CN101645500B - Carbon-based material inlaid and penetrated with sulfur and aluminum secondary battery using same as cathode active material - Google Patents
Carbon-based material inlaid and penetrated with sulfur and aluminum secondary battery using same as cathode active material Download PDFInfo
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Abstract
The present invention discloses a preparation method of anode active material of a rechargeable aluminum secondary battery, the secondary battery using the anode active material and a preparation method of the secondary battery. The invention aims to provide a high energy aluminum secondary battery of which anode active material has simple preparation process, low cost, no pollution and good circularity and a preparation method of the high energy battery. The anode active material is prepared by adopting a high temperature high pressure inlay and penetrating process to ensure sulfur in carbon-sulfur mixture with sulfur (S8) or sulfenyl compounds to inlay and penetrate into the surface of carbon-base and micropores at 90-300 DEG C and 320-800 DEG C under the pressure of 0.01-5 MPa. The aluminum secondary battery contains an anode prepared by the anode active material, a aluminum cathode and a aluminum electrolyte system. The products of the present invention can be used as power batteries and energy-storage batteries to be widely used in electric bicycles, electric cars, emergency power supplies, peak value adjusting systems of power station and energy-storage systems of new energies such as solar energy, wind energy and the like, and has very broad development prospect.
Description
Technical field
The present invention relates to positive electrode active materials of a kind of novel secondary aluminium cell and preparation method thereof, and the secondary aluminium cell that uses this material.Relate to the electrode material that uses in the electrochemical cell, more particularly, the present invention relates to a kind of preparation " sulphur (S
8), sulfur-based compound or their mixture, described sulfur-based compound comprises organic sulfur and carbon sulphur compound, above-mentioned carbon sulphur compound refers in particular to the compound or the assembly of embedding sulfurizing on the carbon back " method, and use the novel secondary aluminium cell of this positive electrode active materials and the preparation method of this secondary aluminium cell thereof.
Background technology
Along with people to the craving for of high-energy-density power supply, press for the exploitation and the application of cheapness, safety, environmental protection and high performance secondary cell.With aluminium and alloy thereof be negative material, sulfur-based compound with sulphur-sulfide linkage is that the secondary aluminium-sulfur battery of positive pole then is one of battery that satisfies above-mentioned requirements.Aluminium, sulfur materials safety, environmental protection, cheap and aboundresources, battery security is good.The metallic aluminium theoretical energy density is only second to lithium metal (3862mAh/g) up to 2980mAh/g.Its volume and capacity ratio is 8050mAh/cm
3, be about lithium (2040mAh/cm
3) 4 times, the aluminium electrode potential in neutrality and acid medium is-1.66V, is-2.35V that elementary sulfur also has bigger theoretical energy density (1670mAh/g), all is desirable high-energy battery material in alkaline medium.
With elemental sulfur (S
8) for the redox reaction of positive electrode active materials is a multistep electron exchange process, this redox reaction has certain electrochemical reversibility, for elemental sulfur provides theoretical foundation as the electrode for secondary battery active material.
From early stage high temperature Na/S battery to Li/SOCl
2Lithium inorganic electrolyte primary cell arrives the organic nonaqueous electrolyte serondary lithium battery of Li/S again, and people have experienced the historical process of exploration, understanding and a development as cell active materials to sulphur.Elemental sulfur can be as electrode active material by its structure and electrochemical characteristic decision, and during discharge (electrochemical reduction), the sulphur sulfide linkage ruptures, and the oxidation number of sulphur reduces; When recharging (electrochemical oxidation), the sulphur sulfide linkage forms, and the oxidation number of sulphur raises.By this redox reaction, the sulphur in the sulfur-based compound can store and produce power.This sulphur also often is called " activation sulphur ".
The most stable sulfur molecule (the S of thermodynamics under the room temperature
8) be by eight S atoms be connected to form crown, between the sulfur molecule in conjunction with forming the good elemental sulfur of crystallinity.Elemental sulfur does not at room temperature have the existence of sulphion state, is typical electronic and ion insulator, and the sulphur activation is very difficult during therefore as electrode active material.Though elemental sulfur also can activate during under certain condition as high temperature, this condition is that sulphur just is activated and reacts under greater than 350 ℃ of high temperature, and the application prospect of this state is also pessimistic.At first, sulphur is electronics, ion insulator, and the transmission on electrode of electronics and ion is difficulty very, and room temperature electrochemical reaction dynamics speed is very slow, and this just needs to improve the electronic and ionic transmission capacity of negative electrode; Secondly, the poly sulfide intermediate that reduction process produces is soluble in the organic solvent, and the active material loss causes utilization efficiency to reduce, and this just need make poly sulfide can remain in the negative electrode; The 3rd, the sulfide that reaction produces can be deposited on the negative electrode, because its electronic isolation hinders the transmission of electric charge on the one hand, has changed the state of interface of electrode/electrolyte on the other hand again, and this just needs to change the distribution of sulfide in electrode.These problems cause finally that the sulphur active material utilization is low in secondary cell, capacity attenuation is rapid.
