CN105047984A - High lithium ion conductivity lithium sulphur battery capable of restraining shuttle of polysulfide ions - Google Patents
High lithium ion conductivity lithium sulphur battery capable of restraining shuttle of polysulfide ions Download PDFInfo
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- CN105047984A CN105047984A CN201510299365.3A CN201510299365A CN105047984A CN 105047984 A CN105047984 A CN 105047984A CN 201510299365 A CN201510299365 A CN 201510299365A CN 105047984 A CN105047984 A CN 105047984A
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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
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Abstract
The invention relates to the field of batteries, and aims at providing a high lithium ion conductivity lithium sulphur battery capable of restraining shuttle of polysulfide ions. The lithium sulphur battery is to bond electrode material layer of the cathode to the anode with a lithium nitride layer via a binder to enable the electrode material side of the cathode and the lithium nitride layer of the anode to relatively bind to form an integrated lithium sulphur battery; the binder is a PVP modified Li plus type Nafion resin binder or a nano silicon dioxide doped PVP modified Li plus type Nafion resin binder. The lithium sulphur battery of the invention is high in temperature resistance and excellent in safety, and will not generate migration of the polysulfide ions in a charge-discharge process with excellent cycle life. The high conductivity of a macroporous carbon material could effectively improve the electrical conductivity of a sulfur electrode and has excellent large current charge and discharge performance. The lithium sulphur battery not only could be widely applied to a small electronic device, but also could be applied to a large unsteady state electricity generation plant. The lithium sulphur battery of the invention could be used for adjusting electricity, balancing peak valley electricity of electricity use, improving generating efficiency and reducing the generation cost. The electrode material is low in cost, and the preparation technology is simple and easy to operate.
Description
Technical field
The invention relates to field of batteries, relate to a kind of modification lithium-ion conduction macromolecular material that uses as binding agent, nitrogen treatment lithium metal be negative pole without barrier film lithium-sulfur cell, particularly lithium ion conduction macromolecular material method of modifying and utilize nano silicon to adulterate the binding agent and sulfur electrode prepared therefrom that obtain to modification lithium-ion conduction macromolecular material; Lithium metal and high pure nitrogen react the negative pole forming fast lithium ion conductive layer lithium nitride at metallic lithium surface, and by binding agent, the electrode material layer of sulfur electrode are bonded to the lithium-sulfur cell possessing and the lithium metal of nitrogenize lithium layer is formed.
Background technology
Lithium-sulfur cell is the one of lithium ion battery, using element sulphur as the positive electrode of battery, has the advantages such as lightweight, capacity is large, memory-less effect.The specific energy of lithium-sulfur cell is far above the lithium ion battery of commercial extensive use.Further, sulphur is a kind of environmental friendliness element, does not substantially pollute environment.Lithium-sulfur cell is the very promising lithium ion battery of one.
Lithium-sulfur cell take lithium metal as negative material, adopt liquid electrolyte, during electric discharge, negative reaction is that lithium loses electronics and becomes lithium ion, and positive pole reaction generates sulfide for sulphur and lithium ion and electron reaction, and the electrical potential difference of positive pole and negative reaction is the discharge voltage that lithium-sulfur cell provides.Under applied voltage effect, the positive pole of lithium-sulfur cell and negative reaction counter movement, be charging process.Elemental sulfur according to unit mass becomes S completely
2-the electricity that can provide can show that the theoretical discharge specific discharge capacity of sulphur is 1675mAhg
-1, the theoretical discharge specific discharge capacity of simple substance lithium is 3860mAhg
-1.Sulphur and lithium complete reaction generate lithium sulfide (Li
2s), time, the theoretical discharge specific energy of corresponding lithium-sulfur cell is 2600Whkg
-1.Sulphur positive pole and lithium anode are separated the traditional lithium-sulfur cell of formation by micro-pore septum.
