CN105789563A - Electrode composite material, preparation method thereof, positive electrode and battery with same - Google Patents

Electrode composite material, preparation method thereof, positive electrode and battery with same Download PDF

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Publication number
CN105789563A
CN105789563A CN201610213843.9A CN201610213843A CN105789563A CN 105789563 A CN105789563 A CN 105789563A CN 201610213843 A CN201610213843 A CN 201610213843A CN 105789563 A CN105789563 A CN 105789563A
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composite material
electrode composite
battery
polyacrylonitrile
mixture
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陈璞
张永光
祖玛贝·贝克诺夫
南朗端
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Positec Power Tools Suzhou Co Ltd
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Positec Power Tools Suzhou Co Ltd
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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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M10/056—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
    • 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
    • H01M4/137—Electrodes based on electro-active polymers
    • 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
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/604—Polymers containing aliphatic main chain polymers
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
    • H—ELECTRICITY
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

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Abstract

The invention relates to an electrode composite material. The electrode composite material contains ABxCyDz, A is selected from at least one of polypyrrole, polyacrylonitrile and a polyacrylonitrile copolymer, B is selected from elemental sulfur, C is selected from carbon-based materials, D is selected from metallic oxide, x is larger than or equal to 1 and is smaller than or equal to 20, y is larger than or equal to 0 and is smaller than 1, and z is larger than or equal to 0 and is smaller than 1. Compared with the prior art, the electrical conductivity of the electrode composite material is obviously improved, the material is evenly scattered and is smaller in size, the electrochemical performance of the electrode composite material can be improved, and meanwhile the electrode composite material has the good cycle life and the high discharge capacity efficiency. The invention further discloses a preparation method of the electrode composite material, a positive electrode applying the electrode composite material and a battery with the positive electrode.

Description

Electrode composite material and preparation method thereof, positive pole, there is the battery of this positive pole
The application is applicant is called electrode composite material and preparation method thereof, positive pole in the name that 2012.02.13 day applies for, have the battery of this positive pole, and application number is the divisional application of the Chinese invention patent application of 201210031792.X.
Technical field
The present invention relates to a kind of electrode composite material.
The preparation method that the invention still further relates to a kind of electrode composite material.
The invention still further relates to a kind of positive pole with this electrode composite material.
The invention still further relates to a kind of battery with this positive pole.
Background technology
In recent years, along with the development of science and technology, the demand of the especially renewable green energy resource of the energy is more and more prominent, and battery is just playing irreplaceable effect as storage and the conversion equipment of energy.Lithium ion battery has significantly high specific energy and energy density per unit volume because of it, has attracted to pay close attention to widely.Low cost, high-energy-density, long circulation life, the secondary cell of environmental protection is the emphasis of current lithium ion battery exploitation.
Current commercial positive electrode is mainly the lithium transition-metal oxide (such as cobalt acid lithium, LiMn2O4) of stratiform or spinel structure and the LiFePO4 etc. of olivine structural.Cobalt acid lithium (LiCoO2) theoretical capacity relatively large, 275mAh/g, but its price is high, has certain toxicity, and exothermal decomposition reactions easily occurs when overcharging this positive electrode, not only make battery capacity be decreased obviously, cell safety is also resulted in threat simultaneously；LiMn2O4 (LiMn2O4) theoretical capacity be 148mAh/g, actual capacity is lower than 130mAh/g, and the stability of this positive electrode is bad, easily caused by lattice deformability in charge and discharge process, causes that cycle efficieny is on the low side；LiFePO4 (LiFePO4) theoretical capacity be 172mAh/g, the poorly conductive of this positive electrode so that the reversible capacity of battery reduces.Above-mentioned conventional anode material for lithium-ion batteries capacity is general not high, all there are some problems simultaneously yet, it is impossible to meet battery exploitation demand.
The theoretical specific capacity of elemental sulfur is 1675mAh/g, and the theoretical specific energy being assembled into battery with lithium metal can reach 2600mAh/g, far above commercial positive electrode at present, becomes the major trend of present battery development.Elemental sulfur and the inorganic sulphide of sulfur-bearing, organic sulfur compound, polymeric organodisulfide, organic polysulfide, polysulfide are extensively concerned as the positive electrode of high power capacity for compound and carbon-sulfur polymer etc., but these materials still exist some problems.
First, the electric conductivity of elemental sulfur and sulfide itself is very poor, need to add substantial amounts of conductive agent to increase its electric conductivity；Secondly, when elemental sulfur is as positive electrode active materials, although the Li of existence when the elementary sulfur that exists on positive pole time fully charged and completely electric discharge2S is insoluble in polarity organic bath, but many lithium sulfides that part discharge and recharge positive pole exists are soluble in polarity organic bath, it addition, the little molecular sulfur compound produced during polymeric organosulfides electric discharge is also soluble in organic bath, affects the cycle performance of battery.Therefore, how to improve the electric conductivity of material, and solve the problems of dissolution of discharge and recharge intermediate product, improve the cycle performance of battery, be the research emphasis of sulfur-bearing positive electrode.
Chinese patent application CN101891930A provides the sulfur-based composite anode material of a kind of carbon nanotubes, elemental sulfur is inlaid in composite, improve battery capacity, but owing to positive electrode have employed this expensive material of CNT, make this battery cost price high, technique is more complicated, is not suitable for industrialization.
Summary of the invention
The present invention provides a kind of high electrode capacity and the good electrode composite material of electrochemical reversibility.
The invention provides a kind of electrode composite material, described electrode composite material contains ABxCyDz, wherein A at least one in polypyrrole, polyacrylonitrile, polyacrylonitrile copolymer；B is selected from elemental sulfur；C is selected from carbon-based material；D is selected from metal-oxide；Wherein, 1≤x≤20,0≤y < 1,0≤z < 1.
Preferably, y=0,0 < z < 1.
Preferably, 0 < y < 1,0 < z < 1.
Preferably, described polyacrylonitrile copolymer is selected from polyacrylonitrile-methylmethacrylate copolymer, at least one in polyacrylonitrile-polypyrrole copolymer.
Preferably, described carbon-based material is selected from section's qin carbon black, acetylene black, activated carbon, SWCN, multi-walled carbon nano-tubes and at least one in Graphene.
Preferably, described metal-oxide is selected from MgaNibO、MgO、NiO、V2O5、CuO、MgcCudO、La2O3、Zr2O3、Ce2O3And Mn2OfIn at least one；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 invention provides the positive pole of a kind of battery, including electrode composite material recited above.
The invention provides a kind of battery, including positive pole, negative pole and be located at the electrolyte between positive pole and negative pole, described positive pole includes plus plate current-collecting body and electrode composite material recited above.
Preferably, described electrolyte is selected from Kynoar, Kynoar-polymethyl methacrylate copolymer, Kynoar-hexafluoropropylene copolymer and the one in Polyethylene Glycol borate polymer.
Preferably, described plus plate current-collecting body one in aluminium foil, nickel foam, stainless (steel) wire.
The preparation method that the invention provides a kind of electrode composite material, described preparation method comprises the steps:
Elemental sulfur is dissolved in the first solvent, obtain the first solution；At least one in polypyrrole, polyacrylonitrile, polyacrylonitrile copolymer is added in the second solvent, obtains the second solution；At least one in metal-oxide, the first solution, the second solution are mixed and carries out ball milling under an inert gas, obtains mixture, by mixture vacuum drying; remove solvent therein; then it is heated processing under protective atmosphere, natural cooling, obtains electrode composite material；Described first solvent is selected from Carbon bisulfide, toluene, the one in liquid hydrocarbon；Described second solvent is selected from the mixture of dimethylformamide, dimethyl propylene amine, dimethyl propylene amine and lithium chloride and the one in dimethyl sulfoxide.
