CN104269543A - Graphene-cladded sulfur/microporous carbon sphere composite cathode material - Google Patents
Graphene-cladded sulfur/microporous carbon sphere composite cathode material Download PDFInfo
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- CN104269543A CN104269543A CN201410526242.4A CN201410526242A CN104269543A CN 104269543 A CN104269543 A CN 104269543A CN 201410526242 A CN201410526242 A CN 201410526242A CN 104269543 A CN104269543 A CN 104269543A
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- 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
Abstract
The invention discloses a composite cathode material for secondary aluminum batteries. The composite cathode material is formed by compounding microporous carbon spheres, sulfur and graphene, has good electric conductivity and is capable of effectively suppressing that polysulfide dissolves in electrolyte to cause the shuttle effect. The preparation method of the composite cathode material comprises the following steps: firstly compounding the microporous carbon spheres and the sulfur, and then cladding the outer layer of the composition with a graphene sheet layer. The preparation method is simple in process and low in cost, toxic raw materials are not used, environment friendliness is achieved, the energy density is high, the utilization ratio of the sulfur is high, and the rate capability and the cycle performance of the secondary aluminum batteries are improved greatly.
Description
Technical field
The invention belongs to electrochemistry and new forms of energy product scope, relate to a kind of graphene coated sulphur/microporous carbon ball composite material and preparation method thereof.The invention still further relates to a kind of this composite material that adopts is the secondary aluminium cell of positive pole.
Background technology
Along with the fast development of the new powers such as electronics and communication apparatus, electric automobile, wind power generation and photovoltaic generation, the battery performance demand of the mankind to supporting power supply is more and more higher, have that energy is high, cost is low, the life-span is long in the urgent need to exploitation, environmental protection, the electrokinetic cell of battery material aboundresources and reusable edible and energy-storage battery.Compared with conventional electrode materials, the advantages such as element aluminum and sulphur all have that theoretical energy density is large, aboundresources, cheap, environmentally friendly, use safety.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 (2040Ah/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 maximum positive electrode of known energy density.Therefore, aluminium-sulfur battery be all from every side a kind of cheap, energy density is high, the ideal battery of use safety.
At present, still there is many problems in the positive electrode of secondary aluminium cell: one is that the electrical insulating property of elemental sulfur causes the utilance of active matter low; Two be electric discharge time sulphur-sulfur bonds, the Small molecular sulfide of generation is dissolved in electrolyte, causes active electrode mass loss, repeatedly circulation after cause capacity attenuation, cycle performance of battery decline.In order to overcome the defect that elemental sulfur exists, normally elemental sulfur is loaded to and have in the carbon element class material of high-specific surface area, high porosity and excellent conductive performance, form composite positive pole, to limit the various negative effects that sulfur-based compound in cyclic process dissolves in electrolyte and causes thus.
Porous carbon ball has good conductivity, and have very high specific area and pore volume, adsorption capacity is large, the features such as density is little, because porous carbon ball porous carbon or carbon black etc. have higher density, the volume energy density of sulfur electrode can be improved, and then meet commercialization demand.Be more suitable for and sulphur compound, improve its conductivity, and sulphur is adsorbed in space and surface, part polysulfide can be suppressed to dissolve in electrolyte.But the dissolving of polysulfide cannot be avoided completely.Be adsorbed on the sulphur on carbon ball surface, owing to only having absorption affinity, there is no hole to its inhibition, so the electrochemical products polysulfide of this part sulphur more easily dissolves effect of shuttling back and forth in the electrolytic solution, thus reduce the utilance of sulphur.
Graphene is a kind of two dimensional surface nano-carbon material, has high-specific surface area, high conductivity, high mechanical properties and high-termal conductivity, is desirable energy storage material.Graphene coated sulfur materials effectively can suppress the loss of electrode active material sulphur.But because in preparation process, Graphene is very easily reunited, graphene sheet layer is easily stacking, causes the surface area of its conductive network greatly to reduce, the advantage of grapheme material itself can not be shown.
Summary of the invention
(1) goal of the invention
The object of the invention is to solve existing electrode material activity material utilization low, the problems such as cycle life is short, and high rate performance is not good, provide that a kind of preparation technology is simple, specific capacity is high, the anode composite of doubly forthright height, good cycle.
