CN104078700A - Secondary aluminum cell with positive electrode made of double-cladding carbon-sulfur composite material - Google Patents
Secondary aluminum cell with positive electrode made of double-cladding carbon-sulfur composite material Download PDFInfo
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- CN104078700A CN104078700A CN201410314127.0A CN201410314127A CN104078700A CN 104078700 A CN104078700 A CN 104078700A CN 201410314127 A CN201410314127 A CN 201410314127A CN 104078700 A CN104078700 A CN 104078700A
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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
- H01M4/366—Composites as layered products
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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
- 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
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a secondary aluminum cell with a positive electrode made of a double-cladding carbon-sulfur composite material. The secondary aluminum cell comprises the positive electrode, a negative electrode and electrolyte, wherein the active material of the positive electrode is a carbon nano tube-sulfur-graphene composite material, the active material of the negative electrode is a metal aluminum or aluminum alloy, and the electrolyte is non-aqueous aluminiferous electrolyte.
Description
Technical field
The invention belongs to electrochemistry and new forms of energy product scope, relate to a kind of secondary aluminium cell, especially relate to the anodal secondary aluminium cell of a kind of use " carbon nano-tube-sulphur-graphene composite material ".
Background technology
Compare 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/cm
3, be about lithium (2040mAh/cm
3) 4 times, and chemical activity is relatively stable, is desirable negative material; Elementary sulfur also has larger theoretical energy density (1670mAh/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.
Secondary aluminium-sulfur battery is to realize battery charging and discharging by electrochemical reaction reversible between aluminium and sulphur, and the self property of active material aluminium, sulphur directly affects the performance of battery.Yet elemental sulfur is typical electronics and ion insulator, poor electric conductivity during directly as positive electrode active material material, activation difficulty is large, utilance is low, is unfavorable for the performance of battery capacity.And in discharge process, 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, repeatedly after circulation, causes capacity to decay rapidly, and cycle performance of battery is declined very soon.
Therefore, want to improve secondary aluminium-sulfur battery performance, will improve on the one hand the conductivity of sulfur-bearing positive electrode, improve the utilance of positive active material, increase battery capacity; To keep the stability of positive electrode structure on the other hand, suppress the irreversible loss that little molecular sulfur compound is dissolved the capacity bringing, improve the cycle performance of battery.
Research for aluminium-sulfur battery positive electrode, before 2005, mainly concentrate on polymeric organosulfides field, but because polymeric organosulfides material activity temperature is many more than 50 ℃, restricted the scope of application of battery, add that the sulfur content of polymeric organosulfides material own is lower, the DeGrain that cell integrated capacity is promoted, causes the research emphasis of aluminium-sulfur battery positive electrode to turn to gradually carbon/sulphur composite material.。
Summary of the invention
(1) goal of the invention
The object of the present invention is to provide that a kind of novel capacity is large, the secondary aluminium cell of price economy, Environmental Safety.
The present invention also aims to provide a kind of composite material of usining carbon nano-tube, graphene coated elemental sulfur as positive electrode active materials.
The present invention also aims to provide a kind of and take the secondary aluminium cell that " carbon nano-tube-sulphur-graphene composite material " is positive electrode active materials.
Term in the present invention " two aluminium primary cells " for example comprises " aluminum secondary battery ", " secondary aluminium-sulfur battery ", " rechargeable aluminium battery ", " aluminium storage battery ", " aluminium energy-storage battery " and similar concept.
(2) technical scheme
To achieve these goals, the invention provides a kind of secondary aluminium cell, comprising:
(a) positive pole of sulfur-bearing active material, wherein, described sulfur-bearing active material is carbon nano-tube-sulphur-graphene composite material;
(b) non-water is containing aluminium electrolyte;
(c) contain the negative pole of aluminium active material.
The preferred positive pole of electrochemical cell of the present invention, negative pole, electrolytical description below.
Anodal
The positive pole of battery of the present invention comprises positive active material, conductive agent, binding agent and the collector that contains sulfur-bearing active material.Wherein, term " sulfur-bearing active material " 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.
Described in scheme, the positive active material of sulfur-bearing active material is carbon nano-tube-sulphur-graphene composite material.
