CN103618094B - The preparation method of a kind of high-capacity lithium sulfur flow battery and electrode thereof - Google Patents
The preparation method of a kind of high-capacity lithium sulfur flow battery and electrode thereof Download PDFInfo
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- CN103618094B CN103618094B CN201310638320.5A CN201310638320A CN103618094B CN 103618094 B CN103618094 B CN 103618094B CN 201310638320 A CN201310638320 A CN 201310638320A CN 103618094 B CN103618094 B CN 103618094B
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
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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
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- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention relates to field of batteries, aim to provide the preparation method of a kind of high-capacity lithium sulfur flow battery and electrode thereof.The preparation method of this kind of high power lithium sulphur Flow-through electrode, comprises the following steps: preparation has the nickel foam of carbon coating layer, prepares the nickel foam as lithium sulphur flow battery negative pole, prepares the nickel foam as lithium sulphur flow battery positive pole; This kind of high-capacity lithium sulfur flow battery comprises the positive plate being carved with stream, positive pole, barrier film, the negative pole that connect successively and is carved with the negative plate of stream, and positive pole liquid and negative electrode solution.The present invention utilizes the Al of height ratio capacity for negative electrode active material, S is positive electrode active material, with the coated nickel foam of carbon for negative pole, the coated nickel foam of nickel sulfide is positive pole, for lithium sulphur flow battery provides the electrode of high activity, high strength, low flow resistance, greatly improve energy density and the power density of lithium sulphur flow battery.Active material and electrode material with low cost, preparation technology is simple, easy, has broad application prospects.
Description
Technical field
The invention relates to field of batteries, particularly the preparation method of a kind of high-capacity lithium sulfur 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
8polysulfide ion can be formed as S after obtaining electronics
8 2-, S
6 2-, S
4 2-, these polysulfide ions can dissolve 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 most is representational is all-vanadium flow battery.By electrolyte solution, carbon materials electrode, the parts such as bipolar plates and amberplex are formed.By conveying equipment for fluid substances, electrolyte is circulated between pile and storage tank, the vanadium ion completing different valence state in charge/discharge process transforms and the storage of electric energy and release 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, too scale electric power storage energy storage demand can be met; By series winding quantity and the electrode area of monocell in adjustment battery pile, nominal discharge power requirement can be met.2, the life-span is long: battery plus-negative plate reaction completes all in the 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 the charge and discharge cycles of unlimited arbitrary extent in theory, greatly extends the useful life of battery.3, cost is low: in prepared by battery critical material, as the battery such as proton exchange membrane, conductive bipolar plate critical material.By realizing, production domesticization is carried out on a large scale, low-cost production.All-vanadium flow battery is avoided 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 electrolytes is stored in different storage tanks respectively, avoids electrolysis ripple to preserve the self discharge consumption of process completely, through the battery system charge-discharge energy efficiency optimized up to 80%.
Conventional lithium ion flow battery is primarily of compositions such as cell reaction device, positive pole suspension storage tank, negative pole suspension storage tank, liquid pump and closed conduits, positive pole 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, positive pole reaction chamber, porous septum, negative reaction chamber, negative current collector and shell.Liquid pump is used to circulate to suspension during lithium ion flow battery work, 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.
The nonconducting porous septum of electronics is had between usual positive pole reaction chamber and negative reaction chamber, positive electrode active materials particle in positive pole suspension and the negative active core-shell material particle in negative pole suspension are spaced from each other, avoid both positive and negative polarity active material particle directly to contact the short circuit causing inside battery.Positive pole suspension in positive pole reaction chamber and the negative pole suspension in negative reaction chamber can carry out lithium ion exchanged transmission by the electrolyte in porous septum.When the cell is discharged, the lithium ion deintercalation of the negative active core-shell material granule interior in negative reaction chamber and going out, enters electrolyte, and arrives positive pole reaction chamber by porous septum, be 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 external circuit of battery is flowed into by the negative lug of negative current collector, flow into plus plate current-collecting body by positive pole ear after completing acting, finally embed the positive electrode active materials granule interior in positive pole 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's electric energy new technology, the 31st volume the 3rd phase ".
CN102324550 proposes a kind of design preparation method of half liquid stream lithium-sulfur cell; it is characterized in that: half described liquid stream lithium-sulfur cell is with the mixed liquor of the particulate of lithium or Si sill, lithium titanate and Sn sill and electrolyte for negative electrode, with the mixed liquor of the particulate of elemental sulfur, elemental sulfur compound, sulfur-based compound, inorganic sulfur, organic sulfur etc. and electrolyte for anode.
