CN103618094A - High-capacity lithium sulfur flow cell, and preparation method of electrode thereof - Google Patents
High-capacity lithium sulfur flow cell, and preparation method of electrode thereof Download PDFInfo
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Abstract
The invention relates to the field of cells, and aims at providing a high-capacity lithium sulfur flow cell, and a preparation method of an electrode thereof. The preparation method of the electrode of the high-capacity lithium sulfur flow cell comprises the following steps: preparing nickel foam with a carbon coating layer; preparing nickel foam as a cathode of the lithium sulfur flow cell; preparing nickel foam as an anode of the lithium sulfur flow cell. The high-capacity lithium sulfur flow cell comprises an anode plate, an anode, a diaphragm, a cathode, a cathode plate, a positive liquid and a negative liquid which are orderly connected; a flow path is engraved on the anode; the flow path is engraved on the cathode plate. By adopting the high-capacity lithium sulfur flow cell, Al with high specific capacity is taken as a negative activated substance, S is taken as a positive activated substance, carbon-coated nickel foam is taken as the cathode, and nickel sulfide-coated nickel foam is taken as the anode, so that the electrode with high activity, high strength and low flow resistance is supplied to the lithium sulfur flow cell; the energy density and power density of the lithium sulfur flow cell are greatly improved. The activated substances and the electrode material are low in cost, simple and feasible in preparation technology, and wide in application prospect.
Description
Technical field
The invention relates to field of batteries, particularly the preparation method of a kind of large capacity lithium sulphur flow battery and electrode thereof.
Background technology
Sulphur is water insoluble but be dissolved in non-polar solven as carbon disulfide, carbon tetrachloride, cyclohexane etc., and the sulphur of crystal can form one by eight former molecular ring: S
8.S
8obtain can forming polysulfide ion as S after electronics
8 2-, S
6 2-, S
4 2-, these polysulfide ions can be dissolved in organic solvent as ethylene carbonate (EC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), dimethoxy-ethane (DME), DOX (DOL) etc.
Flow battery is a kind of energy-storage battery, and the most representative is all-vanadium flow battery.By electrolyte solution, carbon materials electrode, the parts such as bipolar plates and amberplex form.By conveying equipment for fluid substances, electrolyte is circulated between pile and storage tank, the vanadium ion that completes different valence state in charge/discharge process transforms storage and the release with electric energy mutually.Electrode reaction is: positive pole: VO
2 ++ 2H
++ e=VO
2++ H
2o, E
0=1.00V; Negative pole: V
3++ e=V
2+, E
0=-0.26V; Battery overall reaction VO
2 ++ V
2++ 2H
+=VO
2++ V
3++ H
2o, E
0=1.26V.
All-vanadium flow battery has following characteristics: 1, scale is large: power output and the stored energy capacitance of all-vanadium flow battery are independent of one another.By changing electrolyte quantity in storage tank, can meet too scale electric power storage energy storage demand; By adjusting series winding quantity and the electrode area of monocell in battery pile, can meet specified discharge power requirement.2, the life-span is long: battery plus-negative plate reaction all completes in liquid phase, and charge/discharge process only changes vanadium ion state in solution. and do not have extraneous ion to participate in electrochemical reaction.Electrode only plays transfer electronic action. and itself does not participate in electrochemical reaction, can carry out in theory the charge and discharge cycles of unlimited arbitrary extent, greatly extends the useful life of battery.3, cost is low: aspect prepared by battery critical material, as battery critical materials such as proton exchange membrane, conductive bipolar plate.By realization, domesticize and carry out extensive, low-cost production.All-vanadium flow battery avoids using noble metal catalyst, and cost, well below chemical power sources such as fuel cells, is suitable for tens kilowatts～number mw scale occasion and uses.4, efficiency is high: because the active material in positive and negative half-cell electrolyte is stored in respectively in different storage tanks, avoid electrolysis ripple to preserve the self discharge consumption of process completely, the battery system charge-discharge energy efficiency that process is optimized is up to 80%.
Tradition lithium ion flow battery is mainly comprised of cell reaction device, anodal suspension storage tank, negative pole suspension storage tank, liquid pump and closed conduit etc., anodal suspension storage tank holds the mixture of positive electrode active materials particle, conductive agent and electrolyte, and negative pole suspension storage tank holds the mixture of negative active core-shell material particle, conductive agent and electrolyte.Cell reaction device is the core of lithium ion flow battery, and its structure mainly comprises: plus plate current-collecting body, anodal reaction chamber, porous septum, negative reaction chamber, negative current collector and shell.During lithium ion flow battery work, use liquid pump to circulate to suspension, suspension is by closed conduit continuous flow or intermittent flow between suspension storage tank and cell reaction device under liquid pump or other powered, and flow velocity can regulate according to suspension concentration and ambient temperature.