The charging and discharging reaction of sulfur electrode is more complicated, and its discharge process mainly comprises two steps, respectively corresponding two discharge platforms: (1) corresponding S
8circulus become S
n 2-the chain structure of (3≤n≤7) ion, and and Li
+in conjunction with the poly-lithium sulfide (Li of generation
2s
n), the discharge platform of this reaction on discharge curve near corresponding 2.4 ~ 2.1V; (2) corresponding S
n 2-the chain structure of ion becomes S
2-and S
2 2-and and Li
+in conjunction with generation Li
2s
2and Li
2s, discharge platform longer near 2.1 ~ 1.8V in the corresponding discharge curve of this reaction, this platform is the main discharge region of lithium-sulfur cell.Be positioned at the further reduction that the corresponding elemental sulfur reduction of 2.5 ~ 2.05V potential region generates solvable polysulfide and polysulfide upon discharging, the polysulfide reduction being positioned at 2.05 ~ 1.5V potential region corresponding solvable generates lithium sulfide solid film, and it covers conductive carbon based surface.During charging, Li in sulfur electrode
2s and Li
2s
2oxidized S
8and S
m 2-(6≤m≤7), can not be completely oxidized to S
8, the charging platform of this charging reaction in charging curve near corresponding 2.5 ~ 2.4V.The maximum problem of current lithium-sulfur cell is: in charge and discharge process, form the poly-lithium sulfide being dissolved in electrolyte, poly-lithium sulfide and the negative metal lithium of dissolving react, and cause capacitance loss, cause lithium-sulfur cell capacity fast decay, show the cycle life of extreme difference.
Ion exchange resin be a kind of containing ionic group, to have ion and select through the macromolecule resin of ability.Ion exchange resin needs larger exchange capacity (ion-selective permeability is good, and conductive capability is strong), suitable imbibition ability, and conductivity is high, and selective penetrated property is good, has higher mechanical strength and chemical and thermal stability.Representative amberplex has proton exchange resins, as perfluorinated sulfonic resin, is commonly called as Nafion, is the product that E.I.Du Pont Company produces.It is the raw material of the proton exchange membrane used in fuel cell.Nafion resin through ion-exchange, by Li
+substitute the proton in Nafion film, can Li be obtained
+type Nafion resin, can effectively suppress polysulfide ion to shuttle back and forth for lithium-sulfur cell as barrier film [EnergyEnviron.Sci., 7 (2014) 347-353.].Li
+type Nafion resin water absorbing capacity is strong but Electolyte-absorptive ability is weak.
Polyvinyl alcohol (PVA) is film forming easily, good mechanical performance, and the hot strength of film raises with the degree of polymerization, alcoholysis degree and strengthens.PVA has good cementability, and the degree of polymerization, alcoholysis degree are higher, and adhesive strength is stronger.PVA is linear polymeric, and possessing higher electrolyte absorbability, is the ideal binding agent of resistance to lithium-sulfur cell.
Sulphur in lithium-sulfur cell and the conductivity of lithium sulfide and ionic conductivity extreme difference.The sulfur electrode material preparation method that usual use porous carbon supports sulphur improves the conductivity of sulfur electrode.But the ionic conductivity how improving sulphur and lithium sulfide in porous carbon does not have good method, mainly carry out lithium ion conduction by electrolyte.But after the free electrolyte in electrode dissolves polysulfide ion, shuttling back and forth of aggravation polysulfide ion.Conventional binding agent such as Kynoar (PVDF) can not stop shuttling back and forth of polysulfide ion, thus causes the fast decay of sulfur electrode capacity.
Summary of the invention
The problem to be solved in the present invention is, overcomes deficiency of the prior art, provides a kind of high-lithium ion conduction lithium-sulfur cell suppressing polysulfide ion to shuttle back and forth.This lithium-sulfur cell is using PVP modification lithium-ion conduction macromolecular material as binding agent, and sulfur electrode prepared therefrom and nitrogen treatment lithium anode, form aseptate lithium-sulfur cell.
For solving the problems of the technologies described above, solution of the present invention is:
A kind of high-lithium ion conduction lithium-sulfur cell suppressing polysulfide ion to shuttle back and forth is provided, comprises positive pole, negative pole and electrolyte; This lithium-sulfur cell be by binding agent the electrode material layer of positive pole is bonded to possess nitrogenize lithium layer negative pole on, make that the electrode material side of positive pole is relative with the nitrogenize lithium layer of negative pole to bond, form integrated lithium-sulfur cell;
Described positive pole is prepared by following method: get 1.4g positive electrode, to mix at 70: 20: 20 in mass ratio, be modulated into pasty state with acetylene black (commercially available prod) and binding agent; Get 0.1mL to be coated on circular aluminum film that diameter is 18mm and to dry in the shade, at 100Kg/cm
2pressure make type and obtain positive pole;
Described positive electrode is prepared by following method: be that 7: 3 mechanical mixture are even in mass ratio by elemental sulfur and macropore material with carbon element, be placed in the reactor of 316 stainless steels; Then be heated to 80 DEG C after being vacuumized by reactor, react and complete supporting of sulphur after 5 ~ 10 hours, then product is cooled to 10 ~ 30 DEG C, be i.e. obtained positive electrode;
Described binding agent is PVP modification Li
+type Nafion resinoid bond or nanometer titanium dioxide silicon doping PVP modification Li
+type Nafion resinoid bond;
Described electrolyte is with Li [CF
3sO
2)
2n] (LiTFSI) be solute, dioxolanes (C
3h
6o
2) and EGME (C
4h
10o
2) mixture be solvent; The volume ratio of dioxolanes and EGME is 1: 1, containing one mole of (263g) Li [CF in often liter of electrolyte
3sO
2)
2n].