The preparation method that the invention provides a kind of electrode composite material, described preparation method comprises the steps:
Elemental sulfur is dissolved in the first solvent, obtain the first solution, carbon-based material is immersed in the first solution, carry out vacuum drying subsequently, remove solvent therein, obtain the first mixture；By the first mixture; at least one in metal-oxide; at least one in polypyrrole, polyacrylonitrile, polyacrylonitrile copolymer mixes and carries out ball milling under an inert gas; obtain the second mixture; by the second mixture vacuum drying, remove solvent therein, be then heated processing under protective atmosphere; natural cooling, obtains electrode composite material；Described first solvent is selected from Carbon bisulfide, toluene, the one in liquid hydrocarbon.
The preparation method that the invention provides a kind of electrode composite material, described preparation method comprises the steps:
Elemental sulfur is dissolved in the first solvent, obtain the first solution, carbon-based material is immersed in the first solution, carry out vacuum drying subsequently, remove solvent therein, obtain the first mixture；At least one in polypyrrole, polyacrylonitrile, polyacrylonitrile copolymer is added in the second solvent, obtains the second solution；At least one in metal-oxide, the first mixture, the second solution are mixed and carries out ball milling under an inert gas, obtains the second mixture, by the second mixture vacuum drying; remove solvent therein; then it is heated processing under protective atmosphere, natural cooling, obtains electrode composite material；Described first solvent is selected from Carbon bisulfide, toluene, the one in liquid hydrocarbon；Described second solvent is selected from the mixture of dimethylformamide, dimethyl propylene amine, dimethyl propylene amine and lithium chloride and the one in dimethyl sulfoxide.
Preferably, described metal-oxide is MgaNibO, wherein, 0 < a < 1,0 <b < 1, a+b=1.
The preparation method that present invention also offers a kind of electrode composite material, described preparation method comprises the steps:
By elemental sulfur; the at least one at least one and metal-oxide in polypyrrole, polyacrylonitrile, polyacrylonitrile copolymer is added in solvent; obtain the first mixture; first mixture is carried out ball milling mixing; obtain the second mixture; by the second mixture vacuum drying, it is heated subsequently processing under protective atmosphere or vacuum environment, after cooling, obtains electrode composite material.
Preferably, described metal-oxide includes the mixture of MgO and NiO or the mixture of MgO and CuO.
Preferably, the range of speeds of described ball milling is 200-1300 rev/min, and Ball-milling Time ranges for 0.5-12 hour.
Preferably, the temperature of described heat treated range for 150-450 DEG C, heating treatment time ranges for 1-20 hour.
Preferably, described vacuum drying temperature range is 35 DEG C-75 DEG C, and drying time ranges for 3-12 hour.
Preferably, the one in protective atmosphere mixes with hydrogen selected from argon, nitrogen, argon reducing gas and the reducing gas that nitrogen mixes with hydrogen.
A kind of electrode composite material provided by the invention, and the preparation method of this electrode composite material, preparation method combines mechanical attrition method and solwution method, make the various components well-proportioned distribution of energy of electrode active material, additionally, electrode composite material with the addition of the high carbon-based material of electric conductivity and metal-oxide, improve the electric conductivity of the electrode composite material of sulfur-bearing so that the chemical property of electrode composite material is significantly improved.
Accompanying drawing explanation
Below in conjunction with drawings and embodiments, the invention will be further described.
Fig. 1 is elemental sulfur, KB, the X-ray diffracting spectrum of S/KB and S/KB/PAN；
Fig. 2 is the SEM photograph of PAN/S composite；
Fig. 3 is PAN/S/Mg0.4Ni0.6The SEM photograph of O composite；
Fig. 4 is PAN/S/KB/Mg0.4Ni0.6The SEM photograph of O composite；
Fig. 5 is the cyclic voltammetry curve figure of the battery of embodiment 4 and embodiment 5 offer；
Fig. 6 is the battery discharge and recharge collection of illustrative plates with the speed of 0.2C of embodiment 4 offer；
Fig. 7 is the battery discharge and recharge collection of illustrative plates with the speed of 0.2C of embodiment 5 offer；
Fig. 8 is the ac impedance spectroscopy of the battery of embodiment 4 and embodiment 5 offer；
Fig. 9 is the battery schematic diagram with the discharge capacity efficiency of the discharge rate of 0.2C of embodiment 5 offer；
Figure 10 is the battery discharge and recharge collection of illustrative plates with the speed of 0.2C of embodiment 6 offer；
Figure 11 is elemental sulfur, Mg0.4Ni0.6O and PAN/S/KB/Mg0.4Ni0.6The X-ray diffracting spectrum of each material of O；
Figure 12 is the battery collection of illustrative plates with 0.2C speed discharge and recharge of embodiment 9 offer；
Figure 13 is the battery of embodiment 5 and embodiment 9 offer cycle performance under 0.5C and cycle efficieny collection of illustrative plates；
Figure 14 is embodiment 5 and the battery discharge rates-battery capacity relation schematic diagram of embodiment 9 offer；
Figure 15 is the battery discharge and recharge collection of illustrative plates with the speed of 0.2C of embodiment 11 offer；
Figure 16 is the XRD diffracting spectrum of simple substance S, PPy and S/PPy；
Figure 17 is the TEM picture of S/PPy electrode composite material；
Figure 18 is embodiment 2, the cyclic voltammogram of battery in comparative example 1 and 2；
Figure 19 is the battery constant current charge-discharge collection of illustrative plates in embodiment 2；
Figure 20 is the cycle performance of battery schematic diagram in embodiment 2 and comparative example 1；
Figure 21 is the AC impedance spectrogram of the battery in embodiment 2 and comparative example 1.
Detailed description of the invention
A kind of high electrode capacity and the good electrode composite material of electrochemical reversibility.Electrode composite material contains ABxCyDz, A at least one in polypyrrole (Ppy), polyacrylonitrile (PAN), polyacrylonitrile copolymer.B is selected from elemental sulfur (S)；C is selected from carbon-based material；D is selected from metal-oxide；Wherein, 1≤x≤20,0≤y < 1,0≤z < 1.
Polyacrylonitrile copolymer at least one in PAN-methylmethacrylate copolymer, PAN-PPy.PPy is a kind of high conductive polymer, is widely used in electrode face finish and electrode material；PAN occurs pyrolytic reaction to contain the processes such as the cyclisation of cyano group, dehydrogenation, conjugation, crosslinking at 200-300 DEG C, generate the conjugation coalescence pyrroles with electric conductivity, the low temperature pyrogenation performance of PAN is prepare electrode composite material to provide good carrier, and the double properties that PAN-methylmethacrylate copolymer is more combined with PAN and PPy because possessing the construction unit of PAN, PAN-PPy in its structure therefore all can as the carrier of electrode composite material.Meanwhile, A mass content in electrode composite material is less than 20%.Preferably, A is selected from PAN.
