CN104617247B - Preparation method of tandem laminated lithium-sulfur battery - Google Patents
Preparation method of tandem laminated lithium-sulfur battery Download PDFInfo
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- CN104617247B CN104617247B CN201510027588.4A CN201510027588A CN104617247B CN 104617247 B CN104617247 B CN 104617247B CN 201510027588 A CN201510027588 A CN 201510027588A CN 104617247 B CN104617247 B CN 104617247B
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- lithium
- sulfur cell
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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
- 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
Abstract
The invention relates to the field of batteries, and aims to provide a preparation method of a tandem laminated lithium-sulfur battery. The lithium-sulfur battery comprises a diaphragm, a positive electrode, a negative electrode and an electrolyte, wherein the diaphragm adopts a modified polypropylene composite diaphragm, the positive electrode and the negative electrode are arranged on two sides of the diaphragm to form a sandwich structure, and electrode material sides of the positive electrode and the negative electrode face the diaphragm. According to the preparation method, the working voltage is high, an external contact point is avoided, and miniaturization of a high-voltage lithium-sulfur battery becomes possible; the defect that the traditional lithium ion battery using a liquid electrolyte cannot form the tandem laminated battery is overcome, and the battery safety is improved; transfer of polysulfide ions in charge-discharge processes is avoided, and quite long cycle life is realized; active materials have rich sources and low cost, and are pollution-free and easy to prepare; the electrode materials are low in cost, a preparation technology is simple and feasible, scale production is facilitated, and broad application prospect is realized.
Description
Technical field
The present invention is that, with regard to field of batteries, more particularly to one kind has aluminum/copper bi-metal thin film, copper metal side and lithium metal
Connect, aluminum metal side connects with sulfur electrode material, in being combined that the coated on both sides conductive carbon layer of modified micropore polypropylene screen is formed
The preparation method of barrier film and the series connection lamination lithium-sulfur cell prepared using it.
Background technology
Lithium-sulfur cell is one kind of lithium ion battery, using element sulphur as the positive electrode of battery, with lightweight, capacity
Greatly, the advantages of memory-less effect.The specific energy of lithium-sulfur cell is far above commercial wide variety of lithium ion battery.Also, sulfur
It is a kind of environmental friendliness element, environment is not polluted substantially.Lithium-sulfur cell is a kind of very promising lithium ion battery.
With lithium metal as negative material, using liquid electrolyte, negative reaction loses electronics to lithium-sulfur cell for lithium during electric discharge
It is changed into lithium ion, positive pole reaction is for the electric potential difference that sulfur generates sulfide, positive pole and negative reaction with lithium ion and electron reaction
The discharge voltage provided by lithium-sulfur cell.Under applied voltage effect, the positive pole and negative reaction of lithium-sulfur cell are inversely carried out,
As charging process.S is changed into completely according to the elemental sulfur of unit mass2-The electricity that can be provided can draw the theoretical discharge matter of sulfur
Amount specific capacity is 1675mAh g-1, the theoretical discharge specific discharge capacity of elemental lithium is 3860mAh g-1.Sulfur reacts completely raw with lithium
Into lithium sulfide (Li2When S), the theoretical discharge specific energy of corresponding lithium-sulfur cell is 2600Wh kg-1.But lithium-sulfur cell
Theoretical discharge voltage is only 2.287V, generally less than traditional anode material for lithium-ion batteries such as LiMn2O4 (3.7V), cobalt acid lithium
(3.6V), ternary material (3.5) and LiFePO4 (3.2V), the running voltage for how improving lithium-sulfur cell is urgently to be resolved hurrily asking
Topic.
Conventional lithium ion battery adopts liquid electrolyte, traditional liquid electrolyte that lithium hexafluoro phosphate is dissolved in into ethylene carbonate
Modulate in ester, Allyl carbonate, the mixed solvent of diethyl carbonate composition and form.Using the laminated cell of liquid electrolyte, electricity
Solution liquid mutual conduction.So each pole piece can only take parallel way to connect in traditional lamination lithium ion battery, can only improve lithium from
The battery operated electric current of son, it is impossible to improve the running voltage of battery.Obtaining high voltage can only be connected in series on each battery, and battery
Concatenation, be susceptible to loose contact and operationally easily produce electric spark, formed potential safety hazard.
The laminated cell prepared using gel electrolyte, electrolyte is not turned on, and carries out the concatenation of monocell, obtains high workload
Voltage, the pile of fuel cell is exactly a typical case.By taking hydrogen-oxygen fuel cell pile as an example, hydrogen-oxygen fuel cell is handed over using proton
It is electrolyte to change film, and using the method for component multilamellar superposition high voltage heap is obtained.Pile by multiple cells in a series arrangement
Stacked combination is formed.Bipolar plates are superimposed with membrane electrode (MEA) three-in-one component, embedding sealing part, Jing between each monomer
Forward and backward end plate is toggled after compressing with screw rod fastening, that is, constitute proton exchange film fuel cell electric piling.The core of pile is MEA groups
Part and bipolar plates.MEA is that the carbon fiber paper electrode that two are coated with Nafion solution and Pt catalyst is respectively placed in into Jing to locate in advance
The PEM both sides of reason, make catalyst near PEM, are molded under uniform temperature and pressure and make, and bipolar plates are normal
It is made with graphite cake material.When pile works, hydrogen and oxygen are introduced respectively by import, the distribution of Jing pile gases main channel
To the bipolar plates of each monocell, Jing bipolar plates water conservancy diversion is evenly distributed to electrode, and being contacted with catalyst by electrode support is carried out
Electrochemical reaction.