Tradition sodium-sulphur battery sodium is metal liquid, there is 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.Conventional 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 in metal cabinet or metal tube, form negative electrode and anode, therefore response area is less, and being difficult to provides big current and high-power output.
Summary of the invention
Main purpose of the present invention is to overcome deficiency of the prior art, provides a kind of normal temperature work, and the preparation method of Large Copacity, 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:
A kind of preparation method 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 DEG C to liquid, again nickel foam is immersed in liquid carbon source material, then variable rheostat and power supply in the series connection of nickel foam two ends, namely energising is carried out from heating (its principle and effect are equal to electric-heating-wire-heating), variable rheostat is used for by controlling size of current, and then controls the temperature of 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 polymer (as molecular weight is less than or equal to polyethylene glycol, the polyacrylic acid of 10000), higher aliphatic (monohydric alcohol of C6 ~ C26) or the higher fatty acids (monocarboxylic acid of C6 ~ C26) that molecular weight is less than or equal to 10000;
Step B: the nickel foam with carbon coating layer obtained in steps A is placed in Muffle furnace, under inert gas shielding, calcines 5 ~ 10 hours, forms Ni in the nickel interface of nickel foam at 800 ~ 1000 DEG C
3c, obtained nickel foam is namely as the negative pole of lithium sulphur flow battery;
Step C: by formation colloidal solution soluble in water for colloid sulphur, then colloidal solution is coated nickel foam, the mass ratio of Ni and S is made to be 100 ~ 1000:1, dry in the shade to be placed in vitreosil pipe and be heated to 900 DEG C, react after 6 hours, nickel foam is coated with nickel sulfide, and obtained nickel foam is namely as the positive pole of lithium sulphur flow battery.
As further improvement, in steps A, the polymer that molecular weight is less than or equal to 10000 adopts molecular weight to be less than or equal to polyethylene glycol, the polyacrylic acid of 10000, and higher aliphatic adopts octadecyl alcolol C
18h
37oH, higher fatty acids adopts stearic acid C
17h
35cOOH.
As further improvement, the thickness of the nickel foam carbon coating layer formed 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 high-capacity lithium sulfur flow battery prepared based on obtained lithium sulphur Flow-through electrode is provided, described high-capacity lithium sulfur flow battery comprises the positive plate being carved with stream, positive pole, barrier film, the negative pole that connect successively and is carved with the negative plate of stream, and positive pole liquid and negative electrode solution; Described barrier film is microporous polypropylene film, and for separating positive pole and negative pole, positive pole adopts positive pole obtained in step C, and negative pole adopts negative pole obtained in step B; Positive plate is provided with positive pole liquid ingress pipe and positive pole liquid delivery line, and positive pole liquid is flowed by the stream on positive pole liquid ingress pipe, positive plate and positive pole liquid delivery line, and infiltrates positive pole generation electrochemical reaction; Negative plate is provided with negative pole liquid ingress pipe and negative pole liquid delivery line, and negative electrode solution is flowed by the stream on negative pole liquid ingress pipe, negative plate and negative pole liquid delivery line, and infiltrates negative pole generation electrochemical reaction;
Positive pole liquid refers in electrolyte the suspension-turbid liquid being mixed with lithium sulfide powder and being formed, and negative electrode solution refers in electrolyte the suspension-turbid liquid being mixed with aluminium powder and being formed; 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; Wherein LiPF
6concentration be 1 mol/L, the volume ratio of ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, carbon disulfide is 1:1:1:1, and carbon disulfide here can replace to carbon tetrachloride or cyclohexane.
As further improvement, in described high-capacity lithium sulfur flow battery, be also provided with positive pole sealing ring between positive pole and barrier film, be also provided with negative pole sealing ring between barrier film and negative pole, positive pole 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 positive pole liquid is 1 ~ 50 micron.
As further improvement, the aluminium powder in described negative electrode solution is 1 ~ 50 micron.
