CN105304871B - A kind of sulphur of metallic cover/nickel cobalt manganese oxidate for lithium electrode material preparation method - Google Patents

A kind of sulphur of metallic cover/nickel cobalt manganese oxidate for lithium electrode material preparation method Download PDF

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CN105304871B
CN105304871B CN201510606994.6A CN201510606994A CN105304871B CN 105304871 B CN105304871 B CN 105304871B CN 201510606994 A CN201510606994 A CN 201510606994A CN 105304871 B CN105304871 B CN 105304871B
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sulphur
electrode material
nickel cobalt
cobalt manganese
lithium
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CN105304871A (en
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范美强
安彦玲
李婷
陈金丹
曾立伟
鞠强建
杨秀茹
吴汉美
陈达
陈海潮
李超
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China Jiliang University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 preparation method of the sulphur of metallic cover/nickel cobalt manganese oxidate for lithium electrode material, pass through mechanical ball mill mix sulphur/nickel cobalt manganese oxidate for lithium, then depositing metal oxide, alcohol reduction, drying, sulphur/nickel cobalt manganese oxidate for lithium electrode material of metallic cover is obtained；Sulphur accounts for the 65~90% of electrode material gross mass, and nickel cobalt manganese oxidate for lithium accounts for the 3~20% of electrode material gross mass, and cladding metal accounts for the 7~15% of electrode material gross mass；Metal is copper, silver, tungsten, one kind of gold or two kinds；When the electrode material is used for lithium-sulphur cell positive electrode, there is good specific capacity and excellent multiplying power and cycle performance：There is good application prospect in field of batteries.