Traditional lithium ion battery separator mostly is the polyolefin porous membrane of high-strength thin-film, and such as Celgard barrier films are limited
The Celgard 2000 of company's production, with electronic isolation, it is ensured that the mechanical isolation of both positive and negative polarity；There are certain aperture and hole
Rate, it is ensured that low resistance and high ionic conductivity (lithium ion has good permeability)；Electrolyte resistance corrosion (possess chemistry and
Electrochemical stability)；Electrolyte wellability is good and high imbibition ability；Enough mechanical properties (puncture strength, tensile strength etc.).
But the polysulfide ion produced in lithium-sulfur cell charge and discharge process can readily pass through barrier film, react with the lithium metal of negative pole, disappear
The just very effective active material of consumption：Sulfur, so as to cause the drastically decline of lithium-sulfur cell capacity, shows the battery cycle life of extreme difference.
Ion exchange resin is a kind of macromolecule resin that containing ionic group, to ion there is selection to pass through ability.From
Sub-exchange resin needs larger exchange capacity (ion-selective permeability is good, and conductive capability is strong), and appropriate imbibition ability is conductive
Property it is high, selective penetrated property is good, with higher mechanical strength and chemically and thermally stability.Representative ion exchange membrane has proton
Exchanger resin, such as perfluorinated sulfonic resin, are commonly called as Nafion, are the product of E.I.Du Pont Company's production.It is used in fuel cell
The raw material of PEM.Nafion resins through ion exchange, by Li+The proton in Nafion membrane is substituted, Li is obtained+Type
Nafion resins, for lithium-sulfur cell as barrier film [Energy Environ.Sci., 7 (2014) 347-353.].But Li+
Lithium concentration is limited in type Nafion membrane, can also adsorb polysulfide ion, causes the loss of positive electrode active material, causes capacity to decline
Move back.And Li+Type Nafion membrane intensity is weaker, it is impossible to resists and formed on lithium electrode dendrite, and to cause barrier film to penetrate short circuit is caused.
In addition, Li+Type Nafion membrane electrolyte absorbability is poor, presents higher internal resistance, is unfavorable for high current charge-discharge.
The content of the invention
The technical problem to be solved in the present invention is to overcome deficiency of the prior art, there is provided one kind concatenation lamination lithium sulfur electricity
The preparation method in pond.The present invention is in the modified Li of polyethylene glycol oxide (PEO)+Type perfluorinated sulfonic resin (Li+- Nafion) it is raw material system
On the basis of standby modified polypropene film, the preparation of the composite diaphragm formed in the coated on both sides conductive carbon layer of modified polypropene film
Method and the series connection lamination lithium-sulfur cell prepared using it.
To solve above-mentioned technical problem, the solution of the present invention is：
A kind of preparation method of the modified polypropene composite diaphragm for lithium-sulfur cell is provided, is comprised the steps：
(1) preparation of PEO modification lithium-ions exchanger resin
Take 10g LiOH to add to 20wt% perfluorinated sulfonic resins (Nafion) solution (originating from E.I.Du Pont Company) of 100mL
In, after stirring 30 minutes, the LiOH of surplus is fallen in centrifugation, obtains Li+Type perfluor sulfoacid resin solution；Take Li+Type perfluorinated sulfonic acid
Resin solution 100mL, adds polyethylene glycol oxide (PEO, city dealer) and 50mL deionized waters that 2g molecular weight is 500,000g/mol,
Stirring 1 hour, obtains the modified Li of PEO+Type perfluor sulfoacid resin solution；After spray drying, the modified Li of PEO are obtained+Type perfluorinated sulfonic acid
Toner；
(2) preparation of modified polypropene composite diaphragm
At 60 DEG C, the modified Li of PEO of 0.07g are taken+Type perfluorinated sulfonic resin powder is dissolved in the N-Methyl pyrrolidone of 2g
(NMP) in, 0.07g acetylene blacks are added to stir；Take the capillary polypropylene that 0.5mL homomixtures drip to the city dealer of a diameter of 19mm
On film (city dealer), after being vacuum dried 12 hours at 60 DEG C, in another side Deca 0.5ml homomixture again, at 60 DEG C 12 are vacuum dried
Hour, obtain modified polypropene composite diaphragm.
Because acetylene black is difficult to the micropore into the dealer's microporous polypropylene membrane that enters the market, only PEO is modified Li+Type perfluorinated sulfonic resin
Enter the micropore of the dealer's microporous polypropylene membrane that enters the market, obtain modified polypropene layer.Define in modified polypropene layer both sides and be modified by PEO
Li+The conductive layer of type perfluorinated sulfonic resin bonding acetylene black.