In the present invention, described negative pole is prepared by following method: metal lithium sheet is processed 0.2 hour in the blanket of nitrogen that 25 DEG C are placed in purity 99.999%, namely obtains the negative pole possessing nitrogenize lithium layer.
In the present invention, described macropore material with carbon element is prepared by following method: take hydrophilic nano CaCO that particle diameter be 15 ~ 40nm at 1: 1 in mass ratio
3(city buys to resell, the product as Warner, Ruicheng nano material Co., Ltd) and each 10g of glucose, be added in 100ml deionized water, and ultrasonic vibration mixes 30 minutes makes glucose dissolve and and Nano-meter CaCO3
3be uniformly dispersed; Heating evaporates the water, and then solidifies 2 hours at 160 DEG C; Cured product is warming up to 700 DEG C under nitrogen atmosphere protection, constant temperature carbonization 2 hours; Again 900 DEG C of constant temperature carbonizations 2 hours; Carbonized product is successively with nitric acid, the deionized water washing of 5wt% concentration, then at 120 DEG C, vacuumize, after 4 hours, obtains macropore material with carbon element.
In the present invention, described PVP modification Li
+type Nafion resinoid bond is prepared by following method: get 20gLiOH and be added in 200mlNafion solution (20wt% originates from E.I.Du Pont Company), stir after 30 minutes, and superfluous LiOH is fallen in centrifugation, obtains Li
+-Nafion solution; Vacuumize, obtains Li
+type Nafion resin; To being dissolved with 1gLi
+in the 10gN-methyl pyrrolidone (NMP) of type Nafion resin, add 0.9gPVP; The mass ratio of Nafion resin and PVP is stir 1 hour at 1: 0.9,25 DEG C, obtains PVP modification Li
+type Nafion resinoid bond.
In the present invention, described nanometer titanium dioxide silicon doping PVP modification Li
+type Nafion resinoid bond is prepared by following method: get 20gLiOH and be added in 200mlNafion solution (20wt% originates from E.I.Du Pont Company), stir after 30 minutes, and superfluous LiOH is fallen in centrifugation, obtains Li
+-Nafion solution; Vacuumize, obtains Li
+type Nafion resin; To being dissolved with 2gLi
+in the 10gN-methyl pyrrolidone (NMP) of type Nafion resin, add 0.9gPVP and nano silicon respectively; The mass ratio of Nafion resin, PVP, nano silicon and NMP is 2: 0.9: 0.9: 10, stirs 1 hour, namely obtain nanometer titanium dioxide silicon doping PVP modification Li+ type Nafion resinoid bond at 25 DEG C.
Invention further provides the preparation method of the high-lithium ion conduction lithium-sulfur cell suppressing polysulfide ion to shuttle back and forth, comprise the following steps:
(1) metal lithium sheet is processed 0.2 ~ 2 hour in the atmosphere that 25 DEG C are placed in High Purity Nitrogen (purity 99.999%);
(2) get 0.5mL binding agent drip to diameter be 17mm in the metal lithium sheet of nitrogen process, vacuumize 12 hours at 60 DEG C, forms the metal lithium sheet of one side containing binder material and nitrogenize lithium layer;
(3) after the electrode material face of positive pole drips 0.5mL binding agent, by bonding with the electrode material face of positive pole for the lithium sheet processing layer side of above-mentioned lithium nitride process and binding agent Mulching treatment, vacuumize 12 hours at 60 DEG C, obtains integrated lithium-sulfur cell battery core;
(4) integrated lithium-sulfur cell battery core to be soaked in electrolyte 1 hour;
(5) filter paper is utilized to suck excess electrolyte;
(6) in lithium sheet metal untreated side, pad that diameter is 17mm, thick 1mm, voidage are after the foam nickel sheet of 98%, seal after adding sealing ring and battery cover, obtain button lithium-sulfur cell;
Described electrolyte is with Li [CF
3sO
2)
2n] (LiTFSI) be solute, dioxolanes (C
3h
6o
2) and EGME (C
4h
10o
2) mixture be solvent; The volume ratio of dioxolanes and EGME is 1: 1, containing one mole of (263g) Li [CF in often liter of electrolyte
3sO
2)
2n];
Described binding agent is PVP modification Li
+the binding agent of type Nafion resin or nanometer titanium dioxide silicon doping PVP modification Li
+type Nafion resinoid bond.
