CN105006558B - The cathode of lithium and its solution-type semi-liquid lithium-sulfur battery of a kind of surface hydriding processing - Google Patents

The cathode of lithium and its solution-type semi-liquid lithium-sulfur battery of a kind of surface hydriding processing Download PDF

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CN105006558B
CN105006558B CN201510300271.3A CN201510300271A CN105006558B CN 105006558 B CN105006558 B CN 105006558B CN 201510300271 A CN201510300271 A CN 201510300271A CN 105006558 B CN105006558 B CN 105006558B
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lithium
solution
type
catholyte
pole
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CN105006558A (en
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刘宾虹
李洲鹏
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Zhejiang University ZJU
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The present invention relates to flow battery field, it is desirable to provide the cathode of lithium and its solution-type semi-liquid lithium-sulfur battery of a kind of surface hydriding processing.The negative pole of the lithium-sulfur cell is to set to set positive plate on the outside of negative plate, positive pole on the outside of the cathode of lithium that surface hydriding is handled, negative pole；It is carved with positive plate in stream, stream and is full of solution-type catholyte, stream two ends sets catholyte ingress pipe and catholyte delivery line respectively；Barrier film is Li+ type perfluorinated sulfonic resin barrier films；Positive pole is prepared with Li+ type Nafion resinoid bonds.The liquid stream lithium battery of solution-type half of the present invention has good charge and discharge cycles stability and high-rate charge-discharge capability, greatly improves the energy density and power density of lithium-sulfur cell.Large-scale unstable state generating power station is can be widely used for, plays a part of electric adjustment；Also the peak-trough electricity of electricity consumption can be balanced, generating efficiency is improved, cost of electricity-generating is reduced.Because the energy density of the liquid stream lithium battery of solution-type half is far longer than traditional flow battery, it can also be used as electrical vehicular power power supply.

Description

The cathode of lithium and its solution-type semi-liquid lithium-sulfur battery of a kind of surface hydriding processing
Technical field
The present invention is on flow battery field, the cathode of lithium of more particularly to a kind of surface hydriding processing and its using without solid The solution-type semi-liquid lithium-sulfur battery of state material catholyte.
Background technology
Full flow battery is a kind of energy-storage battery, and most representational is all-vanadium flow battery.By electrolyte solution, carbon The parts such as cellulosic material electrode, bipolar plates and amberplex are constituted.Catholyte and anolyte are made in electricity by conveying equipment for fluid substances Circulated between heap and storage tank, the vanadium ion of completion different valence state mutually converts the storage with electric energy in charge/discharge process Deposit and discharge, wherein catholyte and anolyte are all solution.Lived using solid-state the pole that half flow battery may be defined as in battery Material, another pole uses liquid active material (being solution rather than suspension).
In existing flow battery technology, semi-solid flow cell is nominally closer to half flow battery, and its structure is set Meter is similar to full flow battery, but the difference is that semi-solid flow cell is the suspension for storing the energy in solid mixt In.Positive pole and negative electrode active material in the battery suspended particulate of electrolyte in battery are constituted.Positive pole and negative pole being The suspension of matter is kept apart by having infiltrative porous ion film, passes through positive pole and the suspension liquid movement of negative electrode active material Produce electric energy.Although CN102324550 proposes a kind of nominal half flow battery, but is exactly one in practical structures and principle Plant the design preparation method of semisolid liquid stream, it is characterised in that：Described semi-liquid lithium-sulfur battery is with the particulate of lithium or Si bases The mixed liquor of material, lithium titanate and Sn sills and electrolyte be negative pole, with elemental sulfur, simple substance sulfur compound, sulfur-based compound, The particulate of inorganic sulfur, organic sulfur etc. and the mixed liquor of electrolyte are positive pole.Catholyte and anode are also suspension.
Semisolid liquid stream lithium-sulfur cell battery is mainly deposited by cell reaction device, positive pole suspension storage tank, negative pole suspension The compositions such as storage tank, liquid pump and sealing pipeline, positive pole suspension storage tank holds positive electrode active materials particle, conductive agent and electrolyte Mixture, 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 includes：Plus plate current-collecting body, positive pole reaction chamber, porous septum, negative pole are anti- Answer chamber, negative current collector and shell.There is the nonconducting porous septum of electronics between positive pole reaction chamber and negative reaction chamber, by positive pole The negative active core-shell material particle in positive electrode active materials particle and negative pole suspension in suspension is spaced from each other, it is to avoid both positive and negative polarity Active material particle directly contact causes the short circuit of inside battery.Positive pole suspension and negative reaction intracavitary in positive pole reaction chamber Negative pole suspension lithium ion exchanged transmission can be carried out by electrolyte in porous septum.When the cell is discharged, negative pole is anti- Answer the lithium ion deintercalation inside the negative active core-shell material particle in chamber and go out, reached just into electrolyte, and by porous septum Pole reaction chamber, is embedded into inside positive electrode active materials particle；At the same time, in the negative active core-shell material particle in negative reaction chamber The electronics in portion flows into negative current collector, and the external circuit for the negative lug inflow battery for passing through negative current collector, completes acting Plus plate current-collecting body is flowed into by positive pole ear afterwards, is finally embedded in inside the positive electrode active materials particle in positive pole reaction chamber.Battery The process of charging is in contrast.