Invention further provides using the lithium-sulfur cell of the modified polypropene composite diaphragm, including barrier film, positive pole,
Negative pole and electrolyte；The barrier film is modified polypropene composite diaphragm；Positive pole and negative pole are separately positioned on barrier film both sides and form three
Mingzhi's structure, and the electrode material side of positive pole and negative pole is made towards barrier film.
In the present invention, the preparation method of the positive pole is：
By positive electrode 1.4g, mix with acetylene black (commercially available prod) and binding agent in mass ratio 70: 15: 15, grinding is equal
2g mixture is taken after even, 2g is added as the N-Methyl pyrrolidone (NMP) of dispersant, is modulated into after pasty state and is taken 0.1ml coatings
To on the aluminum metal side of the aluminium film or aluminum/copper bi-metal thin film of a diameter of 18mm and dry in the shade；In 100Kg cm-2Pressure under suppress
Molding, respectively obtains the proper pole that electrode base material is aluminium film and the middle positive pole that electrode base material is aluminum/Copper thin film；The proper pole
It is the positive pole contacted with battery case, the middle positive pole is the positive pole not contacted with battery case；The binding agent is described
PEO modification lithium-ion exchanger resins；
The positive electrode is prepared by following methods：In mass ratio it is 7: 3 machines by elemental sulfur and macropore material with carbon element
Tool mix homogeneously, is placed in the reactor of 316 stainless steels, then by reactor evacuation post-heating to 80 DEG C, reaction 5～
Supporting for sulfur is completed after 10 hours, then product is cooled to into 10～30 DEG C, that is, positive electrode is obtained；
The preparation method of the macropore material with carbon element is：
In mass ratio 1: 1 weighs the hydrophilic nano CaCO that particle diameter is 15～40nm3(city buys to resell, such as Ruicheng Warner nanometer material
The product of material company limited) and each 10g of glucose, adding into 100mL deionized waters, supersonic vibration mixing makes Fructus Vitis viniferae in 30 minutes
Sugar dissolving and and Nano-meter CaCO33It is uniformly dispersed；Heating evaporates the water, and then solidifies 6 hours at 160 DEG C；Cured product is existed
900 DEG C are warming up under nitrogen atmosphere protection, constant temperature is carbonized 2 hours；Carbonized product successively with the hydrochloric acid of 5wt% concentration, 80 DEG C
The sodium hydroxide solution and deionized water wash of 30wt% concentration, then freeze-day with constant temperature after 4 hours, obtains macropore carbon materials at 120 DEG C
Material.
In the present invention, the aluminum/copper bi-metal thin film be by thickness for 0.1mm copper film and aluminium film in 300 DEG C of hot pressing and
Into pressure during hot pressing is 500Kg cm-2。
Present invention also offers a kind of method for preparing concatenation lamination lithium-sulfur cell using aforementioned lithium-sulfur cell, including it is following
Step：
The configuration of step A, electrolyte
With Li [CF3SO2)2N] (LiTFSI) be solute, dioxolanes (C3H6O2) and ethylene glycol monomethyl ether (C4H10O2) it is mixed
It is 1: 1 that compound is the volume ratio of solvent, dioxolanes and ethylene glycol monomethyl ether, and one mole of (263g) Li is contained in one liter of electrolyte
[CF3SO2)2N]；Modified polypropene composite diaphragm described in claim 1 is soaked in the electrolytic solution 24 hours；
The assembling of step B, series connection lamination lithium-sulfur cell
(1) by the proper pole (sulfur electrode：A diameter of 18mm, positive electrode is coated in aluminium film) it is placed in outside button cell
In shell (city dealer), rectify pole (its sulfur electrode base material aluminium film) and contact with battery case；
(2) the modified polypropene composite diaphragm (a diameter of 19mm) after immersion is placed on proper pole (sulfur electrode)；
(3) the lithium metal piece of a diameter of 18mm, thickness 0.2mm is placed on modified polypropene composite diaphragm；
(4) take the middle positive pole to be placed on lithium metal piece, the copper gold of the base material aluminum/copper bi-metal thin film of middle positive pole
Category side contacts with lithium metal piece；Will immersion post-modification polypropylene composite materials barrier film (a diameter of 19mm) be placed in proper pole (sulfur electrode) it
On；The lithium metal piece of a diameter of 18mm, thickness 0.2mm is placed on modified polypropene composite diaphragm；
(5) on pad after a diameter of 18mm, thickness 1mm, the foam nickel sheet that voidage is 98%, plus after sealing ring and battery cover it is close
Envelope, obtains the battery of button two concatenation lithium-sulfur cell (its battery structure is as shown in Figure 1)；Wherein,
After step (1) to (3), direct execution step (5) will obtain monomer lithium-sulfur cell；Or
Sequentially pass through step (1) to (5) and then obtain two batteries series connection lithium-sulfur cell；Or
Step (1) is sequentially passed through to (5) and per repeat step (4) once, the series connection of a battery will be increased more；That is, Jing
Step (1) to (3) repeat step (4) n times afterwards, then execution step (5) are crossed, the lamination electricity of N+2 lithium-sulfur cell concatenation will be obtained
Pond, now the height of battery case should increase that (its theoretical work voltage can reach single lithium sulfur electricity according to the increase of lamination number
N+2 times of pond).