Existing carbon sulfur materials, what have just adds conductive agent carbon class material in elemental sulfur, it is a kind of physics mixture of carbon sulphur, though increased the electric conductivity of material, to the reversible reaction of sulphur without any influence;
The carbon sulphur clad material that also has is also just under argon gas emptying condition of normal pressure, by the absorption of static state heating with realization carbon sulphur.But owing to there is not pressure in tube furnace, be close to unlimitedly, the sulphur heating and gasifying is discharged with argon gas later on greatly, and loss is a lot, the one, and covering amount is few, coating efficiency is low; The 2nd, sulphur only is adsorbed on the surface, and reversibility is poor.
In elemental sulfur, add carbon class conductive agent, just increased the conductivity of electrode, to the reversible reaction of sulphur without any help; Coat sulphur with tube furnace under normal pressure static state, coating efficiency is low, and the sulphur loss is big; Do not form between carbon sulphur yet and change thing, generate the solubility polysulfide, be dissolved in the ion electrolyte, generate the unordered sulphur of irreversible reaction through reaction; Coat not have stir under normal pressure static state, coats inhomogeneously, bottom carbon also easily lumps.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of positive electrode active materials that is used for secondary aluminium cell is provided, this active material can improve anodal electrochemical reversibility, reduces the positive electrode capacity loss.
Another object of the present invention provides the anode active material composition that is used for secondary aluminium cell, and it gives anodal high power capacity by increasing positive electrode active materials relative quantity therein.
A further object of the present invention provides a kind of preparation method who comprises the positive electrode active materials that is used for secondary aluminium cell.
The present invention also provides a kind of manufacture method that comprises the secondary aluminium cell positive pole of above-mentioned positive electrode active materials.
Further purpose of the present invention provides a kind of secondary aluminium cell that comprises above-mentioned positive pole.
The form that the present invention is directed to sulphur is a lot, elemental sulfur is that insulator, sulphur and the polysulfide of ion and electronics is non-conductive basically at ambient temperature, and discharging product be the solubility polysulfide, it can be dissolved in the ion electrolyte, generate irreversible reaction unordered sulphur, cause problems such as the quick damage of battery capacity subtracts, studying on the structure of sulphur positive electrode He on the preparation method.The preparation of carbon back embedding sulfurizing material makes sulphur become possibility as the aluminum secondary battery positive electrode.
The present invention is realized by following technical proposals:
The preparation method of positive electrode active materials, described positive electrode active materials comprises sulphur (S
8), sulfur-based compound or their mixture, this sulfur-based compound comprises organic sulfur and carbon sulphur compound, it is characterized in that: this method has following steps: get carbon, graphite, in the activated carbon one or both and elemental sulfur powder are by weight mixing, when getting carbon, graphite, when a kind of the and elemental sulfur powder in the activated carbon mixes by weight, the weight ratio of the weight ratio of C: S=0.5～3: 1～5 or C: S=10～60g: 20～100g, add alcohol ball milling mixing 1-10 hour, put into 85～95 ℃ of bakings of vacuum drying chamber 8～12 hours after the taking-up, after oozing in the jar carbon after adding above-mentioned mixing oven dry and sulphur powder, the high pressure embedding seals, open the logical argon gas of pressurized tank intake ﹠ exhaust valves and squeezed emptying gas 1 hour, closing vent valve treats to close intake valve after pressure rises to 0.01～0.5 MPa, resistance furnace begins to high pressure embedding and oozes a jar heating, when furnace temperature is raised to 90～300 ℃, keep 0.5～10h, be warmed up to 320～800 ℃ again, keep 1～10h, stop to heat, with coming out of the stove after the stove cooling, grinding is sieved, add conductive agent and adhesive, anode active material composition composition and weight percentage are: sulphur (S
8), sulfur-based compound or their mixture, this sulfur-based compound comprises organic sulfur and carbon sulphur compound: 60～90 weight %, binding agent 5～20 weight %, conductive agent 5～20 weight % make the positive electrode active materials slurry.
The preparation method of positive electrode active materials as previously discussed is characterized in that: above-mentioned positive electrode active materials comprises sulphur (S
8), sulfur-based compound or their mixture, this sulfur-based compound comprises that organic sulfur and carbon sulphur compound are carbon back embedding sulfurizing, anode active material composition composition and weight percentage are: carbon back embedding sulfurizing 60～90 weight %, binding agent 5～20 weight %, conductive agent 5～20 weight % make the positive electrode active materials slurry.