Traditional lithium-sulfur cell is that, using element sulphur as anode, lithium metal has conventional lithium ion as one kind of negative pole Battery structure without molten sulfur battery, both positive and negative polarity active material is all solid matter.But from unlike conventional lithium ion battery, lithium sulphur The positive electrode active material sulphur of battery produces the intermediate product for being dissolved in electrolyte in charge and discharge process：Polysulfide ion.Sulfur electrode fills Electricity and exoelectrical reaction are more complicated, and its discharge process mainly includes two steps, and two discharge platforms are corresponded to respectively：(1) correspondence S8 Cyclic structure be changed into Sn 2-The chain structure of (3≤n≤7) ion, and and Li+With reference to the poly- lithium sulfide (Li of generation2Sn), the reaction Discharge platform on discharge curve near 2.4~2.1V of correspondence；(2) correspondence Sn 2-The chain structure of ion is changed into S2-And S2 2-And With Li+With reference to generation Li2S2And Li2Discharge platform longer near 2.1~1.8V in S, reaction correspondence discharge curve, this is put down Platform is the main discharge region of lithium-sulfur cell.Being located at the correspondence elemental sulfur reduction generation of 2.5~2.05V potential regions upon discharging can The further reduction of molten polysulfide and polysulfide, positioned at the solvable polysulfide of 2.05~1.5V potential regions correspondence also It is primary into lithium sulfide solid film, it is covered in conductive carbon matrix surface.During charging, Li in sulfur electrode2S and Li2S2It is oxidized S8With Sm 2-(6≤m≤7), can not be completely oxidized to S8, charging of the charging reaction in charging curve near 2.5~2.4V of correspondence Platform.It is the problem of lithium-sulfur cell maximum at present：Formed in charge and discharge process and be dissolved in the poly- lithium sulfide of electrolyte, dissolving it is poly- Lithium sulfide reacts with negative metal lithium, causes capacitance loss, causes lithium-sulfur cell capacity fast decay, show the circulation of extreme difference Life-span.Moreover, battery capacity is limited to the load sulfur content of battery, it is impossible to adjust, be not suitable for battery with ultra large capacity.And flow battery Then different, battery capacity depends on the usage amount of catholyte, therefore the capacity of battery can easily be adjusted, as photovoltaic Generating, the optimal candidate of wind power generation energy storage.
Buy to resell two water lithium rhodanate (LiSCN2H in city2O be) the long monocline acicular crystal of white, easy moisture absorption, have in water compared with Big solubility.Generally by equimolar Ba (SCN)2And Li2SO4Solution is mixed, and solution is crystallized after being subcooled and is obtained two water thiocyanic acids Lithium.Anhydrous lithium rhodanate can be obtained by Sulfur with lithium cyanide congruent melting.Anhydrous lithium rhodanate dissolves in the electrolysis of lithium-sulfur cell In liquid, formed catholyte, can as flow battery positive electrode active material.
The content of the invention
The technical problem to be solved in the present invention is to overcome of the prior art not enough there is provided a kind of work of normal temperature, and great Rong Amount, high-power, high efficiency, long-life hydrogen surface treatment cathode of lithium, and use the solution-type catholyte without solid matter Semi-liquid lithium-sulfur battery.
In order to solve the above technical problems, the solution of the present invention is：
A kind of cathode of lithium of surface hydriding processing is provided, prepared by following methods：
Under argon atmospher protection, with 10Kg/cm2Pressure metal lithium sheet is pressed onto on copper film, formed it is long it is generous be 30 × 20 × 4mm base material of cathode；Base material of cathode is placed at 200 DEG C in the nitrogen atmosphere of purity 99.999% and handled 1~3 hour, Obtain the cathode of lithium that metallic lithium surface possesses lithium hydride protective layer.