Compared with prior art, the invention has the beneficial effects as follows：
Series connection lamination lithium-sulfur cell prepared by the present invention, it is high with running voltage, without external contact, make high pressure lithium-sulfur cell
Miniaturization is possibly realized.Overcoming cannot form the disadvantage of series connection laminated cell using the conventional lithium ion battery of liquid electrolyte
End, improves battery security.There is no the migration of polysulfide ion in charge and discharge process, therefore with fabulous cycle life.
Both can extensive compact electronic device such as mobile phone, notebook computer, it can also be used to which electric motor car, unmanned plane, wind-power electricity generation, solar energy are sent out
The large-scale unstable state generating power station such as electricity, tidal power generation, plays a part of electric adjustment, balances the peak-trough electricity of electricity consumption, improves and generates electricity
Efficiency, reduces cost of electricity-generating.Active substance abundance, it is with low cost, it is pollution-free, easily prepare.Electrode material cost is cheap, system
It is standby process is simple, easy, be conducive to large-scale production, have broad application prospects.
Description of the drawings
Fig. 1 is the structure chart that the button of room temperature work in the present invention concatenates lamination lithium-sulfur cell.
Fig. 2 is 25 DEG C of two batteries concatenation lamination lithium-sulfur cell in monomer lithium-sulfur cell in embodiment 11 and embodiment 11
Lower 5th week charging and discharging curve.
Fig. 3 is that charge and discharge circulation life is illustrated at 25 DEG C of the battery of button two concatenation lamination lithium-sulfur cell in embodiment 11
Figure.
Reference in figure is：1-1 button cell shells；1-2 rectifies pole；1-2-1 positive electrodes；1-2-2 aluminium films；1-
3 modified polypropene composite diaphragms；1-3-1 conductive layers；1-3-2 modified polypropene layers；1-4 lithium metal pieces；Positive pole in the middle of 1-5；1-
The copper metal side of 5-1 aluminum/copper bi-metal thin film；The aluminum metal side of 1-5-2 aluminum/copper bi-metal thin film；1-5-3 positive electrodes；1-6
Foam nickel sheet；1-7 sealing rings；1-8 battery covers.2-1 is monomer lithium-sulfur cell charging curve；2-2 is the electric discharge of monomer lithium-sulfur cell
Curve；2-3 is that two batteries concatenate lithium-sulfur cell charging curve；2-4 is that two batteries concatenate lithium-sulfur cell discharge curve.3-1 two is electric
Pond concatenates lamination lithium-sulfur cell inducing capacity fading curve；3-2 is that two batteries concatenate lamination lithium-sulfur cell efficiency for charge-discharge curve.
Specific embodiment
Below in conjunction with the accompanying drawings the present invention is described in further detail with specific embodiment：
A kind of room temperature work proposed by the present invention, using the concatenation lamination lithium-sulfur cell of gel electrolyte, overcome lithium sulfur electricity
The low shortcoming of pond running voltage, a kind of new lamination lithium-sulfur cell for obtaining.The battery unit is by positive pole, and modified polypropene is multiple
Close barrier film and lithium metal piece is constituted, positive electrode side is opposite with barrier film and lithium metal piece forms sandwich structure.By battery list
The repetition superposition of unit obtains concatenating lamination lithium-sulfur cell.
A kind of preparation method of concatenation lamination lithium-sulfur cell barrier film is provided, following step is specifically included：
(1) the modified Li of PEO+- Nafion is prepared and comprised the following steps：
Take 10g LiOH to add into 100mL Nafion solutions (20wt% originates from E.I.Du Pont Company), after stirring 30 minutes,
The LiOH of surplus is fallen in centrifugation, obtains Li+- Nafion solution；By Li+- Nafion solution 100mL, adds 2g cities dealer PEO (to divide
Son amount is 500,000g mol-1) and 50mL deionized waters, stir 1 hour, obtain the modified Li of PEO+- Nafion solution, spray dried
After dry, the modified Li of PEO are obtained+- Nafion powder；
(2) modified polypropene composite diaphragm is prepared and comprised the following steps：
At 60 DEG C, by the modified Li of above-mentioned PEO+- Nafion powder (0.07g) is dissolved in NMP (2g), adds 0.07g acetylene blacks
Stir, take city's dealer's microporous polypropylene membrane that 0.5ml drips to a diameter of 19mm：It is true at 60 DEG C at 2000,60 DEG C of Celgard
Sky be dried 12 hours after again in another side Deca 0.5mL, obtain after being vacuum dried 12 hours at 60 DEG C modified polypropene it is compound every
Film；By the modified Li of PEO wherein in the conductive carbon layer of modified polypropene composite diaphragm both sides+- Nafion is binding agent by acetylene
Black granule is bonded on film.
Based on the series connection lamination lithium-sulfur cell of the modified polypropene composite diaphragm, including being soaked with modified poly- the third of electrolyte
Alkene composite diaphragm, proper pole, middle positive pole, negative pole, nickel foam, sealing ring, battery case and battery cover.