Microporous carbon ball, specific area is large, its aperture very little (<2nm), sulphur can better be made to be strapped in narrow hole, to carry out reaction in-situ, suppress its effect of shuttling back and forth, be strapped in the sulphur in bottleneck pore simultaneously, its particle diameter is very little, large with the contact area in hole, can improve the utilance of sulphur and the reversible capacity at circulation time.But along with repeatedly cycle charge discharge, pore structure can suffer certain infringement, or polysulfide departs from constraint, and is dissolved in electrolyte.Be adsorbed on the elemental sulfur of microporous carbon outer surface of ball in addition, its intensity in bond is more weak, and the contact area of itself and carbon is little, and conductivity is not good, so the utilance of this part elemental sulfur is relatively poor.In order to overcome the above problems, the present invention is at sulphur/microporous carbon ball composite material surface evenly one or more layers graphene sheet layer coated, effectively can improve the conductivity of the elemental sulfur of load on sulphur/microporous carbon ball composite material outer surface, and can further improve the utilance of active material sulphur, improve high-rate charge-discharge capability.And the coated loss by dissolution can adsorbing further, stop, suppress intermediate product sulfur-based compound of Graphene, effectively improves the charge-discharge performance of battery.
The present invention also aims to provide a kind of method preparing above-mentioned anode composite.
The present invention also aims to provide a kind of secondary aluminium cell comprising above-mentioned anode composite.
Term " secondary aluminium cell " in the present invention comprises such as " aluminum secondary battery ", " secondary aluminium-sulfur battery ", " rechargeable aluminium battery ", " aluminium storage battery ", " aluminium energy-storage battery " and similar concept.
(2) technical scheme
For achieving the above object, the invention provides following technical scheme:
A kind of anode of secondary battery composite material, it is characterized in that, described composite material comprises:
A) microporous carbon ball;
B) elemental sulfur; With
C) Graphene.
Anode of secondary battery composite material described in scheme, is characterized in that, described microporous carbon ball has hollow ball structure, and the diameter of its ball is 100 ~ 400nm, and specific area is 500 ~ 1000m
2/ g, average pore size is 0.4 ~ 1.5nm.
Anode of secondary battery composite material described in scheme, is characterized in that, described elemental sulfur in microporous carbon ball aperture and surface, forms sulphur/microporous carbon ball composite material by hot melt diffusion way uniform load.
Anode of secondary battery composite material described in scheme, is characterized in that described graphene sheet layer is evenly coated on sulphur/microporous carbon ball composite material surface, and coated graphene sheet layer is the few number of plies (<10 layer).
Anode of secondary battery composite material described in scheme, is characterized in that comprising 50 ~ 80wt% sulphur, 5 ~ 20wt% microporous carbon ball, 1 ~ 20wt% Graphene.
The preparation method of the anode of secondary battery composite material described in scheme, is characterized in that, comprise the following steps:
The preparation of step 1 microporous carbon ball: carbon source be dissolved in sulfonic acid, is heated to 100 ~ 200 DEG C, and reaction 8 ~ 12h, forms black suspension, filtration drying, is heated to 800 ~ 1000 DEG C of sintering 2h ~ 4h under inert atmosphere protection;
Step 2 composite sulfur: by the microporous carbon ball prepared and elemental sulfur in mass ratio 1:5 ~ 1:15 put into tube furnace, under inert gas shielding, be heated to 100 ~ 400 DEG C keep 4 ~ 8h to obtain sulphur/microporous carbon ball composite material;
Step 3 coated graphite alkene: graphite oxide ultrasonic disperse is formed homogeneous graphene oxide solution in deionized water, joins sulphur/microporous carbon ball composite material in the solution of graphene oxide and stirs and ultrasonicly make it fully mix; Seal in the reactor of the mixed solution PTFE of falling people; Then reactor is put in people's baking oven and be warming up to 120 ~ 200 DEG C, keep 4 ~ 8h, carry out hydrothermal reduction graphene coated, be finally cooled to room temperature; Carry out suction filtration, drying obtains graphene coated sulphur/microporous carbon ball composite material.
The preparation method of the anode of secondary battery composite material described in scheme, is characterized in that, the carbon source described in step 1 selects at least one in sucrose, glucose, maltose, fructose.
Scheme also provides a kind of secondary aluminium cell, comprises positive pole, negative pole and electrolyte, it is characterized in that: (a) positive pole; B () is containing aluminum honeycomb; C () non-water is containing aluminium electrolyte.
The positive pole of battery of the present invention comprises positive active material, conductive agent, binding agent and collector.
