CN107845771A - The anode composite and its preparation and chemical cell of a kind of sulphur and manganese dioxide - Google Patents

The anode composite and its preparation and chemical cell of a kind of sulphur and manganese dioxide Download PDF

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CN107845771A
CN107845771A CN201610839013.7A CN201610839013A CN107845771A CN 107845771 A CN107845771 A CN 107845771A CN 201610839013 A CN201610839013 A CN 201610839013A CN 107845771 A CN107845771 A CN 107845771A
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lithium
manganese dioxide
sulphur
active material
anode composite
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张洪章
张华民
李先锋
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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 relates to a kind of sulphur and the anode composite of manganese dioxide, is made up of collector and the coating coated in the collection liquid surface, and the material of the coating is made up of active material, conductive agent and binding agent, and the mass ratio of three is (60~80):(10~20):(1~10)；The active material is made up of sulfur materials and manganese dioxide, and wherein manganese dioxide accounts for the 20%~70% of active material quality, and coating layer thickness is 10~200um, and the face load amount of active material is 1.0~7.0mg/cm2.The chemical cell of sulphur proposed by the present invention/manganese dioxide anode composite assembling improves the discharge voltage of positive pole and discharged than energy, has preparation technology simple, is suitable for large-scale industrial production.

Description

The anode composite and its preparation and chemical cell of a kind of sulphur and manganese dioxide
Technical field
The present invention relates to battery electrode material field, more particularly to a kind of composite positive pole and its preparation and application.
Background technology
Lithium sulphur galvanic cell is the high-energy-density electrochmical power source of more research of receiving much attention and put into recent years.With elemental sulfur It is as follows for the lithium sulphur original battery electrochemistry reaction of positive pole：S8+Li→Li2Sx(1≤x≤8)→Li2S.According to final reduction reaction Product Li2S is calculated, and the theoretical specific capacity of elemental sulfur is 1672mAh/g, and lithium metal has theoretical specific capacity 3860mAh/g, Li/S The theoretical energy density of redox couple is up to 2600Wh/kg, it is seen then that lithium sulphur/manganese dioxide primary battery has energy density height The characteristics of, had a extensive future in special power supply field.
The electric discharge of simple substance sulfur materials is divided into two stages：First stage, the reduction of sulphur, generation dissolubility is preferably middle to produce Thing Li2S4, the kinetics is quick, causes the diffusion of more sulphions；Second stage, smaller more sulphur of generation dissolubility difference Ion, Li2S is deposited, and the kinetics is slower, is blocked positive pole micropore structure, increase polarization, is reduced discharge capacity.This Two processes are controlled by the dissolving kinetics of diffusion of more lithium sulfides, and speed is very slow, causes the big multiplying power discharging of lithium sulphur galvanic cell Can be poor.
The content of the invention
The present invention solves the problems, such as be existing lithium sulphur/manganese dioxide primary battery because kinetic reaction speed is low, cause greatly Current discharge ability；To solve described problem, the present invention provides a kind of sulphur/manganese dioxide anode composite, and preparation method thereof And lithium sulphur/manganese dioxide chemical cell using it as positive pole.
To achieve the above object, the concrete technical scheme that the present invention uses is as follows：
A kind of anode composite of sulphur and manganese dioxide, is made up of collector and the coating coated in the collection liquid surface, The material of the coating is made up of active material, conductive agent and binding agent, and the mass ratio of three is (60~80):(10~ 20):(1~10)；The active material is made up of sulfur materials and manganese dioxide, and wherein manganese dioxide accounts for active material quality 20%~70%, coating layer thickness is 10~200um, and the face load amount of active material is 1.0~7.0mg/cm2。
Sulfur materials uniformly mix with manganese dioxide in active material；Sulfur materials are that elemental sulfur or sulphur carbon are compound in active material One or two or more kinds in material, the sulphur carbon composite are made up of carbon and sulphur, and sulphur accounts for mass ratio as 50%~90%.
Conductive agent is acetylene black, Ketjen black, CNT, graphene, electrically conductive graphite, conductive carbon fibre, the one of electric capacity carbon Kind is two or more；
Binding agent is Kynoar, polytetrafluoroethylene (PTFE), butadiene-styrene rubber, the one or more of cellulose；
Collector is one kind in aluminium foil, carbon coated aluminum foil, corrosive aluminum foil.