Between common anodal reaction chamber and negative reaction chamber, there is the nonconducting porous septum of electronics, negative active core-shell material particle in positive electrode active materials particle in anodal suspension and negative pole suspension is spaced from each other, avoids both positive and negative polarity active material particle directly to contact the short circuit that causes inside battery.Anodal suspension and the negative pole suspension in negative reaction chamber in anodal reaction chamber can carry out lithium ion exchanged transmission by the electrolyte in porous septum.When battery discharge, the lithium ion of the negative active core-shell material granule interior in negative reaction chamber takes off embedding and goes out, and enters electrolyte, and arrives anodal reaction chamber by porous septum, is embedded into positive electrode active materials granule interior; Meanwhile, the electronics of the negative active core-shell material granule interior in negative reaction chamber flows into negative current collector, and the negative lug of passing through negative current collector flows into the external circuit of battery, after completing acting, by positive pole ear, flow into plus plate current-collecting body, finally embed the positive electrode active materials granule interior in anodal reaction chamber.The process of battery charging in contrast.Traditional negative active core-shell material is graphite powder, and positive electrode active materials is cobalt acid lithium < < electrician electric energy new technology, the 31st volume the 3rd phase > >.
CN102324550 has proposed a kind of design preparation method of half liquid stream lithium-sulfur cell; it is characterized in that: described half liquid stream lithium-sulfur cell is that to take the particulate of lithium or the mixed liquor of Si sill, lithium titanate and Sn sill and electrolyte be negative electrode, take the particulate of elemental sulfur, elemental sulfur compound, sulfur-based compound, inorganic sulfur, organic sulfur etc. and the mixed liquor of electrolyte is anode.
Tradition sodium-sulphur battery sodium is metal liquid, has subject matter: 1, working temperature is high; 2, be unsuitable for discontinuous operation, the continuous switching of high low temperature easily causes the leakage of pile, and fatigue of materials is damaged; 3, flow battery scale can not be too large relatively.And the operating voltage of all-vanadium flow battery is low, energy density is low.Tradition lithium ion flow battery adopts graphite as active material, but the embedding lithium capacity of graphite can only reach 372mAhg
-1, energy density is also lower.And the half liquid stream lithium-sulfur cell that CN102324550 proposes do not use collector electrode, but form negative electrode and anode in metal cabinet or metal tube, so response area is less, be difficult to provide large electric current and high-power output.
Summary of the invention
Main purpose of the present invention is to overcome deficiency of the prior art, and a kind of normal temperature work is provided, and the preparation method of large capacity, high-power, high efficiency, long-life, free of contamination low-cost lithium sulphur flow battery and electrode thereof.For solving the problems of the technologies described above, solution of the present invention is:
The preparation method that a kind of high power lithium sulphur Flow-through electrode is provided, specifically comprises the following steps:
Steps A: get carbon source material and be heated to 100～150 ℃ to liquid, nickel foam is immersed in liquid carbon source material again, then variable rheostat and power supply on connecting at nickel foam two ends, energising is carried out from heating (its principle and effect are equal to electric-heating-wire-heating), variable rheostat is for passing through to control size of current, and then the temperature of control nickel foam; When nickel foam temperature reaches the carburizing temperature of carbon source material, carbon source material forms carbon coating layer in the inner surface generation carbonization of nickel foam; Described carbon source material is that molecular weight is less than or equal to 10000 polymer (as molecular weight is less than or equal to 10000 polyethylene glycol, polyacrylic acid), higher aliphatic (monohydric alcohol of C6～C26) or higher fatty acids (monocarboxylic acid of C6～C26);
Step B: the nickel foam with carbon coating layer making in steps A is placed in to Muffle furnace, under inert gas shielding, calcines at 800～1000 ℃ 5～10 hours, form Ni in the nickel interface of nickel foam
3c, the nickel foam making is as the negative pole of lithium sulphur flow battery;
Step C: by colloid sulphur formation colloidal solution soluble in water, then colloidal solution is coated to nickel foam, the mass ratio that makes Ni and S is 100～1000:1, dry in the shade to be placed in vitreosil pipe and be heated to 900 ℃, react after 6 hours, nickel foam is coated with nickel sulfide, and the nickel foam making is as the positive pole of lithium sulphur flow battery.
As further improvement, in steps A, molecular weight is less than or equal to 10000 polymer and adopts molecular weight to be less than or equal to 10000 polyethylene glycol, polyacrylic acid, and higher aliphatic adopts 18 alcohol C
18h
37oH, higher fatty acids adopts stearic acid C
17h
35cOOH.
As further improvement, the thickness of the nickel foam carbon coating layer forming in described steps A is 0.1～1 micron.
As further improvement, the inert gas in described step B adopts argon gas or nitrogen.
