The more preferably aluminium collector of carbon coating, more easily covers the coating that comprises positive active material, has lower contact resistance, and can suppress the corrosion of sulfide.
Secondary aluminium cell described in scheme also can comprise the barrier film between positive pole and negative pole.Suitable solid porous diaphragm material includes but not limited to: polyolefin is as polyethylene and polypropylene, glass fiber filter paper and ceramic material.Other example that is applicable to diaphragm material of the present invention is to comprise micropore pseudobochmite layer, and it can be the form of free-standing film or be coated directly onto on an electrode.
Negative pole
Described in scheme containing aluminium negative active core-shell material, include but not limited to: aluminum metal, for example aluminium foil and be deposited on the aluminium on base material; Aluminium alloy, comprises and contains at least one element of being selected from Li, Na, K, Ca, Fe, Co, Ni, Cu, Zn, Mn, Sn, Pb, Ma, Ga, In, Cr, Ge and the alloy of Al.
Electrolyte
Nonaqueous electrolytic solution described in scheme, is characterized in that, described nonaqueous electrolytic solution comprises halogen aluminic acid type ionic liquid.
Halogen aluminic acid type ionic liquid described in scheme, is characterized in that, described halogen aluminic acid type ionic liquid is ionic liquid-aluminum halide system.
Ionic liquid-aluminum halide system described in scheme, is characterized in that, the mol ratio of described ionic liquid-aluminum halide is 1:1.1-3.0.
Ionic liquid-aluminum halide system described in scheme, is characterized in that, the cation of described ionic liquid comprises imidazol ion, pyridinium ion, pyrroles's ion, piperidines ion, morpholine ion, quaternary ammonium salt ion ， quaternary alkylphosphonium salt ion and tertiary sulfosalt ion; Anion comprises Cl-, Br-, and I-, PF6-, BF4-, CN-, SCN-, [N (CF3SO2) 2]-, [N (CN) 2]-plasma.Include but not limited to aluminium chloride-triethylamine hydrochloride, aluminium chloride-chlorination 1-butyl-3-methylimidazole, aluminium chloride-phenyl trimethyl ammonium chloride, aluminium bromide-1-ethyl-3-methyllimidazolium bromide plasma liquid.
Ionic liquid-aluminum halide system described in scheme, is characterized in that, described aluminum halide is the one in aluminium chloride, aluminium bromide or silver iodide.
The preparation method of the secondary aluminium-sulfur battery described in scheme is as follows:
By positive electrode active materials, conductive agent, binding agent (ratio is 7:2:1), making active material slurry is applied on the nickel foam substrate that 0.6mm is thick, oven dry roll to 0.33 millimeter be cut into 40mm wide × the long pole piece of 15mm, be wound into battery core with the thick barrier film of 0.16mm and the negative pole made as negative active core-shell material with aluminium flake and pack nickel plating box hat into, the halogen aluminic acid il electrolyte of reinjecting, secondary aluminium cell is made in sealing.
(3) beneficial effect
Using " carbon/sulfuration Benzoheterocyclic compounds composite material " provided by the invention during as positive electrode active materials: the hexatomic ring that contains S-S key in the molecular structure of sulfuration Benzoheterocyclic compounds, in battery charge and discharge process, the S-S key that plays energy storage effect disconnects and the compound intramolecule that occurs over just, do not produce other containing the little molecule of S, reduce the loss probability of active material S, thereby ensured the cycle performance that battery is outstanding.
Embodiment
Below with reference to embodiment, the technique effect of design of the present invention, concrete structure and generation is described further, to understand fully object of the present invention, feature and effect.
The following examples have been described several execution mode of the present invention, and they are only illustrative, and nonrestrictive.
Embodiment mono-
Step 1, the processing of material with carbon element
By 60 DEG C of backflow 3h of the concentrated sulfuric acid for the mesoporous carbon of buying, it is in 75% ethanol water that the meso-porous carbon material after refluxing is disperseed with volume fraction, and 20 DEG C of thermostatic ultrasonics are processed 12h.Filtration under diminished pressure, after gained mesoporous carbon precipitation cyclic washing under condition of nitrogen gas 60 DEG C of dry 24h, finish dealing with, for subsequent use.