The preparation method of the positive electrode is comprised the following steps：
In mass ratio it is 7 by elemental sulfur and macropore material with carbon element：3 mechanical mixture are uniform, are placed in the reaction of 316 stainless steels
In device, then by reactor evacuation post-heating to 80 DEG C, reaction completes supporting for sulfur after 5～10 hours, then by product
10～30 DEG C are cooled to, that is, positive electrode is obtained；
The preparation method of the macropore material with carbon element, comprises the following steps：
In mass ratio 1: 1 weighs the production of Ruicheng Warner nano material company limited, and particle diameter is the hydrophilic of 15～40nm
Nano-meter CaCO3310g each with glucose, adds into 100mL deionized waters, and supersonic vibration mixing makes glucose dissolve simultaneously for 30 minutes
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 successively with hydrochloric acid, 80 DEG C of the 30wt% concentration of 5wt% concentration
Sodium hydroxide solution, deionized water wash, then freeze-day with constant temperature after 4 hours, obtains macropore material with carbon element at 120 DEG C；
The preparation method of the positive pole is comprised the following steps：
By positive electrode 1.4g, mix with acetylene black and binding agent in mass ratio 70: 15: 15, take 2g after grinding is uniform and add
Enter the N-Methyl pyrrolidone (NMP as dispersant:2g), then it is modulated into and takes 0.1mL after pasty state and be coated to a diameter of 18mm
Aluminium film or aluminum/copper bi-metal thin film aluminum metal side and dry in the shade；In 100Kg cm-2Pressure under it is compressing, respectively obtain
Electrode base material for aluminium film proper pole and electrode base material for aluminum/Copper thin film middle positive pole；It is described rectify extremely with battery case
The positive pole of contact, the positive pole that the centre is not just extremely contacting with battery case；The binding agent is the modified Li of above-mentioned PEO+-
Nafion；Acetylene black is the product of commercially available Ningxia belite Chemical Co., Ltd. production.
The preparation method of the series connection lamination lithium-sulfur cell is comprised the following steps：
Above-mentioned modified polypropene composite diaphragm is soaked in the electrolytic solution 24 hours；Electrolyte is with Li [CF3SO2)2N]
(LiTFSI) it is solute, dioxolanes (C3H6O2) and ethylene glycol monomethyl ether (C4H10O2) mixture be solvent, dioxolanes and second
The volume ratio of glycol methyl ether is 1：1, one mole of (263g) LiTFSI is contained in one liter of electrolyte.Modified polypropene composite diaphragm is in electricity
Gel electrolyte is formed after soaking in solution liquid in former polypropylene screen micropore and its both sides conductive layer.
The assembling of the series connection lamination lithium-sulfur cell is comprised the following steps：
(1) by above-mentioned proper pole 1-2 (sulfur electrodes：A diameter of 18mm, positive electrode 1-2-1 is coated in aluminium film 1-2-2)
In being placed in city dealer button cell shell 1-1, sulfur electrode base material aluminium film is contacted with battery case；
(2) by above-mentioned modified polypropene composite diaphragm 1-3 (a diameter of 19mm, the conduction for being soaked in 24 hours in electrolyte
Layer 1-3-1, modified polypropene layer 1-3-2) it is placed on sulfur electrode；
(3) the lithium metal piece 1-4 of a diameter of 18mm, thickness 0.2mm is placed on barrier film；
(4) take middle positive pole 1-5 be placed on lithium metal piece 1-4 (the copper metal layer 1-5-1 of aluminum/copper bi-metal thin film,
The aluminum metal layer 1-5-2 of aluminum/copper bi-metal thin film, positive electrode material layer 1-5-3), the base material aluminum/copper bi-metal of middle positive pole 1-5
Copper metal side 1-5-1, the lithium metal piece 1-4 contact of thin film；The above-mentioned modified polypropene for being soaked in 24 hours in electrolyte is answered
Close barrier film 1-3 (a diameter of 19mm, 1-4-1 are conductive layer, modified polypropene layer 1-4-2) to be placed on sulfur electrode；Will be a diameter of
18mm, the lithium metal piece 1-4 of thickness 0.2mm are placed on barrier film；
(5) on pad after a diameter of 18mm, thickness 1mm, foam nickel sheet 1-6 that voidage is 98%, plus sealing ring 1-7 and battery
Seal after lid 1-8, obtain the battery of button two concatenation lithium-sulfur cell；
The aluminum/copper bi-metal thin film is that copper film and aluminium film by thickness for 0.1mm are formed in 300 DEG C of hot pressing, and pressure is
500Kg cm-2。
The professional and technical personnel that the following examples can make this professional is more fully understood the present invention, but not with any side
Formula limits the present invention.
Embodiment one：It is prepared by macropore material with carbon element
In mass ratio 1: 1 weighs the production of Ruicheng Warner nano material company limited, and particle diameter is the hydrophilic of 15～40nm
Nano-meter CaCO3310g each with glucose, adds into 100mL deionized waters, and supersonic vibration mixing makes glucose dissolve simultaneously for 30 minutes
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 successively with hydrochloric acid, 80 DEG C of the 30wt% concentration of 5wt% concentration
Sodium hydroxide solution, deionized water wash, then freeze-day with constant temperature after 4 hours, obtains macropore material with carbon element at 120 DEG C.