Positive active material described in scheme is the anode composite described in claim 1.
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), polystyrenebutadienes copolymer (SBR), Viton and polyurethane, PVP, polyethyl acrylate, polyvinyl chloride, polyacrylonitrile, polycaprolactam, polybutadiene, polyisoprene, polyacrylic acid, and derivative, mixture or copolymer.
Collector described in scheme includes but not limited to stainless steel, copper, nickel, titanium, aluminium.More preferably the aluminium collector of carbon coating, more easily covers the coating comprising 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 separator material includes but not limited to: polyolefin is as polyethylene and polypropylene, glass fiber filter paper and ceramic material.
Described in scheme containing aluminum honeycomb active material, include but not limited to: aluminum metal, such as aluminium foil and the aluminium that is deposited on base material; Aluminium alloy, comprises the alloy containing at least one element be selected from Li, Na, K, Ca, Fe, Co, Ni, Cu, Zn, Mn, Sn, Pb, Ma, Ga, In, Cr, Ge and Al.
Non-water described in scheme is organic salt-aluminum halide system ionic liquid containing aluminium electrolyte, and wherein, the mol ratio of organic salt and aluminum halide is 1:1.1 ~ 3.0.
In organic salt described in scheme-aluminum halide system, the cation of organic salt comprises imidazol ion, pyridinium ion, pyrrolidinium ion, piperidines ion, morpholinium 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.
Organic salt described in scheme-aluminum halide system, is characterized in that, described aluminum halide is the one in aluminium chloride, aluminium bromide or silver iodide.
Described in scheme, the preparation method of secondary aluminium cell 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 thick nickel foam substrate of 0.6mm, oven dry roll to 0.33 millimeter be cut into 40mm wide × the long pole piece of 15mm, the barrier film thick with 0.16mm and be wound into battery core with aluminium flake as the negative pole that negative active core-shell material is made and load nickel plating box hat, reinject electrolyte, and secondary aluminium cell is made in sealing.
(3) beneficial effect
Sulphur/microporous carbon ball the anode composite of a kind of Surface coating Graphene provided by the invention, has given full play to original advantage of both microporous carbon ball and Graphene, has had following beneficial effect:
(1) microporous carbon ball has good conductivity, and be pore structure, good conductive channel can be provided to have very high specific area and pore volume, adsorption capacity is large, the more active material of energy load, and the aperture of micropore is very narrow and small, can it be made to carry out reaction in-situ by more effective constraint sulphur, suppress the stripping of sulphur in battery charge and discharge process, thus the loss slowing down sulphur effectively improves the utilance of elemental sulfur, thus improve its cycle performance., the coated loss by dissolution also can adsorbing further, stop, suppress intermediate product sulfur-based compound of Graphene, effectively improves the charge-discharge performance of battery.
(2) elemental sulfur enters in the narrow and small hole of microporous carbon ball, form the nano-sulfur particles that diameter is less, see on the whole, improve the contact area of elemental sulfur and conductive carbon, because elemental sulfur is insulator, its needs to contact with the material with satisfactory electrical conductivity transmits electronics and electrochemical reaction could occur, so higher surface area, further increases the utilance of sulphur.
(3) outer field graphene sheet layer is evenly coated on; the contact resistance that the elemental sulfur that effectively can reduce load on sulphur/microporous carbon outer surface of ball produces; and the utilance that constraint protective effect can further improve active material sulphur is played to the active material of outer surface, improves high-rate charge-discharge capability.
(4) embodiment
Be described further below with reference to the technique effect of embodiment to design of the present invention, concrete structure and generation, to understand object of the present invention, characteristic sum effect fully.The following examples describe several execution mode of the present invention, and they are only illustrative, and nonrestrictive.
Embodiment 1
(1) preparation of microporous carbon ball: be that carbon source adds the solution of 6mol sulfonic acid formation containing 5% sucrose with glucose, be heated to 120 DEG C, reaction 10h, forms black suspension, filtration drying, is heated to 1000 DEG C of sintering 2h under inert atmosphere protection.
(2) microporous carbon ball and composite sulfur: by the microporous carbon ball prepared and elemental sulfur in mass ratio 1:5 put into tube furnace,
Being heated to 150 DEG C under inert gas shielding keeps 6h to obtain sulphur/microporous carbon ball composite material.