(1) sulfur materials, manganese dioxide, conductive agent, binding agent and solvent blending and stirring are formed into suspended slurry, solvent is It is more than one or both of water, ethanol, methanol, isopropanol, ethylene glycol, NMP, DMF, DMAC；Solids content in slurry is 5%~50%；
(2) suspended slurry is coated on collector, and heat drying, form anode composite.
Drying temperature is 60 DEG C~100 DEG C, 2~24 hours drying times.
The chemical cell includes：Any anode composite in lithium anode, claim 1-4, positioned at negative pole and Barrier film between anode composite, electrolyte is filled between negative pole and barrier film and between anode composite and barrier film.
Also include outer cover packaging, described anode composite, lithium anode, barrier film, electrolyte are contained in battery case bag In dress.
Lithium anode is lithium or lithium and silicon, boron, aluminium, the alloy or hybrid metal of copper, and the content of lithium is total not less than negative pole The 70% of content.
Barrier film is perforated membrane, solid electrolyte membrane or the gel electrolyte membrane for allowing lithium ion conduction；
Perforated membrane is with one or both of polyethylene, polypropylene, aramid fiber, nylon, polyimides, cellulose above material Expect the barrier film for material, porosity is between 50%~80%, and aperture is between 10~500nm, and thickness is in 8~50um；
Solid electrolyte film is the barrier film formed with the inorganic lithium ion conductor such as LiPON, LiPS, LiSICON, thickness 10~ 50um；
Gel electrolyte membrane is using polyethylene glycol, polyvinyl alcohol, Kynoar, polymethyl methacrylate as material Gel state barrier film, porosity is between 50%~80%, and aperture is 10~500nm, and thickness is in 8~50um.
Electrolyte is using ether as solvent, using lithium salts as electrolyte solution；
The species of ether is glycol dimethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dioxolanes One or both of more than；It is preferred that glycol dimethyl ether：Dioxolanes=1：1 compound ether；
The species of lithium salts is lithium hexafluoro phosphate, lithium trifluoromethanesulp,onylimide, trifluorosulfonimide lithium, lithium bromide, iodate In lithium, lithium perchlorate, trifluoromethyl sulfonic acid lithium, hexafluoroarsenate lithium, LiBF4, bis trifluoromethyl lithium oxalate, boron lithium oxalate One or more.
Beneficial effects of the present invention are as follows：
The preparation method of sulphur proposed by the present invention/manganese dioxide anode composite, using the titanium dioxide with electro-chemical activity Manganese is as additive, because manganese dioxide has catalytic performance, can accelerate sulphur in the reaction speed of electrode interior, so that high carrying capacity Sulphur positive pole heavy-current discharge；On the other hand, manganese dioxide has electro-chemical activity, does not influence discharge capacity, while improve just Energy is compared in the discharge voltage of pole, the electric discharge for being advantageous to improve lithium sulphur/manganese dioxide primary battery.The preparation technology of the present invention is simple, It is suitable for large-scale industrial production.
Brief description of the drawings
Fig. 1 is the manganese dioxide that the embodiment of the present invention 1 provides:Elemental sulfur=50:50 (mass ratio) composite sulfur positive electrodes Discharge curve first.
Fig. 2 is the manganese dioxide that the embodiment of the present invention 2 provides:Elemental sulfur=70:30 (mass ratio) composite sulfur positive electrodes Discharge curve first.
Fig. 3 is the manganese dioxide that the embodiment of the present invention 3 provides:Elemental sulfur=30:70 (mass ratio) composite sulfur positive electrodes Discharge curve first.
Fig. 4 is the manganese dioxide that the embodiment of the present invention 4 provides:Elemental sulfur=10:90 (mass ratio) composite sulfur positive electrodes Discharge curve first.
Fig. 5 is the manganese dioxide that the embodiment of the present invention 5 provides:Elemental sulfur=50:50 (mass ratio) composite sulfur positive electrodes Flexible package galvanic cell discharge curve first.
Fig. 6 is the manganese dioxide that the embodiment of the present invention 6 provides:Elemental sulfur=50:50 (mass ratio) composite sulfur positive electrodes Flexible package galvanic cell discharge curve first.
The discharge curve first for the elemental sulfur positive electrode that Fig. 7 comparative examples 1 of the present invention provide.
The discharge curve first for the elemental sulfur positive electrode that Fig. 8 comparative examples 2 of the present invention provide.
Embodiment
The embodiment of the present invention is further described with accompanying drawing with reference to embodiments.