Step 2, also [d]-1' of preparation 5-amino-Isosorbide-5-Nitrae-dihydrobenzene azoles, 2'-bis-thioneines:
(1) prepare 1,2-dibromo methyl-3-nitro benzene (compound 2)
By 1,2-dimethyl-3-nitrobenzene, N-bromo-succinimide (NBS) and benzoyl peroxide in molar ratio 1:2:0.03 add back flow reaction 8-12h in carbon tetrachloride.After reaction finishes, remove by filter imines precipitation, the decompression distillation on Rotary Evaporators of gained filtrate removes desolventizing. the brown oil of gained, through ethyl alcohol recrystallization, is obtained to yellow crystals 1,2-dibromo methyl-3-nitro benzene.
1,2-dimethyl-3-nitrobenzene 1,2-dibromo methyl-3-nitro benzene
(2) prepare 1,2-bis-(thiosulfuric acid methyl sodium salt)-3-nitrobenzene (compound 3)
The ethanolic solution of compound 2 and five water sodium thiosulfate (compound 2 is 1:2 with five water sodium thiosulfate mol ratios) is heated to 50 DEG C and reacts 4h, filter while hot, gained sediment washs with ethanol, obtain white powder solid, 1,2-bis-(thiosulfuric acid methyl sodium salt)-3-nitrobenzene.
1,2-bis-(thiosulfuric acid methyl sodium salt)-3-nitrobenzene
(3) prepare also [d]-1' of 5-nitro-Isosorbide-5-Nitrae-dihydrobenzene azoles, 2'-bis-thioneines (compound 4)
By the aqueous solution of formation concentration 0.06mmol/ml soluble in water compound 3, then add wherein and contain 10% concentrated sulfuric acid aqueous solution, add again the hydrogen peroxide of concentration 30%, compound 3 aqueous solution: concentrated sulfuric acid aqueous solution: hydrogen peroxide volume ratio=10:2:1, after adding hot mixt to 50 DEG C reaction 3h. reaction and finishing, the yellow mercury oxide that collection is separated out, filtrate chloroform extraction, organic phase anhydrous magnesium sulfate drying, except desolventizing obtains yellow solid. merge gained solid silica gel column chromatography twice, with chloroform give eluent, obtain yellow solid 5-nitro-1, also [d]-1' of 4-dihydrobenzene azoles, 2'-bis-thioneines.
Also [d]-1' of 5-nitro-Isosorbide-5-Nitrae-dihydrobenzene azoles, 2'-bis-thioneines
(4) prepare also [d]-1' of 5-amino-Isosorbide-5-Nitrae-dihydrobenzene azoles, 2'-bis-thioneines
In the NH4Cl/Fe aqueous solution (NH4Cl:Fe mol ratio=1:0.5), drip compound 4 ethanolic solutions that concentration is 0.05mmol/ml; the volume ratio of the NH4Cl/Fe aqueous solution and compound 4 ethanolic solutions is 1:1; 3h. that reactant mixture is refluxed under N2 gas protection treats that solution cooled and filtered removes iron powder; gained filtrate chloroform extraction; organic phase is with after anhydrous magnesium sulfate drying, and removal of solvent under reduced pressure obtains yellow solid, i.e. 5-amino-1; also [d]-1' of 4-dihydrobenzene azoles, 2'-bis-thioneines.
Step 3, preparation " also [d]-1' of mesoporous carbon/5-amino-Isosorbide-5-Nitrae-dihydrobenzene azoles, 2'-bis-thioneines " composite material
By the mesoporous carbon of processing and also [d]-1' of 5-amino-Isosorbide-5-Nitrae-dihydrobenzene azoles, 2'-bis-thioneines are after 1:1 mixes in mass ratio, 70-80 DEG C of heating 6h under argon gas condition, after cooling, make " also [d]-1' of mesoporous carbon/5-amino-Isosorbide-5-Nitrae-dihydrobenzene azoles, 2'-bis-thioneines " composite material.
Embodiment bis-
In step 3, by mesoporous carbon and also [d]-1' of 5-amino-Isosorbide-5-Nitrae-dihydrobenzene azoles, 2'-bis-thioneines in mass ratio 1:2 mix, and other are with embodiment mono-.