The preparation method of carbon back embedding sulfurizing positive electrode active materials as previously discussed, it is characterized in that: this method has following steps: get carbon, graphite, in the activated carbon one or both and elemental sulfur powder are by weight mixing, when getting carbon, graphite, when a kind of the and elemental sulfur powder in the activated carbon mixes by weight, C: S=1: the weight ratio of 3 weight ratios or C: S=20g: 60g, adding the alcohol ball milling mixed 2 hours, put into 90 ℃ of bakings of vacuum drying chamber 10 hours after the taking-up, after oozing in the jar carbon after adding above-mentioned mixing oven dry and sulphur powder, the high pressure embedding seals, open the logical argon gas of pressurized tank intake ﹠ exhaust valves and squeeze emptying gas half an hour, closing vent valve treats to close intake valve after pressure rises to 0.1 MPa, resistance furnace begins to high pressure embedding and oozes a jar heating, when furnace temperature is raised to 200 ℃, keep 2h, be warmed up to 450 ℃ again, keep 3h, stop to heat, with coming out of the stove after the stove cooling, grinding is sieved, add conductive agent and adhesive, the composition of anode plate and weight percentage are: carbon back embedding sulfurizing 70 weight %, binding agent 10 weight %, conductive agent 20 weight % make the positive electrode active materials slurry.
A kind of aluminum secondary battery comprises the aluminum secondary battery that is made of anode plate, negative plates and electrolyte, barrier film, and described negative material is aluminium and alloy thereof; Described electrolyte is characterized in that for containing aluminum ions ionic liquid positive electrode active materials comprises sulphur (S
8), sulfur-based compound or their mixture, this sulfur-based compound comprises organic sulfur and carbon sulphur compound, anode active material composition composition and weight percentage are: sulphur (S
8), sulfur-based compound or their mixture 60～90 weight %, binding agent 5～20 weight %, conductive agent 5～20 weight %, above-mentioned binding agent are a kind of in polyethylene glycol oxide or the polyvinyl alcohol, and above-mentioned conductive agent is a kind of in acetylene black, the electrically conductive graphite or both mixtures.
Aluminum secondary battery as previously discussed comprises the aluminum secondary battery that is made of anode plate, negative plates and electrolyte, barrier film, and described negative material is aluminium and alloy thereof; Described electrolyte is characterized in that for containing aluminum ions ionic liquid, described sulphur (S
8), sulfur-based compound or their mixture be carbon back embedding sulfurizing, the composition of anode plate and weight percentage are: carbon back embedding sulfurizing 60-90 weight %, binding agent 5-20 weight %, conductive agent 5-20 weight %.
Aluminum secondary battery as previously discussed comprises the aluminum secondary battery that is made of anode plate, negative plates and electrolyte, barrier film, and described negative material is aluminium and alloy thereof; Described electrolyte is characterized in that for containing aluminum ions ionic liquid the composition of anode plate and weight percentage are: carbon back embedding sulfurizing 70 weight %, binding agent 10 weight %, conductive agent 20 weight %.
The preparation method of aluminum secondary battery is characterized in that: this method has following steps:
1) preparation sulphur (S
8), the positive electrode active materials of sulfur-based compound or their mixture, this sulfur-based compound comprises organic sulfur and carbon sulphur compound, get carbon, graphite, in the activated carbon one or both and elemental sulfur powder are by weight mixing, when getting carbon, graphite, when a kind of the and elemental sulfur powder in the activated carbon mixes by weight, the weight ratio of the weight ratio of C: S=0.5～3: 1～5 or C: S=10～60g: 20～100g, adding the alcohol ball milling mixed 1～10 hour, put into 85～95 ℃ of bakings of vacuum drying chamber 8～12 hours after the taking-up, after oozing in the jar carbon after adding above-mentioned mixing oven dry and sulphur powder, the high pressure embedding seals, open the logical argon gas of pressurized tank intake ﹠ exhaust valves and squeezed emptying gas 1 hour, closing vent valve treats to close intake valve after pressure rises to 0.01～0.5 MPa, resistance furnace begins to high pressure embedding and oozes a jar heating, when furnace temperature is raised to 90～300 ℃, keep 0.5～10h, be warmed up to 320～800 ℃ again, keep 1～10h, stop to heat, with coming out of the stove after the stove cooling, grinding is sieved, add conductive agent and adhesive, anode active material composition composition and weight percentage are: sulphur (S
8), sulfur-based compound or their mixture 60-90 weight %, conductive agent: 5～20%, adhesive: 5～20%, make the positive electrode active materials slurry;
2) with the above-mentioned positive electrode active materials slurry of making, be coated on the thick nickel foam substrate of 0.10-0.20mm, oven dry roll to 0.4-0.8mm be cut into 30-50mm wide * the long pole piece of 140-160mm, with the thick glass fibre of 0.10-0.20mm non-knit barrier film and be wound into electric stamen with a kind of negative pole of making as negative active core-shell material in aluminium powder or aluminium foil, the aluminium alloy pack in any shell in nickel plating box hat, stainless steel case or the aluminum hull, add organic bath again, seal and make cylindrical aluminium secondary cell or AA type cylindrical aluminium secondary cell.