Described in scheme, in carbon nano-tube-sulphur-graphene composite material, sulfur content is 50～85wt%, and Graphene content is 15～50wt%, and content of carbon nanotubes is 15～50wt%, and the content sum of sulphur, carbon nano-tube, Graphene is 100%.
Described in scheme, in carbon nano-tube-sulphur-graphene composite material, carbon nano-tube is a kind of in Single Walled Carbon Nanotube or multi-walled carbon nano-tubes; Sulphur is elemental sulfur, includes but not limited to high purity sulphur or sublimed sulfur; Graphene is individual layer or few layer graphene.
Described in scheme, the preparation method of carbon nano-tube-sulphur-graphene composite material is as follows:
Step 1, the preparation of carbon nano-tube-sulphur composite material
Carbon nano-tube is mixed in proportion with elemental sulfur, ball milling evenly after, under inert gas shielding, heat a period of time, make carbon nano-tube-sulphur composite material after cooling.
Step 2, the preparation of carbon nano-tube-sulphur-graphene oxide mixture
Carbon nano-tube-sulphur composite material is added in graphene oxide solution, after stirring, carry out ultrasonic dispersion, obtain mixture.
Step 3, the preparation of carbon nano-tube-sulphur-graphene composite material
Mixture in step 2 is heated to 80～95 ℃, adds reducing agent, constant temperature stirs 6～24h.After reaction finishes, filtering mixt, obtains insoluble matter, and washing is dry, obtains carbon nano-tube-sulphur-graphene composite material.
In step 1, the heating-up temperature under described inert gas shielding is 130～180 ℃, and be 1～12h heating time.
In step 2, the graphene oxide concentration in described graphene oxide solution is 0.01mg/ml～10mg/ml.
In step 3, reducing agent includes but not limited to hydrazine hydrate, boron alkali acid sodium.
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.More preferably the 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.
Electrolyte
Non-water described in scheme is organic salt-aluminum halide system containing aluminium electrolyte, and the mol ratio of organic salt and aluminum halide is 1:1.1～3.0.
In organic salt-aluminum halide system described in scheme, the cation of organic salt comprises imidazol ion, pyridinium ion, pyrroles's ion, piperidines ion, morpholine ion, quaternary ammonium salt ion ， quaternary alkylphosphonium salt ion and tertiary sulfosalt ion; The anion of organic salt comprises Cl
-, Br
-, I
-, PF
6 -, BF
4 -, CN
-, SCN
-, [N (CF
3sO
2)
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.
In organic salt-aluminum halide system described in scheme, aluminum halide is a kind of in aluminium chloride, aluminium bromide, silver iodide.
Negative pole
The negative pole containing aluminium active material described in scheme is metal aluminum or aluminum alloy.Metallic aluminium, includes but not limited to aluminium foil, aluminium wire, aluminium flake and is 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.
The preparation method of the secondary aluminium-sulfur battery described in scheme is as follows:
Positive electrode active materials, conductive agent, binding agent are made to active material slurry to be in proportion applied on nickel foam substrate, oven dry rolls makes anode pole piece, with barrier film and use negative pole that negative active core-shell material is made to be wound into battery core to pack nickel plating box hat into, the non-water that reinjects is containing aluminium electrolyte, and secondary aluminium cell is made in sealing.
(3) beneficial effect
(1) secondary aluminium cell provided by the invention, the energy density of take is high, aboundresources, aluminium and sulphur environmentally friendly, stable in properties are electrode active material, is that a kind of capacity is large, the ideal battery of price economy, Environmental Safety.
(2) secondary aluminium cell provided by the invention, use " carbon nano-tube-sulphur-graphene composite material " to substitute elemental sulfur as positive electrode active materials, utilize the conductivity of carbon nano-tube and Graphene to overcome the problem of elemental sulfur poorly conductive, improve positive electrode conductivity, thereby improved the utilance of positive active material; Nano pore in carbon nano-tube is to strong suction-operateds of intermediate product such as little molecular sulfur compounds, can realize fixing to positive electrode active materials sulphur, suppresses, slows down the loss of sulphur, improves cycle performance of battery; The high-specific surface area of Graphene can suppress the dissolving of intermediate product in electrolyte simultaneously, further suppresses, slows down the loss of sulphur, improves cycle performance of battery.