The present invention realizes principles illustrated:
Use PVP modification Li
+type Nafion resin or nanometer titanium dioxide silicon doping PVP modification Li
+when positive pole prepared by type Nafion resinoid bond, at sulphur surface coverage one deck PVP modification Li of macropore carbon endoporus after pole drying
+type Nafion resin or nanometer titanium dioxide silicon doping PVP modification Li
+type Nafion resin, as shown in Figure 1.When lithium-sulfur cell battery core is soaked in electrolyte, PVP modification Li
+type Nafion resin or nanometer titanium dioxide silicon doping PVP modification Li
+pVP Electolyte-absorptive in type Nafion resinoid bond.During lithium-sulfur cell charge and discharge cycles, PVP adsorbs polysulfide ion, sets up polysulfide ion concentration gradient.Li
+type Nafion resin has ionic conduction selectivity, namely allows lithium ion to pass through, but hinders polysulfide ion to pass through.Therefore at PVP modification Li
+type Nafion resin or nanometer titanium dioxide silicon doping PVP modification Li
+in the cover layer that type Nafion resinoid bond is formed, lithium ion can conducting, but does not allow polysulfide ion to pass through.Due to the Li containing lithium ion conduction in binding agent
+form abundant interface after type Nafion resin, particularly nanometer titanium dioxide silicon doping, further provide the transmission channel of lithium ion, substantially increase the conducting power of lithium ion in macropore carbon, the large current discharging capability of battery is significantly improved.
In the present invention, use PVP modification Li
+type Nafion resin provides necessary ionic conduction at positive pole and hinders shuttling back and forth of polysulfide ion simultaneously.And the lithium nitride of negative pole similarly also stops polysulfide ion to pass through, but do not affect lithium ion conduction.Meanwhile, in battery, there is not free electrolyte, also greatly inhibit polysulfide ion to pass the generation of shuttle effect, effectively improve the cyclical stability of lithium-sulfur cell.In conjunction with metallic lithium surface nitrogen treatment and use nanometer titanium dioxide silicon doping PVP modification Li
+type Nafion resin, both positive and negative polarity lithium ion conduction and suppression polysulfide ion shuttle back and forth and are obtained for strengthening, inhibit lithium-sulfur cell inducing capacity fading, the speed capabilities of lithium-sulfur cell of the present invention and stability are greatly improved.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention uses PVP modification Li
+type Nafion resin or nanometer titanium dioxide silicon doping PVP modification Li
+the lithium-sulfur cell of type Nafion resinoid bond and nitrogen process lithium anode, has heatproof high, and fail safe is good.Particularly use nanometer titanium dioxide silicon doping PVP modification Li
+, there is not the migration of polysulfide ion in the lithium-sulfur cell of type Nafion resinoid bond, therefore has fabulous cycle life in charge and discharge process.The high conductivity of macropore material with carbon element effectively improves the conductivity of sulfur electrode, makes lithium-sulfur cell of the present invention possess good high rate during charging-discharging.
Both compact electronic device can be widely used in as mobile phone, notebook computer, also can be used for the large-scale unstable state generating such as electric motor car, unmanned plane, wind power generation, solar power generation, tidal power generation power station, play the effect of electric adjustment, the peak-trough electricity of balance electricity consumption, improve generating efficiency, reduce 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, has broad application prospects.
Accompanying drawing explanation
Fig. 1 is for using PVP modification Li
+type Nafion resin or nanometer titanium dioxide silicon doping PVP modification Li
+after positive pole prepared by type Nafion resinoid bond, the pattern of positive electrode.
Fig. 2 adopts nanometer titanium dioxide silicon doping PVP modification Li in embodiment seven, nine and ten
+type Nafion resin, PVP modification Li
+type Nafion resin and PVDF are as binding agent, and the Performance comparision of the present invention and traditional lithium-sulfur cell, charging or discharging current is 1C.
Reference numeral in figure is: 0-1 is macropore material with carbon element, and 0-2 is macropore material with carbon element endoporus, and 1-1 is for carrying macropore carbon after sulphur, and 1-2 is be carry the sulphur after sulphur in macropore carbon endoporus, and 2-1 is PVP modification Li
+type Nafion resin or nanometer titanium dioxide silicon doping PVP modification Li
+macropore material with carbon element after type Nafion resin covers, 2-2 is the PVP modification Li covering sulphur surface in macropore carbon endoporus
+type Nafion resin or nanometer titanium dioxide silicon doping PVP modification Li
+type Nafion resin.