Invention further provides the solution-type semi-liquid lithium-sulfur battery using foregoing cathode of lithium, its negative pole is the table The hydrotreated cathode of lithium in face, in addition to barrier film and positive pole；Set on the outside of the negative pole and set positive plate on the outside of negative plate, positive pole；Just It is carved with pole plate in stream, stream and is full of solution-type catholyte, stream two ends sets catholyte ingress pipe and catholyte export respectively Pipe；
The solution-type catholyte is prepared by the following method：
(1) 1 mole of anhydrous lithium rhodanate is dissolved in 200mL tetrahydrofurans, adds mole of colloid sulphur, LiSCN and S Than for 1: 7；Mixture is placed in reactor, and heated sealed is to after 60 DEG C, stirring reaction 5 hours；Open reactor, solvent evaporated Tetrahydrofuran, obtains poly- lithium rhodanate and (is also known as polysulfide lithium cyanide, LiS8CN)；
The poly- lithium rhodanates of 0.2~50g are dissolved in 200mL electrolyte, solution-type catholyte is obtained；Electrolyte is with Li [CF3SO2)2N] (LiTFSI) be solute, dioxolanes (C3H6O2) and ethylene glycol monomethyl ether (C3H8O2) mixture be solvent；Two The volume ratio of butyl oxide link and ethylene glycol monomethyl ether is 1: 1, containing one mole of (263g) Li [CF in every liter of electrolyte3SO2)2N]；
The barrier film is Li+Type perfluorinated sulfonic resin barrier film (abbreviation Li+- Nafion), for separating positive pole and negative pole；
The positive pole is prepared by the following method：
Macropore carbon material is taken, is mixed with acetylene black (commercially available prod) and binding agent in mass ratio 70: 20: 10；Using NMP as point Powder is modulated into pasty state；0.2mL is taken to be coated on long a width of 30 × 20mm carbon paper and dry in the shade, with 100Kg/cm2Pressure pressure The type of being made obtains positive pole；The binding agent is Li+Type Nafion resins.
In the present invention, the macropore carbon material is prepared by the following method：
In mass ratio 1: 1 weighs the hydrophilic nano CaCO that particle diameter is 15~40nm3(the limited public affairs of Ruicheng Warner nano material Department's production) and each 10g of glucose, add into 100ml deionized waters, ultrasonic vibration mixing make within 30 minutes glucose dissolving and with Nano-meter CaCO33It is uniformly dispersed；Heating evaporates the water, and then solidifies 6 hours at 160 DEG C；By cured product in nitrogen atmosphere protection Under be warming up to 900 DEG C, constant temperature is carbonized 2 hours；Carbonized product is washed with the nitric acid of 5wt% concentration, deionized water successively, then 120 Freeze-day with constant temperature obtains macropore carbon material after 4 hours at DEG C.
In the present invention, the Li+Type Nafion resins are prepared by the following method：Take 10g LiNO3Add extremely In 100ml Nafion (20wt% originates from E.I.Du Pont Company), after stirring 30 minutes, centrifuge superfluous LiNO3, obtain Li+- Nafion solution；The Li as binding agent is obtained after drying+Type Nafion resins.
In the present invention, the Li+Type perfluorinated sulfonic resin barrier film is prepared by the following method：The Nafion that city is bought to resell Film is immersed in 10wt% LiOH solution, after being handled 1 hour at 80 DEG C, is rinsed with deionized water to water in neutrality, after drying It is dried in vacuo 6 hours at 90 DEG C, obtains Li+Type perfluorinated sulfonic resin barrier film.
In the present invention, further respectively had between the positive pole and barrier film, between negative pole and barrier film by fluorubber be made it is close Seal.
Realization principle description of the present invention：
In hydrogen surface treatment process, hydrogen reacts with lithium metal, in metallic lithium surface formation lithium hydride.
In semi-liquid lithium-sulfur battery discharge process, be electrochemically oxidized in the lithium metal of negative pole, formed lithium ion, lithium from Catholyte of the son through the hydrogenation lithium layer and barrier film on negative pole into side of the positive electrode, by the carbon paper of positive pole be diffused into by macropore carbon, The conversion zone of acetylene black, binding agent composition, poly- lithium rhodanate (LiS8CN) by progressively electrochemical reduction, lithium rhodanate and sulphur are formed Change lithium：
LiS8CN+14Li+=LiSCN+7Li2S
Lithium sulfide is deposited on macropore carbon bore area.Due to Li+- Nafion only allows cation (lithium ion) to conduct, resistance Hinder anion (polysulfide cyanate radical S8CN-With thiocyanate radical SCN-) conduct, and the lithium hydride on cathode of lithium is also avoided that polysulfide cyanogen Sour lithium or lithium rhodanate are contacted with lithium metal, it is therefore prevented that the circulation decline of solution-type semi-liquid lithium-sulfur battery capacity.Charging process In, lithium rhodanate and lithium sulfide progressively take off lithium and generate poly- lithium rhodanate, while lithium ion passes through Li+- Nafion barrier films and negative Hydrogenation lithium layer on extremely, is reduced electrochemically, and forms lithium metal.
Compared with prior art, the beneficial effects of the invention are as follows：
The invention provides the negative pole that a kind of surface has lithium hydride protective layer, and with semisolid liquid stream lithium-sulfur cell and Traditional lithium-sulfur cell working condition semi-liquid lithium-sulfur battery different with operational mode.With positive electrode active material in traditional lithium-sulfur cell S8Property institute insoluble in electrolysis is different, the LiS in catholyte of the present invention8CN is dissolved in electrolyte formation solution, thus mobility is very It is good.Contrast CN102324550 and propose that the catholyte reactivity of suspension is higher.And negative pole uses lithium metal, greatly carries The high energy density of battery.Utilize Li+- Nafion barrier films effectively prevent poly- lithium rhodanate or lithium rhodanate and other polysulfides Shuttle from ion to negative pole.Further, the lithium hydride protective layer of the hydrogenation treatment formation of negative pole, further prevents gold Belong to lithium to react with polysulfide cyanate radical or thiocyanate radical and other polysulfide ions, do not prevent the conduction of lithium ion but.