The preparation method of aluminum secondary battery as previously discussed is characterized in that: this method has following steps:
1) prepares above-mentioned sulphur (S
8), the positive electrode active materials of sulfur-based compound or their mixture, this sulfur-based compound comprises organic sulfur and carbon sulphur compound, above-mentioned positive electrode active materials is a carbon back embedding sulfurizing positive electrode active materials, prepare this carbon back embedding sulfurizing positive electrode active materials: get carbon, graphite, in the activated carbon one or both and elemental sulfur powder are by weight mixing, when getting carbon, graphite, when a kind of the and elemental sulfur powder in the activated carbon mixes by weight, the weight ratio of the weight ratio of C: S=0.5～3: 1～5 or C: S=10～60g: 20～100g, add alcohol ball milling mixing 1-10 hour, put into 85～95 ℃ of bakings of vacuum drying chamber 8～12 hours after the taking-up, after oozing in the jar carbon after adding above-mentioned mixing oven dry and sulphur powder, the high pressure embedding seals, open the logical argon gas of pressurized tank intake ﹠ exhaust valves and squeezed emptying gas 0.5-1.5 hour, closing vent valve treats to close intake valve after pressure rises to 0.01～0.5 MPa, resistance furnace begins to high pressure embedding and oozes a jar heating, when furnace temperature is raised to 90～300 ℃, keep 0.5～10h, be warmed up to 320～800 ℃ again, keep 1～10h, stop to heat, with coming out of the stove after the stove cooling, grinding is sieved, add conductive agent and adhesive, the composition of anode active material composition and content % are by weight counted: carbon back embedding sulfurizing positive electrode active materials: 60～90%, conductive agent: 5～20%, adhesive: 5～20%, make the positive electrode active materials slurry;
2) with the above-mentioned positive electrode active materials slurry of making, be coated on the thick nickel foam substrate of 0.10-0.20mm, oven dry roll to 0.4-0.8mm be cut into 30-50mm wide * the long pole piece of 140-160mm, with the thick glass fibre of 0.10-0.20mm non-knit barrier film and be wound into electric stamen with a kind of negative pole of making as negative active core-shell material in aluminium powder or aluminium foil, the aluminium alloy pack in any shell in nickel plating box hat, stainless steel case or the aluminum hull, add organic bath again, seal and make cylindrical aluminium secondary cell or AA type cylindrical aluminium secondary cell.
The preparation method of aluminum secondary battery as previously discussed is characterized in that: this method has following steps:
1) prepares above-mentioned sulphur (S
8), the positive electrode active materials of sulfur-based compound or their mixture, this sulfur-based compound comprises organic sulfur and carbon sulphur compound, above-mentioned positive electrode active materials is a carbon back embedding sulfurizing positive electrode active materials, prepare this carbon back embedding sulfurizing positive electrode active materials: get carbon, graphite, in the activated carbon one or both and elemental sulfur powder are by weight mixing, when getting carbon, graphite, when a kind of the and elemental sulfur powder in the activated carbon mixes by weight, C: S=1: the weight ratio of 3 weight ratio or C: S=20g: 60g, adding the alcohol ball milling mixed 2 hours, put into 90 ℃ of bakings of vacuum drying chamber 10 hours after the taking-up, after oozing in the jar carbon after adding above-mentioned mixing oven dry and sulphur powder, the high pressure embedding seals, open the logical argon gas of pressurized tank intake ﹠ exhaust valves and squeeze emptying gas half an hour, closing vent valve treats to close intake valve after pressure rises to 0.1 MPa, resistance furnace begins to high pressure embedding and oozes a jar heating, when furnace temperature is raised to 200 ℃, keep 2h, be warmed up to 450 ℃ again, keep 3h, stop to heat, with coming out of the stove after the stove cooling, grinding is sieved, add conductive agent and adhesive, the composition of anode active material composition and content % are by weight counted: carbon back embedding sulfurizing positive electrode active materials: 70%, conductive agent: 20%, adhesive: 10%, make the positive electrode active materials slurry;
2) with the above-mentioned positive electrode active materials slurry of making, be coated on the thick nickel foam substrate of 0.16mm, oven dry rolls to 0,6mm the is cut into 40mm long pole piece of wide * 150mm, knit barrier film and be wound into electric stamen pack into nickel plating box hat, stainless steel case or aluminum hull with the thick glass fibre of 0.16mm is non-with a kind of negative pole of making as negative active core-shell material in aluminium powder or aluminium foil, the aluminium alloy, add organic bath again, seal and make cylindrical aluminium secondary cell or AA type cylindrical aluminium secondary cell.