Embodiment two：It is prepared by positive electrode
The macropore carbon that elemental sulfur and embodiment one are obtained is uniform for 7: 3 mechanical mixture in mass ratio, is placed in 316 rustless steels
In the reactor of material, then by reactor evacuation post-heating to 80 DEG C, reaction completes supporting for sulfur after 5 hours, then will be anti-
Answer product to be cooled to 10 DEG C, that is, positive electrode is obtained.
Embodiment three：Li+The preparation of-Nafion solution
Take 10g LiOH to add into 100mL Nafion (20wt% originates from E.I.Du Pont Company), after stirring 30 minutes, centrifugation
The LiOH of surplus is separated, Li is obtained+- Nafion solution.
Example IV：PEO is modified Li+The preparation of-Nafion resins
The Li that will be obtained in embodiment three+- Nafion solution 100mL, (molecular weight is to add 2g cities dealer's polyethylene glycol oxide
500,000g/mol) and 50mL deionized waters, stir 1 hour, obtain the modified Li of PEO+- Nafion solution, after spray drying, obtains
To the modified Li of PEO+- Nafion powder.
Embodiment five：It is prepared by proper pole
The macropore carbon that elemental sulfur and embodiment one are obtained is uniform for 7: 3 mechanical mixture in mass ratio, is placed in 316 rustless steels
In the reactor of material, then by reactor evacuation post-heating to 80 DEG C, reaction completes supporting for sulfur after 8 hours, then will be anti-
Answer product to be cooled to 25 DEG C, that is, positive electrode is obtained.
By above-mentioned positive electrode 1.4g, mix with acetylene black and binding agent in mass ratio 70: 15: 15, take after grinding is uniform
2g adds the N-Methyl pyrrolidone (NMP as dispersant:2g), be then modulated into after pasty state take 0.1mL be coated to it is a diameter of
In the aluminium film of 18mm and dry in the shade；In 100Kg cm-2Pressure under it is compressing, that is, obtain rectify pole；The binding agent is enforcement
The modified Li of PEO obtained in example four+-Nafion；Acetylene black is the product of commercially available Ningxia belite Chemical Co., Ltd. production.
Embodiment six：The preparation of aluminum/copper bi-metal thin film
By thickness for 0.1mm copper film and aluminium film at 300 DEG C, pressure be 500Kg cm-2Hot pressing obtains aluminum/copper bi-metal
Thin film.
Embodiment seven：It is prepared by middle positive pole
The macropore carbon that elemental sulfur and embodiment one are obtained is uniform for 7: 3 mechanical mixture in mass ratio, is placed in 316 rustless steels
In the reactor of material, then by reactor evacuation post-heating to 80 DEG C, reaction completes supporting for sulfur after 10 hours, then will be anti-
Answer product to be cooled to 30 DEG C, that is, positive electrode is obtained.
By above-mentioned positive electrode 1.4g, mix with acetylene black and binding agent in mass ratio 70: 15: 15, take after grinding is uniform
2g adds the N-Methyl pyrrolidone (NMP as dispersant:2g), be then modulated into after pasty state take 0.1mL be coated to it is a diameter of
On the aluminum metal side of the aluminum of 18mm/copper bi-metal thin film and dry in the shade；In 100Kg cm-2Pressure under it is compressing, obtain centre
Positive pole；The binding agent is the modified Li of the PEO obtained in example IV+-Nafion；Acetylene black is commercially available prod.
Embodiment eight：It is prepared by modified polypropene composite diaphragm
At 60 DEG C, by the modified Li of the PEO obtained in example IV+- Nafion powder (0.07g) is dissolved in NMP (2g), adds
0.07g acetylene blacks stir, and take the Celgard that 0.5ml drips to the Celgard barrier films company limited production of a diameter of 19mm
On 2000, at 60 DEG C, again in another side Deca 0.5mL after being vacuum dried 12 hours, obtain after being vacuum dried 12 hours at 60 DEG C
Modified polypropene composite diaphragm.
Embodiment nine：The process of modified polypropene composite diaphragm
The modified polypropene composite diaphragm that embodiment eight is obtained soaks in the electrolytic solution 24 hours；Electrolyte is with Li
[CF3SO2)2N] (LiTFSI) be solute, dioxolanes (C3H6O2) and ethylene glycol monomethyl ether (C4H10O2) mixture be solvent, two
The volume ratio of butyl oxide link and ethylene glycol monomethyl ether is 1：1, one mole of (263g) LiTFSI is contained in one liter of electrolyte.Modified polypropene is answered
Close after barrier film soaks in the electrolytic solution and form gel electrolyte in former polypropylene screen micropore and its both sides conductive layer.
Embodiment ten：Monomer lithium-sulfur cell is assembled
The proper pole 1-2 (a diameter of 18mm) obtained in embodiment five is placed in into city dealer button cell shell 1-1
(CR2025) in, sulfur electrode base material aluminium film 1-2-2 with battery case is contacted；The immersion of Jing electrolyte will be obtained in embodiment nine
Modified polypropene composite diaphragm 1-3 (a diameter of 19mm) is placed on the positive electrode 1-2-1 of proper pole 1-2；Will be a diameter of
18mm, the lithium metal piece 1-4 of thickness 0.2mm are placed on barrier film 1-3；A diameter of 18mm, thickness 1mm, voidage are 98% on pad
After foam nickel sheet 1-6, plus seal after sealing ring 1-7 and battery cover 1-8, obtain monomer lithium-sulfur cell.Its charging and discharging curve such as Fig. 2
Shown, wherein 2-1 is its charging curve, and 2-2 is its discharge curve, and charging and discharging currents are 0.8A.
