CN103972580B - A kind of lithium-sulfur cell - Google Patents
A kind of lithium-sulfur cell Download PDFInfo
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- CN103972580B CN103972580B CN201310047928.0A CN201310047928A CN103972580B CN 103972580 B CN103972580 B CN 103972580B CN 201310047928 A CN201310047928 A CN 201310047928A CN 103972580 B CN103972580 B CN 103972580B
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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
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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 present invention provides a kind of lithium-sulfur cell, and including anode, cathode and electrolyte, the anode includes positive active material, and the positive active material includes composite positive pole, and the cathode includes negative electrode active material；The electrolyte is all solid state, and the electrolyte includes polyethylene oxide, lithium salts and inert filler.In lithium-sulfur cell provided by the invention, all solid state electrolyte is used in combination with positive active material, can preferably it inhibit in lithium-sulfur cell charge and discharge process, the dissolving of the more lithium sulfides of intermediate product, the loss of elemental sulfur in composite positive pole is reduced, improves the utilization rate of positive active material and the cycle performance of battery.
Description
Technical field
The invention belongs to electrochemical energy storage fields, and in particular to a kind of lithium-sulfur cell.
Background technology
In recent years, with the development of science and technology, the demand of especially renewable green energy resource is more and more prominent to the energy, battery
Storage and conversion equipment as energy just play irreplaceable role.Lithium ion battery has very high mass ratio because of it
Energy and energy density per unit volume have attracted extensive concern.Low cost, high-energy density, long circulation life, environmentally protective is secondary
Battery is the emphasis of current lithium ion battery exploitation.
The positive electrode of commercialization at present is mainly lithium transition-metal oxide (such as cobalt acid of stratiform or spinel structure
Lithium, LiMn2O4) and olivine structural LiFePO4 etc..Cobalt acid lithium (LiCoO2) theoretical capacity it is relatively large, 275mAh/g,
But its price is high, has certain toxicity, and exothermal decomposition reactions easily occur when overcharging for the positive electrode, not only make battery capacity
It is decreased obviously, while threat is also resulted in cell safety；LiMn2O4 (LiMn2O4) theoretical capacity for 148mAh/g, actual capacity
Less than 130mAh/g, the stability of the positive electrode is bad, and lattice deformability is easily caused in charge and discharge process, and cycle is caused to be imitated
Rate is relatively low；LiFePO4 (LiFePO4) theoretical capacity for 172mAh/g, the poorly conductive of the positive electrode so that battery
Reversible capacity reduces.Above-mentioned common anode material for lithium-ion batteries capacity is not generally high, while also there are problems that, it is impossible to
Meet battery exploitation demand.
The theoretical specific capacity of elemental sulfur is 1675mAh/g, and the theory that battery is assembled into lithium metal can reach than energy
2600mAh/g far above the positive electrode of commercialization at present, becomes the main trend of present battery development.But in charge and discharge
In electric process, elemental sulfur can be converted into polysulfide, and polysulfide can be dissolved in liquid organic solution liquid, these active materials
Loss can then lead to the deterioration of cycle performance of battery, result in lithium-sulfur cell and be limited in practical applications.Although it is found that
In all solid state battery structure, contact of the solid with solid can prevent more vulcanizations that electrode reaction is formed in lithium-sulfur cell
The dissolving of object, but in existing lithium-sulfur cell system, the matching of electrolyte and battery still has some problems, therefore need
A kind of new lithium-sulfur cell system is found, further improves the cycle performance of battery.
Invention content
The present invention is intended to provide a kind of lithium-sulfur cell that specific capacity is high, high temperature cyclic performance is good.
The present invention provides a kind of lithium-sulfur cell, and including anode, cathode and electrolyte, the anode includes positive electrode active material
Matter, the positive active material include composite positive pole, and the cathode includes negative electrode active material；The electrolyte is complete solid
State, the electrolyte include polyethylene oxide, lithium salts and inert filler.
The present invention provides a kind of lithium-sulfur cell, it is preferred that the lithium salts is LiTFSI, and the inert filler is glued for nanometer
Soil.
The present invention provides a kind of lithium-sulfur cell, it is preferred that the EO bases in the polyethylene oxide and the Li in the lithium salts
Molar ratio be 16-24:1.
The present invention provides a kind of lithium-sulfur cell, it is preferred that described lazy using polyethylene oxide and the gross mass of lithium salts as 100%
Property filler mass ratio be 4-6%.