The preparation method of aluminum secondary battery as previously discussed, it is characterized in that: above-mentioned positive electrode active materials is a carbon back embedding sulfurizing positive electrode active materials, during preparation carbon back embedding sulfurizing positive electrode active materials, use the binary carbon back, activated carbon and elemental sulfur powder are mixed with graphite, and concrete ratio is an active carbon: elemental sulfur: graphite by weight=0.5～0.8: 5: 0.2～0.5; The discharge gram volume is raise, wherein active carbon: elemental sulfur: graphite by weight=0.8: 5: 0.2 preferred; The discharge gram volume is raise.
Should be noted that: above-mentioned carbon back embedding sulfurizing is meant by heating, pressurization and stirrings of rolling fast, make gaseous state and liquid sulfur embed and infilter in the micropore of material with carbon element, thus a kind of technology that realization sulphur is coated.
The manufacture method of a kind of secondary aluminium cell positive pole that the present invention includes is that above-mentioned positive electrode active materials, conductive agent and binding agent are blended in the organic solvent with the preparation anode active material composition.Then this composition is coated on and forms the positive electrode active materials coating on the collector.
Positive electrode active materials comprises sulphur (S
8), sulfur-based compound or their mixture.Sulfur-based compound comprises organic sulfur and carbon sulphur compound, is preferably carbon back embedding sulfurizing.
Conductive agent comprises carbon back, graphite based conducting material and conducting polymer, as active carbon, carbon black, acetylene carbon black, super carbon black Super-P, graphite, polyaniline, polyacetylene, polypyrrole, polythiophene etc.Electric conducting material can use separately or being used in combination of two or more above-mentioned electric conducting materials.
Binding agent comprises polyvinyl acetate, polyvinyl alcohol, polyethylene glycol oxide, polyvinylpyrrolidone, polyvinylether, polymethyl methacrylate, Kynoar, polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyvinyl pyridine, polystyrene, and their derivative, mixture and copolymer.
Organic solvent comprises acetonitrile, methyl alcohol, ethanol, acetone, oxolane, water and isopropyl alcohol.
Collector comprises the electric conducting material of stainless steel, carbon, copper, aluminium, nickel.It can be a kind in the form such as foam, net, paper tinsel, sheet of metal and the carbon cloth.
Positive electrode active materials among the present invention is a kind of carbon back embedding sulfurizing material, makes by a kind of " carbon back embedding sulfurizing " technology." carbon back embedding sulfurizing " is meant by the embedding of a kind of carbon sulphur high pressure and oozes device (this is a utility model patent of applying for), with the heating of carbon sulphur mixture, pressurization and the stirring of rolling fast that is placed in one, make the carbon sulfur materials in the stove compound more equably, make gaseous sulfur and molten sulfur embed and infilter in the micropore of material with carbon element, thereby realize that sulphur is coated in the carbon degree of depth, improve the invertibity of sulphur positive electrode active materials and a kind of technology of specific capacity.
Can solve the conductivity problems of sulphur by the carbon back embedding sulfurizing material of above technology manufacturing, the reversibility of sulphur is greatly improved, improve the utilance and the electrochemical efficiency of sulphur.
Negative material is aluminium and alloy thereof.Aluminium alloy is one or more in aluminium and lithium, sodium, potassium, gallium, indium, thallium, iron, cobalt, nickel, copper, zinc, manganese, tin, lead, magnesium, calcium, chromium, germanium etc.The form of aluminum or aluminum alloy can be a kind in ultra micro, ultra-fine or nano powder, silk, net, sheet, paper tinsel, foam etc.
Electrolyte comprises and contains aluminium or do not contain aluminium ion liquid, as aluminum halide with quaternary ammonium salt, quaternary alkylphosphonium salt, the formed halogen aluminic acid of season sulfosalt ionic liquid.Be preferably room temperature chlorine aluminic acid ionic liquid.