2-3 be PVDF as binding agent, use the lithium-sulfur cell 1C discharge cycles stability of micro-pore septum; 2-4 is PVP modification Li
+type Nafion resin as binding agent, without barrier film lithium-sulfur cell 1C discharge cycles stability; 2-5 is nanometer titanium dioxide silicon doping PVP modification Li
+type Nafion resin as binding agent, without barrier film lithium-sulfur cell 1C discharge cycles stability.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail:
Embodiment one: prepared by macropore material with carbon element
In mass ratio 1: 1 take Warner, Ruicheng nano material Co., Ltd produce, particle diameter is the hydrophilic nano CaCO of 15 ~ 40nm
310g each with glucose, is added in 100ml deionized water, and ultrasonic vibration mixes 30 minutes makes glucose dissolve and and Nano-meter CaCO3
3be uniformly dispersed; Heating evaporates the water, and heating evaporates the water, and then solidifies 2 hours at 160 DEG C; Cured product is warming up to 700 DEG C under nitrogen atmosphere protection, constant temperature carbonization 2 hours; Again 900 DEG C of constant temperature carbonizations 2 hours; Carbonized product is successively with nitric acid, the deionized water washing of 5wt% concentration, then at 120 DEG C, vacuumize, after 4 hours, obtains macropore material with carbon element.
Embodiment two: prepared by positive electrode
Be that 7: 3 mechanical mixture are even in mass ratio by the macropore carbon obtained in elemental sulfur and embodiment one, be placed in the reactor of 316 stainless steels, then 80 DEG C are heated to after being vacuumized by reactor, react and complete supporting of sulphur after 5 hours, again product is cooled to 25 DEG C, i.e. obtained positive electrode.
Embodiment three: Li
+the preparation of-Nafion resin
Getting 20gLiOH is added in 100mlNafion (20wt% originates from E.I.Du Pont Company), stirs after 30 minutes, and superfluous LiOH is fallen in centrifugation, obtains Li
+-Nafion solution.Li is obtained after vacuumize
+-Nafion resin.
Embodiment four: PVP modification Li
+the preparation of type Nafion resinoid bond
1gLi
+type Nafion resin is dissolved in 1-METHYLPYRROLIDONE (NMP) 10g, adds 0.9gPVP; The mass ratio of Nafion resin and PVP is that 1: 0.9,25 DEG C of stirrings obtained PVP modification Li after 1 hour
+type Nafion resinoid bond.
Embodiment five: nanometer titanium dioxide silicon doping PVP modification Li
+prepared by type Nafion resinoid bond
1gLi
+type Nafion resin is dissolved in 1-METHYLPYRROLIDONE (NMP) 10g, adds 0.9gPVP and nano silicon respectively; The mass ratio of Nafion resin, PVP, nano silicon and NMP is that 2: 0.9: 0.9: 10,25 DEG C of stirrings obtained nanometer titanium dioxide silicon doping PVP modification Li after 1 hour
+type Nafion resinoid bond.
Embodiment six: prepared by positive pole
Be that 7: 3 mechanical mixture are even in mass ratio by the macropore carbon obtained in elemental sulfur and embodiment one, be placed in the reactor of 316 stainless steels, then 80 DEG C are heated to after being vacuumized by reactor, react and complete supporting of sulphur after 8 hours, again product is cooled to 20 DEG C, i.e. obtained positive electrode.
Get above-mentioned 1.4g positive electrode, the nanometer titanium dioxide silicon doping PVP modification Li obtained with acetylene black (commercially available prod) and embodiment five
+type Nafion resinoid bond is 70: 20: 20 mixing in mass ratio; Be modulated into pasty state; Get 0.1mL to be coated on circular aluminum film that diameter is 18mm and to dry in the shade, at 100Kg/cm
2pressure make type and obtain positive pole; Acetylene black is the product that commercially available Ningxia belite Chemical Co., Ltd. produces.
Embodiment seven: the preparation of traditional lithium-sulfur cell
The positive electrode 1.4g positive electrode of preparation in Example two, in mass ratio with acetylene black (commercially available prod) and PVDF grind evenly after get 2g add 1-METHYLPYRROLIDONE (NMP:2g) as dispersant at 70: 20: 20, get 0.1ml after being then modulated into pasty state and to be coated on circular aluminum film that diameter is 18mm and to dry in the shade; At 100Kg/cm
2pressure make type, namely obtain traditional positive pole.The city that is placed in of positive pole is bought to resell button cell shell, and the electrode base material aluminium film of positive pole contacts with battery case; Microporous polypropylene membrane is placed on positive pole; Be 17mm by diameter, the lithium sheet metal of thick 0.2mm is placed on barrier film; On pad, diameter is 17mm, thick 1mm, voidage be after the foam nickel sheet of 98%, adds electrolyte 0.5mL, seals after adding sealing ring and battery cover, obtain traditional lithium-sulfur cell.
