CN105304871A - Preparation method of metal-clad S/Ni-Co-Mn-Li oxide electrode material - Google Patents
Preparation method of metal-clad S/Ni-Co-Mn-Li oxide electrode material Download PDFInfo
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- 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
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Abstract
The invention relates to a preparation method of a metal-clad S/Ni-Co-Mn-Li oxide electrode material. The metal-coated S/Ni-Co-Mn-Li oxide electrode material is obtained through mechanically milling and mixing S/Ni-Co-Mn-Li oxide and then carrying out metal oxide deposition, diol reduction and drying; the mass of S accounts for 65 to 90 percent of the total mass of the electrode material, the mass of the Ni-Co-Mn-Li oxide accounts for 3 to 20 percent of the total mass of the electrode material, and the mass of clad metal accounts for 7 to 15 percent of the total mass of the electrode material; metal is one or two of Cu, Ag, W and Au; very good specific capacity, excellent multiplying power and excellent circulating performance are obtained when the electrode material is used for a positive electrode of a Li-S battery; the preparation method has a very good application prospect in the field of batteries.
Description
Technical field
The present invention relates to a kind of preparation method of electrode material, be specifically related to a kind of sulphur/nickel cobalt manganese oxidate for lithium electrode material preparation method of metallic cover.
Background technology
Lithium-sulfur cell is very promising battery of new generation.But change in volume etc., cause capacity rapid decay in cyclic process, utilization efficiency low in poorly conductive, charge and discharge process.Current attainable lithium-sulfur cell actual specific capacity is far below theoretical specific capacity.Surface modification is the common method of the conductivity improving sulphur.Lot of documents and patent adopt porous conductive material with carbon element to support sulphur simple substance, show the high rate performance of high specific capacity, good cycle performance and excellence.GengXY (GengXY, RaoM, LiXP.J.SolidStateElectrochem., 2013,17:987-992.) has prepared sulphur/carbon nano tube compound material, and first discharge specific capacity is 900mAh/g, and 100 times recycle ratio capacity keeps 700mAh/g.Direct precipitation method is adopted to prepare sulphur/multi-wall carbon nano-tube composite material; When current density is 0.02C, first discharge specific capacity is 1229mAh/g, and after 50 circulations, capacity remains on more than 800mAh/g.In order to improve the chemical property of sulphur/carbon composite further, Wang (WangC, WanW, ChenJT, ZhouHH.JMater.Chem.A, 2013,1:1716-1723) has prepared the MWCNTs/S/PPy composite material with double-nucleocapsid structure; 200mA/g, first discharge specific capacity is 1517mAh/g; 1500mA/g, 200 circulations, specific capacity 560mAh/g.Undeniable, the material with carbon element that hole dimension is little effectively limits the granular size of sulphur simple substance, the satisfactory electrical conductivity of material with carbon element improves the conductance of elemental sulfur simultaneously. but the tap density adding membership reduction sulfur electrode material of carbon, and the material with carbon element price of electric conductivity excellence is high at present, virtually limit its widely using in sulfur electrode preparation.
Summary of the invention
The object of the invention is the sulphur/nickel cobalt manganese oxidate for lithium electrode material preparation method providing a kind of metallic cover, overcomes the defect of existing technology of preparing, improves high rate performance and the cycle life of sulfur electrode material.For achieving the above object, technical scheme of the present invention is: by mechanical ball milling mix sulphur/nickel cobalt manganese oxidate for lithium, and then depositing metal oxide, alcohol reduction, oven dry, obtain the sulphur/nickel cobalt manganese oxidate for lithium of metallic cover; Sulphur accounts for 65 ~ 90% of electrode material gross mass, and nickel cobalt manganese oxidate for lithium accounts for 3 ~ 20% of electrode material gross mass, and clad metal accounts for 7 ~ 15% of electrode material gross mass; Metal be copper, silver, tungsten, gold one or two kinds; A preparation method for the sulphur/nickel cobalt manganese oxidate for lithium electrode material of metallic cover, it comprises the following steps:
1) sulphur, nickel cobalt manganese oxidate for lithium is weighed by a certain percentage; Argon gas atmosphere, mechanical ball milling 2 ~ 20h;
2) step 1 product be dispersed in soluble metal salt solution and add surfactant, stirring 1 ~ 10h; Then slowly drip aqueous slkali, stir 2 ~ 5h; Filtering drying, 60 ~ 120 DEG C leave standstill 1 ~ 10h, obtain sulphur/nickel cobalt manganese oxidate for lithium electrode material that metal oxide is coated;
3) sulphur coated for metal oxide/nickel cobalt manganese oxidate for lithium electrode material atmosphere protection is heated to 60 ~ 120 DEG C, passes into the alcohol vapor of C1 ~ C4; Reduction obtains the sulphur/nickel cobalt manganese oxidate for lithium electrode material of metallic cover.