The preparation of carbon back embedding sulfurizing material of the present invention and compared with the prior art following beneficial effect is arranged as the aluminum secondary battery of positive electrode active materials and the preparation method of aluminum secondary battery:
1. the whole process of carbon back embedding sulfurizing material preparation of the present invention is to carry out under vacuum or airtight condition, and therefore whole process is pollution-free, has good environmental benefit;
2. aluminium, sulphur resource are extremely abundant, and the preparation process of cell positive material is simple, and preparation technology is simple, and preparation cost is low, therefore, has good economic benefits;
3. material of the present invention has the energy density height, with this aluminum secondary battery energy density height for preparing, and good cycle, therefore, resource can be used repeatedly;
4. both solved the conductivity problems of sulphur by the carbon back embedding sulfurizing material of this technology manufacturing, the reversibility of sulphur is greatly improved, the preparation method has also improved the utilance and the electrochemical efficiency of sulphur, therefore, product of the present invention can be used as the energy-storage system that electrokinetic cell and energy-storage battery are widely used for new forms of energy such as electric bicycle, electric automobile, Emergency Power, peak-load regulation, solar energy and wind energy, has very vast potential for future development.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
Get a kind of and elemental sulfur powder in carbon, graphite, the activated carbon by C: S=1: 3 or 20g: the 60g weight ratio, add the alcohol ball milling and mixed 2 hours, put into vacuum drying chamber after the taking-up and dried by the fire 10 hours for 90 ℃; After carbon after adding above-mentioned mixing oven dry and sulphur powder are oozed in the jar in the high pressure embedding, seal, open the logical argon gas of pressurized tank intake ﹠ exhaust valves and squeeze emptying gas half an hour; Close vent valve and treat to close intake valve after pressure rises to 0.1 MPa, resistance furnace begins to high pressure embedding and oozes a jar heating.When furnace temperature is raised to 200 ℃, keep 2h; Be warmed up to 450 ℃ again, keep 3h; Stop to heat, with coming out of the stove after the stove cooling, grinding is sieved, add conductive agent and adhesive, its ratio is 7: 2: 1 by weight, make the positive electrode active materials slurry, be coated on the thick nickel foam substrate of 0.16mm, oven dry roll to 0.6mm be cut into 40mm wide * the long pole piece of 150mm, knit barrier film and with aluminium powder or aluminium foil with the thick glass fibre of 0.16mm is non-, a kind of negative pole of making as negative active core-shell material is wound into the electric stamen nickel plating box hat of packing in the aluminium alloy, stainless steel case or aluminum hull, add organic bath again, seal and make cylinder secondary aluminium cell or AA type cylinder secondary aluminium cell.
Embodiment 2
By the method preparation identical with embodiment 1, just the part by weight with activated carbon and sulphur is adjusted into 1: 4; Increase the high pressure embedding milliosmolarity of sulphur, improved anodal specific capacity.
Embodiment 3
By the method preparation identical with embodiment 1, just the part by weight with carbon back and sulphur is adjusted into 1: 5; Increase the embedding milliosmolarity of sulphur, improved anodal specific capacity
Embodiment 4
By the method preparation identical with embodiment 1, what only be to use is the binary carbon back, and promptly activated carbon and elemental sulfur powder are mixed with graphite, and concrete ratio is activated carbon by weight: elemental sulfur powder: graphite=0.5: 5: 0.5.
Embodiment 5
By the method preparation identical with embodiment 1, what only be to use is the binary carbon back, and promptly mixed with graphite at activated carbon and elemental sulfur powder, concrete ratio is activated carbon by weight: elemental sulfur powder: graphite=0.8: 5: 0.2.
The comparative example 6
Get a kind of and elemental sulfur powder in carbon, graphite, the activated carbon by C: S=1: 3 or 20g: the 60g weight ratio, add the alcohol ball milling and mixed 2 hours, put into vacuum drying chamber after the taking-up and dried by the fire 10 hours for 90 ℃; Leave in the pincers pots, place in the tube furnace, logical argon gas squeezes emptying gas half an hour; Keep 2h when beginning 200 ℃ then; 450 ℃ keep 3h; Stop to heat, with coming out of the stove after the stove cooling, other step is identical with embodiment 1.
The embedding milliosmolarity and the electrical property of sulphur see the following form
The embedding milliosmolarity discharge gram volume discharge platform remarks of carbon-sulfur ratio sulphur
Embodiment 1 61.94% 323.1mAh/g 1.62V
Embodiment 2 69.52% 359.6mAh/g 1.59V
Embodiment 3 80.68% 417.5mAh/g 1.58V
Embodiment 4 75.47% 341.3mAh/g 1.68V
Embodiment 5 76.30% 364.9mAh/g 1.66V
Comparative example 640.13% 208.5mAh/g 1.54V
As can be seen from the table:
Along with the adjustment of carbon-sulfur ratio example, the embedding milliosmolarity of sulphur is in rising trend;
With the adjustment of carbon-sulfur ratio example, the embedding milliosmolarity of sulphur rises, and the discharge gram volume also all has rising;
The discharge platform of binary carbon back embedding sulfurizing will be compared than embodiment 6 and exceed 0.12V, exceeds 0.08V than unit embedding sulfurizing;
When embodiment 1 compares with comparative example 6, as can be seen: when other conditions are identical: high pressure has produced good effect, and the embedding milliosmolarity of sulphur has been improved, and the discharge gram volume has also improved.