The large capacity lithium sulphur flow battery of preparing based on prepared lithium sulphur Flow-through electrode is provided, described large capacity lithium sulphur flow battery comprises the positive plate that is carved with stream, positive pole, barrier film, the negative pole connecting successively and is carved with the negative plate of stream, and anodal liquid and negative pole liquid; Described barrier film is microporous polypropylene film, for separating positive pole and negative pole, and the anodal positive pole making in step C that adopts, negative pole adopts the negative pole making in step B; Positive plate is provided with anodal liquid ingress pipe and anodal liquid delivery line, and anodal liquid flows by the stream on anodal liquid ingress pipe, positive plate and anodal liquid delivery line, and infiltrates the anodal electrochemical reaction that occurs; Negative plate is provided with negative pole liquid ingress pipe and negative pole liquid delivery line, and negative pole liquid flows by the stream on negative pole liquid ingress pipe, negative plate and negative pole liquid delivery line, and infiltrates negative pole generation electrochemical reaction;
Anodal liquid refers to the suspension-turbid liquid that is mixed with the formation of lithium sulfide powder in electrolyte, and negative pole liquid refers to the suspension-turbid liquid that is mixed with aluminium powder formation in electrolyte; The solute of electrolyte is LiPF
6, the solvent of electrolyte is the mixture of ethylene carbonate (EC), methyl ethyl carbonate (EMC), dimethyl carbonate (DMC) and carbon disulfide; LiPF wherein
6concentration be 1 mol/L, the volume ratio of ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, carbon disulfide is 1:1:1:1, and the carbon disulfide here can replace to carbon tetrachloride or cyclohexane.
As further improvement, in described large capacity lithium sulphur flow battery, between positive pole and barrier film, be also provided with anodal sealing ring, between barrier film and negative pole, be also provided with negative pole sealing ring, anodal sealing ring and negative pole sealing ring are all the sealing rings that fluorubber is made.
As further improvement, the lithium sulfide powder in described anodal liquid is 1～50 micron.
As further improvement, the aluminium powder in described negative pole liquid is 1～50 micron.
The control method of the large capacity lithium sulphur flow battery based on described is provided, and when large capacity lithium sulphur flow battery is charged, first side of the positive electrode is under the catalytic action of nickel sulfide, and lithium sulfide generation electrochemical oxidation forms S
8: 8Li
2s=16Li
++ S
8+ 16e, S
8be dissolved in electrolyte, Li
+through barrier film, arrive negative pole, at the carbon-coating formation LiC of negative pole
6: C
6+ Li
++ e=LiC
6, Li then
+liC on negative pole
6catalytic action under there is electrochemical reducting reaction and form AlLi alloy powder: Al+Li
++ e=AlLi, AlLi further charging obtains Li
9al
4: 4AlLi+5Li
++ 5e=Li
9al
4; When large capacity lithium sulphur flow battery is discharged, the back reaction of above-mentioned reaction occurs respectively at anodal and negative pole, realize generating, its cell reaction is: 16Li
9al
4+ 9S
8=64Al+72Li
2s.
Compared with prior art, the invention has the beneficial effects as follows:
It is negative electrode active material that the present invention utilizes the Al of height ratio capacity, S is positive electrode active material, the coated nickel foam of the carbon of take is negative pole, the coated nickel foam of nickel sulfide is anodal, for lithium sulphur flow battery provides the electrode of high activity, high strength, low flow resistance, energy density and the power density of lithium sulphur flow battery have greatly been improved, can be widely used in the large-scale unstable state generating such as wind power generation, solar power generation, tidal power generation power station, play the effect of electric adjustment, also can be applicable to stable state generating power station, the peak-trough electricity of balance electricity consumption, improves generating efficiency, reduces cost of electricity-generating.Active material source is abundant, with low cost, pollution-free, easily preparation.Electrode material cost is cheap, and preparation technology simply, easily goes, and is conducive to large-scale production, can effectively reduce flow battery cost, has broad application prospects.
Accompanying drawing explanation
Fig. 1 is the assembly drawing of a kind of large capacity lithium sulphur flow battery of the present invention.
Fig. 2 is the charge-discharge performance figure of battery in embodiment.
Reference numeral in figure is: 1 positive plate; 2 positive poles; 3 anodal sealing rings; 4 barrier films; 5 negative pole sealing rings; 6 negative poles; 7 negative plates; 8 anodal liquid ingress pipes; 9 anodal liquid delivery lines; 10 negative pole liquid ingress pipes; 11 negative pole liquid delivery lines; 12 charging curves; 13 discharge curves.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail:
A preparation method for high power lithium sulphur Flow-through electrode, specifically comprises the following steps:
Steps A: get carbon source material and be heated to 100～150 ℃ to liquid, nickel foam is immersed in liquid carbon source material again, then variable rheostat and power supply on connecting at nickel foam two ends, energising is carried out from heating, its principle and effect are equal to electric-heating-wire-heating, variable rheostat is for passing through to control size of current, and then the temperature of control nickel foam.When nickel foam temperature reaches the carburizing temperature of carbon source material, carbon source material forms the carbon coating layer of 0.1～1 micron thickness in the inner surface generation carbonization of nickel foam.Described carbon source material is that molecular weight is less than or equal to 10000 polymer (molecular weight is less than or equal to 10000 polyethylene glycol, polyacrylic acid), higher aliphatic (monohydric alcohol of C6～C26) and higher fatty acids (monocarboxylic acid of C6～C26), molecular weight is less than or equal to 10000 polymer employing polyethylene glycol, polyacrylic acid, higher aliphatic adopts, and higher fatty acids adopts.