Carbon-based material is selected from section's qin carbon black (KB), acetylene black, activated carbon, SWCN, at least one in multi-walled carbon nano-tubes, Graphene.The specific surface that the general general character of carbon-based material is characterized as being is very big, has stronger adsorption function, also has excellent electric conductivity simultaneously, is well suited as conduction adding material.As preferred scheme, C is about 30nm selected from the particle size of KB, KB, and specific surface area has but reached 1400m2/ g, there is superpower absorbability simultaneously, it is possible not only to improve the electric conductivity of material, and in the process preparing composite, the specific surface area big because of it and strong absorbability, that can effectively suppress composite gathers agglomerating phenomenon so that the particle size of electrode composite material is less and is more evenly distributed, decrease the evolving path of lithium ion, also improve the ionic conductivity of material.It addition, the price of KB is also relatively cheap, the cost of the electrode composite material containing KB is relatively low, and has practicality.
Metal-oxide is selected from MgaNibO、MgO、NiO、V2O5、CuO、MgcCudO、La2O3、Zr2O3、Ce2O3And Mn2OfIn at least one；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, D is selected from Mg0.6Ni0.4O, Mg0.6Ni0.4O is possible not only to improve further the electric conductivity of electrode composite material, and can suppress the dissolving of the many lithium sulfides of discharge and recharge intermediate product, improves the utilization rate of elemental sulfur so that the cycle performance of battery is greatly improved.
Although elemental sulfur has considerable theoretical specific capacity, but under room temperature, elemental sulfur is the insulator of electronics and ion, and the lithium-sulfur cell of the elemental sulfur positive pole composition of sulfur content 100% is at room temperature impossible carry out discharge and recharge.Therefore, sulfur electrode must be added to certain electronics and ionic conductor.The electrode composite material of sulfur-bearing in the present invention, it is intended to improve the electric conductivity of sulfur-bearing electrode composite material, make the capacity of electrode and cycle performance improve.
A kind of electrode composite material, electrode composite material contains ABxCyDz, A at least one in polypyrrole (Ppy), polyacrylonitrile (PAN), polyacrylonitrile copolymer.B is selected from elemental sulfur (S)；C is selected from carbon-based material；D is selected from metal-oxide；Wherein, 1≤x≤20, y=0,0 < z < 1.
A kind of electrode composite material, electrode composite material contains ABxCyDz, A at least one in polypyrrole (Ppy), polyacrylonitrile (PAN), polyacrylonitrile copolymer.B is selected from elemental sulfur (S)；C is selected from carbon-based material；D is selected from metal-oxide；Wherein, 1≤x≤20,0 < y < 1,0 < z < 1.
In a particular embodiment, electrode composite material contains the binary electrode composite material PAN/S of PAN, S.
In a preferred embodiment, electrode composite material contains the ternary electrode composite PAN/S/KB of PAN, S, KB.
In preferred embodiment, electrode composite material contains PAN, S, KB, Mg0.6Ni0.4The quaternary electrode composite material PAN/S/KB/Mg of O0.6Ni0.4O。
Electrode composite material recited above can as battery positive electrode active material, and electrode composite material and plus plate current-collecting body constitute the positive pole of a kind of battery in the lump.
A kind of battery, including positive pole, negative pole and be located at the electrolyte between positive pole and negative pole.
Positive pole includes plus plate current-collecting body and positive active material.Positive active material contains above-mentioned electrode composite material, and electrode composite material accounts for the 50-90% of positive active material gross weight, and wherein, positive active material also comprises electrically conductive material and binding agent.In preferred embodiment, the weight proportion of the electrode composite material in positive active material is 80%.
Electrically conductive material is selected from one or more in conducting polymer, activated carbon, Graphene, carbon black, carbon fiber, metallic fiber, metal dust and foil.In preferably embodiment, electrically conductive material comprises KB.
Binding agent is selected from polyethylene oxide, polypropylene oxide, the mixture of polyacrylonitrile, polyimides, polyester, polyethers, fluorinated polymer, the one gathered in divinyl Polyethylene Glycol, polyethyleneglycol diacrylate, glycol dimethacrylates or above-mentioned polymer and derivant.In preferably embodiment, binding agent comprises Kynoar (PVDF).Binding agent accounts for the 1-30% of positive active material gross weight.
Plus plate current-collecting body is selected from the one being but not limited only in nickel foam, aluminium foil or stainless (steel) wire.As preferred scheme, plus plate current-collecting body is nickel foam.
Negative pole is lithium metal or lithium alloy.
Electrolyte at least includes electrolyte lithium salt and mixed organic solvents, and in a particular embodiment, electrolyte is containing lithium hexafluoro phosphate (LiPF6) ethylene carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) mixed solution.
Electrolyte lithium salt can include but are not limited to lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), lithium perchlorate (LiClO4), trifluoromethyl sulfonic acid lithium (LiCF3SO3), bis trifluoromethyl sulfimide lithium (LiN (CF3SO2)2).Electrolyte adds lithium salts and can effectively increase electrolytical ionic conductance.
Electrolytical solvent can be common organic solvent, such as dimethoxy-ethane (DME), ethylene carbonic ether (EC), carbovinate fat (DEC), propylene carbonate (PC), 1,3-dioxolane (DIOX), various ether, glyme, lactone, sulfone, sulfolane or thing mixed above.Such as adopt 1,3-dioxolane (DIOX)；It can also be polymer, such as PVDF, Kynoar-polymethyl methacrylate copolymer (PVDF-PMMA), Kynoar-hexafluoropropylene copolymer (PVDF-HFP), Polyethylene Glycol borate polymer (PEG-borateesters).
Electrolyte is arranged in the battery with the form of gel, is conducive to stoping the seepage of potential battery electrolyte, it is to avoid to environment, also improve the safety of battery simultaneously.The battery that the specific embodiment of the present invention provides, if needing in battery structure to adopt barrier film, barrier film is organic porous material or glass fiber material, and the aperture of barrier film is 0.001-100 micron, and porosity is 20-95%.
In a particular embodiment, by electrode composite material, electrically conductive material KB, binding agent PVDF mixing, add organic solvent as dispersant, prepare anode sizing agent.Adopt any method that can provide substantially homogeneous coat on the whole surface of plus plate current-collecting body, prepared anode active material slurry is deposited on the surface of plus plate current-collecting body.For example, it is possible to by scraper for coating method (doctorblade), coiling pull bar method (wireddrawrod) method, silk screen printing or additive method.By the evaporation under normal pressure or low pressure and ambient temperature or high temperature, it is possible to will remove solvent in anode active material slurry layer, the speed of removal of solvents is preferably and keeps being basically unchanged along pulp surface.Subsequently prepared positive pole is assembled into together with negative pole, electrolyte, barrier film CR2032 button cell.
The preparation method that present invention is disclosed a kind of electrode composite material, preparation method comprises the steps:
Elemental sulfur is dissolved in the first solvent, obtain the first solution；At least one in polypyrrole, polyacrylonitrile, polyacrylonitrile copolymer is added in the second solvent, obtains the second solution；At least one in metal-oxide, the first solution, the second solution are mixed and carries out ball milling under an inert gas, obtains mixture, by mixture vacuum drying; remove solvent therein; then it is heated processing under protective atmosphere, natural cooling, obtains electrode composite material；First solvent is selected from Carbon bisulfide, toluene, the one in liquid hydrocarbon；Second solvent is selected from the mixture of dimethylformamide, dimethyl propylene amine, dimethyl propylene amine and lithium chloride and the one in dimethyl sulfoxide.
By mechanical milling process, making at least one in metal-oxide, the first solution, the second solution be mixed to get more uniform, concrete, the range of speeds of mechanical milling process is 200-1300 rev/min, and Ball-milling Time ranges for 1-20 hour.Mechanical milling process is to carry out under an inert gas, is in order to avoid there is other side reaction in mechanical milling process thus material is produced impact.