(3) coated graphite alkene: configuration concentration is the graphene oxide water solution of 8mg/ml, and ultrasonic disperse 5h, then adds
Enter reducing agent ammoniacal liquor, 48h is reacted under ultrasound condition, obtaining graphene dispersing solution, is the graphene dispersing solution of 4wt% through vacuum filtration, the obtained Graphene content of washing, and sulphur/microporous carbon ball composite material joins in the solution of graphene oxide and stirs and ultrasonicly make it fully mix; Seal in the reactor of the mixed solution PTFE of falling people, then reactor is put in people's baking oven and be warming up to 150 DEG C, keep 6h to carry out hydrothermal reduction graphene coated, be finally cooled to room temperature; Carry out suction filtration, drying obtains graphene coated sulphur/microporous carbon ball composite material.
Embodiment 2
(1) preparation of microporous carbon ball: be that carbon source adds the solution of 6mol sulfonic acid formation containing 5% sucrose with glucose, be heated to 120 DEG C, reaction 10h, forms black suspension, filtration drying, is heated to 1000 DEG C of sintering 2h under inert atmosphere protection.
(2) microporous carbon ball and composite sulfur: by the microporous carbon ball prepared and elemental sulfur in mass ratio 1:5 put into tube furnace, be heated to 150 DEG C under inert gas shielding and keep 6h to obtain sulphur/microporous carbon ball composite material.
(3) coated graphite alkene: configuration concentration is the graphene oxide water solution of 16mg/ml, ultrasonic disperse 5h, then reducing agent ammoniacal liquor is added, 48h is reacted under ultrasound condition, obtain graphene dispersing solution, be the graphene dispersing solution of 8wt% through vacuum filtration, the obtained Graphene content of washing, sulphur/microporous carbon ball composite material joins in the solution of graphene oxide and stirs and ultrasonicly make it fully mix.Seal in the reactor of the mixed solution PTFE of falling people; Then reactor is put in people's baking oven and be warming up to 150 DEG C, keep 6h to carry out hydrothermal reduction graphene coated, be finally cooled to room temperature; Carry out suction filtration, drying obtains graphene coated sulphur/microporous carbon ball composite material.
Embodiment 3
(1) preparation of microporous carbon ball: be that carbon source adds the solution of 6mol sulfonic acid formation containing 5% sucrose with glucose, be heated to 120 DEG C, reaction 10h, forms black suspension, filtration drying, is heated to 1000 DEG C of sintering 2h under inert atmosphere protection.
(2) microporous carbon ball and composite sulfur: by the microporous carbon ball prepared and elemental sulfur in mass ratio 1:5 put into tube furnace, be heated to 150 DEG C under inert gas shielding and keep 6h to obtain sulphur/microporous carbon ball composite material.
(3) coated graphite alkene: configuration concentration is the graphene oxide water solution of 24mg/ml, ultrasonic disperse 5h, then reducing agent ammoniacal liquor is added, 48h is reacted under ultrasound condition, obtain graphene dispersing solution, be the graphene dispersing solution of 12wt% through vacuum filtration, the obtained Graphene content of washing, sulphur/microporous carbon ball composite material joins in the solution of graphene oxide and stirs and ultrasonicly make it fully mix; Seal in the reactor of the mixed solution PTFE of falling people; Then reactor is put in people's baking oven and be warming up to 150 DEG C, keep 6h to carry out hydrothermal reduction graphene coated, be finally cooled to room temperature; Carry out suction filtration, drying obtains graphene coated sulphur/microporous carbon ball composite material.
Embodiment 4
(1) preparation of microporous carbon ball: be that carbon source adds the solution of 6mol sulfonic acid formation containing 5% sucrose with glucose, be heated to 120 DEG C, reaction 10h, forms black suspension, filtration drying, is heated to 1000 DEG C of sintering 2h under inert atmosphere protection.
(2) microporous carbon ball and composite sulfur: by the microporous carbon ball prepared and elemental sulfur in mass ratio 1:8 put into tube furnace, be heated to 150 DEG C under inert gas shielding and keep 6h to obtain sulphur/microporous carbon ball composite material.