Embodiment 1
It is prepared by active material：According to manganese dioxide:Elemental sulfur=50:50 (mass ratioes) weigh respective material, preliminary mixing After be placed in ground and mixed in mortar, prepare the active material of mixing manganese dioxide additive.Sulphur/manganese dioxide anode composite system It is standby：Weigh 0.2g binding agents Kynoar (PVDF) to be dissolved in 1-METHYLPYRROLIDONE (NMP), stirring forms uniformly molten Liquid；Weigh 0.4g conductive agent acetylene blacks to be added in above-mentioned binder solution, be sufficiently stirred to form uniform conductive agent suspension； Then the active material that 1.4g is pre-mixed is added, is sufficiently stirred to form stable slurry suspension.Using scraper by this slurry Coated on corrosive aluminum foil collector, 70 DEG C of dryings 2 hours, until NMP volatilizations are complete.Active material in pole piece after drying:Lead Electric agent:Binding agent=70:20:10.The face load amount for controlling the active material of coating is 7.0mg/cm2。
Lithium sulphur/manganese dioxide button cell assembling test：The sulphur of preparation/manganese dioxide anode composite is punched into Φ 16mm Circular pole piece, dried 24 hours in 70 DEG C of vacuum drying chamber.Under dry air or inert atmosphere conditions, with lithium metal Piece is negative pole, and Tonen V20EHD are barrier film, double (trifluoromethane sulfonic acid acyl group) imine lithium (the LiTFSI)/dioxies penta of 1.5mol/L Ring (DOL) 1,2- dimethoxy-ethanes (DME) (volume ratio 1:1) it is electrolyte, it is former is assembled into CR2016 lithiums sulphur/manganese dioxide Battery.Battery is discharged with the current densities of 500mA/g active materials, and sulfur-bearing/manganese dioxide composite positive pole discharges song first Line is as shown in figure 1, specific discharge capacity is 501mAh/g (relative to gross activity material).
Embodiment 2
It is prepared by active material：According to manganese dioxide:Elemental sulfur=70:30 (mass ratioes) weigh respective material, preliminary mixing After be placed in ground and mixed in mortar, prepare the active material of sulphur mixing manganese dioxide.
It is prepared by sulphur/manganese dioxide anode composite：Weigh 0.1g binding agents Kynoar (PVDF) and be dissolved in N- methyl pyrroles In pyrrolidone (NMP), stirring forms homogeneous solution；Weigh 0.2g conductive agent superconductions carbon black (Super P) and be added to above-mentioned bonding In agent solution, it is sufficiently stirred to form uniform suspension；Then the active material that 0.7g is pre-mixed is added, is sufficiently stirred to be formed Stable slurry suspension.Using scraper by this slurry coated on corrosive aluminum foil collector, 70 DEG C of drying 2 hours, up to NMP Volatilization is complete.Active material in pole piece after drying:Conductive agent:Binding agent=70:20:10.Control coating surface density be 7.0mg/cm2。
The assembling test of lithium sulphur button cell：The sulphur of preparation/manganese dioxide anode composite is punched into Φ 16mm circular pole Piece, dried 24 hours in 70 DEG C of vacuum drying chamber.It is negative using metal lithium sheet under dry air or inert atmosphere conditions Pole, Tonen V20EHD are barrier film, double (trifluoromethane sulfonic acid acyl group) imine lithium (the LiTFSI)/dioxolanes of 1.5mol/L (DOL) 1,2- dimethoxy-ethanes (DME) (volume ratio 1:1) it is electrolyte, is assembled into the former electricity of CR2016 lithiums sulphur/manganese dioxide Pond.Battery is discharged with the current densities of 500mA/g active materials, and discharge curve is such as first for the composite sulfur positive electrode containing additive Shown in Fig. 2, specific discharge capacity is 710mAh/g (relative to gross activity material).
Embodiment 3
It is prepared by active material：According to manganese dioxide:Elemental sulfur=30:70 (mass ratioes) weigh respective material, preliminary mixing After be placed in ground and mixed in mortar, prepare the active material of mixing manganese dioxide additive.