Description

A kind of sulphur of metallic cover/nickel cobalt manganese oxidate for lithium electrode material preparation method
Technical field
The present invention relates to a kind of preparation method of electrode material, and in particular to a kind of sulphur of metallic cover/nickel cobalt manganese lithia Compound electrode material preparation method.
Background technology
Lithium-sulfur cell is very promising battery of new generation.But Volume Changes etc. in poorly conductive, charge and discharge process, Cause capacity rapid decay, utilization efficiency in cyclic process low.Current achievable lithium-sulfur cell actual specific capacity is far below reason By specific capacity.Surface is modified the common method for the electric conductivity for being raising sulphur.Lot of documents and patent use porous conductive carbon materials Material supports sulphur simple substance, shows high specific capacity, good cycle performance and excellent high rate performance.Geng XY (Geng XY, Rao M, Li XP.J.Solid State Electrochem., 2013,17：It is compound 987-992.) to be prepared for sulphur/CNT Material, first discharge specific capacity 900mAh/g, 100 times circulation specific capacity keeps 700mAh/g.Prepared using direct precipitation method Sulphur/multi-wall carbon nano-tube composite material；When current density is 0.02C, first discharge specific capacity 1229mAh/g, 50 circulations Afterwards, capacity is maintained at more than 800mAh/g.In order to further improve the chemical property of sulphur/carbon composite, Wang (Wang C, Wan W, Chen JT, Zhou HH.J Mater.Chem.A, 2013,1：1716-1723) it is prepared for double-nucleocapsid structure MWCNTs/S/PPy composites；200mA/g, first discharge specific capacity 1517mAh/g；1500mA/g, 200 circulations, Specific capacity 560mAh/g.Undeniably, size small carbon material in hole effectively limits the granular size of sulphur simple substance, while carbon material The satisfactory electrical conductivity conductance but carbon that improve elemental sulfur addition can reduce the tap density of sulfur electrode material, and at present The excellent carbon material price of electric conductivity is high, virtually limits its widely using in sulfur electrode preparation.
The content of the invention
Present invention aims at providing a kind of sulphur of metallic cover/nickel cobalt manganese oxidate for lithium electrode material preparation method, gram The defects of taking existing technology of preparing, improve the high rate performance and cycle life of sulfur electrode material.For achieving the above object, originally The technical scheme of invention is：By mechanical ball mill mix sulphur/nickel cobalt manganese oxidate for lithium, then depositing metal oxide, alcohol reduction, Drying, obtain sulphur/nickel cobalt manganese oxidate for lithium of metallic cover；Sulphur accounts for the 65~90% of electrode material gross mass, nickel cobalt manganese lithia Compound accounts for the 3~20% of electrode material gross mass, and cladding metal accounts for the 7~15% of electrode material gross mass；Metal be copper, silver, Tungsten, one kind of gold or two kinds；A kind of preparation method of the sulphur of metallic cover/nickel cobalt manganese oxidate for lithium electrode material, it include with Lower step：
1) sulphur, nickel cobalt manganese oxidate for lithium are weighed by a certain percentage；Argon gas atmosphere, 2~20h of mechanical ball mill；
2) step 1 product is dispersed in soluble metal salt solution and adds surfactant, stir 1~10h；Then delay It is slow that aqueous slkali is added dropwise, stir 2~5h；Filtering drying, 60~120 DEG C of 1~10h of standing, obtains sulphur/nickel that metal oxide coats Cobalt manganese oxidate for lithium electrode material；
3) sulphur/nickel cobalt manganese oxidate for lithium electrode material atmosphere protection that metal oxide coats is heated to 60~120 DEG C, It is passed through C1~C4 alcohol vapor；Reduction obtains sulphur/nickel cobalt manganese oxidate for lithium electrode material of metallic cover.
The soluble metallic salt of the step 2 is one kind of soluble copper, silver, tungsten, the inorganic salts of gold or organic salt；
The alkali of the step 2 is sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, one kind of ammoniacal liquor；
The alkali of the step 2 is controlled 1.05~5 with metal salt mol ratio；
The alcohol of the step 3 and the mol ratio of oxide are controlled 1.05~5；
A kind of preparation method of the sulphur of metallic cover provided by the invention/nickel cobalt manganese oxidate for lithium electrode material, it is and other Sulphur method for preparing anode material is compared, and is had the following advantages that：
1) present invention process is simple and convenient to operate, and is advantageous to industrialized production.
2) sulfur electrode material mixed with nickel cobalt manganese oxidate for lithium, metallic cover；The structure is not only advantageous to electronics conduction, and And sulphur simple substance particle is prevented to be come off during charge and discharge cycles.
3) in the sulphur of metallic cover/nickel cobalt manganese oxidate for lithium electrode material, sulphur accounts for the 65~90% of electrode material gross mass, Nickel cobalt manganese oxidate for lithium accounts for the 3~20% of electrode material gross mass, and metal accounts for the 7~15% of electrode material gross mass；It is prepared Core shell structure sulfur electrode material, both maintained the high rate performance of nickel cobalt manganese oxidate for lithium, again keep sulphur high power capacity；Have Height ratio capacity and long circulation life；After 1C is circulated 100 times, capacity is more than 200mAh/g.
Brief description of the drawings：
Fig. 1 is the cycle performance of sulfur electrode material of the present invention.
Embodiment
In order to further understand the content, features and effects of the present invention, hereby lifting following examples, describe in detail such as Under：