There is provided the control method based on described high-capacity lithium sulfur flow battery, when charging to high-capacity lithium sulfur flow battery, 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
+then arrive negative pole through barrier film, form LiC at the carbon-coating of negative pole
6: C
6+ Li
++ e=LiC
6, then Li
+liC on negative pole
6catalytic action under there is electrochemical reducting reaction and form AlLi alloy powder: Al+Li
++ e=AlLi, AlLi charge further and obtain Li
9al
4: 4AlLi+5Li
++ 5e=Li
9al
4; When discharging to high-capacity lithium sulfur flow battery, the back reaction of above-mentioned reaction occurs respectively at positive pole 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:
The present invention utilizes the Al of height ratio capacity for negative electrode active material, S is positive electrode active material, with the coated nickel foam of carbon for negative pole, the coated nickel foam of nickel sulfide is positive pole, for lithium sulphur flow battery provides the electrode of high activity, high strength, low flow resistance, greatly improve energy density and the power density of lithium sulphur flow battery, the large-scale unstable state generating such as wind power generation, solar power generation, tidal power generation power station can be widely used in, 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 abundance, with low cost, pollution-free, easily prepare.Electrode material cost is cheap, and preparation technology is simple, easy, is conducive to large-scale production, can effectively reduce flow battery cost, have broad application prospects.
Accompanying drawing explanation
Fig. 1 is the assembly drawing of a kind of high-capacity lithium sulfur 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 positive pole sealing rings; 4 barrier films; 5 negative pole sealing rings; 6 negative poles; 7 negative plates; 8 positive pole liquid ingress pipes; 9 positive pole 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 DEG C to liquid, again nickel foam is immersed in liquid carbon source material, then variable rheostat and power supply in the series connection of nickel foam two ends, namely energising is carried out from heating, its principle and effect are equal to electric-heating-wire-heating, variable rheostat is used for by controlling size of current, and then controls the temperature of 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 polymer (molecular weight is less than or equal to polyethylene glycol, the polyacrylic acid of 10000), higher aliphatic (monohydric alcohol of C6 ~ C26) and the higher fatty acids (monocarboxylic acid of C6 ~ C26) that molecular weight is less than or equal to 10000, molecular weight is less than or equal to polymer employing polyethylene glycol, the polyacrylic acid of 10000, higher aliphatic adopts, and higher fatty acids adopts.
Step B: the nickel foam with carbon coating layer obtained in steps A is placed in Muffle furnace, under argon gas or nitrogen protection, calcines 5 ~ 10 hours, forms Ni in the nickel interface of nickel foam at 800 ~ 1000 DEG C
3c, obtained nickel foam is namely as the negative pole of lithium sulphur flow battery.
Step C: by formation colloidal solution soluble in water for colloid sulphur, then colloidal solution is coated nickel foam, the mass ratio of Ni and S is made to be 100 ~ 1000:1, dry in the shade to be placed in vitreosil pipe and be heated to 900 DEG C, react after 6 hours, nickel foam is coated with nickel sulfide, and obtained nickel foam is namely as the positive pole of lithium sulphur flow battery.
As shown in Figure 1, utilize high-capacity lithium sulfur flow battery prepared by obtained lithium sulphur Flow-through electrode, comprise the positive plate 1 being carved with stream, positive pole 2, positive pole sealing ring 3, barrier film 4, negative pole sealing ring 5, the negative pole 6 that connect successively and be carved with the negative plate 7 of stream, and positive pole liquid and negative electrode solution.Described barrier film 4 is microporous polypropylene film, and for separating positive pole 2 and negative pole 6, positive pole 2 adopts positive pole obtained in step C, and negative pole 6 adopts negative pole obtained in step B.Positive plate 1 is provided with positive pole liquid ingress pipe 8 and positive pole liquid delivery line 9, and positive pole liquid is flowed by the stream on positive pole liquid ingress pipe 8, positive plate 1 and positive pole liquid delivery line 9, and infiltrates positive pole 2 electrochemical reaction occurs.Negative plate 7 is provided with negative pole liquid ingress pipe 10 and negative pole liquid delivery line 11, and negative electrode solution is flowed 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 electrochemical reaction occurs.
Positive pole liquid refers in electrolyte the suspension-turbid liquid that the lithium sulfide powder being mixed with 1 ~ 50 micron is formed, negative electrode solution refers in electrolyte that the suspension-turbid liquid that the aluminium powder being mixed with 1 ~ 50 micron is formed, the capacity of high-capacity lithium sulfur flow battery just depend on the content of aluminium in lithium sulfide in positive pole liquid and negative electrode solution.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; Wherein LiPF
6concentration be 1 mol/L, the volume ratio of ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, carbon disulfide is 1:1:1:1, and carbon disulfide here can replace to carbon tetrachloride or cyclohexane.