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-
By carbon nano-tube, elemental sulfur, Graphene in mass ratio for 1:7:2 prepares carbon nano-tube-sulphur-graphene composite material.
Step 1, the preparation of carbon nano-tube-sulphur composite material
By carbon nano-tube, elemental sulfur, be 1:7 mixing, ball milling 5h in mass ratio; Under inert gas shielding, by the carbon nano-tube after ball milling, 155 ℃ of heated at constant temperature 3h of sulphur mixture, make carbon nano-tube-sulphur composite material after cooling.
Step 2, the preparation of carbon nano-tube-sulphur-graphene oxide mixture
The ratio that is 4:1 in carbon nano-tube-sulphur composite material and graphene oxide mass ratio, adds carbon nano-tube-sulphur composite material in graphene oxide solution (0.3g/ml), stirs 4h, and ultrasonic dispersion 1h, obtains mixture.
Step 3, the preparation of carbon nano-tube-sulphur-graphene composite material
Mixture is heated to 80～95 ℃, in the ratio of 1ml hydrazine hydrate/100g graphene oxide, adds hydrazine hydrate, constant temperature stirs 12h.After reaction finishes, filtering mixt, obtains insoluble matter, and washing is dry, obtains carbon nano-tube-sulphur-graphene composite material.
Embodiment bis-
By carbon nano-tube, elemental sulfur, Graphene, prepare carbon nano-tube-sulphur-graphene composite material in mass ratio for 1:8:1, other are with embodiment mono-.
Embodiment tri-
By carbon nano-tube, elemental sulfur, Graphene, prepare carbon nano-tube-sulphur-graphene composite material in mass ratio for 2:7:1, other are with embodiment mono-.
By carbon nano-tube-sulphur-graphene composite material, conductive agent acetylene black and the binding agent PVDF of embodiment mono-, two, three preparations (7:2:1) mixing in proportion, 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 making 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.
Made battery is carried out to charge and discharge cycles test, with 1C, charge to 2.2V, 0.5C electric discharge, discharge cut-off voltage is 1.2 V, test result is as follows:
(1) the made battery of embodiment mono-material, open circuit voltage 1.72V, discharge capacity 520mAh, circulates after 50 times first, discharge capacity 358mAh, capacity attenuation rate is 31.2%.
(2) the made battery of embodiment bis-material, open circuit voltage 1.75V, discharge capacity 554mAh, circulates after 50 times first, discharge capacity 373mAh, capacity attenuation rate is 32.7%.
(3) the made battery of embodiment tri-material, battery open circuit voltage 1.73V, discharge capacity 523mAh, circulates after 50 times first, discharge capacity 365mAh, capacity attenuation rate is 30.2%.
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 situation that do not depart from the spirit and scope of the present invention described in appended claims and equivalent thereof, can make various modifications and replacement to it.
Claims (7)
1. a secondary aluminium cell, comprising:
(a) positive pole of sulfur-bearing active material, wherein, described sulfur-bearing active material is carbon nano-tube-sulphur-graphene composite material;
(b) non-water is containing aluminium electrolyte;
(c) contain the negative pole of aluminium active material.
2. secondary aluminium cell as claimed in claim 1, it is characterized in that: in described sulfur-bearing active material, sulfur content is 50～85wt%, and Graphene content is 15～50wt%, content of carbon nanotubes is 15～50wt%, and the content sum of sulphur, carbon nano-tube, Graphene is 100%.
3. secondary aluminium cell as claimed in claim 1, is characterized in that: in described carbon nano-tube-sulphur-graphene composite material, carbon nano-tube is a kind of in Single Walled Carbon Nanotube or multi-walled carbon nano-tubes; Sulphur is elemental sulfur; Graphene is individual layer or few layer graphene.
4. secondary aluminium cell as claimed in claim 1, is characterized in that: described non-water is organic salt-aluminum halide system containing aluminium electrolyte, and the mol ratio of organic salt and aluminum halide is 1:1.1～3.0.