It is prepared by sulphur/manganese dioxide anode composite：Weigh 0.1g binding agents Kynoar (PVDF) and be dissolved in N- methyl pyrroles In pyrrolidone (NMP), stirring forms homogeneous solution；Weigh 0.2g conductive agent superconductions carbon black (Super P) and be added to above-mentioned bonding In agent solution, it is sufficiently stirred to form uniform suspension；Then the active material that 0.7g is pre-mixed is added, is sufficiently stirred to be formed Stable slurry suspension.Using scraper by this slurry coated on corrosive aluminum foil collector, 70 DEG C of drying 2 hours, up to NMP Volatilization is complete.Active material in pole piece after drying:Conductive agent:Binding agent=70:20:10.The surface density for controlling coating is 7mg/ cm2。
The assembling test of lithium sulphur button cell：The sulphur of preparation/manganese dioxide anode composite is punched into Φ 16mm circular pole Piece, dried 24 hours in 70 DEG C of vacuum drying chamber.It is negative using metal lithium sheet under dry air or inert atmosphere conditions Pole, celgard2325 are barrier film, double (trifluoromethane sulfonic acid acyl group) imine lithium (the LiTFSI)/dioxolanes (DOL) of 1.5mol/L 1,2- dimethoxy-ethanes (DME) (volume ratio 1:1) it is electrolyte, is assembled into CR2016 lithiums sulphur/manganese dioxide primary battery.Electricity Pond is discharged with the current densities of 500mA/g active materials, the discharge curve such as Fig. 3 institutes first of the composite sulfur positive electrode containing additive Show, specific discharge capacity is 950mAh/g (relative to gross activity material).
Embodiment 4
It is prepared by active material：According to manganese dioxide:Elemental sulfur=10:90 (mass ratioes) weigh respective material, preliminary mixing After be placed in ground and mixed in mortar, prepare the active material of mixing manganese dioxide additive.
It is prepared by sulphur/manganese dioxide anode composite：Weigh 0.1g binding agents Kynoar (PVDF) and be dissolved in N- methyl pyrroles In pyrrolidone (NMP), stirring forms homogeneous solution；Weigh 0.2g conductive agent superconductions carbon black (Super P) and be added to above-mentioned bonding In agent solution, it is sufficiently stirred to form uniform suspension；Then the active material that 0.7g is pre-mixed is added, is sufficiently stirred to be formed Stable slurry suspension.Using scraper by this slurry coated on corrosive aluminum foil collector, 70 DEG C of drying 2 hours, up to NMP Volatilization is complete.Active material in pole piece after drying:Conductive agent:Binding agent=70:20:10.Control coating surface density be 5.0mg/cm2。
The assembling test of lithium sulphur button cell：The sulphur of preparation/manganese dioxide anode composite is punched into Φ 16mm circular pole Piece, dried 24 hours in 70 DEG C of vacuum drying chamber.It is negative using metal lithium sheet under dry air or inert atmosphere conditions Pole, Tonen V20EHD are barrier film, double (trifluoromethane sulfonic acid acyl group) imine lithium (the LiTFSI)/dioxolanes of 1.5mol/L (DOL) 1,2- dimethoxy-ethanes (DME) (volume ratio 1:1) it is electrolyte, is assembled into the former electricity of CR2016 lithiums sulphur/manganese dioxide Pond.Battery is discharged with the current densities of 500mA/g active materials, and discharge curve is such as first for the composite sulfur positive electrode containing additive Shown in Fig. 4, specific discharge capacity is 1220mAh/g (relative to gross activity material).
Embodiment 5
It is prepared by active material：According to manganese dioxide:Elemental sulfur=50:50 (mass ratioes) weigh respective material, preliminary mixing After be placed in ground and mixed in mortar, prepare the active material of mixing manganese dioxide additive.
It is prepared by sulphur/manganese dioxide anode composite：Weigh 10g binding agents Kynoar (PVDF) and be dissolved in N- methylpyrroles In alkanone (NMP), stirring forms homogeneous solution；Weighing 20g conductive agent superconductions carbon black (Super P), to be added to above-mentioned binding agent molten In liquid, it is sufficiently stirred to form uniform suspension；Then the active material that 70g is pre-mixed is added, is sufficiently stirred to form stabilization Slurry suspension.Using scraper by this slurry coated on corrosive aluminum foil collector, 70 DEG C of drying 2 hours, until NMP volatilizations Completely.Active material in pole piece after drying:Conductive agent:Binding agent=70:20:10.The surface density for controlling coating is 10.0mg/ cm2。
The assembling test of lithium sulphur flexible package galvanic cell：The sulphur of preparation/manganese dioxide anode composite is punched into 50 × 77mm length Square pole piece, dried 24 hours in 70 DEG C of vacuum drying chamber.Under dry air or inert atmosphere conditions, with same size 0.1mm thickness metal lithium bands are negative plate, and Tonen V20EHD are barrier film, and 10g 1.5mol/L double (trifluoromethane sulfonic acid acyl groups) are sub- Amine lithium (LiTFSI)/dioxolanes (DOL)+1,2- dimethoxy-ethanes (DME) (volume ratio 1:1) it is electrolyte, plastic-aluminum is multiple Conjunction film is packaging shell, is assembled into 10Ah lithium sulphur galvanic cells.Battery is discharged with 500mA/g current densities, discharge curve such as Fig. 5 institutes Show.