Embodiment eight: negative pole nitrogen treatment
Metal lithium sheet is processed 0.2 hour in the atmosphere that 25 DEG C are placed in High Purity Nitrogen (purity 99.999%), namely obtains the negative pole possessing nitrogenize lithium layer.
Embodiment nine: with PVP modification Li
+type Nafion resin be binding agent without barrier film lithium-sulfur cell
1gLi
+type Nafion resin is dissolved in 1-METHYLPYRROLIDONE (NMP) 10g, adds 0.9gPVP; The mass ratio of Nafion resin and PVP is 1:0.9, and 25 DEG C of stirrings obtained PVP modification Li after 1 hour
+type Nafion resinoid bond.
Metal lithium sheet is processed 1 hour in the atmosphere that 25 DEG C are placed in High Purity Nitrogen (purity 99.999%), obtains negative pole.
Be that 7: 3 mechanical mixture are even in mass ratio by the macropore carbon obtained in elemental sulfur and embodiment one, be placed in the reactor of 316 stainless steels, then 80 DEG C are heated to after being vacuumized by reactor, react and complete supporting of sulphur after 8 hours, again product is cooled to 20 DEG C, i.e. obtained positive electrode.Get above-mentioned 1.4g positive electrode, with acetylene black (commercially available prod) and above-mentioned PVP modification Li
+type Nafion resinoid bond is 70: 20: 20 mixing in mass ratio; Be modulated into pasty state; Get 0.1mL to be coated on aluminium film that diameter is 18mm and to dry in the shade, at 100Kg/cm
2pressure make type and obtain positive pole; Acetylene black is the product that commercially available Ningxia belite Chemical Co., Ltd. produces.
Getting the above-mentioned binding agent of 0.5mL drips in the above-mentioned nitrogen process metal lithium sheet that diameter is 17mm, and at 60 DEG C, vacuumize forms the metal lithium sheet containing binder material and nitrogenize lithium layer after 12 hours; After the electrode material face of positive pole drips 0.5mL above-mentioned binding agent, by bonding with the electrode material face of positive pole for the processing layer side of the lithium sheet of above-mentioned lithium nitride process and binding agent Mulching treatment, vacuumize 12 hours at 60 DEG C, obtains integrated lithium-sulfur cell battery core.
Integrated lithium-sulfur cell battery core to be soaked in electrolyte 1 hour, described electrolyte is with Li [CF
3sO
2)
2n] (LiTFSI) be solute, dioxolanes (C
3h
6o
2) and EGME (C
4h
10o
2) mixture be solvent, the volume ratio of dioxolanes and EGME is 1: 1, containing one mole of (263g) Li [CF in often liter of electrolyte
3sO
2)
2n];
In lithium sheet metal untreated side, pad after utilizing filter paper to suck excess electrolyte that diameter is 17mm, thick 1mm, voidage are after the foam nickel sheet of 98%, seal after adding sealing ring and battery cover, obtain with PVP modification Li
+type Nafion resin be binding agent without barrier film lithium-sulfur cell.
Embodiment ten: with nanometer titanium dioxide silicon doping PVP modification Li
+type Nafion resin be binding agent without barrier film lithium-sulfur cell
Metal lithium sheet is processed 2 hours in the atmosphere that 25 DEG C are placed in High Purity Nitrogen (purity 99.999%), namely obtains the negative pole possessing nitrogenize lithium layer.
The nanometer titanium dioxide silicon doping PVP modification Li obtained in Example five
+type Nafion resinoid bond 0.5mL, drips in above-mentioned nitrogen process metal lithium sheet that diameter is 17mm, and at 60 DEG C, vacuumize forms the metal lithium sheet containing binder material and nitrogenize lithium layer after 12 hours; After the binding agent 0.5mL obtained in the positive electrode face dropping embodiment five of preparation in embodiment six, by bonding with the electrode material face of positive pole for the processing layer side of the lithium sheet of above-mentioned lithium nitride process and binding agent Mulching treatment, vacuumize 12 hours at 60 DEG C, obtains integrated lithium-sulfur cell battery core.