(3) coated graphite alkene: configuration concentration is the graphene oxide water solution of 16mg/ml, ultrasonic disperse 5h, then reducing agent ammoniacal liquor is added, 48h is reacted under ultrasound condition, obtain graphene dispersing solution, be the graphene dispersing solution of 8wt% through vacuum filtration, the obtained Graphene content of washing, sulphur/microporous carbon ball composite material joins in the solution of graphene oxide and stirs and ultrasonicly make it fully mix.Seal in the reactor of the mixed solution PTFE of falling people.Then reactor is put in people's baking oven and be warming up to 150 DEG C, keep 6h.Carry out hydrothermal reduction graphene coated, be finally cooled to room temperature.Carry out suction filtration, drying.Obtain graphene coated sulphur/microporous carbon ball composite material.
Embodiment 5
(1) preparation of microporous carbon ball: be that carbon source adds the solution of 6mol sulfonic acid formation containing 5% sucrose with glucose, be heated to 120 DEG C, reaction 10h, forms black suspension, filtration drying, is heated to 1000 DEG C of sintering 2h under inert atmosphere protection.
(2) microporous carbon ball and composite sulfur: by the microporous carbon ball prepared and elemental sulfur in mass ratio 1:10 put into tube furnace, be heated to 150 DEG C under inert gas shielding and keep 6h to obtain sulphur/microporous carbon ball composite material.
(3) coated graphite alkene: configuration concentration is the graphene oxide water solution of 16mg/mL, ultrasonic disperse 5h, then reducing agent ammoniacal liquor is added, 48h is reacted under ultrasound condition, obtain graphene dispersing solution, be the graphene dispersing solution of 8wt% through vacuum filtration, the obtained Graphene content of washing, sulphur/microporous carbon ball composite material joins in the solution of graphene oxide and stirs and ultrasonicly make it fully mix; Seal in the reactor of the mixed solution PTFE of falling people; Then reactor is put in people's baking oven and be warming up to 150 DEG C, keep 6h to carry out hydrothermal reduction graphene coated, be finally cooled to room temperature.Carry out suction filtration, drying obtains graphene coated sulphur/microporous carbon ball composite material.
Embodiment 6
Graphene coated sulphur embodiment 1,2,3,4,5 prepared/microporous carbon ball composite material, conductive agent acetylene black and binding agent PVDF be (75:15:10) mixing in proportion, making active material slurry is applied on the thick nickel foam substrate of 0.6mm, oven dry roll to 0.33 millimeter be cut into 40mm wide × the long pole piece of 15mm, the glass fibre thick with 0.16mm is non-to be knitted barrier film and is wound into battery core loading nickel plating box hat with aluminium flake as the negative pole that negative active core-shell material is made, reinject aluminium chloride-triethylamine hydrochloride ionic liquid electrolyte, and AA type secondary aluminium cell is made in sealing.
Embodiment 7
Carry out charge and discharge cycles test to made battery, charge to 2.5V with 1C, 0.1C discharges, and discharge cut-off voltage is 1.2V, and test result is as follows:
(1) the made battery of embodiment 1 material, open circuit voltage 1.68V, first discharge capacity 610mAh, circulate after 50 times, capability retention 75%.
(2) the made battery of embodiment 2 material, open circuit voltage 1.70V, first discharge capacity 694mAh, circulate after 50 times, capability retention 85%.
(3) the made battery of embodiment 3 material, battery open circuit voltage 1.68V, first discharge capacity 623mAh, circulate after 50 times, capability retention 80%.
(4) the made battery of embodiment 4 material, battery open circuit voltage 1.68V, first discharge capacity 750mAh, circulate after 50 times, capability retention 87%.
(5) the made battery of embodiment 5 material, battery open circuit voltage 1.70V, first discharge capacity 705mAh, circulate after 50 times, capability retention 83%.
Although reference embodiment is to invention has been detailed description, but those skilled in the art is to be understood that, when not departing from the spirit and scope of the present invention described in appended claims and equivalent thereof, various amendment and replacement can be made to it.
Claims (8)
1. an anode of secondary battery composite material, is characterized in that, described composite material comprises:
A) microporous carbon ball;
B) elemental sulfur; With
C) Graphene.
2. anode of secondary battery composite material as claimed in claim 1, it is characterized in that, described microporous carbon ball has hollow ball structure, and the diameter of its ball is 100 ~ 400nm, and specific area is 500 ~ 1000m
2/ g, average pore size is 0.4 ~ 1.5nm.
3. anode of secondary battery composite material as claimed in claim 1, is characterized in that, described elemental sulfur in microporous carbon ball aperture and surface, forms sulphur/microporous carbon ball composite material by hot melt diffusion way uniform load.