When charging to above-mentioned high-capacity lithium sulfur flow battery, 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
+then arrive negative pole through barrier film, form LiC at the carbon-coating of negative pole
6: C
6+ Li
++ e=LiC
6, then Li
+liC on negative pole
6catalytic action under there is electrochemical reducting reaction and form AlLi alloy powder: Al+Li
++ e=AlLi, AlLi charge further and obtain Li
9al
4: 4AlLi+5Li
++ 5e=Li
9al
4; When discharging to high-capacity lithium sulfur flow battery, the back reaction of above-mentioned reaction occurs respectively at positive pole 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 2234mAhg
-1, the specific capacity of sulphur is up to also 1675mAhg
-1, far away higher than the capacity of the cobalt acid lithium battery of commercial extensive use, be generally less than 150mAhg
-1, therefore, the lithium sulphur flow battery of height ratio capacity can be obtained respectively as the active material of positive pole 2 and negative pole 6 by S and Al
The following examples can make professional and technical personnel's comprehend the present invention of this specialty, 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 be dissolved in ethanol, then by the ethanolic solution of sulphur instillation water, drip while stir, sulphur colloidal sol can be obtained, after drying, obtain colloid sulphur.General purity is higher, is mainly used in pharmaceutically.The matrix used material of nickel foam is the open cell foamed plastic of porous, adopt chemical nickel plating, vacuum nickel plating and leaching conducting resinl (palladium colloidal sol, submicron order aquadag etc.) three kinds of methods all can prepare conductive layer, through nickel preplating just can 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 excellent, it is one of optimum electrode material manufacturing cadmium nickel battery and nickel-hydrogen battery.Colloid sulphur and nickel foam have commercially available.
Embodiment one: electric heating carbonization
By molecular weight be 10000 polyethylene glycol be heated to 100 DEG C and melt, be that the nickel foam of 95% is immersed by voidage, nickel foam two ends connect 220V power supply electrified regulation, and current density controls at 0.1 ~ 1Acm
-2, the temperature controlling nickel foam is 250 ~ 350 DEG C and carries out carbonization formation carbon coating layer.The carbonization initial stage can use larger current density, when the temperature of nickel foam is more than 350 DEG C, can reduce current density, and carburizing temperature is adjusted within 250 ~ 350 DEG C of scopes.
When to change as molecular weight be the polyethylene glycol of 400 to carbon source material, owing to be just liquid under its room temperature, just energising carbonization can be carried out without the need to heating.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, just can carries out energising carbonization without the need to heating.And for cerinic acid or cerinic acid, such as cerinic acid CH
3(CH
2)
24cOOH, just need to be heated to 100 DEG C melt after, could be energized carbonization.
Embodiment two: prepared by negative pole
By molecular weight be 5000 polyacrylic acid be heated to 120 DEG C and melt, be that the nickel foam of 95% is immersed by voidage, nickel foam two ends connect 220V power supply electrified regulation, and current density controls at 0.1 ~ 1Acm
-2, the temperature controlling nickel foam is 250 ~ 350 DEG C and carries out carbonization formation carbon coating layer.The carbonization initial stage can use larger current density; when the temperature of nickel foam is more than 350 DEG C; current density can be reduced; carburizing temperature is made to adjust within 250 ~ 350 DEG C of scopes; take out when carbon-coating reaches 0.1 micron thickness; be placed in Muffle furnace under nitrogen protection, calcine 10 hours at 800 DEG C, 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 three: prepared by positive pole
Formation colloidal solution soluble in water for colloid sulphur is coated the nickel foam that voidage is 95%, the mass ratio of Ni and S is 100:1, dry in the shade to be placed in vitreosil pipe and be heated to 900 DEG C, react and within 6 hours, obtain the coated nickel foam of nickel sulfide, as the positive pole of lithium sulphur flow battery.