Embodiment tri-
In step 3, by mesoporous carbon and also [d]-1' of 5-amino-Isosorbide-5-Nitrae-dihydrobenzene azoles, 2'-bis-thioneines in mass ratio 1:3 mix, and other are with embodiment mono-.
Embodiment tetra-
Taking embodiment mono-material as positive electrode active materials, adding conductive agent acetylene black, binding agent PVDF(ratio is 7:2:1), making active material slurry is applied on the nickel foam substrate that 0.6mm is thick, oven dry roll to 0.33 millimeter be cut into 40mm wide × the long pole piece of 15mm, be wound into battery core with the thick non-negative pole of knitting barrier film and make as negative active core-shell material with aluminium flake of glass fibre of 0.16mm and pack nickel plating box hat into, aluminium chloride-triethylamine hydrochloride ionic liquid electrolyte that reinjects, AA type secondary aluminium cell is made in sealing.
The made aluminium-sulfur battery of above-described embodiment material is carried out to charge-discharge test, charge to 2.2V with 1C, 0.5C electric discharge, discharge cut-off voltage is 1.2 V.Battery open circuit voltage 1.78V, discharge capacity 551mAh first, circulates after 50 times, discharge capacity 396mAh, capacity attenuation rate is 28.1%.
Embodiment five
Taking embodiment bis-materials as positive electrode active materials, adding conductive agent acetylene black, binding agent PVDF(ratio is 7:2:1), making active material slurry is applied on the nickel foam substrate that 0.6mm is thick, oven dry roll to 0.33 millimeter be cut into 40mm wide × the long pole piece of 15mm, be wound into battery core with the thick non-negative pole of knitting barrier film and make as negative active core-shell material with aluminium flake of glass fibre of 0.16mm and pack nickel plating box hat into, aluminium chloride-triethylamine hydrochloride ionic liquid electrolyte that reinjects, AA type secondary aluminium cell is made in sealing.Battery open circuit voltage 1.81V, discharge capacity 577mAh first, circulates after 50 times, discharge capacity 412mAh, capacity attenuation rate is 28.6%.
Embodiment six
Taking embodiment tri-materials as positive electrode active materials, adding conductive agent acetylene black, binding agent PVDF(ratio is 7:2:1), making active material slurry is applied on the nickel foam substrate that 0.6mm is thick, oven dry roll to 0.33 millimeter be cut into 40mm wide × the long pole piece of 15mm, be wound into battery core with the thick non-negative pole of knitting barrier film and make as negative active core-shell material with aluminium flake of glass fibre of 0.16mm and pack nickel plating box hat into, aluminium chloride-triethylamine hydrochloride ionic liquid electrolyte that reinjects, AA type secondary aluminium cell is made in sealing.Battery open circuit voltage 1.83V, discharge capacity 601mAh first, circulates after 50 times, discharge capacity 424mAh, capacity attenuation rate is 29.5%.
Although the present invention is described in detail with reference to embodiment, but those skilled in the art is to be understood that, in the case of the spirit and scope of the present invention described in not departing from appended claims and equivalent thereof, can make various amendments and replacement to it.
Claims (10)
1. a secondary aluminium cell, it comprises:
(a) positive pole that comprises electro-chemical activity sulphur-containing substance; Wherein, described electro-chemical activity sulphur-containing substance is carbon/sulfuration Benzoheterocyclic compounds composite material;
(b) containing the negative pole of aluminium active material; With
(c) nonaqueous electrolytic solution.
2. secondary aluminium cell as claimed in claim 1, is characterized in that, the general formula of described sulfuration Benzoheterocyclic compounds is:
Wherein, X functional group is the electron-donating groups such as amino, hydroxyl, alkoxyl, ester group, aminoacyl, amine aldehyde radical, alkyl.
3. secondary aluminium cell as claimed in claim 1, is characterized in that, the material with carbon element using in described carbon/sulfuration Benzoheterocyclic compounds composite material, can select mesoporous carbon, Graphene, carbon nano-tube, graphite, active carbon.
4. secondary aluminium cell as claimed in claim 1, is characterized in that, in described carbon/sulfuration Benzoheterocyclic compounds composite material, carbon is 1:1～10 with the mass ratio of sulfuration Benzoheterocyclic compounds.