5. secondary aluminium cell as claimed in claim 4, is characterized in that: the cation of described organic salt comprises imidazol ion, pyridinium ion, pyrroles's ion, piperidines ion, morpholine ion, quaternary ammonium salt ion ， quaternary alkylphosphonium salt ion and tertiary sulfosalt ion; The anion of organic salt comprises Cl
-, Br
-, I
-, PF
6 -, BF
4 -, CN
-, SCN
-, [N (CF
3sO
2)
2]
-, [N (CN)
2]
-plasma.
6. secondary aluminium cell as claimed in claim 4, is characterized in that: described aluminum halide is a kind of in aluminium chloride, aluminium bromide or silver iodide.
7. secondary aluminium cell as claimed in claim 1, is characterized in that: the described negative pole containing aluminium active material is metal aluminum or aluminum alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410314127.0A CN104078700A (en) | 2014-07-03 | 2014-07-03 | Secondary aluminum cell with positive electrode made of double-cladding carbon-sulfur composite material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410314127.0A CN104078700A (en) | 2014-07-03 | 2014-07-03 | Secondary aluminum cell with positive electrode made of double-cladding carbon-sulfur composite material |
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|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104269516A (en) * | 2014-10-11 | 2015-01-07 | 南京中储新能源有限公司 | Composite positive electrode for secondary battery based on vertically-oriented graphene |
| CN104393233A (en) * | 2014-10-10 | 2015-03-04 | 南京中储新能源有限公司 | Graphene array-based carbon-sulfur composite electrode and secondary cell |
| CN105529463A (en) * | 2015-12-09 | 2016-04-27 | 江苏科技大学 | A secondary aluminum ion battery with high cycle performance and preparation method thereof |
| CN113228349A (en) * | 2019-05-14 | 2021-08-06 | 株式会社Lg化学 | Sulfur-carbon composite, and positive electrode and lithium secondary battery each containing the sulfur-carbon composite |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101645500A (en) * | 2009-09-08 | 2010-02-10 | 无锡欧力达新能源电力科技有限公司 | Carbon-based material inlaid and penetrated with sulfur and aluminum secondary battery using same as cathode active material |
| CN101764255A (en) * | 2009-11-20 | 2010-06-30 | 无锡欧力达新能源电力科技有限公司 | Rechargeable aluminum-sulfur battery and preparation method thereof |
| CN103000864A (en) * | 2012-10-25 | 2013-03-27 | 北京理工大学 | Sulfur composite cathode material and preparation method thereof |
-
2014
- 2014-07-03 CN CN201410314127.0A patent/CN104078700A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101645500A (en) * | 2009-09-08 | 2010-02-10 | 无锡欧力达新能源电力科技有限公司 | Carbon-based material inlaid and penetrated with sulfur and aluminum secondary battery using same as cathode active material |
| CN101764255A (en) * | 2009-11-20 | 2010-06-30 | 无锡欧力达新能源电力科技有限公司 | Rechargeable aluminum-sulfur battery and preparation method thereof |
| CN103000864A (en) * | 2012-10-25 | 2013-03-27 | 北京理工大学 | Sulfur composite cathode material and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104393233A (en) * | 2014-10-10 | 2015-03-04 | 南京中储新能源有限公司 | Graphene array-based carbon-sulfur composite electrode and secondary cell |
| CN104269516A (en) * | 2014-10-11 | 2015-01-07 | 南京中储新能源有限公司 | Composite positive electrode for secondary battery based on vertically-oriented graphene |
| CN104269516B (en) * | 2014-10-11 | 2016-08-17 | 南京中储新能源有限公司 | A kind of secondary cell anode composite based on vertical orientated Graphene |
| CN105529463A (en) * | 2015-12-09 | 2016-04-27 | 江苏科技大学 | A secondary aluminum ion battery with high cycle performance and preparation method thereof |
| CN113228349A (en) * | 2019-05-14 | 2021-08-06 | 株式会社Lg化学 | Sulfur-carbon composite, and positive electrode and lithium secondary battery each containing the sulfur-carbon composite |
| US11967702B2 (en) | 2019-05-14 | 2024-04-23 | Lg Energy Solution, Ltd. | Sulfur-carbon composite, and cathode and lithium secondary battery each comprising same |
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Application publication date: 20141001 |