Embodiment 6
It is prepared by active material：According to manganese dioxide:Sulphur carbon composite=50:50 (mass ratioes) weigh respective material, just It is placed in after step mixing in ball grinder, with 250r/min rotating speed ball milling 12 hours, prepares the activity of mixing manganese dioxide additive Material.
It is prepared by sulphur/manganese dioxide anode composite：Weigh 0.1g binding agents Kynoar (PVDF) and be dissolved in N- methyl pyrroles In pyrrolidone (NMP), stirring forms homogeneous solution；Weigh 0.1g conductive agent superconductions carbon black (Super P) and be added to above-mentioned bonding In agent solution, it is sufficiently stirred to form uniform suspension；Then the active material that 0.8g is pre-mixed is added, is sufficiently stirred to be formed Stable slurry suspension.Using scraper by this slurry coated on corrosive aluminum foil collector, 70 DEG C of drying 2 hours, up to NMP Volatilization is complete.Active material in pole piece after drying:Conductive agent:Binding agent=80:10:10.Control coating surface density be 7.0mg/cm2。
The assembling test of lithium sulphur button cell：The sulphur of preparation/manganese dioxide anode composite is punched into Φ 16mm circular pole Piece, dried 24 hours in 70 DEG C of vacuum drying chamber.It is negative using metal lithium sheet under dry air or inert atmosphere conditions Pole, Tonen V20EHD are barrier film, double (trifluoromethane sulfonic acid acyl group) imine lithium (the LiTFSI)/dioxolanes of 1.5mol/L (DOL) 1,2- dimethoxy-ethanes (DME) (volume ratio 1:1) it is electrolyte, is assembled into the former electricity of CR2016 lithiums sulphur/manganese dioxide Pond.Battery is discharged with the current density of 1000mA/g active materials, and specific discharge capacity is 789mAh/g (relative to gross activity thing Matter), discharge curve is as shown in Figure 6.
Embodiment 7
It is prepared by active material：According to manganese dioxide:Elemental sulfur=50:50 (mass ratioes) weigh respective material, preliminary mixing After be placed in ground and mixed in mortar, prepare the active material of mixing manganese dioxide additive.
It is prepared by sulphur/manganese dioxide anode composite：Weigh 0.1g binding agents Kynoar (PVDF) and be dissolved in N- methyl pyrroles In pyrrolidone (NMP), stirring forms homogeneous solution；Weigh 0.2g conductive agent superconductions carbon black (Super P) and 0.1g conductive agents are led Electric carbon fiber (VGCF) is added in above-mentioned binder solution, is sufficiently stirred to form uniform conductive agent suspension；Then add The active material that 0.6g is pre-mixed, it is sufficiently stirred to form stable slurry suspension.This slurry is covered using scraper In carbon aluminum foil current collector, 70 DEG C of dryings 2 hours, until NMP volatilizations are complete.Active material in pole piece after drying:Conductive agent:Bond Agent=60:30:10.The surface density for controlling coating is 7.0mg/cm2。
The assembling test of lithium sulphur button cell：The sulphur of preparation/manganese dioxide anode composite is punched into Φ 16mm circular pole Piece, dried 24 hours in 70 DEG C of vacuum drying chamber.It is negative using metal lithium sheet under dry air or inert atmosphere conditions Pole, Tonen V20EHD are barrier film, double (trifluoromethane sulfonic acid acyl group) imine lithium (the LiTFSI)/dioxolanes of 1.5mol/L (DOL) 1,2- dimethoxy-ethanes (DME) (volume ratio 1:1) it is electrolyte, is assembled into the former electricity of CR2016 lithiums sulphur/manganese dioxide Pond.Battery is discharged with the current density of 500mA/g active materials, and specific discharge capacity is 800mAh/g (relative to gross activity thing Matter).