The present invention provides a kind of lithium-sulfur cell, it is preferred that the composite positive pole further include polypyrrole, polyacrylonitrile or
At least one of polyacrylonitrile copolymer.
The present invention provides a kind of lithium-sulfur cell, it is preferred that using the gross mass of composite positive pole as 100%, the poly- pyrrole
It coughs up, the mass percent of polyacrylonitrile or polyacrylonitrile copolymer is 2-40%.
The present invention provides a kind of lithium-sulfur cell, it is preferred that the composite positive pole further includes metal oxide, the gold
Belong to oxide and be selected from MgaNibO、MgO、NiO、V2O5、CuO、MgcCudO、La2O3、Zr2O3、Ce2O3And Mn2OfIn at least one
Kind；Wherein, 0<a<1、0<b<1、a+b=1；0<c<1、0<d<1、c+d=1；The value of f is 2 or 3 or 4 or 7.
The present invention provides a kind of lithium-sulfur cell, it is preferred that using the gross mass of composite positive pole as 100%, the metal oxygen
The mass percent of compound is not higher than 20%.
The present invention provides a kind of lithium-sulfur cell, it is preferred that the composite positive pole include elemental sulfur, polyacrylonitrile and
Mg0.6Ni0.4O；Elemental sulfur, polyacrylonitrile and Mg in the composite positive pole0.6Ni0.4The mass ratio of O is 4:1:0.3.
The present invention provides a kind of lithium-sulfur cell, it is preferred that the positive active material further includes conductive agent, LiTFSI, gathers
Ethylene oxide；In the positive active material, the quality of the composite positive pole and conductive agent, LiTFSI and polyethylene oxide
Than being 55:25:15:5.
Lithium-sulfur cell provided by the invention, using including polyethylene oxide（PEO）, lithium salts and inert filler all solid state electricity
Xie Zhi, while play a dual role of diaphragm and electrolyte, in addition, using containing conductive more preferable and electrolyte knot of the present invention
The anode of the better positive active material of effect is closed, is used in combination with the electrolyte of the present invention, can preferably inhibit lithium sulphur electric
In the charge and discharge process of pond, the dissolving of the more lithium sulfides of intermediate product reduces the loss of elemental sulfur in composite positive pole, improves anode
The utilization rate and cyclical stability of active material, while also avoid with liquid electrolyte or gel state electrolyte and lithium metal
Timing, lithium anode easily generate dendrite, break through diaphragm and the problem of short circuit.
Description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is cycle performance curve graph of the battery at 60 DEG C in embodiment 1.
Specific embodiment
The present invention provides a kind of lithium-sulfur cell, and including anode, cathode and electrolyte, the anode includes positive electrode active material
Matter, the positive active material include composite positive pole, and the cathode includes negative electrode active material；The electrolyte is complete solid
State, the electrolyte include polyethylene oxide（PEO）, lithium salts and inert filler.Wherein, inert filler specifically refers to be not involved in electricity
The filler of chemical reaction.
The present invention provides a kind of lithium-sulfur cell, it is preferred that the lithium salts is LiTFSI, LiClO4Or LiCF3SO3；It is described lazy
Property filler be nanoclay or nano silicon dioxide.It is further preferred that the lithium salts is LiTFSI, the inert filler is receives
Rice clay.The present invention provides a kind of lithium-sulfur cell, using including polyethylene oxide（PEO）, lithium salts and inert filler it is all solid state
Electrolyte has higher ionic conductivity, can play a dual role of electrolyte and diaphragm simultaneously, and make positive-active
The utilization rate and cycle performance of substance are greatly improved.
In lithium-sulfur cell provided by the invention, it is preferred that the molar ratio of EO bases and the Li in the lithium salts in the PEO
For 16-24:1.Using the gross mass of PEO and lithium salts as 100%, the mass ratio of the inert filler is 4-6%.Preferably, the PEO
Molecular weight be 0.8 × 106-1.2×106。
In lithium-sulfur cell provided by the invention, a kind of electrolyte preparation method is provided：It is first that LiTFSI is molten at room temperature
It is 0.8 × 10 by molecular weight after LiTFSI is dissolved completely in acetonitrile in 99.8% acetonitrile6-1.2×106PEO add
Enter, dissolved 10-14 hours at 45-75 DEG C, the molar ratio of EO bases and Li in LiTFSI are 16-24 in PEO:1；Then it adds in and receives
Rice clay particle, by ultrasonic disperse and stirring, obtains homogeneous phase solution.Under the conditions of 45-75 DEG C of vacuum, solution is poured into Teflon
Synthetic fibre（Teflon）In disk, solvent is made to volatilize, the mixed film of PEO and LiTFSI are obtained after solvent completely volatilization, by film
1-3h is dried under the conditions of 100-140 DEG C of vacuum to get to PEO-LiTFSI- nano-clay-ploymer films.