Embodiment 1
A kind of composition design of the lithium sulfide of metallic cover/nickel cobalt manganese oxidate for lithium electrode material is：
LiNi1/3Co1/3Mn1/3O2, 10wt%；Sulphur, 75wt%；Copper, mass fraction 15wt%；
A kind of preparation method of the sulphur of copper clad/nickel cobalt manganese oxidate for lithium electrode material：Comprise the following steps：
1) sulphur, nickel cobalt manganese oxidate for lithium are weighed by a certain percentage；Argon gas atmosphere, mechanical ball mill 10h；
2) step 1 product is dispersed in soluble copper chloride solution and adds surfactant, stir 5h；Then slowly drip It is hydrogenated with sodium hydroxide solution；Stir 2h；The mol ratio of sodium hydroxide and copper chloride is controlled 2.1；Filtering drying, 100 DEG C of standings 10h, obtain sulphur/nickel cobalt manganese oxidate for lithium electrode material of oxidation copper clad；
3) sulphur/nickel cobalt manganese oxidate for lithium electrode material atmosphere protection for aoxidizing copper clad is heated to 110 DEG C, is passed through ethanol Steam；The mol ratio of ethanol and cupric oxide is 4；Reduction obtains sulphur/nickel cobalt manganese oxidate for lithium electrode material of copper clad.
The preparation and performance test of sulfur electrode；By sulfur electrode material, acetylene black and PVDF in mass ratio 80: 10: 5 in NMP Middle mixing, coated in being electrode film on aluminium foil, metal lithium sheet is that CELGARD 2400 is barrier film, 1mol/L's to electrode LiPF6/EC+DMCWEI is electrolyte, is assembled into button cell in full of Ar glove boxes, is entered using Land battery test systems Row constant current charge-discharge test.Fig. 1 is cycle performance of the system in 0.1C and 1C.The 0.1C of the sulfur electrode of system 1 discharge capacities first 618mAh/g, 1C discharge, after 100 circulations, discharge capacity 203mAh/g.
Embodiment 2
A kind of composition design of lithium sulfide/nickel cobalt manganese oxidate for lithium electrode material of silver cladding is：
LiNi0.4Co0.2Mn0.4O2, 15wt%；Sulphur, 70%；Silver, mass fraction 15wt%；
A kind of preparation method of sulphur/nickel cobalt manganese oxidate for lithium electrode material of silver cladding：Comprise the following steps：
1) sulphur, nickel cobalt manganese oxidate for lithium are weighed by a certain percentage；Argon gas atmosphere, mechanical ball mill 5h；
2) step 1 product is dispersed in silver nitrate solution and adds surfactant, stir 10h；Then it is slow Potassium hydroxide solution is added dropwise；Stir 5h；The mol ratio of potassium hydroxide and silver nitrate is controlled 3；Filtering drying, 80 DEG C of standing 10h, Obtain sulphur/nickel cobalt manganese oxidate for lithium electrode material of silver oxide cladding；
3) sulphur/nickel cobalt manganese oxidate for lithium electrode material atmosphere protection that silver oxide coats is heated to 90 DEG C, is passed through methanol Steam；The mol ratio of methanol and silver oxide is 2；Reduction obtains sulphur/nickel cobalt manganese oxidate for lithium electrode material of silver cladding.
The preparation and performance test of sulfur electrode；By sulfur electrode material, acetylene black and PVDF in mass ratio 80: 10: 5 in NMP Middle mixing, coated in being electrode film on aluminium foil, metal lithium sheet is that CELGARD 2400 is barrier film, 1mol/L's to electrode LiPF6/EC+DMCWEI is electrolyte, is assembled into button cell in full of Ar glove boxes, is entered using Land battery test systems Row constant current charge-discharge test.Discharge capacity 620mAh/g, 1C's 0.1C of the sulfur electrode of system 2 discharge first, after 100 circulations, put Capacitance 220mAh/g.
Embodiment 3
A kind of composition design of lithium sulfide/nickel cobalt manganese oxidate for lithium electrode material of tungsten cladding is：
LiNi05Co0.2Mn0.3O2, 20wt%；Sulphur, 65%；Tungsten, mass fraction 15wt%；
A kind of preparation method of sulphur/nickel cobalt manganese oxidate for lithium electrode material of tungsten cladding：Comprise the following steps：
1) sulphur, nickel cobalt manganese oxidate for lithium are weighed by a certain percentage；Argon gas atmosphere, mechanical ball mill 10h；
2) step 1 product is dispersed in soluble nitric acid tungsten solution and adds surfactant, stir 5h；Then slowly drip It is hydrogenated with sodium hydroxide solution；Stir 2h；The mol ratio of sodium hydroxide and nitric acid tungsten is controlled 2.1；Filtering drying, 100 DEG C of standings 10h, obtain sulphur/nickel cobalt manganese oxidate for lithium electrode material of tungsten oxide cladding；
3) sulphur/nickel cobalt manganese oxidate for lithium electrode material atmosphere protection that tungsten oxide coats is heated to 110 DEG C, is passed through ethanol Steam；The mol ratio of ethanol and cupric oxide is 4；Reduction obtains sulphur/nickel cobalt manganese oxidate for lithium electrode material of tungsten cladding.
The preparation and performance test of sulfur electrode；By sulfur electrode material, acetylene black and PVDF in mass ratio 80: 10: 5 in NMP Middle mixing, coated in being electrode film on aluminium foil, metal lithium sheet is that CELGARD 2400 is barrier film, 1mol/L's to electrode LiPF6/EC+DMCWEI is electrolyte, is assembled into button cell in full of Ar glove boxes, is entered using Land battery test systems Row constant current charge-discharge test.Discharge capacity is more than 600mAh/g, 1C electric discharges, 100 circulations to the 0.1C of the sulfur electrode of system 3 first Afterwards, discharge capacity is more than 200mAh/g.
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with A variety of changes, modification can be carried out to these embodiments, replace without departing from the principles and spirit of the present invention by understanding And modification, the scope of the present invention is defined by the appended.