Preferably, metal-oxide includes MgaNibO, wherein, 0 < a < 1,0 <b < 1, a+b=1.In a specific embodiment, metal-oxide is Mg0.6Ni0.4O。
The mixture obtained by ball milling carries out vacuum drying treatment, concrete, and vacuum drying temperature range is 35-75 DEG C, and drying time ranges for 3-12 hour.
It is heated dried mixture further processing; concrete; the temperature range of heat treated is 150-450 DEG C, and heating treatment time ranges for 1-20 hour, reducing gas that protective atmosphere mixes with hydrogen selected from argon, nitrogen or argon and the reducing gas that nitrogen mixes with hydrogen.
Specific to, in this preparation method, elemental sulfur being dissolved in organic solvent Carbon bisulfide (CS2) in, obtain the CS of sulfur-bearing2Solution, is dissolved in PAN and obtains the DMF solution containing PAN in organic solvent dimethylformamide (DMF), then by the CS of sulfur-bearing2Solution, containing the DMF solution of PAN, Mg0.6Ni0.4O is mixed together and carries out mechanical ball milling under argon shield, ball milling is prepared thing and carries out vacuum drying, remove solvent therein, is then heated under a nitrogen processing, natural cooling, obtains electrode composite material.
The preparation method that present invention further teaches a kind of electrode composite material, preparation method comprises the steps:
Elemental sulfur is dissolved in the first solvent, obtain the first solution, carbon-based material is immersed in the first solution, carry out vacuum drying subsequently, remove solvent therein, obtain the first mixture；By the first mixture; at least one in metal-oxide; at least one in polypyrrole, polyacrylonitrile, polyacrylonitrile copolymer mixes and carries out ball milling under an inert gas; obtain the second mixture; by the second mixture vacuum drying, remove solvent therein, be then heated processing under protective atmosphere; natural cooling, obtains electrode composite material；First solvent is selected from Carbon bisulfide, toluene, the one in liquid hydrocarbon.
By mechanical milling process, make the first mixture, at least one in metal-oxide, at least one in polypyrrole, polyacrylonitrile, polyacrylonitrile copolymer is mixed to get more uniform, concrete, the range of speeds of mechanical milling process is 200-1300 rev/min, and Ball-milling Time ranges for 1-20 hour.Mechanical milling process is to carry out under an inert gas, is in order to avoid there is other side reaction in mechanical milling process thus material is produced impact.
Preferably, metal-oxide includes MgaNibO, wherein, 0 < a < 1,0 <b < 1, a+b=1.In a specific embodiment, metal-oxide is Mg0.6Ni0.4O。
The second mixture obtained by ball milling carries out vacuum drying treatment, concrete, and vacuum drying temperature range is 35-75 DEG C, and drying time ranges for 3-12 hour.
It is heated dried second mixture further processing; concrete; the temperature range of heat treated is 150-450 DEG C, and heating treatment time ranges for 1-20 hour, reducing gas that protective atmosphere mixes with hydrogen selected from argon, nitrogen or argon and the reducing gas that nitrogen mixes with hydrogen.
Specific to, in this preparation method, elemental sulfur being dissolved in organic solvent CS2In, obtain the CS of sulfur-bearing2Solution, is immersed in the CS of sulfur-bearing by KB2In solution, carry out vacuum drying subsequently and remove solvent C S2Obtain the first mixture；Then by the first mixture, PAN, Mg0.6Ni0.4O is mixed to be incorporated under argon shield and carries out mechanical ball milling, ball milling is prepared thing and carries out vacuum drying, remove solvent therein, is then heated under a nitrogen processing, natural cooling, obtains electrode composite material.
The preparation method that present invention further teaches a kind of electrode composite material, preparation method comprises the steps:
Elemental sulfur is dissolved in the first solvent, obtain the first solution, carbon-based material is immersed in the first solution, carry out vacuum drying subsequently, remove solvent therein, obtain the first mixture；At least one in polypyrrole, polyacrylonitrile, polyacrylonitrile copolymer is added in the second solvent, obtains the second solution；At least one, the first mixture, the second solution in metal-oxide are mixed and carries out ball milling under an inert gas, obtains the second mixture, by the second mixture vacuum drying; remove solvent therein; then it is heated processing under protective atmosphere, natural cooling, obtains electrode composite material.First solvent is selected from Carbon bisulfide, toluene, the one in liquid hydrocarbon；Second solvent is selected from the mixture of dimethylformamide, dimethyl propylene amine, dimethyl propylene amine and lithium chloride and the one in dimethyl sulfoxide.
By mechanical milling process, making at least one in metal-oxide, the first mixture, the second solution be mixed to get more uniform, concrete, the range of speeds of mechanical milling process is 200-1300 rev/min, and Ball-milling Time ranges for 1-20 hour.Mechanical milling process is to carry out under an inert gas, is in order to avoid there is other side reaction in mechanical milling process thus material is produced impact.
Preferably, metal-oxide includes MgaNibO, wherein, 0 < a < 1,0 <b < 1, a+b=1.In a specific embodiment, metal-oxide is Mg0.6Ni0.4O。
The second mixture obtained by ball milling carries out vacuum drying treatment, concrete, and vacuum drying temperature range is 35-75 DEG C, and drying time ranges for 3-12 hour.
It is heated dried second mixture further processing; concrete; the temperature range of heat treated is 150-450 DEG C, and heating treatment time ranges for 1-20 hour, reducing gas that protective atmosphere mixes with hydrogen selected from argon, nitrogen or argon and the reducing gas that nitrogen mixes with hydrogen.
Specific to, in this preparation method, elemental sulfur being dissolved in organic solvent CS2In, obtain the CS of sulfur-bearing2Solution, is immersed in the CS of sulfur-bearing by KB2In solution, carry out vacuum drying subsequently and remove solvent C S2Obtain the first mixture；PAN is dissolved in DMF and obtains the DMF solution containing PAN, then by the first mixture, containing the DMF solution of PAN, Mg0.6Ni0.4O is mixed to be incorporated under argon shield and carries out mechanical ball milling, ball milling is prepared thing and carries out vacuum drying, remove solvent therein, is then heated processing under protective atmosphere, natural cooling, obtains electrode composite material.
The preparation method that present invention further teaches a kind of electrode composite material, preparation method comprises the steps:
By elemental sulfur; the at least one at least one and metal-oxide in polypyrrole, polyacrylonitrile, polyacrylonitrile copolymer is added in solvent; obtain the first mixture; first mixture is carried out ball milling mixing; obtain the second mixture; by the second mixture vacuum drying, it is heated subsequently processing under protective atmosphere or vacuum environment, after cooling, obtains electrode composite material.
Preferably, the weight percentage ranges of elemental sulfur is 60-95%, and at least one weight percentage ranges in polypyrrole, polyacrylonitrile, polyacrylonitrile copolymer is 2-40%, and at least one weight percentage ranges in metal-oxide is 0-20%.Solvent includes but are not limited to the one in ethanol, N-Methyl pyrrolidone.
In a specific embodiment, metal-oxide includes Mg0.6Ni0.4O or Mg0.8Cu0.2O.Preferably, metal-oxide includes the mixture of MgO and NiO or the mixture of MgO and CuO.
Concrete, the range of speeds of mechanical milling process is 200-1300 rev/min, and Ball-milling Time ranges for 1-20 hour.