In lithium-sulfur cell provided by the invention, it is preferred that the composite positive pole further includes polypyrrole（PPy）, poly- third
Alkene nitrile（PAN）Or at least one of polyacrylonitrile copolymer.Preferably, using the gross mass of composite positive pole as 100%, institute
The mass percent for stating polypyrrole, polyacrylonitrile or polyacrylonitrile copolymer is 2-40%.It is further preferred that polyacrylonitrile is total to
Polymers is selected from least one of PAN- methylmethacrylate copolymers, PAN-PPy.PPy is a kind of high conductive poly-
Object is closed, is widely used in electrode face finish and electrode material；PAN issues raw pyrolytic reaction at 200-300 DEG C and includes
The processes such as the cyclisation of cyano, dehydrogenation, conjugation, crosslinking, generate it is conductive can conjugation coalescence pyrroles, the Low Temperature Thermal of PAN
Solution performance provides good carrier to prepare composite positive pole, and PAN- methylmethacrylate copolymers are because in its structure
Has the structural unit of PAN, PAN-PPy is more combined with the double properties of PAN and PPy therefore can be used as positive electrode active materials
Carrier.
The present invention provides a kind of lithium-sulfur cell, it is preferred that the composite positive pole further includes metal oxide, the gold
Belong to oxide and be selected from MgaNibO、MgO、NiO、V2O5、CuO、MgcCudO、La2O3、Zr2O3、Ce2O3And Mn2OfIn at least one
Kind；Wherein, 0<a<1、0<b<1、a+b=1；0<c<1、0<d<1、c+d=1；The value of f is 2 or 3 or 4 or 7.Preferably, with compound
The gross mass of positive electrode is 100%, and the mass percent of the metal oxide is not higher than 20%.It is it is further preferred that golden
Belong to oxide and be selected from Mg0.6Ni0.4O, Mg0.6Ni0.4O can not only further improve the electric conductivity of composite positive pole, Er Qieneng
Enough inhibit the dissolving of the more lithium sulfides of charge and discharge intermediate product, improve the utilization rate of elemental sulfur so that the cycle performance of battery obtains
To very big raising.
The present invention provides a kind of lithium-sulfur cell, it is preferred that the composite positive pole include elemental sulfur, polyacrylonitrile and
Mg0.6Ni0.4O, it is preferred that elemental sulfur, polyacrylonitrile and Mg in the composite positive pole0.6Ni0.4The mass ratio of O is 4:1:
0.3, using the better composite positive pole of the electric conductivity, and including polyethylene oxide（PEO）, lithium salts and inert filler it is complete solid
State electrolyte is used in combination, and can preferably inhibit in lithium-sulfur cell charge and discharge process, the dissolving of the more lithium sulfides of intermediate product subtracts
The loss of elemental sulfur in few composite positive pole improves the utilization rate and cyclical stability of positive active material.
In lithium-sulfur cell provided by the invention, composite positive pole accounts for the 50-90% of positive active material total weight, preferably
Embodiment in, the weight ratio of the composite positive pole in positive active material is 80%.
In lithium-sulfur cell provided by the invention, a kind of preparation method of composite positive pole is provided：Elemental sulfur is dissolved in
In one solvent, the first solution is obtained；At least one of polypyrrole, polyacrylonitrile, polyacrylonitrile copolymer are added to second
In solvent, the second solution is obtained；At least one of metal oxide, the first solution, the second solution are mixed and in indifferent gas
Ball milling is carried out under body, obtains mixture, mixture is dried in vacuo, removes solvent therein, is then carried out under protective atmosphere
Heat treatment, natural cooling obtain positive electrode active materials；First solvent is selected from carbon disulfide, toluene, one kind in liquid hydrocarbon；
Second solvent is selected from dimethylformamide, dimethyl propylene amine, and the mixture and dimethyl of dimethyl propylene amine and lithium chloride are sub-
One kind in sulfone.
By mechanical milling process, at least one of metal oxide, the first solution, the second solution is made to mix more equal
It is even, specifically, the range of speeds of mechanical milling process is 200-1300 revs/min, Ball-milling Time ranging from 1-20 hours.Mechanical milling process is
It carries out under an inert gas, is in order to avoid other side reactions occur in mechanical milling process so as to be had an impact to material.