Step B: the nickel foam with carbon coating layer making in steps A is placed in to Muffle furnace, under argon gas or nitrogen protection, calcines at 800～1000 ℃ 5～10 hours, form Ni in the nickel interface of nickel foam
3c, the nickel foam making is as the negative pole of lithium sulphur flow battery.
Step C: by colloid sulphur formation colloidal solution soluble in water, then colloidal solution is coated to nickel foam, the mass ratio that makes Ni and S is 100～1000:1, dry in the shade to be placed in vitreosil pipe and be heated to 900 ℃, react after 6 hours, nickel foam is coated with nickel sulfide, and the nickel foam making is as the positive pole of lithium sulphur flow battery.
As shown in Figure 1, large capacity lithium sulphur flow battery prepared by the lithium sulphur Flow-through electrode that utilization makes, comprise the positive plate that is carved with stream 1, positive pole 2, anodal sealing ring 3, barrier film 4, negative pole sealing ring 5, the negative pole 6 connecting successively and the negative plate 7 that is carved with stream, and anodal liquid and negative pole liquid.Described barrier film 4 is microporous polypropylene film, and for separating positive pole 2 and negative pole 6, anodal 2 adopt the positive pole making in step C, and negative pole 6 adopts the negative pole making in step B.Positive plate 1 is provided with anodal liquid ingress pipe 8 and anodal liquid delivery line 9, and anodal liquid flows by the stream on anodal liquid ingress pipe 8, positive plate 1 and anodal liquid delivery line 9, and infiltrates anodal 2 generation electrochemical reactions.Negative plate 7 is provided with negative pole liquid ingress pipe 10 and negative pole liquid delivery line 11, and negative pole liquid flows by the stream on negative pole liquid ingress pipe 10, negative plate 7 and negative pole liquid delivery line 11, and infiltrates negative pole 6 generation electrochemical reactions.
Anodal liquid refers to the suspension-turbid liquid that is mixed with the lithium sulfide powder formation of 1～50 micron in electrolyte, negative pole liquid refers to and in electrolyte, is mixed with the suspension-turbid liquid that the aluminium powder of 1～50 micron forms, and the capacity of large capacity lithium sulphur flow battery just depends on the content of aluminium in lithium sulfide in anodal liquid and negative pole liquid.The solute of electrolyte is LiPF
6, the solvent of electrolyte is the mixture of ethylene carbonate (EC), methyl ethyl carbonate (EMC), dimethyl carbonate (DMC) and carbon disulfide; LiPF wherein
6concentration be 1 mol/L, the volume ratio of ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, carbon disulfide is 1:1:1:1, and the carbon disulfide here can replace to carbon tetrachloride or cyclohexane.
When above-mentioned large capacity lithium sulphur flow battery is charged, first side of the positive electrode is under the catalytic action of nickel sulfide, and lithium sulfide generation electrochemical oxidation forms S
8: 8Li
2s=16Li
++ S
8+ 16e, S
8be dissolved in electrolyte, Li
+through barrier film, arrive negative pole, at the carbon-coating formation LiC of negative pole
6: C
6+ Li
++ e=LiC
6, Li then
+liC on negative pole
6catalytic action under there is electrochemical reducting reaction and form AlLi alloy powder: Al+Li
++ e=AlLi, AlLi further charging obtains Li
9al
4: 4AlLi+5Li
++ 5e=Li
9al
4; When large capacity lithium sulphur flow battery is discharged, the back reaction of above-mentioned reaction occurs respectively at anodal and negative pole, realize generating, its cell reaction is: 16Li
9al
4+ 9S
8=64Al+72Li
2s.
Li
9al
4there is very high theoretical specific capacity, up to 2234mAh g
-1, the specific capacity of sulphur is up to also 1675mAh g
-1, higher than the capacity of the cobalt acid lithium battery of commercial extensive use, be generally less than 150mAhg far away
-1, therefore, by S and Al, as the active material of positive pole 2 and negative pole 6, can obtain respectively the lithium sulphur flow battery of height ratio capacity
The following examples can make this professional professional and technical personnel's comprehend the present invention, but do not limit the present invention in any way.