Therefore, the liquid stream lithium battery of solution-type half of the invention has good charge and discharge cycles stability and high magnification charge and discharge Electrical property, greatly improves the energy density and power density of lithium-sulfur cell.Can be widely used for wind-power electricity generation, solar power generation, The large-scale unstable state generating power station such as tidal power generation, plays a part of electric adjustment, can also be applied to stable state generating power station, and balance is used The peak-trough electricity of electricity, improves generating efficiency, reduces cost of electricity-generating.Due to the energy density of the liquid stream lithium battery of solution-type half of the present invention It is far longer than traditional flow battery, therefore can be also used as the electrical source of power of electric car.
Because polysulfide cyanic acid lithium chemistry is stable, different, polysulfide must be carried out under protective atmosphere from synthesis lithium sulfide Cyanic acid lithium can just can be produced under household condition, and active material abundance is with low cost, pollution-free, thus electrode material With low cost, preparation technology is simple, easy, is conducive to large-scale production, flow battery cost can be effectively reduced, with wide Application prospect.
Meanwhile, the lithium hydride protective layer of negative pole is stable in dry air, is conducive to improving the peace of lithium-sulfur cell production Entirely.The generation of Li dendrite on negative pole in battery charge and discharge process can also be suppressed using the cathode of lithium with lithium hydride protective layer, carried The high reliability of battery, improves safety in utilization.
Brief description of the drawings
Fig. 1 is the assembling figure of solution-type semi-liquid lithium-sulfur battery in the present invention.
Fig. 2 is solution-type semi-liquid lithium-sulfur battery discharge performance figure in embodiment seven.
Reference in figure is：1-1 positive plates；1-1-1 catholyte ingress pipes；1-1-2 catholyte delivery lines；1-1-3 Stream；1-2 positive poles；1-2-1 carbon papers；1-2-2 conversion zones；1-3 sealing rings；1-4 barrier films；1-5 negative poles；1-5-1 lithium metals；1-5- 2 lithium hydride protective layers；1-6 negative plates；2-1 discharge curves.
Embodiment
Ethanol is dissolved in using sulphur, the characteristics of being slightly soluble in water.Sulphur is first dissolved in ethanol, then the ethanol solution of sulphur is instilled into water In, stirred in drop, sulphur colloidal sol can be obtained, colloid sulphur is obtained after drying.Colloid sulphur is commercially available.
The present invention is described in further detail with embodiment below in conjunction with the accompanying drawings：
The surface treatment method of lithium electrode：
Under argon atmospher protection, in 10Kg/cm2Pressure under metal lithium sheet is pressed onto on copper film, formed it is long it is generous be 30 × 20 × 4mm negative pole；Metal lithium sheet is handled 1~3 hour in 200 DEG C of atmosphere for being placed in High Purity Hydrogen (purity 99.999%) Obtain the negative pole for possessing hydrogenation lithium layer protection.
A kind of preparation method of solution-type semi-liquid lithium-sulfur battery, specifically includes following steps：
Step A：It is prepared by positive pole
1.4g macropore carbon materials are taken, are mixed with acetylene black (commercially available prod) and binding agent in mass ratio 70: 20: 10；With NMP (2g) is that dispersant is modulated into pasty state；1mL is taken to be coated to length and width：On 30 × 20mm carbon paper and dry in the shade, in 100Kg/cm2Pressure It is compressing under power to obtain positive pole；
The binding agent is Li+Type Nafion resins, preparation method is：Take 10g LiNO3Add to 100ml Nafion In (20wt% originates from E.I.Du Pont Company), after stirring 30 minutes, centrifuge superfluous LiNO3, obtain Li+- Nafion solution, Li is obtained after drying+Type Nafion resins.
The preparation method of the macropore carbon material is：
In mass ratio 1: 1 weighs the production of Ruicheng Warner nano material Co., Ltd, and particle diameter is 15~40nm hydrophily Nano-meter CaCO33With each 10g of glucose, add into 100ml deionized waters, ultrasonic vibration mixing makes glucose dissolving for 30 minutes simultaneously With Nano-meter CaCO33It is uniformly dispersed；Heating evaporates the water, and then solidifies 6 hours at 160 DEG C；Cured product is protected in blanket of nitrogen 900 DEG C are warming up under shield, constant temperature is carbonized 2 hours；Carbonized product is washed with the nitric acid of 5wt% concentration, deionized water successively, then Freeze-day with constant temperature obtains macropore carbon material after 4 hours at 120 DEG C.