The mixture that ball milling is obtained carries out vacuum drying treatment, specifically, vacuum drying temperature range is 35-75
DEG C, ranging from 3-12 hours drying time.
Dried mixture is further heated, specifically, the temperature range of heat treatment is 150-450
DEG C, heating treatment time ranging from 1-20 hours, protective atmosphere is selected from the reducing gas that argon gas, nitrogen or argon gas are mixed with hydrogen
And the reducing gas that nitrogen is mixed with hydrogen.
Can be in specific implementation：Elemental sulfur is dissolved in organic solvent carbon disulfide (CS2) in, obtain the CS of sulfur-bearing2It is molten
PAN is dissolved in and obtains the DMF solution containing PAN in organic solvent dimethylformamide (DMF), then by sulfur-bearing by liquid
CS2Solution, the DMF solution containing PAN, Mg0.6Ni0.4O is mixed together and carries out mechanical ball mill under protection of argon gas, by ball milling system
It obtains object to be dried in vacuo, removes solvent therein, then heated under a nitrogen, natural cooling obtains PAN/S/
Mg0.6Ni0.4O。
In lithium-sulfur cell provided by the invention, the preparation method of another composite positive pole is also provided：By elemental sulfur,
At least one of polypyrrole, polyacrylonitrile, polyacrylonitrile copolymer and at least one of metal oxide are added to solvent
In, the first mixture is obtained, the first mixture is subjected to ball milling mixing, the second mixture is obtained, the second mixture vacuum is done
It is dry, then heated under protective atmosphere or vacuum environment, positive active material is obtained after cooling.
Preferably, the weight percentage ranges of elemental sulfur be 60-95%, polypyrrole, polyacrylonitrile, polyacrylonitrile copolymer
At least one of weight percentage ranges be at least one of 2-40%, metal oxide weight percentage ranges be
0-20%.Solvent includes but are not limited to one kind in ethyl alcohol, N-Methyl pyrrolidone.
Specifically, the range of speeds of mechanical milling process is 200-1300 revs/min, Ball-milling Time ranging from 1-20 hours.
During vacuum drying treatment, vacuum drying temperature range is 35-75 DEG C, ranging from 3-12 hours drying time.
In specific embodiment, it is dried in vacuo 3 hours at 50 DEG C by mixture made from mechanical ball mill.
During heat treatment, ranging from 150-450 DEG C of the temperature of heat treatment, heating treatment time is not less than 1 hour.It is excellent
Choosing, ranging from 250-400 DEG C of the temperature of heat treatment, the time range of heat treatment is 1-20 hours.Heat treatment is
It is carried out under protective atmosphere or vacuum environment, specifically, protective atmosphere is selected from argon gas or nitrogen.
Can be in specific implementation：By elemental sulfur, PAN and Mg0.6Ni0.4O, which is dissolved in ethyl alcohol, obtains the first mixture, ethyl alcohol
Make elemental sulfur, PAN and Mg as dispersant0.6Ni0.4O mixes more uniform.First mixture is subjected to ball-milling treatment, is obtained
Second mixture, the second mixture is dry in vacuum drying chamber, then heat 3h under 300 DEG C, argon gas protection, it is cold
But PAN/S/Mg is obtained afterwards0.6Ni0.4O。
The present invention provides a kind of lithium-sulfur cell, it is preferred that positive active material further includes conductive agent, lithium salts and bonding agent.
Conductive agent is selected from conducting polymer, section's qin carbon black (KB), acetylene black（AB）, activated carbon, single-walled carbon nanotube, multi-wall carbon nano-tube
It is one or more in pipe, activated carbon, graphene, carbon black, carbon fiber, metallic fiber, metal powder and sheet metal；
Preferably in embodiment, conductive agent includes acetylene black（AB）.Binding agent be selected from polyethylene oxide, polypropylene oxide, poly- third
Alkene nitrile, polyimides, polyester, polyethers, fluorinated polymer, poly- divinyl polyethylene glycol, polyethyleneglycol diacrylate, poly- second
The mixture and derivative of one kind or above-mentioned polymer in glycol dimethacrylate；In preferably embodiment, binding agent
Include PEO.Lithium salts is selected from LiTFSI, LiClO4Or LiCF3SO3In one kind；In preferably embodiment, positive active material
In lithium salts and all solid state electrolyte in lithium salts used be same substance；In preferably embodiment, lithium salts LiTFSI.More
In excellent embodiment, positive active material includes composite positive pole and conductive agent, LiTFSI and PEO, preferably and electrolyte
In LiTFSI and PEO match, improve the combination of anode and electrolyte, wherein, composite positive pole and conductive agent,
The mass ratio of LiTFSI and PEO is 55:25:15:5.