Utilize sulphur to be dissolved in ethanol, be slightly soluble in the feature of water, first sulphur is dissolved in to ethanol, then the ethanolic solution of sulphur is splashed in water, while dripping, stir, can obtain sulphur colloidal sol, after being dried, obtain colloid sulphur.General purity is higher, is mainly used in pharmaceutically.The open cell foamed plastic that the matrix used material of nickel foam is porous, adopt chemical nickel plating, vacuum nickel plating and soak conducting resinl (palladium colloidal sol, submicron order aquadags etc.) three kinds of methods all can be prepared conductive layer, through nickel preplating just can be in general sulfate nickel plating electrolyte plating thick nickel, by calcination, reduction, the annealing operation three-dimensional netted foam nickel material that just available can be good, it is one of optimum electrode material of manufacturing by cadmium nickel battery and nickel-hydrogen battery.Colloid sulphur and nickel foam have commercially available.
Embodiment mono-: electric heating carbonization
The polyethylene glycol that is 10000 by molecular weight is heated to 100 ℃ and melts, and the nickel foam that is 95% by voidage is immersed, and nickel foam two ends connect 220V power supply energising heating, and current density is controlled at 0.1～1A cm
-2, the temperature of controlling nickel foam is 250～350 ℃ and carries out carbonization formation carbon coating layer.The carbonization initial stage can be used compared with high current density, when the temperature of nickel foam surpasses 350 ℃, can reduce current density, makes within carburizing temperature adjusts to 250～350 ℃ of scopes.
When the carbon source material polyethylene glycol that to change as molecular weight be 400, owing to be just liquid under its room temperature, without heating the carbonization of just can switching on.Equally, for C
6fatty alcohol as 2-hexanol C
6h
13oH, and aliphatic acid is as n-caproic acid C
5h
11cOOH, is also liquid under room temperature, without heating the carbonization of just can switching on.And for cerinic acid or cerinic acid, such as cerinic acid CH
3(CH
2)
24cOOH, just need to be heated to 100 ℃ melt after, the carbonization of could switching on.
Embodiment bis-: negative pole preparation
The polyacrylic acid that is 5000 by molecular weight is heated to 120 ℃ and melts, and the nickel foam that is 95% by voidage is immersed, and nickel foam two ends connect 220V power supply energising heating, and current density is controlled at 0.1～1A cm
-2, the temperature of controlling nickel foam is 250～350 ℃ and carries out carbonization formation carbon coating layer.The carbonization initial stage can be used compared with high current density; when the temperature of nickel foam is over 350 ℃; can reduce current density; make within carburizing temperature adjusts to 250～350 ℃ of scopes; when reaching 0.1 micron thickness, takes out carbon-coating; be placed in Muffle furnace under nitrogen protection, calcine 10 hours at 800 ℃, make carbon-coating and nickel interface form Ni
3c, increases the adhesion between carbon-coating and nickel foam, obtains the negative pole of lithium sulphur flow battery.
Embodiment tri-: anodal preparation
It is 95% nickel foam that colloid sulphur formation colloidal solution soluble in water is coated to voidage, the mass ratio of Ni and S is 100:1, drying in the shade to be placed in vitreosil pipe is heated to 900 ℃, reacts and within 6 hours, obtains the coated nickel foam of nickel sulfide, as the positive pole of lithium sulphur flow battery.
Embodiment tetra-: lithium sulphur flow battery forms
By 18 alcohol, i.e. C
18higher alcohol C
18h
37oH, is heated to 150 ℃ and melts, and the nickel foam that is 95% by voidage is immersed, and nickel foam two ends connect 220V power supply energising heating, and current density is controlled at 0.1～1A cm
-2, the temperature of controlling nickel foam is 250～350 ℃ and carries out carbonization formation carbon coating layer.The carbonization initial stage can be used compared with high current density, when the temperature of nickel foam surpasses 350 ℃, can reduce current density; make within carburizing temperature adjusts to 250～350 ℃ of scopes, when carbon-coating reaches 0.5 micron thickness, to take out, be placed in Muffle furnace under argon shield; at 900 ℃, calcine 8 hours, obtain negative pole.
It is 95% nickel foam that colloid sulphur formation colloidal solution soluble in water is coated to voidage, and the mass ratio of Ni and S is 500:1, dries in the shade to be placed in vitreosil pipe to be heated to 900 ℃, reacts and within 6 hours, obtains the coated nickel foam of nickel sulfide, as positive pole.
Anodal 2 and negative pole 6 use microporous polypropylene films separate, by being carved with positive plate 1, anodal 2, barrier film 4, the negative pole 6 of stream, the negative plate 7 that is carved with stream is combined into battery, as shown in Figure 1.Electrolyte is with LiPF
6for solute, LiPF
6concentration be 1 mol/L, the mixture of ethylene carbonate (EC), methyl ethyl carbonate (EMC), dimethyl carbonate (DMC), carbon disulfide (or carbon tetrachloride, cyclohexane) is solvent, and the volume ratio of ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate and carbon disulfide (or carbon tetrachloride, cyclohexane) is 1:1:1:1.