Integrated lithium-sulfur cell battery core to be soaked in electrolyte 1 hour, described electrolyte is with Li [CF
3sO
2)
2n] (LiTFSI) be solute, dioxolanes (C
3h
6o
2) and EGME (C
4h
10o
2) mixture be solvent, the volume ratio of dioxolanes and EGME is 1: 1, containing one mole of (263g) Li [CF in often liter of electrolyte
3sO
2)
2n];
In lithium sheet metal untreated side, pad after utilizing filter paper to suck excess electrolyte that diameter is 17mm, thick 1mm, voidage are after the foam nickel sheet of 98%, seal after adding sealing ring and battery cover, obtain with nanometer titanium dioxide silicon doping PVP modification Li
+type Nafion resin be binding agent without barrier film lithium-sulfur cell.
Fig. 2 is nanometer titanium dioxide silicon doping PVP modification Li
+type Nafion resin and PVP modification Li
+type Nafion resin is the high-multiplying power discharge cycle performance without barrier film lithium-sulfur cell of binding agent.With use PVDF binding agent, use traditional lithium-sulfur cell that microporous polypropylene membrane and metal lithium sheet are negative pole to compare, use nanometer titanium dioxide silicon doping PVP modification Li
+the lithium-sulfur cell high-multiplying power discharge cycle performance of type Nafion resin to be the lithium metal of binding agent and surfaces nitrided process be negative pole significantly improves.
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 (6)
1. the high-lithium ion conduction lithium-sulfur cell suppressing polysulfide ion to shuttle back and forth, comprises positive pole, negative pole and electrolyte; It is characterized in that, this lithium-sulfur cell be by binding agent the electrode material layer of positive pole is bonded to possess nitrogenize lithium layer negative pole on, make that the electrode material side of positive pole is relative with the nitrogenize lithium layer of negative pole to bond, form integrated lithium-sulfur cell;
Described positive pole is prepared by following method: get 1.4g positive electrode, to mix at 70: 20: 20 in mass ratio, be modulated into pasty state with acetylene black and binding agent; Get 0.1mL to be coated on circular aluminum film that diameter is 18mm and to dry in the shade, at 100Kg/cm
2pressure make type and obtain positive pole;
Described positive electrode is prepared by following method: be that 7: 3 mechanical mixture are even in mass ratio by elemental sulfur and macropore material with carbon element, be placed in the reactor of 316 stainless steels; Then be heated to 80 DEG C after being vacuumized by reactor, react and complete supporting of sulphur after 5 ~ 10 hours, then product is cooled to 10 ~ 30 DEG C, be i.e. obtained positive electrode;
Described binding agent is PVP modification Li
+type Nafion resinoid bond or nanometer titanium dioxide silicon doping PVP modification Li
+type Nafion resinoid bond;
Described electrolyte is with Li [CF
3sO
2)
2n] be solute, the mixture of dioxolanes and EGME is solvent; The volume ratio of dioxolanes and EGME is 1: 1, containing one mole of Li [CF in often liter of electrolyte
3sO
2)
2n].
2. lithium-sulfur cell according to claim 1, is characterized in that, described negative pole is prepared by following method: metal lithium sheet is processed 0.2 hour in the blanket of nitrogen that 25 DEG C are placed in purity 99.999%, namely obtains the negative pole possessing nitrogenize lithium layer.
3. lithium-sulfur cell according to claim 1, is characterized in that, described macropore material with carbon element is prepared by following method:
Take hydrophilic nano CaCO that particle diameter be 15 ~ 40nm at 1: 1 in mass ratio
310g each with glucose, is added in 100ml deionized water, and ultrasonic vibration mixes 30 minutes makes glucose dissolve and and Nano-meter CaCO3
3be uniformly dispersed; Heating evaporates the water, and then solidifies 2 hours at 160 DEG C; Cured product is warming up to 700 DEG C under nitrogen atmosphere protection, constant temperature carbonization 2 hours; Again 900 DEG C of constant temperature carbonizations 2 hours; Carbonized product is successively with nitric acid, the deionized water washing of 5wt% concentration, then at 120 DEG C, vacuumize, after 4 hours, obtains macropore material with carbon element.
4. according to the lithium-sulfur cell described in Claims 1-4 any one, it is characterized in that, described PVP modification Li
+type Nafion resinoid bond is prepared by following method:
Getting 20gLiOH is added in 200mlNafion solution, stirs after 30 minutes, and superfluous LiOH is fallen in centrifugation, obtains Li
+-Nafion solution; Vacuumize, obtains Li
+type Nafion resin;
To being dissolved with 1gLi
+in the 10gN-methyl pyrrolidone of type Nafion resin, add 0.9gPVP; The mass ratio of Nafion resin and PVP is stir 1 hour at 1: 0.9,25 DEG C, obtains PVP modification Li
+type Nafion resinoid bond.