Claims (6)
1. the preparation method of positive electrode active materials, positive electrode active materials is a carbon back embedding sulfurizing positive electrode active materials,
It is characterized in that: this method has following steps: get one or both and elemental sulfur powder in graphite, the activated carbon by weight mixing, when a kind of the and elemental sulfur powder in getting graphite, activated carbon mixes by weight, the weight ratio of C: S=0.5～3: 1～5; Add alcohol ball milling mixing 1-10 hour, put into 85～95 ℃ of bakings of vacuum drying chamber 8～12 hours after the taking-up, after oozing in the jar carbon after adding above-mentioned mixing oven dry and sulphur powder, the high pressure embedding seals, opening the high pressure embedding oozes the logical argon gas of canister incoming gas valve and vent valve and squeezed emptying gas 1 hour, closing vent valve treats to close intake valve after pressure rises to 0.01～0.5 MPa, resistance furnace begins to high pressure embedding and oozes a jar heating, when furnace temperature is raised to 90～300 ℃, keep 0.5～10h, be warmed up to 320～800 ℃ again, keep 1～10h, stop to heat, with coming out of the stove after the stove cooling, grinding is sieved, and adds conductive agent and adhesive, anode active material composition composition and weight percentage are: the content of carbon back embedding sulfurizing positive electrode active materials is: 60～90 weight %, binding agent 5～20 weight %, conductive agent 5～20 weight % make the positive electrode active materials slurry.
2. the preparation method of positive electrode active materials as claimed in claim 1,
It is characterized in that: this method has following steps: get one or both and elemental sulfur powder in graphite, the activated carbon by weight mixing, and when a kind of and elemental sulfur powder in getting graphite, activated carbon mixes by weight, C: S=1: 3 weight ratios; Adding the alcohol ball milling mixed 2 hours, put into 90 ℃ of bakings of vacuum drying chamber 10 hours after the taking-up, after oozing in the jar carbon after adding above-mentioned mixing oven dry and sulphur powder, the high pressure embedding seals, opening the high pressure embedding oozes the logical argon gas of canister incoming gas valve and vent valve and squeezed emptying gas 1 hour, closing vent valve treats to close intake valve after pressure rises to 0.1 MPa, resistance furnace begins to high pressure embedding and oozes a jar heating, when furnace temperature is raised to 200 ℃, keep 2h, be warmed up to 450 ℃ again, keep 3h, stop to heat, with coming out of the stove after the stove cooling, grinding is sieved, and adds conductive agent and adhesive, the composition of anode plate and weight percentage are: carbon back embedding sulfurizing 70 weight %, binding agent 10 weight %, conductive agent 20 weight % make the positive electrode active materials slurry.
3. the preparation method of aluminum secondary battery,
It is characterized in that: this method has following steps:
1) preparation carbon back embedding sulfurizing positive electrode active materials, get one or both and elemental sulfur powder in graphite, the activated carbon by weight mixing, when a kind of the and elemental sulfur powder in getting graphite, activated carbon mixes by weight, the weight ratio of C: S=0.5～3: 1～5; Adding the alcohol ball milling mixed 1～10 hour, put into 85～95 ℃ of bakings of vacuum drying chamber 8～12 hours after the taking-up, after oozing in the jar carbon after adding above-mentioned mixing oven dry and sulphur powder, the high pressure embedding seals, opening the high pressure embedding oozes the logical argon gas of canister incoming gas valve and vent valve and squeezed emptying gas 1 hour, closing vent valve treats to close intake valve after pressure rises to 0.01～0.5 MPa, resistance furnace begins to high pressure embedding and oozes a jar heating, when furnace temperature is raised to 90～300 ℃, keep 0.5～10h, be warmed up to 320～800 ℃ again, keep 1～10h, stop to heat, with coming out of the stove after the stove cooling, grinding is sieved, and adds conductive agent and adhesive, anode active material composition composition and weight percentage are: carbon back embedding sulfurizing positive electrode active materials 60-90 weight %, conductive agent: 5～20 weight %, adhesive: 5～20 weight %, make the positive electrode active materials slurry;
2) with the above-mentioned positive electrode active materials slurry of making, be coated on the thick nickel foam substrate of 0.10-0.20mm, oven dry roll to 0.4-0.8mm be cut into 30-50mm wide * the long pole piece of 140-160mm, with the thick glass fibre of 0.10-0.20mm non-knit barrier film and be wound into electric stamen with a kind of negative pole of making as negative active core-shell material in aluminium powder or aluminium foil, the aluminium alloy pack in any shell in nickel plating box hat, stainless steel case or the aluminum hull, add organic bath again, seal and make the cylindrical aluminium secondary cell.