In lithium-sulfur cell provided by the invention, anode further includes plus plate current-collecting body, and plus plate current-collecting body is selected from and is but not limited only to
One kind in nickel foam, aluminium foil or stainless (steel) wire.Scheme more preferably, plus plate current-collecting body are nickel foam.
In lithium-sulfur cell provided by the invention, by composite positive pole, conductive agent acetylene black（AB）, LiTFSI and binding agent
PEO is mixed, and adds in organic solvent as dispersant, anode active material slurry is made.Using it is any can be in plus plate current-collecting body
Whole surface on the method for substantially homogeneous coat is provided, anode active material slurry obtained is deposited into anode collection
On the surface of body.For example, scraper for coating method (doctor blade), coiling pull rod method (wired draw rod) can be passed through
Method, silk-screen printing or other methods.It, can be by anode by the evaporation under normal pressure or low pressure and environment temperature or high temperature
Solvent removal in active material slurry layer, the speed of solvent removal are preferably basically unchanged along pulp surface holding.Then
Positive electrode and negative electrode obtained, electrolyte are assembled into battery together.
In a preferred embodiment, by PAN/S/Mg0.6Ni0.4O materials, conductive agent acetylene black（AB）, LiTFSI and bonding
Agent PEO is according to 55:25:15:5 mass ratio mixing, adds in N-Methyl pyrrolidone as solvent, obtained slurry is passed through
In circular shaped foam nickel set fluid of the blade coating technology coated in a diameter of 1cm, it is dried in vacuo 14 hours at 60 DEG C, in tablet press machine
Positive plate, the i.e. anode as battery of the present invention is made in the pressure lower sheeting of 8MPa.
In lithium-sulfur cell provided by the invention, negative electrode active material can restore in charge and discharge process-deposit or deviate from-
Embedded lithium ion, specifically, cathode can be lithium metal or lithium alloy.
Lithium-sulfur cell provided by the invention is made of above-mentioned anode, cathode and electrolyte.Polymer Electrolyte PEO-lithium
Salt-inert filler not only when electrolyte but also worked as diaphragm, served both functions, while the electrolyte and PAN/S/Mg0.6Ni0.4O materials
Good combination is played, can preferably be inhibited in lithium-sulfur cell charge and discharge process, the dissolving of the more lithium sulfides of intermediate product,
The loss of elemental sulfur in composite positive pole is reduced, improves the utilization rate and cyclical stability of positive active material so that battery
With good cycle performance and high specific capacity, especially at 60 DEG C, the cycle performance of battery is more excellent.
Below by embodiment, the present invention is further described.
Embodiment 1
The preparation of electrolyte：First LiTFSI is dissolved in 99.8% acetonitrile at room temperature, treats that LiTFSI is dissolved completely in second
It is 1 × 10 by molecular weight after in nitrile6PEO add in, dissolve 12h at 60 DEG C, mole of EO bases and Li in LiTFSI in PEO
Than being 20:1；Then 5% nanoclay particles are added in, by ultrasonic disperse and stirring, obtain homogeneous phase solution.In 60 DEG C of items of vacuum
Under part, solution is poured into Teflon disks, and solvent is made to volatilize, and the mixing of PEO and LiTFSI are obtained after solvent completely volatilization
Film is dried under the conditions of 120 DEG C of vacuum 2h to get to PEO-LiTFSI- nano-clay-ploymer films by film.