Embodiment 11：The concatenation lithium-sulfur cell assembling of two batteries
The proper pole 1-2 (a diameter of 18mm) obtained in embodiment five is placed in into city dealer button cell shell 1-1
(CR2025) in, sulfur electrode base material aluminium film 1-2-2 with battery case is contacted；The immersion of Jing electrolyte will be obtained in embodiment nine
Modified polypropene composite diaphragm 1-3 (a diameter of 19mm) is placed on the positive electrode 1-2-1 of proper pole 1-2；Will be a diameter of
18mm, the lithium metal piece 1-4 of thickness 0.2mm are placed on barrier film 1-3；The middle positive pole 1-5 obtained in embodiment seven is (a diameter of
18mm) it is placed on lithium metal piece 1-4, the copper metal side 1-5-1 and lithium of the base material aluminum/copper bi-metal thin film of middle positive pole 1-5
Sheet metal 1-4 is contacted；The above-mentioned modified polypropene composite diaphragm 1-3 for being soaked in 24 hours in electrolyte is placed in into middle positive pole 1-
On 5 positive electrode 1-5-3；The lithium metal piece 1-4 of a diameter of 18mm, thickness 0.2mm is placed on barrier film；It is a diameter of on pad
After 18mm, thickness 1mm, foam nickel sheet 1-6 that voidage is 98%, plus seal after sealing ring 1-7 and battery cover 1-8, obtain two electric
Pond concatenates lithium-sulfur cell.
Fig. 2 is the comparison that monomer lithium-sulfur cell and two batteries concatenate lithium-sulfur cell running voltage, and wherein 2-1 is monomer lithium sulfur
Battery charging curve, 2-2 is monomer lithium-sulfur cell discharge curve, and 2-3 is that two batteries concatenate lithium-sulfur cell charging curve, and 2-4 is
Two batteries concatenate lithium-sulfur cell discharge curve, and charging and discharging currents are 0.8A.Fig. 3 is that two batteries concatenate lithium-sulfur cell charge and discharge cycles
Life performance, 3-1 is that two batteries concatenate lamination lithium-sulfur cell inducing capacity fading curve；3-2 is that two batteries concatenate lamination lithium-sulfur cell
Efficiency for charge-discharge curve.Charging and discharging currents are 0.8A.
Embodiment 12：Many batteries concatenate lithium-sulfur cell
During the proper pole 1-2 (a diameter of 18mm) obtained in embodiment five is placed in into battery case 1-1, sulfur electrode base material aluminum
Film 1-2-2 with battery case is contacted；The modified polypropene composite diaphragm 1-3 of Jing electrolyte immersion will be obtained in embodiment nine
(a diameter of 19mm) is placed on the positive electrode 1-2-1 of proper pole 1-2；By a diameter of 18mm, the lithium metal piece 1- of thickness 0.2mm
4 are placed on barrier film 1-3；By the middle positive pole 1-5 (a diameter of 18mm) obtained in embodiment seven be placed in lithium metal piece 1-4 it
On, the copper metal side 1-5-1 of the base material aluminum/copper bi-metal thin film of middle positive pole 1-5 is contacted with lithium metal piece 1-4；By above-mentioned leaching
The modified polypropene composite diaphragm 1-3 for steeping 24 hours in electrolyte is placed in the middle of 1-5 on the positive electrode 1-5-3 of positive pole；
The 1-4 lithium metal pieces of a diameter of 18mm, thickness 0.2mm are placed on barrier film；With middle positive pole 1-5/ modified polypropenes it is compound every
Film 1-3/ lithium metal pieces 1-4 is recurring units, per repeat step once, increases the series connection of a battery more；Finally, diameter on pad
After for 18mm, thickness 1mm, foam nickel sheet 1-6 that voidage is 98%, plus seal after sealing ring 1-7 and battery cover 1-8, obtain many
Battery concatenates lithium-sulfur cell.With the presence of positive pole in the middle of n, the Stringing cells number of many battery concatenation lithium-sulfur cells is n+1；It is theoretical
Running voltage can reach n+1 times of single lithium-sulfur cell.Now the height of battery case should increase according to the increase of lamination number.
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
The all deformations for going out or associating, are considered as protection scope of the present invention.