4. anode of secondary battery composite material as claimed in claim 1, it is characterized in that described graphene sheet layer is evenly coated on sulphur/microporous carbon ball composite material surface, and coated graphene sheet layer is the few number of plies (<10 layer).
5. anode of secondary battery composite material as claimed in claim 1, is characterized in that comprising 50 ~ 80wt% sulphur, 5 ~ 30wt% microporous carbon ball, 1 ~ 20wt% Graphene.
6. a preparation method for anode of secondary battery composite material according to claim 1, is characterized in that, comprise the following steps:
The preparation of step 1 microporous carbon ball: carbon source be dissolved in sulfonic acid, is heated to 100 ~ 200 DEG C, and reaction 8 ~ 12h forms black suspension, filtration drying, is heated to 800 ~ 1000 DEG C of sintering 2h ~ 4h under inert atmosphere protection;
Step 2 composite sulfur: by the microporous carbon ball prepared and elemental sulfur in mass ratio 1:5 ~ 1:15 put into tube furnace, under inert gas shielding, be heated to 100 ~ 400 DEG C keep 4 ~ 8h to obtain sulphur/microporous carbon ball composite material;
Step 3 coated graphite alkene: graphite oxide ultrasonic disperse is formed homogeneous graphene oxide solution in deionized water, joins sulphur/microporous carbon ball composite material in the solution of graphene oxide and stirs and ultrasonicly make it fully mix; Seal in the reactor of the mixed solution PTFE of falling people, then reactor is put in people's baking oven and be warming up to 120 ~ 200 DEG C, keep 4 ~ 8 h, carry out hydrothermal reduction graphene coated, be finally cooled to room temperature; Carry out suction filtration, drying obtains graphene coated sulphur/microporous carbon ball composite material.
7. the preparation method of anode of secondary battery composite material as claimed in claim 6, is characterized in that, the carbon source described in step 1 selects at least one in sucrose, glucose, maltose, fructose.
8. a secondary aluminium cell, comprising:
Anode composite described in (a) claim 1;
B () is containing aluminum honeycomb active material;
C () non-water is containing aluminium electrolyte.
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| CN104882594A (en) * | 2015-04-16 | 2015-09-02 | 中国人民解放军国防科学技术大学 | Three-dimensional graphene-hollow carbon sphere nano composite and preparation method thereof |
| CN105576193A (en) * | 2015-12-21 | 2016-05-11 | 张志平 | Multi-layer carbon-sulfur composite positive electrode structure of aluminum ion battery and preparation method of multi-layer carbon-sulfur composite positive electrode structure of aluminum ion battery |
| CN105810915A (en) * | 2016-05-16 | 2016-07-27 | 北京化工大学 | Preparation of graphene-coated sulfur-embedded ordered mesoporous carbon sphere composite material and application of ordered mesoporous carbon sphere composite material as lithium-sulfur battery positive electrode material |
| CN106450423A (en) * | 2016-09-30 | 2017-02-22 | 上海空间电源研究所 | High-specific-energy flexible integrated electrode and preparation method therefor |
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| CN107768643A (en) * | 2017-10-19 | 2018-03-06 | 山东大学 | A kind of carbon ball/sulphur/redox graphene composite for lithium-sulfur cell and preparation method thereof |
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| CN109291450A (en) * | 2018-09-13 | 2019-02-01 | 中北大学 | A kind of high-performance nano graphene foaming aluminum and preparation method thereof and prepare material |
| CN109755499A (en) * | 2018-12-03 | 2019-05-14 | 河南师范大学 | A kind of iron nickel secondary batteries cathode additive agent, preparation method and iron-based negative plate and application using the additive |
| CN110506026A (en) * | 2017-03-15 | 2019-11-26 | 迪金森公司 | Include the carbon nano-structured compound of untreated cellular |
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| CN107342401A (en) * | 2017-06-02 | 2017-11-10 | 深圳启辰新能源科技有限公司 | Multi-functional film layer carbon coated/sulphur composite positive pole of conducting polymer/ionomer/graphene and preparation method thereof |
| CN107342401B (en) * | 2017-06-02 | 2018-08-10 | 深圳启辰新能源科技有限公司 | Multi-functional film layer carbon coated/sulphur composite positive pole of conducting polymer/ionomer/graphene and preparation method thereof |
| CN107768643A (en) * | 2017-10-19 | 2018-03-06 | 山东大学 | A kind of carbon ball/sulphur/redox graphene composite for lithium-sulfur cell and preparation method thereof |
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