Embodiment five: the generating of lithium sulphur flow battery
By stearic acid, i.e. C
18higher fatty acids C
17h
35cOOH, is heated to 150 ℃ and melts, and the nickel foam that is 95% by voidage is immersed, and nickel foam two ends connect 220V power supply energising heating, and current density is controlled at 0.1～1A cm
-2, the temperature of controlling nickel foam is 250～350 ℃ and carries out carbonization formation carbon coating layer.The carbonization initial stage can be used compared with high current density, when the temperature of nickel foam surpasses 350 ℃, can reduce current density; make within carburizing temperature adjusts to 250～350 ℃ of scopes, when carbon-coating reaches 1 micron thickness, to take out, be placed in Muffle furnace under argon shield; at 1000 ℃, calcine 5 hours, obtain negative pole.
It is 95% nickel foam that colloid sulphur formation colloidal solution soluble in water is coated to voidage, and the mass ratio of Ni and S is 1000:1, dries in the shade to be placed in vitreosil pipe to be heated to 900 ℃, reacts and within 6 hours, obtains the coated nickel foam of nickel sulfide, as positive pole.
Anodal 2 and negative pole 6 use microporous polypropylene films separate, by being carved with positive plate 1, anodal 2, barrier film 4, the negative pole 6 of stream, the negative plate 7 that is carved with stream is combined into battery.Electrolyte is with LiPF
6for solute, the mixture of ethylene carbonate (EC), methyl ethyl carbonate (EMC), dimethyl carbonate (DMC), carbon tetrachloride is solvent, LiPF
6concentration be 1 mol/L, the volume ratio of ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate and carbon tetrachloride is 1:1:1:1.The electrolyte of 150 grams, the lithium sulfide powder of 1～50 micron being sneaked into 500 milliliters forms suspension-turbid liquid as anodal liquid, and the electrolyte of 150 grams of the aluminium powders of 1～50 micron being sneaked into 500 milliliters forms suspension-turbid liquid as negative pole liquid.Anodal liquid and negative pole liquid are sent into positive pole 2 and negative pole 6 with peristaltic pump by the anodal liquid on positive plate 1 and negative plate 7 and negative pole liquid ingress pipe respectively.During charging, at side of the positive electrode, under the catalytic action of nickel sulfide, lithium sulfide generation electrochemical oxidation forms S
8:
8Li
2S=16Li
++S
8+16e
S
8be dissolved in electrolyte, Li
+through barrier film 4, arrive negative pole 6, at the carbon-coating formation LiC of negative pole 6
6:
C
6+Li
+=LiC
6+e
Then Li
+liC on negative pole 6
6catalytic action under there is electrochemical reducting reaction and form AlLi alloy powder:
Al+Li
++e=AlLi
AlLi further charging obtains Li
9al
4:
4AlLi+5Li
++5e=Li
9Al
4
Lithium sulphur flow battery when electric discharge, anodal 2 and negative pole 6 there is respectively the back reaction of above-mentioned reaction.The charge-discharge performance of battery as shown in Figure 2.Battery capacity is determined by the amount of the positive electrode active material adding and negative electrode active material.
Finally, it should be noted that above what enumerate is only specific embodiments of the invention.Obviously, the invention is not restricted to above embodiment, can also have a lot of distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (9)
1. a preparation method for high power lithium sulphur Flow-through electrode, is characterized in that, specifically comprises the following steps:
Steps A: get carbon source material and be heated to 100～150 ℃ to liquid, nickel foam is immersed in liquid carbon source material, then variable rheostat and power supply in the series connection of nickel foam two ends, switch on and carry out from heating again, variable rheostat is for passing through to control size of current, and then the temperature of control nickel foam; When nickel foam temperature reaches the carburizing temperature of carbon source material, carbon source material forms carbon coating layer in the inner surface generation carbonization of nickel foam; Described carbon source material is that molecular weight is less than or equal to 10000 polymer, higher aliphatic or higher fatty acids;
Step B: the nickel foam with carbon coating layer making in steps A is placed in to Muffle furnace, under inert gas shielding, calcines at 800～1000 ℃ 5～10 hours, form Ni in the nickel interface of nickel foam
3c, the nickel foam making is as the negative pole of lithium sulphur flow battery;
Step C: by colloid sulphur formation colloidal solution soluble in water, then colloidal solution is coated to nickel foam, the mass ratio that makes Ni and S is 100～1000:1, dry in the shade to be placed in vitreosil pipe and be heated to 900 ℃, react after 6 hours, nickel foam is coated with nickel sulfide, and the nickel foam making is as the positive pole of lithium sulphur flow battery.