Claims (1)

  1. A kind of 1. preparation method of the sulphur of metallic cover/nickel cobalt manganese oxidate for lithium electrode material, it is characterised in that：Pass through mechanical ball Mix sulphur/nickel cobalt manganese oxidate for lithium is ground, then depositing metal oxide, alcohol reduction, drying, obtain sulphur/nickel cobalt of metallic cover Manganese oxidate for lithium electrode material；Sulphur accounts for the 65~90% of electrode material gross mass, and nickel cobalt manganese oxidate for lithium accounts for the total matter of electrode material The 3~20% of amount, cladding metal account for the 7~15% of electrode material gross mass；Metal is copper, silver, tungsten, one kind of gold or two kinds；. A kind of preparation method of the sulphur of metallic cover/nickel cobalt manganese oxidate for lithium electrode material, it comprises the following steps：
    1) sulphur, nickel cobalt manganese oxidate for lithium are weighed by a certain percentage；Argon gas atmosphere, 2~20h of mechanical ball mill；
    2) step 1 product is dispersed in soluble metal salt solution and adds surfactant, stir 1~10h；Then slowly drip Add aqueous slkali, stir 2~5h；Filtering drying, 60~120 DEG C of 1~10h of standing, obtains sulphur/nickel cobalt manganese that metal oxide coats Oxidate for lithium electrode material；
    Wherein, soluble metal salt is one kind of soluble copper, silver, tungsten, the inorganic salts of gold or organic salt；Alkali and metal salt Mol ratio control 1.05~5；Alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, one kind of ammoniacal liquor；
    3) sulphur/nickel cobalt manganese oxidate for lithium electrode material atmosphere protection that metal oxide coats is heated to 60~120 DEG C, be passed through C1~C4 alcohol vapor；Reduction obtains sulphur/nickel cobalt manganese oxidate for lithium electrode material of metallic cover；
    Wherein, the control of the mol ratio of alcohol and oxide is 1.05~5.
CN201510606994.6A 2015-09-16 2015-09-16 A kind of sulphur of metallic cover/nickel cobalt manganese oxidate for lithium electrode material preparation method Expired - Fee Related CN105304871B (en)

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CN108063257A (en) * 2017-12-14 2018-05-22 厦门大学 A kind of preparation method and applications of metal shell layer cladding sulphur composite positive pole
CN108428866B (en) * 2018-03-06 2021-08-17 昆明理工大学 Method for improving electrode capacity by in-situ reduction of clad metal
CN109786701B (en) * 2018-12-29 2022-07-08 桂林电器科学研究院有限公司 Modified LiNi0.8Co0.1Mn0.1O2Preparation method of ternary cathode material, product and battery

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CN103066255A (en) * 2012-12-26 2013-04-24 浙江工业大学 A nano-metal coated sulfur composite material and applications thereof
CN103055870A (en) * 2013-01-24 2013-04-24 中国科学院青岛生物能源与过程研究所 Nickel/copper catalyst and preparation method thereof, and method for directly preparing 1,2-hexanediol from cellulosan by using nickel/copper catalyst
CN103579590A (en) * 2013-05-09 2014-02-12 中国地质大学（武汉） Preparation method for coating anode material of lithium battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103066255A (en) * 2012-12-26 2013-04-24 浙江工业大学 A nano-metal coated sulfur composite material and applications thereof
CN103055870A (en) * 2013-01-24 2013-04-24 中国科学院青岛生物能源与过程研究所 Nickel/copper catalyst and preparation method thereof, and method for directly preparing 1,2-hexanediol from cellulosan by using nickel/copper catalyst
CN103579590A (en) * 2013-05-09 2014-02-12 中国地质大学（武汉） Preparation method for coating anode material of lithium battery

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