Step B：Li+It is prepared by type perfluorinated sulfonic resin barrier film
The Nafion membrane that city is bought to resell is immersed in 10wt% LiOH solution, after being handled 1 hour at 80 DEG C, uses deionized water Rinsing, in neutrality, is dried in vacuo 6 hours at 90 DEG C after drying to water, obtains Li+Type perfluorinated sulfonic resin barrier film.
Step C：It is prepared by solution-type semi-liquid lithium-sulfur battery catholyte
1 mole of anhydrous lithium rhodanate is dissolved in 200mL THF, colloid sulphur is added, LiSCN and S mol ratio are 1：7, put In reactor, heated sealed is to 60 DEG C, and stirring reaction 1~5 hour opens reactor, and solvent evaporated THF obtains polysulfide cyanogen Sour lithium (is also known as polysulfide lithium cyanide, LiS8CN).Poly- lithium rhodanate is dissolved in electrolyte and obtains solution-type semi-liquid lithium-sulfur battery the moon Pole liquid, electrolyte is with Li [CF3SO2)2N] (LiTFSI) be solute, dioxolanes (C3H6O2) and the mixture of ethylene glycol monomethyl ether be The volume ratio of solvent, dioxolanes and ethylene glycol monomethyl ether is 1: 1, containing one mole of (263g) Li [CF in one liter of electrolyte3SO2)2N]。
As shown in figure 1, the solution-type semi-liquid lithium-sulfur battery prepared using obtained both positive and negative polarity and barrier film, including connect successively The positive plate 1-1 for being carved with stream that connects, positive pole 1-2, sealing ring 1-3, barrier film 1-4, sealing ring 1-3, negative pole 1-5 and it is carved with negative pole The negative plate 1-6 of mounting groove, and catholyte.The barrier film 1-4 is Li+Type perfluorinated sulfonic resin barrier film, for separating positive pole 1-2 and negative pole 1-5.Positive pole 1-2 uses obtained positive pole in step A, and negative pole 1-5 uses obtained negative pole in step B.Positive plate 1-1 be provided with catholyte ingress pipe 1-1-1 and catholyte delivery line 1-1-2, catholyte by catholyte ingress pipe 1-1-1, enter Enter the stream 1-1-3 on positive plate 1-1, excluded by catholyte delivery line 1-1-2.Catholyte passes through the carbon paper on positive pole 1-2 1-2-1 is diffused into conversion zone 1-2-2 and occurs electrochemical reaction.Negative plate 1-6 is provided with pole mounting groove.
Catholyte refers to the solution dissolved with the formation of poly- lithium rhodanate in electrolyte, and the capacity of semi-liquid lithium-sulfur battery is depended on The content of poly- lithium rhodanate in catholyte.Electrolyte is with Li [CF3SO2)2N] (LiTFSI) be solute, dioxolanes (C3H6O2) and The mixture of ethylene glycol monomethyl ether is solvent, and the volume ratio of dioxolanes and ethylene glycol monomethyl ether is to be rubbed containing one in 1: 1, every liter of electrolyte You are (263g) Li [CF3SO2)2N]；
To in above-mentioned semi-liquid lithium-sulfur battery discharge process, being electrochemically oxidized in negative pole 1-5 lithium metal 1-5-1, shape Into lithium ion：
Li=Li++e
Lithium ion enters the catholyte of side of the positive electrode through the hydrogenation lithium layer 1-5-2 on negative pole 1-5, in positive pole 1-2 reaction Poly- lithium rhodanate (LiS on layer 1-2-2 macropore carbon bore area8CN) by progressively electrochemical reduction, lithium rhodanate and sulphur are formed Change lithium：
LiS8CN+14Li+=LiSCN+7Li2S+14e
Lithium sulfide is deposited on macropore carbon bore area.The further embedding lithiums of LiSCN：
LiSCN+2Li+=LiCN+Li2S+2e
Due to Li+- Nafion only allows cation (lithium ion) to conduct, and hinders anion (polysulfide cyanate radical S8CN-And sulphur Cyanate radical SCN-) conduct, and the lithium hydride 1-5-2 on negative pole 1-5 is also avoided that poly- lithium rhodanate or lithium rhodanate connect therewith Touch, it is therefore prevented that the circulation decline of semi-liquid lithium-sulfur battery capacity.In charging process, on positive pole 1-2 and negative pole 1-5 occur respectively The back reaction of reaction is stated, lithium rhodanate and lithium sulfide progressively take off lithium and form poly- lithium rhodanate, while lithium ion passes through Li+- Hydrogenation lithium layer 1-5-2 on Nafion barrier films 1-4 and negative pole 1-5, is reduced electrochemically, and forms lithium metal 1-5-1.
Lithium metal has very high theoretical specific capacity (3830mAh g-1), LiS8CN specific capacity is up to 5770mAh g-1, Significantly larger than commercial wide variety of cobalt acid lithium battery capacity (<150mAh g-1), therefore, by LiS8CN and lithium metal point The semi-liquid lithium-sulfur battery of high-energy-density is not can obtain as positive pole 1-2 and negative pole 1-5 active material.