2. the preparation method of a kind of high power lithium sulphur Flow-through electrode according to claim 1, it is characterized in that, in steps A, molecular weight is less than or equal to 10000 polymer and adopts molecular weight to be less than or equal to 10000 polyethylene glycol, polyacrylic acid, and higher aliphatic adopts 18 alcohol C
18h
37oH, higher fatty acids adopts stearic acid C
17h
35cOOH.
3. the preparation method of a kind of high power lithium sulphur Flow-through electrode according to claim 1, is characterized in that, the thickness of the nickel foam carbon coating layer forming in described steps A is 0.1～1 micron.
4. the preparation method of a kind of high power lithium sulphur Flow-through electrode according to claim 1, is characterized in that, the inert gas in described step B adopts argon gas or nitrogen.
5. the large capacity lithium sulphur flow battery of preparing based on the prepared lithium sulphur of claim 1 Flow-through electrode, it is characterized in that, described large capacity lithium sulphur flow battery comprises the positive plate that is carved with stream, positive pole, barrier film, the negative pole connecting successively and is carved with the negative plate of stream, and anodal liquid and negative pole liquid; Described barrier film is microporous polypropylene film, for separating positive pole and negative pole, and the anodal positive pole making in step C that adopts, negative pole adopts the negative pole making in step B; Positive plate is provided with anodal liquid ingress pipe and anodal liquid delivery line, and anodal liquid flows by the stream on anodal liquid ingress pipe, positive plate and anodal liquid delivery line, and infiltrates the anodal electrochemical reaction that occurs; Negative plate is provided with negative pole liquid ingress pipe and negative pole liquid delivery line, and negative pole liquid flows by the stream on negative pole liquid ingress pipe, negative plate and negative pole liquid delivery line, and infiltrates negative pole generation electrochemical reaction;
Anodal liquid refers to the suspension-turbid liquid that is mixed with the formation of lithium sulfide powder in electrolyte, and negative pole liquid refers to the suspension-turbid liquid that is mixed with aluminium powder formation in electrolyte; The solute of electrolyte is LiPF
6, the solvent of electrolyte is the mixture of ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate and carbon disulfide; LiPF wherein
6concentration be 1 mol/L, the volume ratio of ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, carbon disulfide is 1:1:1:1, and the carbon disulfide here can replace to carbon tetrachloride or cyclohexane.
6. a kind of large capacity lithium sulphur flow battery according to claim 5, it is characterized in that, in described large capacity lithium sulphur flow battery, between positive pole and barrier film, be also provided with anodal sealing ring, between barrier film and negative pole, be also provided with negative pole sealing ring, anodal sealing ring and negative pole sealing ring are all the sealing rings that fluorubber is made.
7. a kind of large capacity lithium sulphur flow battery according to claim 5, is characterized in that, the lithium sulfide powder in described anodal liquid is 1～50 micron.
8. a kind of large capacity lithium sulphur flow battery according to claim 5, is characterized in that, the aluminium powder in described negative pole liquid is 1～50 micron.
9. the control method based on large capacity lithium sulphur flow battery claimed in claim 5, is characterized in that, when large capacity lithium sulphur flow battery is charged, first side of the positive electrode is under the catalytic action of nickel sulfide, and lithium sulfide generation electrochemical oxidation forms S
8: 8Li
2s=16Li
++ S
8+ 16e, S
8be dissolved in electrolyte, Li
+through barrier film, arrive negative pole, at the carbon-coating formation LiC of negative pole
6: C
6+ Li
++ e=LiC
6, Li then
+liC on negative pole
6catalytic action under there is electrochemical reducting reaction and form AlLi alloy powder: Al+Li
++ e=AlLi, AlLi further charging obtains Li
9al
4: 4AlLi+5Li
++ 5e=Li
9al
4; When large capacity lithium sulphur flow battery is discharged, the back reaction of above-mentioned reaction occurs respectively at anodal and negative pole, realize generating, its cell reaction is: 16Li
9al
4+ 9S
8=64Al+72Li
2s.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104157851A (en) * | 2014-07-14 | 2014-11-19 | 浙江大学 | Lithium sulfur battery adopting stannous sulfide as anchoring center and preparation method of positive electrode of lithium sulfur battery |