The preparation of anode：The elemental sulfur of 4g is dissolved in 30cm3CS2In, PAN is dissolved in DMF, will then be contained single
The CS of matter sulphur2Solution, DMF solution and Mg containing PAN0.6Ni0.4O, which is mixed and is put into ball mill, carries out ball milling, ball mill
Rotating speed is 800 revs/min, and Ball-milling Time is 2 hours, and then obtained object is dried in vacuo 3 hours at 65 DEG C, therein molten to remove
Agent then heats desciccate 3 hours at argon gas protection, 350 DEG C, and last natural cooling obtains anode composite material
Expect PAN/S/Mg0.4Ni0.6O.In preparation process, PAN/S/Mg before heat treatment0.4Ni0.6The content ratio of O is S:PAN:
Mg0.4Ni0.6O=4:1:0.3.By composite positive pole PAN/S/Mg0.6Ni0.4O, conductive agent acetylene black（AB）, LiTFSI and bonding
Agent PEO is according to 55:25:15:5 mass ratio mixing, adds in N-Methyl pyrrolidone as solvent, obtained slurry is passed through
In circular shaped foam nickel set fluid of the blade coating technology coated in a diameter of 1cm, it is dried in vacuo 14 hours at 60 DEG C, in tablet press machine
Positive plate is made in the pressure lower sheeting of 8MPa.
The preparation of battery：Using positive plate obtained as anode, lithium metal is cathode, and PEO-LiTFSI- nanoclays polymerize
Object film is electrolyte and diaphragm, and CR2032 button cells are assembled into the glove box full of argon gas.
Battery performance test
At room temperature by battery standing obtained for a period of time after, constant current charge-discharge is carried out to battery, charge-discharge magnification is
0.1C(1C=1672mAh g-1), voltage range 1-3V.Based on the content of S in positive electrode come calculate the specific capacity of battery and
Current density.
Fig. 1 is cycle performance curve of the battery at 60 DEG C in embodiment 1, it can be seen that the electric discharge specific volume in battery first week
Amount is up to 997.5mAh g-1, for cycle after 50 weeks, the specific discharge capacity of battery stills remain in 697.2mAh g-1。
Embodiment 2
The preparation of electrolyte：It is in the same manner as in Example 1
The preparation of anode：With embodiment 1 the difference lies in：In preparation process, PAN/S/ before heat treatment
Mg0.4Ni0.6The content ratio of O is S:PAN:Mg0.4Ni0.6O=4:1:0.6。
The preparation of battery：Using positive plate obtained as anode, lithium metal is cathode, and PEO-LiTFSI- nanoclays polymerize
Object film is electrolyte and diaphragm, and CR2032 button cells are assembled into the glove box full of argon gas.
Embodiment 3
The preparation of electrolyte：It is in the same manner as in Example 1
The preparation of anode：The elemental sulfur of 4g is dissolved in 30cm3CS2In, PAN is dissolved in DMF, will then be contained single
The CS of matter sulphur2Solution, the DMF solution containing PAN, which mix and be put into ball mill, carries out ball milling, the rotating speed of ball mill for 800 turns/
Point, Ball-milling Time is 2 hours, and then obtained object is dried in vacuo 3 hours at 65 DEG C, then will be dry to remove solvent therein
Dry product heats 3 hours at argon gas protection, 350 DEG C, and last natural cooling obtains composite positive pole PAN/S.It prepares
In the process, the content ratio of PAN/S is S before heat treatment:PAN=4:1.By composite positive pole PAN/S, conductive agent acetylene black
（AB）, LiTFSI and binding agent PEO be according to 55:25:15:5 mass ratio mixing, adds in N-Methyl pyrrolidone as molten
Obtained slurry is coated in by blade coating technology in the circular shaped foam nickel set fluid of a diameter of 1cm, vacuum at 60 DEG C by agent
It is 14 hours dry, positive plate is made in the pressure lower sheeting of tablet press machine 8MPa.
The preparation of battery：Using positive plate obtained as anode, lithium metal is cathode, and PEO-LiTFSI- nanoclays polymerize
Object film is electrolyte and diaphragm, and CR2032 button cells are assembled into the glove box full of argon gas.
Embodiment 4
The preparation of electrolyte：It is in the same manner as in Example 1
The preparation of anode：The elemental sulfur of 4g is dissolved in 30cm3CS2In, then by the CS containing elemental sulfur2Solution, with
Mg0.6Ni0.4O, which is mixed and is put into ball mill, carries out ball milling, and the rotating speed of ball mill is 800 revs/min, and Ball-milling Time is 2 hours, then
Object is made to be dried in vacuo 3 hours at 65 DEG C, to remove solvent therein, then by desciccate at argon gas protection, 350 DEG C
Heat treatment 3 hours, last natural cooling obtains composite positive pole S/Mg0.4Ni0.6O.In preparation process, before heat treatment
S/Mg0.4Ni0.6The content ratio of O is S:Mg0.4Ni0.6O=4:0.5.By composite positive pole S/Mg0.6Ni0.4O, conductive agent acetylene black
（AB）, LiTFSI and binding agent PEO be according to 55:25:15:5 mass ratio mixing, adds in N-Methyl pyrrolidone as molten
Obtained slurry is coated in by blade coating technology in the circular shaped foam nickel set fluid of a diameter of 1cm, vacuum at 60 DEG C by agent
It is 14 hours dry, positive plate is made in the pressure lower sheeting of tablet press machine 8MPa.