4. the preparation method of aluminum secondary battery as claimed in claim 3,
It is characterized in that: this method has following steps:
1) the above-mentioned carbon back embedding sulfurizing positive electrode active materials of preparation: get one or both and elemental sulfur powder in graphite, the activated carbon by weight mixing, when a kind of and elemental sulfur powder in getting graphite, activated carbon mixes by weight, C: S=1: 3 weight ratio; Adding the alcohol ball milling mixed 2 hours, put into 90 ℃ of bakings of vacuum drying chamber 10 hours after the taking-up, after oozing in the jar carbon after adding above-mentioned mixing oven dry and sulphur powder, the high pressure embedding seals, opening the high pressure embedding oozes the logical argon gas of canister incoming gas valve and vent valve and squeezed emptying gas 1 hour, closing vent valve treats to close intake valve after pressure rises to 0.1 MPa, resistance furnace begins to high pressure embedding and oozes a jar heating, when furnace temperature is raised to 200 ℃, keep 2h, be warmed up to 450 ℃ again, keep 3h, stop to heat, with coming out of the stove after the stove cooling, grinding is sieved, and adds conductive agent and adhesive, the composition of anode active material composition and content % are by weight counted: carbon back embedding sulfurizing positive electrode active materials: 70%, conductive agent: 20%, adhesive: 10%, make the positive electrode active materials slurry;
2) with the above-mentioned positive electrode active materials slurry of making, be coated on the thick nickel foam substrate of 0.16mm, oven dry roll to 0.6mm be cut into 40mm wide * the long pole piece of 150mm, knit barrier film and be wound into electric stamen pack into nickel plating box hat, stainless steel case or aluminum hull with the thick glass fibre of 0.16mm is non-with a kind of negative pole of making as negative active core-shell material in aluminium powder or aluminium foil, the aluminium alloy, add organic bath again, seal and make the cylindrical aluminium secondary cell.
5. the preparation method of aluminum secondary battery as claimed in claim 3,
It is characterized in that: above-mentioned positive electrode active materials is a carbon back embedding sulfurizing positive electrode active materials, during preparation carbon back embedding sulfurizing positive electrode active materials, use the binary carbon back, activated carbon and elemental sulfur powder are mixed with graphite, and concrete ratio is active carbon by weight: elemental sulfur: graphite=0.5～0.8: 5: 0.2～0.5.
6. the preparation method of aluminum secondary battery as claimed in claim 3,
It is characterized in that: above-mentioned positive electrode active materials is a carbon back embedding sulfurizing positive electrode active materials, during preparation carbon back embedding sulfurizing positive electrode active materials, use the binary carbon back, activated carbon and elemental sulfur powder are mixed with graphite, and concrete ratio is active carbon by weight: elemental sulfur: graphite=0.8: 5: 0.2.
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| KR101384198B1 (en) * | 2011-05-31 | 2014-04-25 | 한양대학교 산학협력단 | Manufacturing method of carbon sulfur complex, carbon sulfur complex made by the same, lithium sulfur battery including the same |
| JP2013182845A (en) * | 2012-03-05 | 2013-09-12 | Showa Denko Kk | Negative electrode active material for lithium secondary battery, and method for producing the same |
| CN103022443A (en) * | 2012-12-05 | 2013-04-03 | 上海锦众信息科技有限公司 | Method for preparing positive-pole carbon-based composite material for lithium-sulfur battery |
| CN104078700A (en) * | 2014-07-03 | 2014-10-01 | 南京中储新能源有限公司 | Secondary aluminum cell with positive electrode made of double-cladding carbon-sulfur composite material |
| CN104183835B (en) * | 2014-08-22 | 2015-09-23 | 南京中储新能源有限公司 | A kind of aluminium carbon aerogel composite material and the secondary aluminium cell as negative pole |
| CN104393264B (en) * | 2014-12-01 | 2017-01-04 | 贵州中伟正源新材料有限公司 | high-capacity battery 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 |
| JP6621442B2 (en) | 2016-05-17 | 2019-12-18 | 財團法人工業技術研究院Ｉｎｄｕｓｔｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ | Metal ion battery |
| TWI611618B (en) | 2016-12-16 | 2018-01-11 | 財團法人工業技術研究院 | Metal-ion battery |
| CN108640114B (en) * | 2018-05-16 | 2021-04-13 | 合肥工业大学 | Double-body type active carbon vacuum sulfurizing device and using method thereof |
| CN111354905B (en) * | 2020-02-10 | 2022-03-22 | 北京理工大学 | Composite interlayer type diaphragm for aluminum-sulfur battery and preparation method thereof |
| CN111668481B (en) * | 2020-05-27 | 2021-12-03 | 北京科技大学 | Preparation method of metal aluminum secondary battery with multi-group organic micromolecules as positive electrode |
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