The soluble metallic salt of described step 2 is the copper of solubility, silver, tungsten, the inorganic salts of gold or the one of organic salt;
The alkali of described step 2 is the one of NaOH, potassium hydroxide, calcium hydroxide, barium hydroxide, ammoniacal liquor;
Alkali and the slaine mol ratio of described step 2 control 1.05 ~ 5;
The alcohol of described step 3 and the mol ratio of oxide control 1.05 ~ 5;
The preparation method of the sulphur/nickel cobalt manganese oxidate for lithium electrode material of a kind of metallic cover provided by the invention, compared with other sulphur method for preparing anode material, tool has the following advantages:
1) present invention process is simple, easy to operate, is conducive to suitability for industrialized production.
2) sulfur electrode material mix with nickel cobalt manganese oxidate for lithium, metallic cover; This structure is not only conducive to electrical conductivity, and stops sulphur simple substance particle to come off in charge and discharge cycles process.
3), in the sulphur/nickel cobalt manganese oxidate for lithium electrode material of metallic cover, sulphur accounts for 65 ~ 90% of electrode material gross mass, and nickel cobalt manganese oxidate for lithium accounts for 3 ~ 20% of electrode material gross mass, and metal accounts for 7 ~ 15% of electrode material gross mass; The sulfur electrode material of prepared nucleocapsid structure, had both maintained the high rate performance of nickel cobalt manganese oxidate for lithium, had kept again the high power capacity of sulphur; There is height ratio capacity and long circulation life; 1C circulates after 100 times, and capacity is greater than 200mAh/g.
Accompanying drawing illustrates:
Fig. 1 is the cycle performance of sulfur electrode material of the present invention.
Embodiment
For summary of the invention of the present invention, Characteristic can be understood further, hereby lift following examples, be described in detail as follows:
Embodiment 1
A kind of Composition Design of lithium sulfide/nickel cobalt manganese oxidate for lithium electrode material of metallic cover is:
LiNi
1/3co
1/3mn
1/3o
2, 10wt%; Sulphur, 75wt%; Copper, mass fraction 15wt%;
A kind of preparation method of sulphur/nickel cobalt manganese oxidate for lithium electrode material of copper clad: comprise the following steps:
1) sulphur, nickel cobalt manganese oxidate for lithium is weighed by a certain percentage; Argon gas atmosphere, mechanical ball milling 10h;
2) step 1 product be dispersed in solubility copper chloride solution and add surfactant, stirring 5h; Then slowly sodium hydroxide solution is dripped; Stir 2h; The mol ratio of NaOH and copper chloride controls 2.1; Filtering drying, 100 DEG C of standing 10h, obtain sulphur/nickel cobalt manganese oxidate for lithium electrode material that cupric oxide is coated;
3) sulphur coated for cupric oxide/nickel cobalt manganese oxidate for lithium electrode material atmosphere protection is heated to 110 DEG C, passes into alcohol vapor; The mol ratio of ethanol and cupric oxide is 4; Reduction obtains the sulphur/nickel cobalt manganese oxidate for lithium electrode material of copper clad.
The preparation and property test of sulfur electrode; Sulfur electrode material, acetylene black and PVDF among NMPs to be mixed in mass ratio at 80: 10: 5, be coated on aluminium foil is electrode film, metal lithium sheet is to electrode, CELGARD2400 is barrier film, the LiPF6/EC+DMCWEI of 1mol/L is electrolyte, be assembled into button cell being full of in Ar glove box, adopt Land battery test system to carry out constant current charge-discharge test.Fig. 1 is the cycle performance of system at 0.1C and 1C.0.1C discharge capacity 618mAh/g, the 1C electric discharge first of system 1 sulfur electrode, after 100 circulations, discharge capacity 203mAh/g.