The preparation of battery：Using positive plate obtained as anode, lithium metal is cathode, and PEO-LiTFSI- nanoclays polymerize
Object film is electrolyte and diaphragm, and CR2032 button cells are assembled into the glove box full of argon gas.
Embodiment 5
The preparation of electrolyte：It is in the same manner as in Example 1
The preparation of anode：With embodiment 1 the difference lies in：By composite positive pole PAN/S/Mg0.6Ni0.4O, conduction
Agent acetylene black（AB）, LiTFSI and binding agent PEO be according to 60:23:12:5 mass ratio mixing, adds in N-Methyl pyrrolidone
As solvent, obtained slurry is coated in by blade coating technology in the circular shaped foam nickel set fluid of a diameter of 1cm, 60 DEG C
Lower vacuum drying 14 hours, positive plate is made in the pressure lower sheeting of tablet press machine 8MPa.
The preparation of battery：Using positive plate obtained as anode, lithium metal is cathode, and PEO-LiTFSI- nanoclays polymerize
Object film is electrolyte and diaphragm, and CR2032 button cells are assembled into the glove box full of argon gas.
Embodiment 6
The preparation of electrolyte：With embodiment 1 the difference lies in：The molecular weight for adding in PEO is 1.2 × 106；In PEO
The molar ratio of EO bases and Li in LiTFSI are 16:1；The amount for adding in nanoclay particles is 6%.
The preparation of anode：It is in the same manner as in Example 1.
The preparation of battery：Using positive plate obtained as anode, lithium metal is cathode, and PEO-LiTFSI- nanoclays polymerize
Object film is electrolyte and diaphragm, and CR2032 button cells are assembled into the glove box full of argon gas.
Embodiment 7
The preparation of electrolyte：With embodiment 1 the difference lies in：EO bases and the molar ratio of Li in LiTFSI are in PEO
24:1；The inert filler of addition is 5% nano silicon dioxide, obtains PEO-LiTFSI- nano silicon dioxide thin polymer films.
The preparation of anode：It is in the same manner as in Example 1.
The preparation of battery：Using positive plate obtained as anode, lithium metal is cathode, and PEO-LiTFSI- nanoclays polymerize
Object film is electrolyte and diaphragm, and CR2032 button cells are assembled into the glove box full of argon gas.
Embodiment 8
The preparation of electrolyte：With embodiment 1 the difference lies in：Lithium salts used is LiCF3SO3, obtain PEO-
LiCF3SO3Nano-clay-ploymer film.
The preparation of anode：With embodiment 1 the difference lies in：By composite positive pole PAN/S/Mg0.6Ni0.4O, conduction
Agent acetylene black（AB）、LiCF3SO3With binding agent PEO according to 55:25:15:5 mass ratio mixing.
The preparation of battery：Using positive plate obtained as anode, lithium metal is cathode, PEO-LiCF3SO3Nanoclay polymerize
Object film is electrolyte and diaphragm, and CR2032 button cells are assembled into the glove box full of argon gas.
Although inventor has done technical scheme of the present invention more detailed elaboration and has enumerated, it should be understood that for
For those skilled in the art, above-described embodiment is modified and/or the flexible or equivalent alternative solution of use is obvious
, cannot all be detached from the essence of spirit of the present invention, the term occurred in the present invention be used for elaboration to technical solution of the present invention and
Understand, can not be construed as limiting the invention.
Claims (9)
1. a kind of lithium-sulfur cell, including anode, cathode and electrolyte, the anode includes positive active material, and the anode is lived
Property substance include composite positive pole, the cathode include negative electrode active material, it is characterised in that：The electrolyte is complete solid
State, the electrolyte includes polyethylene oxide, lithium salts and inert filler, using polyethylene oxide and the gross mass of lithium salts as 100%,
The mass percent of the inert filler is 4-6%, and the positive active material further includes conductive agent, lithium salts and polycyclic oxygen second
Alkane, the lithium salts in lithium salts and the positive active material in all solid state electrolyte are same substance.
2. lithium-sulfur cell as described in claim 1, it is characterised in that：The lithium salts is LiTFSI, and the inert filler is receives
Rice clay.