Embodiment four: lithium sulphur flow battery is formed
By octadecyl alcolol, i.e. C
18higher alcohol C
18h
37oH, is heated to 150 DEG C and melts, and be that the nickel foam of 95% is immersed by voidage, nickel foam two ends connect 220V power supply electrified regulation, and current density controls at 0.1 ~ 1Acm
-2, the temperature controlling nickel foam is 250 ~ 350 DEG C and carries out carbonization formation carbon coating layer.The carbonization initial stage can use larger current density, when the temperature of nickel foam is more than 350 DEG C, can reduce current density; carburizing temperature is adjusted within 250 ~ 350 DEG C of scopes, takes out when carbon-coating reaches 0.5 micron thickness, be placed in Muffle furnace under argon shield; calcine 8 hours at 900 DEG C, obtain negative pole.
Formation colloidal solution soluble in water for colloid sulphur is coated the nickel foam that voidage is 95%, and the mass ratio of Ni and S is 500:1, and drying in the shade to be placed in vitreosil pipe is heated to 900 DEG C, reacts and within 6 hours, obtains the coated nickel foam of nickel sulfide, as positive pole.
Positive pole 2 and negative pole 6 separate with microporous polypropylene film, and by being carved with the positive plate 1 of stream, positive pole 2, barrier film 4, negative pole 6, the negative plate 7 that is carved with stream be 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: lithium sulphur flow battery generates electricity
By stearic acid, i.e. C
18higher fatty acids C
17h
35cOOH, is heated to 150 DEG C and melts, and be that the nickel foam of 95% is immersed by voidage, nickel foam two ends connect 220V power supply electrified regulation, and current density controls at 0.1 ~ 1Acm
-2, the temperature controlling nickel foam is 250 ~ 350 DEG C and carries out carbonization formation carbon coating layer.The carbonization initial stage can use larger current density, when the temperature of nickel foam is more than 350 DEG C, can reduce current density; carburizing temperature is adjusted within 250 ~ 350 DEG C of scopes, takes out when carbon-coating reaches 1 micron thickness, be placed in Muffle furnace under argon shield; calcine 5 hours at 1000 DEG C, obtain negative pole.
Formation colloidal solution soluble in water for colloid sulphur is coated the nickel foam that voidage is 95%, and the mass ratio of Ni and S is 1000:1, and drying in the shade to be placed in vitreosil pipe is heated to 900 DEG C, reacts and within 6 hours, obtains the coated nickel foam of nickel sulfide, as positive pole.
Positive pole 2 and negative pole 6 separate with microporous polypropylene film, and by being carved with the positive plate 1 of stream, positive pole 2, barrier film 4, negative pole 6, the negative plate 7 that is carved with stream be 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 150 grams, the lithium sulfide powder of 1 ~ 50 micron being mixed into 500 milliliters forms suspension-turbid liquid as positive pole liquid, and the electrolyte aluminium powder 150 grams of 1 ~ 50 micron being mixed into 500 milliliters forms suspension-turbid liquid as negative electrode solution.Positive pole liquid and negative electrode solution are sent into positive pole 2 and negative pole 6 with peristaltic pump by the positive pole liquid on positive plate 1 and negative plate 7 and negative electrode solution 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
+then arrive negative pole 6 through barrier film 4, form LiC at the carbon-coating 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 charges further and obtains Li
9al
4:
4AlLi+5Li
++5e=Li
9Al
4
During the electric discharge of lithium sulphur flow battery, there is the back reaction of above-mentioned reaction respectively at positive pole 2 and negative pole 6.The charge-discharge performance of battery as shown in Figure 2.Battery capacity determined by the amount of the positive electrode active material added 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, a lot of distortion can also be had.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 DEG C to liquid, immerse in liquid carbon source material by nickel foam again, then variable rheostat and power supply in the series connection of nickel foam two ends, namely energising is carried out from heating, variable rheostat is used for by controlling size of current, and then controls the temperature of 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 polymer, higher aliphatic or the higher fatty acids that molecular weight is less than or equal to 10000;
Step B: the nickel foam with carbon coating layer obtained in steps A is placed in Muffle furnace, under inert gas shielding, calcines 5 ~ 10 hours, forms Ni in the nickel interface of nickel foam at 800 ~ 1000 DEG C
3c, obtained nickel foam is namely as the negative pole of lithium sulphur flow battery;