5. according to the lithium-sulfur cell described in Claims 1-4 any one, it is characterized in that, described nanometer titanium dioxide silicon doping PVP modification Li
+type Nafion resinoid bond is prepared by following method:
Getting 20gLiOH is added in 200mlNafion solution, stirs after 30 minutes, and superfluous LiOH is fallen in centrifugation, obtains Li
+-Nafion solution; Vacuumize, obtains Li
+type Nafion resin;
To being dissolved with 2gLi
+in the 10gN-methyl pyrrolidone of type Nafion resin, add 0.9gPVP and nano silicon respectively; The mass ratio of Nafion resin, PVP, nano silicon and NMP is 2: 0.9: 0.9: 10, stirs 1 hour, namely obtain nanometer titanium dioxide silicon doping PVP modification Li+ type Nafion resinoid bond at 25 DEG C.
6. a preparation method for the high-lithium ion conduction lithium-sulfur cell suppressing polysulfide ion to shuttle back and forth, is characterized in that, comprise the following steps:
(1) metal lithium sheet is processed 0.2 ~ 2 hour in the atmosphere that 25 DEG C are placed in High Purity Nitrogen (purity 99.999%);
(2) get 0.5mL binding agent drip to diameter be 17mm in the metal lithium sheet of nitrogen process, vacuumize 12 hours at 60 DEG C, forms the metal lithium sheet of one side containing binder material and nitrogenize lithium layer;
(3) after the electrode material face of positive pole drips 0.5mL binding agent, by bonding with the electrode material face of positive pole for the lithium sheet processing layer side of above-mentioned lithium nitride process and binding agent Mulching treatment, vacuumize 12 hours at 60 DEG C, obtains integrated lithium-sulfur cell battery core;
(4) integrated lithium-sulfur cell battery core to be soaked in electrolyte 1 hour;
(5) filter paper is utilized to suck excess electrolyte;
(6) in lithium sheet metal untreated side, pad that diameter is 17mm, thick 1mm, voidage are after the foam nickel sheet of 98%, seal after adding sealing ring and battery cover, obtain button lithium-sulfur cell;
Described electrolyte is with Li [CF
3sO
2)
2n] be solute, the mixture of dioxolanes and EGME is solvent; The volume ratio of dioxolanes and EGME is 1: 1, containing one mole of Li [CF in often liter of electrolyte
3sO
2)
2n];
Described binding agent is PVP modification Li
+the binding agent of type Nafion resin or nanometer titanium dioxide silicon doping PVP modification Li
+type Nafion resinoid bond.
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Cited By (5)
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| CN106981635A (en) * | 2017-04-10 | 2017-07-25 | 深圳市佩成科技有限责任公司 | A kind of Nafion membrane/Ti3C2Tx/ sulphur composite |
| CN110571392A (en) * | 2018-06-29 | 2019-12-13 | 华中科技大学 | Functional interlayer material of lithium-sulfur battery and preparation method thereof |
| CN110707325A (en) * | 2019-10-14 | 2020-01-17 | 浙江大学 | Preparation method and application of conductive adhesive based on reinforced polysulfide ion adsorption |
| CN110911662A (en) * | 2019-11-06 | 2020-03-24 | 华南理工大学 | Lithium cathode with protective layer and preparation method and application thereof |
| CN111171185A (en) * | 2020-01-04 | 2020-05-19 | 浙江大学 | Preparation and use method of cyclodextrin series connection polyaniline prepolymer as binder |
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| CN104157909A (en) * | 2014-07-14 | 2014-11-19 | 浙江大学 | Preparation method of lithium sulfur battery membrane electrode |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106981635A (en) * | 2017-04-10 | 2017-07-25 | 深圳市佩成科技有限责任公司 | A kind of Nafion membrane/Ti3C2Tx/ sulphur composite |
| CN110571392A (en) * | 2018-06-29 | 2019-12-13 | 华中科技大学 | Functional interlayer material of lithium-sulfur battery and preparation method thereof |
| CN110707325A (en) * | 2019-10-14 | 2020-01-17 | 浙江大学 | Preparation method and application of conductive adhesive based on reinforced polysulfide ion adsorption |
| CN110911662A (en) * | 2019-11-06 | 2020-03-24 | 华南理工大学 | Lithium cathode with protective layer and preparation method and application thereof |
| CN111171185A (en) * | 2020-01-04 | 2020-05-19 | 浙江大学 | Preparation and use method of cyclodextrin series connection polyaniline prepolymer as binder |
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