3. lithium-sulfur cell as described in claim 1, it is characterised in that：In EO bases and the lithium salts in the polyethylene oxide
Li molar ratio be 16-24:1.
4. lithium-sulfur cell as described in claim 1, it is characterised in that：The composite positive pole further includes polypyrrole, poly- third
At least one of alkene nitrile or polyacrylonitrile copolymer.
5. lithium-sulfur cell as claimed in claim 4, it is characterised in that：It is described using the gross mass of composite positive pole as 100%
The mass percent of polypyrrole, polyacrylonitrile or polyacrylonitrile copolymer is 2-40%.
6. lithium-sulfur cell as described in claim 4 or 5, it is characterised in that：The composite positive pole further includes metal oxidation
Object, the metal oxide are selected from MgaNibO、MgO、NiO、V2O5、CuO、MgcCudO、La2O3、Zr2O3、Ce2O3And Mn2OfIn
At least one；Wherein, 0<a<1、0<b<1st, a+b=1；0<c<1、0<d<1st, c+d=1；The value of f is 2 or 3 or 4 or 7.
7. lithium-sulfur cell as claimed in claim 6, it is characterised in that：It is described using the gross mass of composite positive pole as 100%
The mass percent of metal oxide is not higher than 20%.
8. lithium-sulfur cell as described in claim 1, it is characterised in that：The composite positive pole includes elemental sulfur, polypropylene
Nitrile and Mg0.6Ni0.4O；Elemental sulfur, polyacrylonitrile and Mg in the composite positive pole0.6Ni0.4The mass ratio of O is 4:1:0.3.
9. lithium-sulfur cell as described in claim 1, it is characterised in that：The positive active material further include conductive agent,
LiTFSI and polyethylene oxide；In the positive active material, composite positive pole and conductive agent, LiTFSI and polyethylene oxide
Mass ratio be 55:25:15:5.
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| CN105609767B (en) * | 2016-02-04 | 2017-11-28 | 西安理工大学 | One kind contains additive MgxNi(1‑x)O lithium sulfur battery anode material and preparation method |
| CN109037764A (en) * | 2018-08-29 | 2018-12-18 | 浙江工业大学 | A kind of preparation method of the solid electrolyte of stable lithium an- ode |
| KR102395655B1 (en) * | 2018-10-11 | 2022-05-06 | 주식회사 엘지에너지솔루션 | A solid electrolyte membrane and an all solid type battery comprising the same |
| TWI762238B (en) * | 2021-03-12 | 2022-04-21 | 國立成功大學 | A method for the fabrication of an electroless-metal-plated sulfur nanocomposite, an electroless-metal-plated sulfur cathode which is made from the nanocomposite, and a battery that uses the cathode |
| CN113594540B (en) * | 2021-09-29 | 2021-12-21 | 中南大学 | Composite solid electrolyte and preparation method and application thereof |
| CN114597347A (en) * | 2022-03-15 | 2022-06-07 | 清华大学深圳国际研究生院 | Solid-state lithium-sulfur battery positive electrode and preparation method thereof, and solid-state lithium-sulfur battery and preparation method thereof |
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| CN101183727A (en) * | 2007-12-06 | 2008-05-21 | 哈尔滨工业大学 | All solid state electrolyte and preparing method and application of the same |
| CN101276941A (en) * | 2007-03-29 | 2008-10-01 | Tdk株式会社 | Full solid lithium ion secondary battery and manufacturing method thereof |
| CN102496736A (en) * | 2011-12-27 | 2012-06-13 | 瑞声新能源发展（常州）有限公司 | All-solid-state polymer electrolyte used for lithium-sulfur secondary battery and its preparation method |
| CN102820454A (en) * | 2011-06-11 | 2012-12-12 | 苏州宝时得电动工具有限公司 | Electrode composite material, its preparation method, its anode, and battery possessing anode |
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| CN101183727A (en) * | 2007-12-06 | 2008-05-21 | 哈尔滨工业大学 | All solid state electrolyte and preparing method and application of the same |
| CN102820454A (en) * | 2011-06-11 | 2012-12-12 | 苏州宝时得电动工具有限公司 | Electrode composite material, its preparation method, its anode, and battery possessing anode |
| CN102496736A (en) * | 2011-12-27 | 2012-06-13 | 瑞声新能源发展（常州）有限公司 | All-solid-state polymer electrolyte used for lithium-sulfur secondary battery and its preparation method |
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