During vacuum drying treatment, vacuum drying temperature range is 35-75 DEG C, and drying time ranges for 3-12 hour.In a specific embodiment, mixture vacuum drying 3 hours at 50 DEG C prepared by mechanical ball milling.
During heat treated, the temperature of heat treated range for 150-450 DEG C, heating treatment time is not less than 1 hour.Preferably, the temperature of heat treated range for 250-400 DEG C, the time range of heat treated is 1-20 hour.Heat treated carries out under protective atmosphere or vacuum environment, concrete, and protective atmosphere is selected from argon or nitrogen.
Specific in this preparation method, by elemental sulfur, PAN and Mg0.6Ni0.4O dissolves in and obtains the first mixture in ethanol, and ethanol makes elemental sulfur, PAN and Mg as dispersant0.6Ni0.4O is mixed to get more uniform.First mixture is carried out ball-milling treatment, obtains the second mixture, by the second mixture in vacuum drying oven dry, subsequently at 300 DEG C, heat treated 3h under argon shield, after cooling, obtain electrode composite material PAN/S/Mg0.6Ni0.4O。
The preparation method of electrode composite material provided by the invention combines solwution method, mechanical attrition method, dried and heat treated, make electrode composite material each component can evenly, smaller dispersion, each component of the electrode composite material obtained by this preparation method can dispersion evenly, the particle size of electrode composite material is also less simultaneously.
Below by embodiment, the present invention is further described.
Embodiment 1
The elemental sulfur of 4g is dissolved in 30cm3Carbon bisulfide (CS2) in, polyacrylonitrile (PAN) is dissolved in dimethylformamide (DMF), subsequently two kinds of solution are mixed, vacuum drying 3 hours at 65 DEG C, to remove solvent therein, then put in tube furnace by product, heat under argon gas to 350 DEG C to be incubated and within 3 hours, be heated processing, make sulfur fusing and react with polyacrylonitrile, last natural cooling, obtaining binary electrode composite material S/PAN.In preparation process, the content of the binary electrode composite material S/PAN before heat treated is than for S:PAN=4:1.
Fig. 1 is the X-ray diffracting spectrum of elemental sulfur, KB and the composite being prepared gained by Mechanical Method and solwution method.As can be seen from Figure: in S/KB and PAN/S/KB, the characteristic peak of sulfur disappears, sublimed sulfur can precipitate the sulfur solid forming highly crystalline when being cooled to room temperature, this phenomenon illustrates in the micropore that elemental sulfur can penetrate into carbon back grid-gap that polyacrylonitrile formed and material in the molten state, simultaneously also can subparticipation binding reaction, form sulfenyl composite.It addition, S-containing composite is weighed before and after heat treated, the loss amount of sulfur is probably 10%.
Fig. 2 is the microscopic appearance of the S/PAN composite obtained by sem observation.As can be seen from Figure: binary composite S/PAN can penetrate in the micropore of carbon back grid-gap that polyacrylonitrile formed and material due to elemental sulfur in the molten state, simultaneously also can subparticipation binding reaction, form sulfenyl composite, material structure surface smoother.
Embodiment 2
The elemental sulfur of 4g is dissolved in 30cm3CS2In, PAN is dissolved in DMF, subsequently by the CS containing elemental sulfur2Solution, DMF solution containing PAN and Mg0.6Ni0.4O mixes and puts into ball mill and carries out ball milling; the rotating speed of ball mill is 800 revs/min; Ball-milling Time is 2 hours; prepare thing vacuum drying 3 hours at 65 DEG C subsequently; to remove solvent therein; then by desciccate at argon shield, heat treated 3 hours, last natural cooling at 350 DEG C, obtain ternary electrode composite PAN/S/Mg0.4Ni0.6O.In preparation process, PAN/S/Mg before heat treated0.4Ni0.6The content of O is than for S:PAN:Mg0.4Ni0.6O=4:1:0.3.
That Fig. 3 represents is the PAN/S/Mg arrived by sem observation0.4Ni0.6The microscopic appearance of O composite.As can be seen from Figure: PAN/S/Mg0.4Ni0.6Very big difference, PAN/S/Mg is there is in O and S/PAN on microscopic appearance0.4Ni0.6O body structure surface is relatively rough, and is formed by substantial amounts of nano-particle agglomeration, i.e. PAN/S/Mg0.4Ni0.6The available reactivity area of O material surface increases, and is namely the activity increase of material.It addition, binary is likely due to the addition of Mg in binary electrode composite material to the change of ternary electrode composite microscopic appearance0.4Ni0.6After O, material structure surface defines Mg0.4Ni0.6O surface layer, surface layer can make material surface more stable, and therefore, the chemical property of ternary electrode composite is improved.
Embodiment 3
The elemental sulfur of 4g is dissolved in 30cm3CS2In, KB is immersed in this solution simultaneously, carries out vacuum drying subsequently, remove solvent C S2, obtain the mixture of S/KB；PAN is dissolved in DMF, by the mixture of S/KB, DMF solution containing PAN and Mg0.6Ni0.4O mixes and puts into ball mill and carries out ball milling; the rotating speed of ball mill is 800 revs/min; Ball-milling Time is 2 hours; prepare thing vacuum drying 3 hours at 65 DEG C subsequently; to remove solvent therein; then by product in argon shield, heat treated 3 hours at 350 DEG C, and natural cooling, obtain quaternary electrode composite material PAN/S/KB/Mg0.4Ni0.6O.In experiment, PAN/S/KB/Mg before heat treated0.4Ni0.6The content of O is than for S:PAN:KB:Mg0.4Ni0.6O=4:1:0.25:0.25.
Fig. 4 is the PAN/S/KB/Mg arrived by sem observation0.4Ni0.6The micro-structure diagram of O.Adding KB in positive electrode and can not only increase the electric conductivity of positive electrode, that can also suppress positive electrode in mechanical milling process gathers agglomerating phenomenon simultaneously.From figure 5 it can be seen that relative to ternary electrode composite, greatly suppress the reunion of material in quaternary electrode composite material owing to adding KB, the particle size of quaternary electrode composite material is less and uniform.Therefore, in ternary electrode composite add KB, be possible not only to improve further the electron conduction of material, simultaneously because reduce lithium ion in smaller positive-active nano material the evolving path thus improve the ionic conductance of material.
Embodiment 4
Binary electrode composite material PAN/S, binding agent PVDF, electrically conductive material KB are mixed with the mass ratio of 8:1:1, add N-Methyl pyrrolidone as solvent, the slurry obtained is coated on nickel foam collector by scraper for coating technology, vacuum drying 24 hours at 50 DEG C, subsequently prepared material is prepared positive plate at tablet machine lower sheeting, with lithium metal for negative pole, porous polypropylene is barrier film, 1mol/L lithium hexafluoro phosphate (LiPF6) ethylene carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) (volume ratio 1:1:1) mixed solution be electrolyte, in the glove box of full argon, it is assembled into CR2032 button cell, under room temperature, carries out battery performance test.
Embodiment 5
By ternary electrode composite PAN/S/Mg0.6Ni0.4O, binding agent PVDF, electrically conductive material KB mix according to the mass ratio of 8:1:1, add N-Methyl pyrrolidone as solvent, the slurry obtained is coated on nickel foam collector by scraper for coating technology, vacuum drying 24 hours at 50 DEG C, positive plate is prepared at tablet machine lower sheeting, with lithium metal for negative pole, porous polypropylene is barrier film, 1mol/LLiPF6The mixed solution of EC, DMC and DEC (volume ratio 1:1:1) be electrolyte, in the glove box of full argon, be assembled into CR2032 button cell.