The present invention is more fully understood in the professional and technical personnel that the following examples can make this professional, but not with any side The formula limitation present invention.
Embodiment one：It is prepared by anhydrous lithium rhodanate
Equimolar elemental sulfur obtains anhydrous lithium rhodanate with congruent melting at 140 DEG C of lithium cyanide.
Embodiment two：It is prepared by negative pole
Under argon atmospher protection, in 10Kg/cm2Pressure under metal lithium sheet is pressed onto on copper film, formed it is long it is generous be 30 × 20 × 4mm negative pole；Metal lithium sheet is handled 1 hour in 200 DEG C of atmosphere for being placed in High Purity Hydrogen (purity 99.999%) To the negative pole for possessing hydrogenation lithium layer protection.
Embodiment three：It is prepared by macropore carbon material
In mass ratio 1: 1 weighs the production of Ruicheng Warner nano material Co., Ltd, and particle diameter is 15~40nm hydrophily Nano-meter CaCO33With each 10g of glucose, add into 100ml deionized waters, ultrasonic vibration mixing makes glucose dissolving for 30 minutes simultaneously With Nano-meter CaCO33It is uniformly dispersed；Heating evaporates the water, and then solidifies 6 hours at 160 DEG C；Cured product is protected in blanket of nitrogen 900 DEG C are warming up under shield, constant temperature is carbonized 2 hours；Carbonized product is washed with the nitric acid of 5wt% concentration, deionized water successively, then Freeze-day with constant temperature obtains macropore carbon material after 4 hours at 120 DEG C.
Example IV：It is prepared by positive pole
The macropore carbon material 1.4g prepared in Example three, with acetylene black (commercially available prod) and binding agent in mass ratio 70 : 20: 10 mixing；It is that dispersant is modulated into pasty state with NMP (2g)；1mL is taken to be coated to length and width：It is on 30 × 20mm carbon paper and cloudy It is dry, in 100Kg/cm2Pressure under compressing obtain positive pole；
Embodiment five：It is prepared by catholyte
Obtained in embodiment one 1 mole of anhydrous lithium rhodanate is dissolved in 200mL THF, 7 moles of colloid sulphur are added, LiSCN and S mol ratio is 1: 7, is placed in reactor, and heated sealed is to 60 DEG C, and stirring reaction 1 hour opens reactor, steams Dry solvent THF, obtains poly- lithium rhodanate (or polysulfide lithium cyanide, LiS8CN)。
Take the poly- lithium rhodanates of 0.2g to be dissolved in electrolyte 200mL and obtain solution-type semi-liquid lithium-sulfur battery catholyte, electrolyte With Li [CF3SO2)2N] (LiTFSI) be solute, dioxolanes (C3H6O2) and ethylene glycol monomethyl ether mixture be solvent, dioxy penta The volume ratio of ring and ethylene glycol monomethyl ether is 1: 1, containing one mole of (263g) Li [CF in every liter of electrolyte3SO2)2N]。
Embodiment six：Li+The preparation of type perfluorinated sulfonic resin barrier film
The films of Nafion 117 that city is bought to resell are immersed in 10wt% LiOH solution, at 80 DEG C handle 1 hour after, spend from Sub- water is rinsed to water in neutrality, is dried in vacuo 6 hours at 90 DEG C after drying, is obtained Li+Type perfluorinated sulfonic resin barrier film.
Embodiment seven：Solution-type semi-liquid lithium-sulfur battery is constituted
Under argon atmospher protection, in 10Kg/cm2Pressure under metal lithium sheet is pressed onto on copper film (thickness 0.1mm), formed The negative pole that it is 30 × 20 × 4mm that length is generous；Metal lithium sheet is located in 25 DEG C of atmosphere for being placed in High Purity Hydrogen (purity 99.999%) Reason obtains the negative pole for possessing hydrogenation lithium layer protection for 2 hours.
The macropore carbon material 1.4g prepared in Example three, with acetylene black (commercially available prod) and binding agent in mass ratio 70 : 20: 10 mixing；It is that dispersant is modulated into pasty state with NMP (2g)；1mL is taken to be coated to length and width：It is on 30 × 20mm carbon paper and cloudy It is dry, in 100Kg/cm2Pressure under compressing obtain positive pole；
Positive pole 1-2 and negative pole 1-5 is with the Li obtained in embodiment six+Type perfluorinated sulfonic resin barrier film is prepared and separated, and will be carved There are stream 1-1-3 positive plate 1-1, positive pole 1-2, barrier film 1-4, negative pole 1-5, the negative plate 1-6 combinations for being carved with negative pole mounting groove There is sealing ring 1-3 to prevent solution leakage, negative pole 1-5 lithium hydride protective layer 1-5-2 courts into battery, between both positive and negative polarity and barrier film To barrier film 1-4, the stream 1-1-3 of positive pole 1-2 conversion zone 1-2-2 towards barrier film and carbon paper 1-2-1 towards positive plate 1-1, such as Shown in Fig. 1.