| CN104882606A (en) * | 2015-06-03 | 2015-09-02 | 浙江大学 | Polysulfide lithium-aluminum organic solution and polysulfide lithium-aluminum battery with polysulfide lithium-aluminum organic solution as catholyte |
| CN105742681A (en) * | 2014-11-10 | 2016-07-06 | 财团法人工业技术研究院 | Electrochemical flow cell assembly and bipolar plate thereof |
| WO2017160712A1 (en) * | 2016-03-17 | 2017-09-21 | Saudi Arabian Oil Company | In-situ gravitational separation of electrolyte solutions in flow redox battery systems |
| CN107534162A (en) * | 2015-04-30 | 2018-01-02 | 标准能量株式会社 | Redox flow batteries |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080311473A1 (en) * | 2007-02-20 | 2008-12-18 | Hideo Sasaoka | Cathode active material for a nonaqueous electrolyte secondary battery and manufacturing method thereof, and a nonaqueous electrolyte secondary battery that uses cathode active material |
| US20100159333A1 (en) * | 2008-12-24 | 2010-06-24 | Ngk Insulators, Ltd. | Plate-like particle for cathode active material of a lithium secondary battery, and a lithium secondary battery |
| US20100327221A1 (en) * | 2007-12-28 | 2010-12-30 | Kazumichi Koga | Lithium manganate for non-aqueous electrolyte secondary battery, process for producing the same, and non-aqueous electrolyte secondary battery |
| CN102956923A (en) * | 2012-10-22 | 2013-03-06 | 中国电子科技集团公司第十八研究所 | Preparation method of lithium-sulfur secondary battery |
| CN103280601A (en) * | 2013-05-27 | 2013-09-04 | 浙江大学 | Method for manufacturing lithium-sulfur battery |
-
2013
- 2013-12-02 CN CN201310638320.5A patent/CN103618094B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080311473A1 (en) * | 2007-02-20 | 2008-12-18 | Hideo Sasaoka | Cathode active material for a nonaqueous electrolyte secondary battery and manufacturing method thereof, and a nonaqueous electrolyte secondary battery that uses cathode active material |
| US20100327221A1 (en) * | 2007-12-28 | 2010-12-30 | Kazumichi Koga | Lithium manganate for non-aqueous electrolyte secondary battery, process for producing the same, and non-aqueous electrolyte secondary battery |
| US20100159333A1 (en) * | 2008-12-24 | 2010-06-24 | Ngk Insulators, Ltd. | Plate-like particle for cathode active material of a lithium secondary battery, and a lithium secondary battery |
| CN102956923A (en) * | 2012-10-22 | 2013-03-06 | 中国电子科技集团公司第十八研究所 | Preparation method of lithium-sulfur secondary battery |
| CN103280601A (en) * | 2013-05-27 | 2013-09-04 | 浙江大学 | Method for manufacturing lithium-sulfur battery |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104157851B (en) * | 2014-07-14 | 2016-08-24 | 浙江大学 | Lithium-sulfur cell with stannous sulfide for grappling center and the preparation method of positive pole thereof |
| CN104157851A (en) * | 2014-07-14 | 2014-11-19 | 浙江大学 | Lithium sulfur battery adopting stannous sulfide as anchoring center and preparation method of positive electrode of lithium sulfur battery |
| CN105742681A (en) * | 2014-11-10 | 2016-07-06 | 财团法人工业技术研究院 | Electrochemical flow cell assembly and bipolar plate thereof |
| CN107534162B (en) * | 2015-04-30 | 2021-04-20 | 标准能量株式会社 | Redox flow battery |
| CN107534162A (en) * | 2015-04-30 | 2018-01-02 | 标准能量株式会社 | Redox flow batteries |
| CN104882606A (en) * | 2015-06-03 | 2015-09-02 | 浙江大学 | Polysulfide lithium-aluminum organic solution and polysulfide lithium-aluminum battery with polysulfide lithium-aluminum organic solution as catholyte |
| WO2017160712A1 (en) * | 2016-03-17 | 2017-09-21 | Saudi Arabian Oil Company | In-situ gravitational separation of electrolyte solutions in flow redox battery systems |
| CN108780912A (en) * | 2016-03-17 | 2018-11-09 | 沙特阿拉伯石油公司 | The Gravity Separation in situ of electrolyte solution in streaming redox battery system |
| JP2019508866A (en) * | 2016-03-17 | 2019-03-28 | サウジ アラビアン オイル カンパニーＳａｕｄｉ Ａｒａｂｉａｎ Ｏｉｌ Ｃｏｍｐａｎｙ | In-situ gravity separation of electrolyte solution in flow redox battery system |
| US10069161B2 (en) | 2016-03-17 | 2018-09-04 | Saudi Arabian Oil Company | In-situ gravitational separation of electrolyte solutions in flow redox battery systems |
| CN108780912B (en) * | 2016-03-17 | 2021-10-08 | 沙特阿拉伯石油公司 | In situ gravity separation of electrolyte solutions in flow redox battery systems |
| CN109361004A (en) * | 2018-11-29 | 2019-02-19 | 南京邮电大学 | A kind of shell structure for liquid stream single battery system |
| CN109361004B (en) * | 2018-11-29 | 2023-08-11 | 南京邮电大学 | Shell structure for flow single battery system |
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| CN110571500A (en) * | 2019-09-18 | 2019-12-13 | 昆明理工大学 | lithium-sulfur semi-flow battery |
| CN110571500B (en) * | 2019-09-18 | 2023-04-07 | 昆明理工大学 | Lithium-sulfur semi-flow battery |
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