Step C: by formation colloidal solution soluble in water for colloid sulphur, then colloidal solution is coated nickel foam, the mass ratio of Ni and S is made to be 100 ~ 1000:1, dry in the shade to be placed in vitreosil pipe and be heated to 900 DEG C, react after 6 hours, nickel foam is coated with nickel sulfide, and obtained nickel foam is namely 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, the polymer that molecular weight is less than or equal to 10000 adopts molecular weight to be not more than polyethylene glycol or the polyacrylic acid of 10000, and higher aliphatic adopts octadecyl alcolol 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 formed 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. based on high-capacity lithium sulfur flow battery prepared by the lithium sulphur Flow-through electrode obtained by claim 1, it is characterized in that, described high-capacity lithium sulfur flow battery comprises the positive plate being carved with stream, positive pole, barrier film, the negative pole that connect successively and is carved with the negative plate of stream, and positive pole liquid and negative electrode solution; Described barrier film is microporous polypropylene film, and for separating positive pole and negative pole, positive pole adopts positive pole obtained in step C, and negative pole adopts negative pole obtained in step B; Positive plate is provided with positive pole liquid ingress pipe and positive pole liquid delivery line, and positive pole liquid is flowed by the stream on positive pole liquid ingress pipe, positive plate and positive pole liquid delivery line, and infiltrates positive pole generation electrochemical reaction; Negative plate is provided with negative pole liquid ingress pipe and negative pole liquid delivery line, and negative electrode solution is flowed by the stream on negative pole liquid ingress pipe, negative plate and negative pole liquid delivery line, and infiltrates negative pole generation electrochemical reaction;
Positive pole liquid refers in electrolyte the suspension-turbid liquid being mixed with lithium sulfide powder and being formed, and negative electrode solution refers in electrolyte the suspension-turbid liquid being mixed with aluminium powder and being formed; 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; Wherein LiPF
6concentration be 1 mol/L, the volume ratio of ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, carbon disulfide is 1:1:1:1, and carbon disulfide here can replace to carbon tetrachloride or cyclohexane.
6. a kind of high-capacity lithium sulfur flow battery according to claim 5, it is characterized in that, in described high-capacity lithium sulfur flow battery, positive pole sealing ring is also provided with between positive pole and barrier film, also be provided with negative pole sealing ring between barrier film and negative pole, positive pole sealing ring and negative pole sealing ring are all the sealing rings that fluorubber is made.
7. a kind of high-capacity lithium sulfur flow battery according to claim 5, is characterized in that, the lithium sulfide powder in described positive pole liquid is 1 ~ 50 micron.
8. a kind of high-capacity lithium sulfur flow battery according to claim 5, is characterized in that, the aluminium powder in described negative electrode solution is 1 ~ 50 micron.
9. based on the control method of high-capacity lithium sulfur flow battery according to claim 5, it is characterized in that, when charging to high-capacity lithium sulfur flow battery, 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
+then arrive negative pole through barrier film, form LiC at the carbon-coating of negative pole
6: C
6+ Li
++ e=LiC
6, then Li
+liC on negative pole
6catalytic action under there is electrochemical reducting reaction and form AlLi alloy powder: Al+Li
++ e=AlLi, AlLi charge further and obtain Li
9al
4: 4AlLi+5Li
++ 5e=Li
9al
4; When discharging to high-capacity lithium sulfur flow battery, the back reaction of above-mentioned reaction occurs respectively at positive pole and negative pole, realize generating, its cell reaction is: 16Li
9al
4+ 9S
8=64Al+72Li
2s.
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| TWI524585B (en) * | 2014-11-10 | 2016-03-01 | 財團法人工業技術研究院 | Electrochemical flow cell assembly and bipolar plate thereof |
| KR101560202B1 (en) * | 2015-04-30 | 2015-10-14 | 스탠다드에너지(주) | Redox flow battery |
| CN104882606B (en) * | 2015-06-03 | 2017-07-18 | 浙江大学 | Poly- aluminium sulfide lithium organic solution and the poly- aluminium sulfide lithium battery using it as catholyte |
| US10069161B2 (en) * | 2016-03-17 | 2018-09-04 | Saudi Arabian Oil Company | In-situ gravitational separation of electrolyte solutions in flow redox battery systems |
| CN109361004B (en) * | 2018-11-29 | 2023-08-11 | 南京邮电大学 | Shell structure for flow single battery system |
| CN110137462B (en) * | 2019-05-10 | 2021-07-23 | 浙江大学 | Preparation method of lithium sulfide/carbon composite material for aluminum/lithium sulfide battery |
| CN110571500B (en) * | 2019-09-18 | 2023-04-07 | 昆明理工大学 | Lithium-sulfur semi-flow battery |
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