5. secondary aluminium cell as claimed in claim 1, is characterized in that, the described aluminium negative pole that contains comprises: aluminum metal or aluminium alloy.
6. secondary aluminium cell as claimed in claim 1, is characterized in that, described nonaqueous electrolytic solution comprises halogen aluminic acid type ionic liquid.
7. secondary aluminium cell as claimed in claim 6, is characterized in that, described halogen aluminic acid type ionic liquid is ionic liquid-aluminum halide system, and the mol ratio of described ionic liquid-aluminum halide is 1:1.1～3.0.
8. secondary aluminium cell as claimed in claim 7, is characterized in that, the cation of described ionic liquid comprises imidazol ion, pyridinium ion, pyrroles's ion, piperidines ion, morpholine ion, quaternary ammonium salt ion ， quaternary alkylphosphonium salt ion and tertiary sulfosalt ion; Anion comprises Cl-, Br-, and I-, PF6-, BF4-, CN-, SCN-, [N (CF3SO2) 2]-, [N (CN) 2]-plasma.
9. secondary aluminium cell as claimed in claim 7, is characterized in that, described aluminum halide is the one in aluminium chloride, aluminium bromide or silver iodide.
10. the preparation method of carbon/sulfuration Benzoheterocyclic compounds composite material: material with carbon element is with sulfuration Benzoheterocyclic compounds after 1:1～10 mix in mass ratio, the lower 80 DEG C of heating 6h of inert conditions, obtain carbon/sulfuration Benzoheterocyclic compounds composite material after cooling.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104218231A (en) * | 2014-10-14 | 2014-12-17 | 南京中储新能源有限公司 | Sulfur-based compound positive electrode materials and secondary battery |
| CN105870453A (en) * | 2016-05-26 | 2016-08-17 | 唐林 | Electrolyte used for aluminum battery and preparation method thereof |
| CN105958121A (en) * | 2016-07-07 | 2016-09-21 | 南方科技大学 | Electrolyte for rapidly charging and discharging aluminum battery and aluminum battery containing electrolyte |
| EP3288548A4 (en) * | 2015-04-30 | 2018-10-31 | Parion Sciences, Inc. | Novel prodrugs of dithiol mucolytic agents |
| CN111082056A (en) * | 2019-12-17 | 2020-04-28 | 山东科技大学 | Secondary aluminum-sulfur battery positive electrode material, battery and preparation method thereof |
| US10968233B2 (en) | 2015-01-30 | 2021-04-06 | Parion Sciences, Inc. | Monothiol mucolytic agents |
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| CN101764254A (en) * | 2009-11-20 | 2010-06-30 | 无锡欧力达新能源电力科技有限公司 | Secondary aluminum battery and preparation method of anode thereof |
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| CN101764257A (en) * | 2009-11-20 | 2010-06-30 | 无锡欧力达新能源电力科技有限公司 | Rechargeable aluminium-sulfur battery and preparation method thereof |
| CN101764254A (en) * | 2009-11-20 | 2010-06-30 | 无锡欧力达新能源电力科技有限公司 | Secondary aluminum battery and preparation method of anode thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104218231A (en) * | 2014-10-14 | 2014-12-17 | 南京中储新能源有限公司 | Sulfur-based compound positive electrode materials and secondary battery |
| US10968233B2 (en) | 2015-01-30 | 2021-04-06 | Parion Sciences, Inc. | Monothiol mucolytic agents |
| EP3288548A4 (en) * | 2015-04-30 | 2018-10-31 | Parion Sciences, Inc. | Novel prodrugs of dithiol mucolytic agents |
| US10526283B2 (en) | 2015-04-30 | 2020-01-07 | Parion Sciences, Inc. | Prodrugs of dithiol mucolytic agents |
| CN105870453A (en) * | 2016-05-26 | 2016-08-17 | 唐林 | Electrolyte used for aluminum battery and preparation method thereof |
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| CN105958121A (en) * | 2016-07-07 | 2016-09-21 | 南方科技大学 | Electrolyte for rapidly charging and discharging aluminum battery and aluminum battery containing electrolyte |
| CN111082056A (en) * | 2019-12-17 | 2020-04-28 | 山东科技大学 | Secondary aluminum-sulfur battery positive electrode material, battery and preparation method thereof |
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