Obtained in embodiment one 1 mole of anhydrous lithium rhodanate is dissolved in 200mL THF, 7 moles of colloid sulphur are added, LiSCN and S mol ratio is 1: 7, is placed in reactor, and heated sealed is to 60 DEG C, and stirring reaction 3 hours opens reactor, steams Dry solvent THF, obtains poly- lithium rhodanate (or polysulfide lithium cyanide, LiS8CN).Take the poly- lithium rhodanates of 2g to be dissolved in electrolyte 200mL to obtain To semi-liquid lithium-sulfur battery catholyte, electrolyte is with Li [CF3SO2)2N] (LiTFSI) be solute, dioxolanes (C3H6O2) and second The mixture of glycol methyl ether is solvent, and the volume ratio of dioxolanes and ethylene glycol monomethyl ether is to contain one mole in 1: 1, one liter of electrolyte (263g)Li[CF3SO2)2N]。
By catholyte peristaltic pump by the catholyte ingress pipe 1-1-1 on positive plate 1-1, diffuse through positive pole 1-2's Carbon paper 1-2-1, into conversion zone 1-2-2, the catholyte reacted is discharged by ingress pipe 1-1-2.
Embodiment seven：Solution-type semi-liquid lithium-sulfur battery generates electricity
Under argon atmospher protection, in 10Kg/cm2Pressure under metal lithium sheet is pressed onto on copper film (0.1mm), formed length and width Thickness is 130 × 150 × 10mm negative pole；Metal lithium sheet is handled in 25 DEG C of atmosphere for being placed in High Purity Hydrogen (purity 99.999%) Obtain within 3 hours the negative pole for possessing hydrogenation lithium layer protection.
Macropore carbon material 100g is taken, is mixed with acetylene black (commercially available prod) and binding agent in mass ratio 70: 20: 10；With NMP (143g) is that dispersant is modulated into pasty state；It is coated on long a width of 130x150mm carbon paper and dries in the shade, in 100Kg/cm2Pressure It is compressing under power to obtain positive pole；
Positive pole 1-2 and negative pole 1-5 is with the Li obtained in embodiment five+Type perfluorinated sulfonic resin barrier film is prepared and separated, and will be carved There are stream 1-1-3 positive plate 1-1, positive pole 1-2, barrier film 1-4, negative pole 1-5, the negative plate 1-6 combinations for being carved with negative pole mounting groove There is sealing ring 1-3 to prevent solution leakage, negative pole 1-5 lithium hydride protective layer 1-5-2 courts into battery, between both positive and negative polarity and barrier film To barrier film 1-4, the stream 1-1-3 of positive pole 1-2 conversion zone 1-2-2 towards barrier film and carbon paper 1-2-1 towards positive plate 1-1.
Obtained in embodiment one 1 mole of anhydrous lithium rhodanate is dissolved in 200mL THF, 7 moles of colloid sulphur are added, LiSCN and S mol ratio is 1: 7, is placed in reactor, and heated sealed is to 60 DEG C, and stirring reaction 5 hours opens reactor, steams Dry solvent THF, obtains poly- lithium rhodanate (or polysulfide lithium cyanide, LiS8CN).The poly- lithium rhodanates of 50g are taken to be dissolved in 200mL electrolyte, Solution-type semi-liquid lithium-sulfur battery catholyte is obtained, electrolyte is with Li [CF3SO2)2N] (LiTFSI) be solute, dioxolanes (C3H6O2) and the mixture of ethylene glycol monomethyl ether be solvent, the volume ratio of dioxolanes and ethylene glycol monomethyl ether is 1: 1, every liter of electrolysis Containing one mole of (263g) Li [CF in liquid3SO2)2N]。
Catholyte peristaltic pump is entered to positive plate 1-1 stream 1-1-3 by the ingress pipe 1-1-1 on positive plate 1-1, The catholyte reacted is discharged by ingress pipe 1-1-2.During electric discharge, negative pole 1-5 lithium metal 1-5-1 be constantly oxidized to lithium from Son, hydrogenation lithium layer 1-5-2 and barrier film 1-4 through negative pole 1-5 enter catholyte.
In positive pole 1-2 conversion zones 1-2-1 macropore carbon endoporus, electrochemical reduction occurs for poly- lithium rhodanate, forms thiocyanic acid Lithium and lithium sulfide：
LiS8CN+14Li+=LiSCN+7Li2S+14e
Lithium sulfide is deposited on macropore carbon bore area, and LiSCN is dissolved in electrolyte.
During charging, the back reaction of above-mentioned reaction occurs respectively in positive pole 1-2 and negative pole 1-5.Li+Ion is passed through from catholyte Barrier film 1-4 reaches negative pole 1-5, through negative pole 1-5 hydrogenation lithium layer 1-5-2 formation lithium metals 1-5-1：
Li++ e=Li
And the lithium sulfide of side of the positive electrode takes off lithium, react to form poly- lithium rhodanate with the LiSCN in electrolyte.