Comparative example 1
It is prepared by sulphur positive pole：0.2g binding agents Kynoar (PVDF) is weighed to be dissolved in 1-METHYLPYRROLIDONE (NMP), Stirring forms homogeneous solution；Weigh 0.4g conductive agent superconductions carbon black (Super P) to be added in above-mentioned binder solution, fully stir Mix to form uniform suspension；Then the elemental sulfurs that grind in advance of 1.4g are added, are sufficiently stirred to form stable slurry and hang Turbid.Using scraper by this slurry coated on corrosive aluminum foil collector, 70 DEG C of drying 2 hours, until NMP volatilizations are completely.
Active material in pole piece after drying:Conductive agent:Binding agent=70:20:10.The surface density for controlling coating is 7mg/ cm2.The assembling test of lithium sulphur button cell：The sulphur positive pole of preparation is punched into Φ 16mm circular pole piece, done in 70 DEG C of vacuum Dried 24 hours in dry case.Under dry air or inert atmosphere conditions, using metal lithium sheet as negative pole, Tonen V20EHD be every Film, double (trifluoromethane sulfonic acid acyl group) imine lithium (LiTFSI)/dioxolanes (DOL) 1, the 2- dimethoxy-ethanes of 1.5mol/L (DME) (volume ratio 1:1) it is electrolyte, is assembled into CR2016 lithium-sulfur cells.Battery is close with the electric current of 500mA/g active materials Degree electric discharge, discharge curve is as shown in fig. 7, the specific discharge capacity of sulphur is 1015mAh/g first.
Anode composite surface density with foregoing addition manganese dioxide additive is under the conditions of, because pole piece carrying capacity is too high, The electric discharge polarization of sulphur is very big.
Comparative example 2
It is prepared by sulphur/manganese dioxide anode composite：Weigh 0.2g binding agents Kynoar (PVDF) and be dissolved in N- methyl pyrroles In pyrrolidone (NMP), stirring forms homogeneous solution；Weigh 0.4g conductive agent superconductions carbon black (Super P) and be added to above-mentioned bonding In agent solution, it is sufficiently stirred to form uniform suspension；Then the elemental sulfur that 1.4g is ground in advance is added, is sufficiently stirred shape Into stable slurry suspension.Using scraper by this slurry coated on corrosive aluminum foil collector, 70 DEG C of drying 2 hours, up to NMP volatilizations are complete.Active material in pole piece after drying:Conductive agent:Binding agent=70:20:10.Control coating surface density be 7.0mg/cm2。
The assembling test of lithium sulphur button cell：The sulphur of preparation/manganese dioxide anode composite is punched into Φ 16mm circular pole Piece, dried 24 hours in 70 DEG C of vacuum drying chamber.It is negative using metal lithium sheet under dry air or inert atmosphere conditions Pole, Tonen V20EHD are barrier film, double (trifluoromethane sulfonic acid acyl group) imine lithium (the LiTFSI)/dioxolanes of 1.5mol/L (DOL) 1,2- dimethoxy-ethanes (DME) (volume ratio 1:1) it is electrolyte, is assembled into the former electricity of CR2016 lithiums sulphur/manganese dioxide Pond.Battery is discharged with the current densities of 500mA/g active materials, and discharge curve is such as first for the composite sulfur positive electrode containing additive Shown in Fig. 8, specific discharge capacity is 703mAh/g (relative to gross activity material).As can be seen from Fig. 8, even if surface density is reduced to 3.0mg/cm2, but polarization of discharging is still very big, and discharge capacity is still lower than adding the anode composite pole piece of manganese dioxide additive.
The present invention is prepared multiple by adding the manganese dioxide additive with electro-chemical activity in sulphur positive pole process Sulphur positive pole is closed, improves the electro-chemical activity of high carrying capacity sulphur positive pole, lithium sulphur/manganese dioxide primary battery is improved and discharges compare energy first. Improve lithium sulphur/manganese dioxide primary battery performance.
Although present disclosure is discussed in detail by above preferred embodiment, but it should be appreciated that above-mentioned Description is not considered as limitation of the present invention.After those skilled in the art have read the above, for the present invention's A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims Sulphur/manganese dioxide anode composite, and preparation method thereof and lithium sulphur/manganese dioxide primary battery using it as positive pole.