Claims (5)
1. the preparation method of the modified polypropene composite diaphragm of lithium-sulfur cell is used for, it is characterised in that comprised the steps：
(1) preparation of PEO modification lithium-ions exchanger resin
Take 10g LiOH to add into the 20wt% perfluor sulfoacid resin solutions of 100mL, after stirring 30 minutes, centrifugation was fallen
Surplus LiOH, obtains Li+Type perfluor sulfoacid resin solution；Take Li+Type perfluor sulfoacid resin solution 100mL, add 2g molecular weight be
500,000g/mol polyethylene glycol oxide and 50mL deionized waters, stir 1 hour, obtain the modified Li of PEO+Type perfluorinated sulfonic resin
Solution；After spray drying, the modified Li of PEO are obtained+Type perfluorinated sulfonic resin powder；
(2) preparation of modified polypropene composite diaphragm
At 60 DEG C, the modified Li of PEO of 0.07g are taken+Type perfluorinated sulfonic resin powder is dissolved in the N-Methyl pyrrolidone of 2g, is added
0.07g acetylene blacks stir；Take 0.5ml homomixtures to drip on the microporous polypropylene membrane of a diameter of 19mm, vacuum is done at 60 DEG C
After dry 12 hours, in another side Deca 0.5ml homomixture again, it is vacuum dried 12 hours at 60 DEG C, obtains modified polypropene and be combined
Barrier film.
2. a kind of lithium-sulfur cell, including barrier film, positive pole, negative pole and electrolyte, it is characterised in that the barrier film is by claim
The modified polypropene composite diaphragm that preparation method described in 1 is obtained；Positive pole and negative pole are separately positioned on barrier film both sides and form Sanming City
Structure is controlled, and makes the electrode material side of positive pole and negative pole towards barrier film.
3. lithium-sulfur cell according to claim 2, it is characterised in that the preparation method of the positive pole is：
By positive electrode 1.4g, mix with acetylene black and binding agent in mass ratio 70: 15: 15, after grinding is uniform 2g mixture taken,
Add 2g as dispersant N-Methyl pyrrolidone, be modulated into after pasty state take 0.1ml be coated to a diameter of 18mm aluminium film and
On the aluminum metal side of aluminum/copper bi-metal thin film and dry in the shade；In 100Kg cm-2Pressure under it is compressing, respectively obtain electrode base
Material for aluminium film proper pole and electrode base material for aluminum/Copper thin film middle positive pole；The proper pole is contacted with battery case
Positive pole, the middle positive pole is the positive pole not contacted with battery case；The binding agent is PEO modification lithium-ion exchanger resins；
The positive electrode is prepared by following methods：Elemental sulfur and macropore material with carbon element is mixed in mass ratio for 7: 3 machineries
Close uniform, be placed in the reactor of 316 stainless steels, then by reactor evacuation post-heating to 80 DEG C, reaction 5～10 is little
When after complete supporting for sulfur, then product is cooled to into 10～30 DEG C, that is, positive electrode is obtained；
The preparation method of the macropore material with carbon element is：
In mass ratio 1: 1 weighs the hydrophilic nano CaCO that particle diameter is 15～40nm310g each with glucose, adds to 100mL and goes
In ionized water, supersonic 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 into 900 DEG C under nitrogen atmosphere protection, constant temperature is carbonized 2 hours；Carbonization is produced
Thing uses successively hydrochloric acid, the sodium hydroxide solution of 80 DEG C of 30wt% concentration and the deionized water wash of 5wt% concentration, then 120 DEG C
Lower freeze-day with constant temperature obtains macropore material with carbon element after 4 hours.
4. lithium-sulfur cell according to claim 3, it is characterised in that the aluminum/copper bi-metal thin film is to be by thickness
The copper film and aluminium film of 0.1mm is formed in 300 DEG C of hot pressing, and pressure during hot pressing is 500Kg cm-2。
5. the method for preparing concatenation lamination lithium-sulfur cell using lithium-sulfur cell described in claim 3, it is characterised in that including following
Step：
The configuration of step A, electrolyte
With Li [CF3SO2)2N] for solute, dioxolanes and ethylene glycol monomethyl ether mixture be solvent, dioxolanes and ethylene glycol
The volume ratio of methyl ether is 1: 1, and one mole of Li [CF is contained in one liter of electrolyte3SO2)2N]；By the preparation method described in claim 1
The modified polypropene composite diaphragm for obtaining soaks in the electrolytic solution 24 hours；
The assembling of step B, series connection lamination lithium-sulfur cell
(1) the proper pole is placed in button cell shell, rectifies pole and contact with battery case；
(2) the modified polypropene composite diaphragm after immersion is placed on proper pole；
(3) the lithium metal piece of a diameter of 18mm, thickness 0.2mm is placed on modified polypropene composite diaphragm；
(4) take the middle positive pole to be placed on lithium metal piece, the copper metal side of the base material aluminum/copper bi-metal thin film of middle positive pole
Contact with lithium metal piece；Immersion post-modification polypropylene composite materials barrier film is placed on middle positive pole；By a diameter of 18mm, thickness
The lithium metal piece of 0.2mm is placed on modified polypropene composite diaphragm；
(5) on pad after a diameter of 18mm, thickness 1mm, the foam nickel sheet that voidage is 98%, plus seal after sealing ring and battery cover,
Obtain the battery of button two concatenation lithium-sulfur cell；Wherein,
Sequentially pass through step (1) to (5) and then obtain two batteries series connection lithium-sulfur cell；Or
Step (1) is sequentially passed through to (5) and per repeat step (4) once, the series connection of a battery will be increased more；That is, Jing Guobu
Suddenly (1) to (3) repeat step (4) n times afterwards, then execution step (5), will obtain the laminated cell of N+2 lithium-sulfur cell concatenation, this
When battery case height increased according to the increase of lamination number.
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