Battery capacity is determined by the positive electrode active material and the amount of negative electrode active material added.Generous using length is 130 × 150 Lithium metal is 102.3g (130 × 150 × 9.9mm) in × 10mm negative pole.When lithium sulphur flow battery discharges, the electric discharge of battery is bent Line is as shown in Figure 2.
Finally it should be noted that listed above is only specific embodiment of the invention.It is clear that the invention is not restricted to Above example, can also there is many variations.One of ordinary skill in the art can directly lead from present disclosure All deformations for going out or associating, are considered as protection scope of the present invention.

Claims (5)

1. a kind of solution-type semi-liquid lithium-sulfur battery, including negative pole, barrier film and positive pole；Characterized in that, the negative pole is surface Set on the outside of hydrotreated cathode of lithium, negative pole and set positive plate on the outside of negative plate, positive pole；It is carved with stream, stream and fills on positive plate Full solution-type catholyte, stream two ends set catholyte ingress pipe and catholyte delivery line respectively；
The cathode of lithium of the surface hydriding processing, is prepared by following methods：
Under argon atmospher protection, with 10Kg/cm2Pressure metal lithium sheet is pressed onto on copper film, formed it is long it is generous be 30 × 20 × 4mm base material of cathode；Base material of cathode is placed at 200 DEG C in the nitrogen atmosphere of purity 99.999% and handled 1~3 hour, is obtained Metallic lithium surface possesses the cathode of lithium of lithium hydride protective layer；
The solution-type catholyte is prepared by the following method：
(1) 1 mole of anhydrous lithium rhodanate is dissolved in 200mL tetrahydrofurans, adds colloid sulphur, LiSCN and S mol ratio are 1∶7；Mixture is placed in reactor, and heated sealed is to after 60 DEG C, stirring reaction 5 hours；Open reactor, solvent evaporated tetrahydrochysene Furans, obtains poly- lithium rhodanate；
The poly- lithium rhodanates of 0.2~50g are dissolved in 200mL electrolyte, solution-type catholyte is obtained；Electrolyte is with Li [CF3SO2)2N] it is solute, the mixture of dioxolanes and ethylene glycol monomethyl ether is solvent；The volume ratio of dioxolanes and ethylene glycol monomethyl ether is 1: 1, containing one mole of Li [CF in every liter of electrolyte3SO2)2N]；
The barrier film is Li+Type perfluorinated sulfonic resin barrier film；
The positive pole is prepared by the following method：
Macropore carbon material is taken, is mixed with acetylene black and binding agent in mass ratio 70: 20: 10；Paste is modulated into by dispersant of NMP Shape；0.2mL is taken to be coated on long a width of 30 × 20mm carbon paper and dry in the shade, with 100Kg/cm2Pressure compressing obtain just Pole；The binding agent is Li+Type Nafion resins.
2. solution-type semi-liquid lithium-sulfur battery according to claim 1, it is characterised in that the macropore carbon material is under The method of stating is prepared：
In mass ratio 1: 1 weighs the hydrophilic nano CaCO that particle diameter is 15~40nm3With each 10g of glucose, add to 100ml and go In ionized water, ultrasonic vibration mixing makes glucose dissolving and and Nano-meter CaCO3 for 30 minutes3It is uniformly dispersed；Heating evaporates the water, so Solidify 6 hours at 160 DEG C afterwards；Cured product is warming up to 900 DEG C under nitrogen atmosphere protection, constant temperature is carbonized 2 hours；Carbonization production Thing is washed with the nitric acid of 5wt% concentration, deionized water successively, then freeze-day with constant temperature after 4 hours, obtains macropore carbon material at 120 DEG C.
3. solution-type semi-liquid lithium-sulfur battery according to claim 1, it is characterised in that the Li+Type Nafion resins lead to Following methods are crossed to prepare：Take 10g LiNO3Add into 100ml Nafion, after stirring 30 minutes, centrifuge Surplus LiNO3, obtain Li+- Nafion solution；The Li as binding agent is obtained after drying+Type Nafion resins.
4. solution-type semi-liquid lithium-sulfur battery according to claim 1, it is characterised in that the Li+Type perfluorinated sulfonic resin Barrier film is prepared by the following method：The Nafion membrane that city is bought to resell is immersed in 10wt% LiOH solution, and 1 is handled at 80 DEG C After hour, rinsed with deionized water to water in neutrality, be dried in vacuo 6 hours at 90 DEG C after drying, obtain Li+Type perfluorinated sulfonic acid Resin barrier film.
5. the solution-type semi-liquid lithium-sulfur battery according to Claims 1-4 any one, it is characterised in that it is described just The sealing ring being made up of fluorubber is further respectively had between pole and barrier film, between negative pole and barrier film.
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