Fig. 5 is the cyclic voltammetry curve figure of the battery of embodiment 4 and embodiment 5 offer.Relatively S/PAN and PAN/S/Mg0.6Ni0.4The oxidoreduction peak of O, it is evident that with the addition of Mg in positive electrode0.6Ni0.4O can improve the chemical property of positive electrode；In cyclic voltammetry curve, PAN/S/Mg0.6Ni0.4O has two reduction peak separated and a sharper oxidation peak, and reduction peak and the oxidation peak of corresponding S/PAN are then more weak and wider.
Fig. 6 and Fig. 7 is the battery discharge and recharge collection of illustrative plates with the speed of 0.2C of embodiment 4 and embodiment 5 offer respectively, as can be seen from the figure: add Mg in positive electrode0.6Ni0.4O mono-aspect can improve battery electrode kinetics, can reduce polarization on the other hand, and the positive pole sulfur active material that these effects adopt electric conductivity poor for positive pole is highly beneficial, adds Mg in the positive electrode active materials of sulfur-bearing0.6Ni0.4O is possible not only to improve the capacity of battery can also improve the energy density of battery.Additionally, PAN/S/Mg0.6Ni0.4The voltage platform of O to be put down relative to S/PAN, and the voltage difference of discharge and recharge simultaneously also decreases, and this phenomenon illustrates PAN/S/Mg0.6Ni0.4The chemical property of O is improved.First week discharge capacity of battery that embodiment 5 provides has reached 650mAhg-1, the reversible capacity of second week is 540mAhg-1。
Fig. 8 is the ac impedance spectroscopy of the battery of embodiment 4 and embodiment 5 offer, it can be seen that PAN/S/Mg0.6Ni0.4The O impedance than S/PAN is substantially little.
Fig. 9 is the battery schematic diagram with the discharge capacity efficiency of the discharge rate of 0.2C of embodiment 5 offer.After 450 weeks, the discharge capacity efficiency of battery still has 80%.
Embodiment 6
In embodiment 6, plus plate current-collecting body adopts aluminium foil, and all the other batteries constitute the same with embodiment 5 with assemble method.
Figure 10 is the battery discharge and recharge collection of illustrative plates with the speed of 0.2C of embodiment 6 offer, and as can be seen from the figure: the voltage platform of discharge and recharge to be put down relative to Fig. 7, the voltage difference of discharge and recharge simultaneously also decreases, same, PAN/S/Mg0.6Ni0.4The chemical property of O is improved.
Embodiment 7
In embodiment 7, battery electrolyte is permeate the 1mol/LLiPF at polymer P VDF-HFP6The mixed solution of EC, DMC and DEC (volume ratio 1:1:1), all the other batteries constitute the same with embodiment 5 with assemble method.
Embodiment 8
In embodiment 8, battery electrolyte is permeate the 1mol/LLiPF in Polyethylene Glycol borate polymer6The mixed solution of EC, DMC and DEC (volume ratio 1:1:1), all the other batteries constitute the same with embodiment 5 with assemble method.
Embodiment 9
By quaternary electrode composite material PAN/S/KB/Mg0.6Ni0.4O, binding agent PVDF, electrically conductive material KB mix with the mass ratio of 8:1:1, add N-Methyl pyrrolidone as solvent, the slurry obtained is coated on nickel foam collector by scraper for coating technology, vacuum drying 24 hours at 50 DEG C, positive plate is prepared at tablet machine lower sheeting, with lithium metal for negative pole, porous polypropylene is barrier film, 1mol/LLiPF6The mixed solution of EC, DMC and DEC (volume ratio 1:1:1) be electrolyte, in the glove box of full argon, be assembled into CR2032 button cell.
Figure 11 is elemental sulfur, Mg0.6Ni0.4O、PAN/S/KB/Mg0.6Ni0.4The X-ray diffracting spectrum of O.As can be seen from Figure: PAN/S/KB/Mg0.6Ni0.4Mg in the X-ray diffracting spectrum of O0.6Ni0.4The characteristic peak of O still exists, and Mg is described0.6Ni0.4O is present in quaternary electrode composite material, and the change of essence does not occur its structure simultaneously.
Figure 12 is the battery collection of illustrative plates with 0.2C speed discharge and recharge of embodiment 9 offer, and as can be seen from the figure the voltage platform of battery is more flat relative to Fig. 7, and the voltage difference of discharge and recharge is also little, with the addition of KB and Mg0.6Ni0.4O quaternary electrode composite material, on the one hand Mg0.6Ni0.4O can improve battery electrode electric conductivity, reduce electrode polarization, KB also improves the electric conductivity of material and stops material to gather agglomerating in the preparation on the other hand, makes the sized particles of electrode composite material be greatly reduced, shortens the lithium ion the evolving path at positive pole, makes battery charge faster.
Figure 13 is the battery of embodiment 5 and embodiment 9 offer cycle performance under 0.5C and cycle efficieny collection of illustrative plates.As can be seen from the figure: the cycle efficieny of both materials is all very good, but with the addition of the PAN/S/KB/Mg of KB0.6Ni0.4The discharge capacity of O is than PAN/S/Mg0.6Ni0.4O wants height.
Figure 14 is embodiment 5 and the battery discharge rates-battery capacity relation schematic diagram of embodiment 9 offer.As can be seen from the figure: under identical discharge rate, PAN/S/KB/Mg0.6Ni0.4The discharge capacity of O is all higher than PAN/S/Mg0.6Ni0.4The discharge capacity of O, illustrates at PAN/S/Mg0.6Ni0.4Add KB in O the chemical property of electrode composite material is significantly improved.It addition, PAN/S/KB/Mg0.6Ni0.4Discharge capacity stable for O can maintain 410mAh/g under 0.5C, relative to PAN/S/Mg0.6Ni0.4The stable discharging capacity of O is 320mAh/g, and meanwhile, quaternary electrode material cycle efficieny after 40 weeks is 100%.
Embodiment 10
Similar with embodiment 9, battery constitutes identical with assemble method.But, in this programme, plus plate current-collecting body adopts aluminium foil.
Embodiment 11
In embodiment 11, battery electrolyte is permeate the 1mol/LLiPF at polymer P VDF-HFP6The mixed solution of EC, DMC and DEC (volume ratio 1:1:1), all the other batteries constitute the same with embodiment 9 with assemble method.
Figure 15 is the battery discharge and recharge collection of illustrative plates with the speed of 0.2C of embodiment 11 offer.As can be seen from the figure: the discharge capacity of the cell attenuation ratio after second week is relatively slow, and discharge capacity was also gone up to some extent when the 20th week simultaneously.
Embodiment 12
In embodiment 12, battery electrolyte is permeate the 1mol/LLiPF in Polyethylene Glycol borate polymer6The mixed solution of EC, DMC and DEC (volume ratio 1:1:1), all the other batteries constitute the same with embodiment 9 with assemble method.