Claims (10)

1. the anode composite of a kind of sulphur and manganese dioxide, it is made up of collector and the coating coated in the collection liquid surface, its It is characterised by：The material of the coating is made up of active material, conductive agent and binding agent, the mass ratio of three for (60~ 80):(10~20):(1~10)；The active material is made up of sulfur materials and manganese dioxide, and wherein manganese dioxide accounts for active matter The 20%~70% of matter quality, coating layer thickness are 10~200um, active material in collection liquid surface face load amount for 1.0~ 7.0mg/cm2。
2. anode composite as claimed in claim 1, it is characterised in that：Sulfur materials uniformly mix with manganese dioxide in active material Close；Sulfur materials are the one or two or more kinds in elemental sulfur or sulphur carbon composite in active material, the sulphur carbon composite It is made up of carbon and sulphur, sulphur accounts for mass ratio as 50%~90%.
3. anode composite as claimed in claim 1, it is characterised in that：Conductive agent is acetylene black, Ketjen black, CNT, stone Black alkene, electrically conductive graphite, conductive carbon fibre, the one or more of electric capacity carbon；
Binding agent is Kynoar, polytetrafluoroethylene (PTFE), butadiene-styrene rubber, the one or more of cellulose；
Collector is one kind in aluminium foil, carbon coated aluminum foil, corrosive aluminum foil.
A kind of 4. preparation method of the anode composite in claim 1-3 described in any one, it is characterised in that：
(1) sulfur materials, manganese dioxide, conductive agent, binding agent and solvent blending and stirring are formed into suspended slurry, solvent is water, second It is more than one or both of alcohol, methanol, isopropanol, ethylene glycol, NMP, DMF, DMAC；Solid masses content in slurry is 5%~50%；
(2) suspended slurry is coated on collector, and heat drying, form anode composite.
5. preparation method as claimed in claim 4, it is characterised in that drying temperature is 60 DEG C~100 DEG C, drying time 2~ 24 hours.
A kind of 6. chemical cell of the anode composite as positive pole described in any one in 1-3 using claim, it is characterised in that： The chemical cell includes：Any anode composite in lithium anode, claim 1-3, positioned at negative pole and anode composite Between barrier film, be filled with electrolyte between negative pole and barrier film and between anode composite and barrier film.
7. chemical cell as claimed in claim 6, it is characterised in that：Also include the outer cover packaging of inner hollow, described answers Positive pole, lithium anode, barrier film, electrolyte is closed to be contained in battery case packaging.
8. chemical cell as claimed in claim 6, it is characterised in that：Lithium anode is in lithium or lithium and silicon, boron, aluminium, copper One or more kinds of alloys or hybrid metal, the content of lithium is not less than negative pole total content in alloy or hybrid metal 70%.
9. chemical cell as claimed in claim 6, it is characterised in that：Barrier film is perforated membrane, the solid for allowing lithium ion conduction Electrolytic film or gel electrolyte membrane；
Perforated membrane be using one or both of polyethylene, polypropylene, aramid fiber, nylon, polyimides, the cellulose above material as The barrier film of material, porosity is between 50%~80%, and aperture is between 10~500nm, and thickness is in 8~50um；
Solid electrolyte film is one or two kinds of in the barrier film formed with the inorganic lithium ion conductor such as LiPON, LiPS, LiSICON More than, 10~50um of thickness；
Gel electrolyte membrane is with one or two kinds of in polyethylene glycol, polyvinyl alcohol, Kynoar, polymethyl methacrylate It is the gel state barrier film of material above, porosity is between 50%~80%, and aperture is 10~500nm, and thickness is in 8~50um.
10. chemical cell as claimed in claim 6, it is characterised in that：Electrolyte is using ether as solvent, using lithium salts as electrolyte Electrolyte；
The species of ether is in glycol dimethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dioxolanes It is one or more kinds of；Preferred volume ratio glycol dimethyl ether：Dioxolanes=1：1 compound ether；The species of lithium salts is hexafluoro Lithium phosphate, lithium trifluoromethanesulp,onylimide, trifluorosulfonimide lithium, lithium bromide, lithium iodide, lithium perchlorate, trifluoromethane sulfonic acid It is more than one or both of lithium, hexafluoroarsenate lithium, LiBF4, bis trifluoromethyl lithium oxalate, boron lithium oxalate.
CN201610839013.7A 2016-09-21 2016-09-21 The anode composite and its preparation and chemical cell of a kind of sulphur and manganese dioxide Pending CN107845771A (en)

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