Embodiment 13
By elemental sulfur, PAN and Mg0.6Ni0.4O is by weight S:PAN:Mg0.6Ni0.4O=4:1:0.25 ball milling mixing 5h, using ethanol as dispersant.By prepared mixture dry 3h at 50 DEG C in vacuum drying oven, subsequently under argon shield, 300 DEG C of heat treated 3h, prepare ternary electrode composite PAN/S/Mg0.6Ni0.4O。
By PAN/S/Mg0.6Ni0.4O, binding agent PVDF, electrically conductive material KB mix with the mass ratio of 8:1:1, add NMP as solvent, prepared slurry is coated on nickel foam collector by scraper for coating technology, vacuum drying 12 hours at 50 DEG C, positive plate is prepared at tablet machine lower sheeting, with lithium metal for negative pole, porous polypropylene is barrier film, 1mol/LLiPF6The mixed solution of EC, DMC and DEC (volume ratio 1:1:1) be electrolyte, in the glove box of full argon, be assembled into CR2032 button cell.
Embodiment 14
Embodiment 14 adopts Mg0.8Cu0.2O substitutes Mg0.6Ni0.4O, prepares ternary electrode composite PAN/S/Mg0.8Cu0.2O, and prepare positive pole and contain PAN/S/Mg0.8Cu0.2The CR2032 button cell of O, battery preparation method and other materials are with embodiment 13.
Embodiment 15
Embodiment 15 adopts the mixture replacing Mg of MgO and NiO0.6Ni0.4O, the weight ratio preparing ternary electrode composite PAN/S/MgO+NiO, MgO and NiO is 6:4, and prepares the CR2032 button cell that positive pole contains PAN/S/MgO+NiO, battery preparation method and other materials with embodiment 13.
Embodiment 16
Embodiment 16 adopts the mixture replacing Mg of MgO and CuO0.6Ni0.4O, the weight ratio preparing ternary electrode composite PAN/S/MgO+CuO, MgO and CuO is 8:2, and prepares the CR2032 button cell that positive pole contains PAN/S/MgO+CuO, battery preparation method and other materials with embodiment 13.
Embodiment 17
Embodiment 17 adopt MgO substitute Mg0.6Ni0.4O, prepares ternary electrode composite PAN/S/MgO, and prepares the CR2032 button cell that positive pole contains PAN/S/MgO, battery preparation method and other materials with embodiment 13.
Embodiment 18
Embodiment 18 adopt NiO substitute Mg0.6Ni0.4O, prepares ternary electrode composite PAN/S/NiO, and prepares the CR2032 button cell that positive pole contains PAN/S/NiO, battery preparation method and other materials with embodiment 13.
Embodiment 19
Embodiment 19 adopts the mixture replacing Mg of CuO0.6Ni0.4O, prepares ternary electrode composite PAN/S/CuO, and prepares the CR2032 button cell that positive pole contains PAN/S/CuO, battery preparation method and other materials with embodiment 13.
Battery performance test in embodiment 13-19
By after prepared battery standing a period of time under room temperature, battery being carried out constant current charge-discharge, charge-discharge magnification is 0.2C (1C=1672mAhg-1), voltage range is 1-3V.Specific capacity and the electric current density of battery is calculated based on the content of S in positive electrode.The chemical property that battery charging and discharging circulates 35 times is as shown in table 1:
Battery charging and discharging in embodiment 13-19 circulates the coulombic efficiency after 35 times all close to 100%, and the battery performance in embodiment 13 is all put up the best performance in discharge capacity with discharge capacitance two.Battery in embodiment 14-17 shows suitable chemical property, illustrates that metal-oxide MgO is the additive mainly making cycle performance of battery improve, and compared to the battery in embodiment 17-19, the chemical property of the battery in embodiment 17 is best.The performance of the battery that embodiment 13 and embodiment 15, embodiment 14 and embodiment 16 provide is suitable, and the same Mg of performance of the additive metal oxide being mixed to get by MgO and NiO is described0.6Ni0.4O is suitable, the same Mg of performance of the additive metal oxide being mixed to get by MgO and CuO0.8Cu0.2O is suitable, but, the preparation technique containing MgO and NiO metal mixture or the positive pole of MgO and CuO metal mixture is relatively prepared containing Mg0.6Ni0.4O、Mg0.8Cu0.2The positive pole of O is simple, easy more economically.
Table 1
Embodiment 20
The cetyl trimethyl ammonium (CTAB) of 12.4g is dissolved in the deionized water of 0.75L, and adds the pyrrole monomer of 0.015L, stir 3h.Subsequently, add 0.045L dissolved with the aqueous solution of 5.1g Ammonium persulfate. to it, as oxidant, come initiated polymerization, solution continuous stirring 24h.All building-up processes all carry out at 0-5 DEG C, the precipitate of final PPy pass through isolated by filtration, fully washed by deionized water, ethanol, and at 70 DEG C vacuum drying 12h.Being mixed according to weight ratio PPy:S=1:2 with elemental sulfur by PPy, ball milling mixing 3h, rotating speed is 600rpm, prepares electrode composite material S/PPy.
Figure 16 is the XRD diffracting spectrum of simple substance S, PPy and S/PPy.As can be seen from the figure: PPy is unbodied.Compared to elemental sulfur, S/PPy occurring in that, the spike of S and peak die down by force.And not observing the phenomenon that peak migrates in figure, it was shown that ball milling does not cause phase transformation, the crystal structure of S still exists in S/PPy.But, in S/PPy, the characteristic peak of S dies down and shows in ball milling, temperature is raised owing to ball milling produces heat and is higher than the fusing point of sulfur, and the sulfur of partial melting state is absorbed by the PPy of loose structure.Further, show that in S/PPy, the content of S is about 65wt%, does not namely result in the loss of elemental sulfur by this preparation method by chemical analysis results.
Figure 17 is the TEM picture of S/PPy electrode composite material, and as can be seen from the figure S/PPy complex is dendritic morphology.
The specific surface area preparing the PPy of gained is 129.8m2g-1, the volume in hole is 0.55cm3g-1, after mixing with S, the specific surface area of S/PPy is only 4.4m2g-1, the volume in hole is 0.052cm3g-1.S/PPy complex specific surface area and hole dimension substantially reduce and show that substantial amounts of sulfur is deposited in the hole of PPy and surface.Uniform deposition S is contained on the S/PPy surface of preparation can improve the electric conductivity of positive pole complex, the capacity of the raising of electric conductivity utilization rate and positive pole sulfur for improving sulfur significantly.Additionally, the S/PPy with dendritic nano-structure can well adapt to the change of volume in charge and discharge process and improve the cycle performance of positive electrode.
In positive electrode, the S containing high level is advantageous for for the battery of structure high-energy-density.Preparation S/PPy process excludes heat treatment step, not only saves the energy, simplify preparation method, loss when simultaneously heat treated sulfur can also be avoided to distil.Furthermore it is also possible to avoid producing poisonous, volatile sulfide under the high temperature conditions.Accordingly, with respect to the method for conventional multi-step process and the sulfenyl material of high-temperature technology preparation conduction, the preparation method provided in the present invention is more simply desirable.
Embodiment 21
The chemical property of S/PPy is studied by the CR2032 button cell containing electrode composite material S/PPy by assembling positive pole.
By S/PPy, binding agent PVDF and conductive agent AB according to weight ratio 8:1:1 mixing in N-Methyl pyrrolidone (NMP), it is on the circular nickel foil of 1cm that the anode sizing agent of gained is laid in diameter, 60 DEG C of vacuum drying 12h.In order to make contact between positive electrode active materials and nickel foil good, positive pole is carried out tabletting process.By weighing accurately, suppress and controlling so that the weight of the electrode prepared is identical with thickness.Battery cathode is lithium metal, and barrier film is the porous polypropylene of the tetraethyleneglycol dimethyl ether solution of the double; two trifluoromethanesulfonimide lithiums (LiTFSI) being impregnated with 1M.Full high purity argon glove box assembles button cell.
Way of contrast 1
According to weight ratio S:AB:PVDF=6:3:1, S, binding agent PVDF and conductive agent AB are mixed with positive pole, and all the other compositions of battery are with embodiment 21.
Way of contrast 2
According to weight ratio PPy:AB:PVDF=6:3:1, PPy, binding agent PVDF and conductive agent AB are mixed with positive pole, and all the other compositions of battery are with embodiment 21.
By embodiment 21, the battery provided in way of contrast 1 and 2 carries out electrochemical property test.
Under constant current, battery is carried out charge-discharge test, electric current density 100mAg-1, voltage range 1-3V.Actual electric current and specific capacity is calculated in reference count for the content of S in positive pole.
Use permanent potential instrument (VMP3, Biologic) that battery is circulated volt-ampere (CV) and AC impedance (AIS) test.CV is to be 1-3V in voltage range, and sweep speed is 0.1mVS-1Under carry out.The frequency range of AC impedance is from 1MHz to 1Hz, and voltage amplitude is 10mV.All electro-chemical tests all at room temperature carry out.
Figure 18 is embodiment 21, the cyclic voltammogram of circulating battery 2 times in way of contrast 1 and 2.As can be seen from the figure: in way of contrast 1, positive pole contains the battery of elemental sulfur and occurs wider reduction peak at 1.5V place, electrochemical process relatively slowly and reversibility poor.In way of contrast 2, positive pole contains the battery of PPy electrochemicaUy inert within the scope of voltage 1-3V, and does not observe obvious electrochemical process.In embodiment 21, positive pole contains the battery of S/PPy, occurs reversible reduction peak respectively at 2V and 2.5V place, and this is due to S and Li+Between there is the electrochemical reaction of multistep.Reflect that PPy improves the electrochemical kinetics of elemental sulfur by CV result.
Figure 19 is the battery constant current charge-discharge collection of illustrative plates of embodiment 21.As can be seen from the figure: during battery discharge, have two platforms, this phenomenon is owing to when Li/S battery charging and discharging circulates, mainly there are two electrochemical reactions at sulfur positive pole.This result is just coincide with CV test.The electrochemical reaction started most is be positioned at the discharge platform that 2.5V place is shorter, and corresponding shows poly-lithium sulfide (Li2Sn, n >=4) generation, this poly-lithium sulfide (Li2Sn, n >=4) and soluble in liquid electrolyte Chinese style.The next one is positioned at the longer discharge curve platform of 2.0V and reflects electrochemical reaction by Li2The transformation of S, generates Li2The kinetics of S is slower compared to poly-lithium sulfide.As can be seen from the figure 2V discharge platform when circulation first time and third time does not have significant difference, and the high voltage platform of circulation in the 3rd week diminishes and circulates after several times and just disappears.After circulation 3 times, discharge capacity of the cell reaches 1050mAhg-1。
Figure 20 is cycle performance of battery schematic diagram in embodiment 21 and way of contrast 1.As can be seen from the figure: the battery of embodiment 21 increases significantly compared to the cycle performance of the battery of way of contrast 1.The battery that in embodiment 21, positive pole contains S/PPy discharge capacity after circulating 25 times is stablized at 600mAhg-1, after circulating 40 times, 500mAhg can also be reached-1.By contrast, the battery in way of contrast 1 along with cycle-index increase discharge capacity decay it is obvious that circulation 40 times after discharge capacity be only 110mAhg-1。
Figure 21 is the ac impedance spectroscopy of the battery in embodiment 21 and way of contrast 1.As can be seen from the figure: in embodiment 21, to contain the battery of S/PPy material little compared to the semi arch of the battery in way of contrast 1 for positive pole, this shows that the charge migration impedance of S/PPy substantially reduces, the conductivity that the main cause of this phenomenon is PPy is higher, and the raising of charge migration speed makes the chemical property of positive pole improve.
Although technical scheme has been done elaboration in greater detail and has enumerated by inventor, it is to be understood that, to those skilled in the art, above-described embodiment is modified and/or flexible or that employing is equivalent replacement scheme is obvious, all can not depart from the essence of spirit of the present invention, the term occurred in the present invention is used for the elaboration to technical solution of the present invention and understanding, can not be construed as limiting the invention.

Claims (10)

1. an electrode composite material, it is characterised in that: described electrode composite material contains ABxCyDz,
Described electrode composite material is through being thermally treated resulting in A, B, C, D, wherein:
A at least one in polypyrrole, polyacrylonitrile, polyacrylonitrile copolymer；
B is selected from elemental sulfur；
C is selected from carbon-based material；
D is selected from metal-oxide, and described metal-oxide is selected from MgaNibO、MgO、NiO、V2O5、CuO、MgcCudO、La2O3、Zr2O3、Ce2O3And Mn2OfIn at least one；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；
Described A, B, C and D weight ratio be 1:x:y:z, wherein, 1≤x≤20,0≤y < 1,0 < z < 1.
2. electrode composite material according to claim 1, it is characterised in that: described polyacrylonitrile copolymer is selected from polyacrylonitrile-methylmethacrylate copolymer, at least one in polyacrylonitrile-polypyrrole copolymer.
3. electrode composite material according to claim 1, it is characterised in that: described carbon-based material is selected from section's qin carbon black, acetylene black, activated carbon, SWCN, multi-walled carbon nano-tubes and at least one in Graphene.
4. a positive pole for battery, including electrode composite material any one of in such as claim 1-3.
5. a battery, including positive pole, negative pole and be located at the electrolyte between positive pole and negative pole, described positive pole includes plus plate current-collecting body and electrode composite material any one of in claim 1-3.
6. battery according to claim 5, it is characterised in that: described electrolyte is selected from Kynoar, Kynoar-polymethyl methacrylate copolymer, Kynoar-hexafluoropropylene copolymer and the one in Polyethylene Glycol borate polymer.
7. battery according to claim 5, it is characterised in that: described plus plate current-collecting body one in aluminium foil, nickel foam, stainless (steel) wire.
8. the preparation method of an electrode composite material, it is characterised in that: described preparation method comprises the steps:
By elemental sulfur; the at least one at least one and metal-oxide in polypyrrole, polyacrylonitrile, polyacrylonitrile copolymer is added in solvent; obtain the first mixture; first mixture is carried out ball milling mixing; obtain the second mixture; by the second mixture vacuum drying, it is heated subsequently processing under protective atmosphere or vacuum environment, after cooling, obtains electrode composite material；Wherein, at least one in polypyrrole, polyacrylonitrile, polyacrylonitrile copolymer, elemental sulfur and mass ratio at least one in metal-oxide are 1:x:z, 1≤x≤20,0 < z < 1；The range of speeds of described ball milling is 200-1300 rev/min, and Ball-milling Time ranges for 0.5-12 hour；The temperature of described heat treated range for 150-450 DEG C, the time range of heat treated is 1-20 hour；Described vacuum drying temperature range is 35-75 DEG C, and drying time ranges for 3-12 hour.
9. preparation method according to claim 8, it is characterised in that: described metal-oxide includes the mixture of MgO and NiO or the mixture of MgO and CuO.
10. preparation method according to claim 8, it is characterised in that: reducing gas that described protective atmosphere mixes with hydrogen selected from argon, nitrogen, argon and the one in the reducing gas that nitrogen mixes with hydrogen.
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