Embodiment 2
The Composition Design of lithium sulfide/nickel cobalt manganese oxidate for lithium electrode material that a kind of silver is coated is:
LiNi
0.4co
0.2mn
0.4o
2, 15wt%; Sulphur, 70%; Silver, mass fraction 15wt%;
The preparation method of sulphur/nickel cobalt manganese oxidate for lithium electrode material that a kind of silver is coated: comprise the following steps:
1) sulphur, nickel cobalt manganese oxidate for lithium is weighed by a certain percentage; Argon gas atmosphere, mechanical ball milling 5h;
2) step 1 product be dispersed in silver nitrate solution and add surfactant, stirring 10h; Then slowly potassium hydroxide solution is dripped; Stir 5h; The mol ratio of potassium hydroxide and silver nitrate controls 3; Filtering drying, 80 DEG C of standing 10h, obtain sulphur/nickel cobalt manganese oxidate for lithium electrode material that silver oxide is coated;
3) sulphur coated for silver oxide/nickel cobalt manganese oxidate for lithium electrode material atmosphere protection is heated to 90 DEG C, passes into methanol vapor; The mol ratio of methyl alcohol and silver oxide is 2; Reduction obtains the coated sulphur/nickel cobalt manganese oxidate for lithium electrode material of silver.
The preparation and property test of sulfur electrode; Sulfur electrode material, acetylene black and PVDF among NMPs to be mixed in mass ratio at 80: 10: 5, be coated on aluminium foil is electrode film, metal lithium sheet is to electrode, CELGARD2400 is barrier film, the LiPF6/EC+DMCWEI of 1mol/L is electrolyte, be assembled into button cell being full of in Ar glove box, adopt Land battery test system to carry out constant current charge-discharge test.0.1C discharge capacity 620mAh/g, the 1C electric discharge first of system 2 sulfur electrode, after 100 circulations, discharge capacity 220mAh/g.
Embodiment 3
The Composition Design of lithium sulfide/nickel cobalt manganese oxidate for lithium electrode material that a kind of tungsten is coated is:
LiNi
05co
0.2mn
0.3o
2, 20wt%; Sulphur, 65%; Tungsten, mass fraction 15wt%;
The preparation method of sulphur/nickel cobalt manganese oxidate for lithium electrode material that a kind of tungsten is coated: comprise the following steps:
1) sulphur, nickel cobalt manganese oxidate for lithium is weighed by a certain percentage; Argon gas atmosphere, mechanical ball milling 10h;
2) step 1 product be dispersed in solubility nitric acid tungsten solution and add surfactant, stirring 5h; Then slowly sodium hydroxide solution is dripped; Stir 2h; The mol ratio of NaOH and nitric acid tungsten controls 2.1; Filtering drying, 100 DEG C of standing 10h, obtain sulphur/nickel cobalt manganese oxidate for lithium electrode material that tungsten oxide is coated;
3) sulphur coated for tungsten oxide/nickel cobalt manganese oxidate for lithium electrode material atmosphere protection is heated to 110 DEG C, passes into alcohol vapor; The mol ratio of ethanol and cupric oxide is 4; Reduction obtains the coated sulphur/nickel cobalt manganese oxidate for lithium electrode material of tungsten.
The preparation and property test of sulfur electrode; Sulfur electrode material, acetylene black and PVDF among NMPs to be mixed in mass ratio at 80: 10: 5, be coated on aluminium foil is electrode film, metal lithium sheet is to electrode, CELGARD2400 is barrier film, the LiPF6/EC+DMCWEI of 1mol/L is electrolyte, be assembled into button cell being full of in Ar glove box, adopt Land battery test system to carry out constant current charge-discharge test.The 0.1C of system 3 sulfur electrode first discharge capacity is greater than 600mAh/g, and 1C discharges, and after 100 circulations, discharge capacity is greater than 200mAh/g.
Although illustrate and describe embodiments of the invention, for the ordinary skill in the art, be appreciated that and can carry out multiple change, amendment, replacement and modification to these embodiments without departing from the principles and spirit of the present invention, scope of the present invention is by claims and equivalents thereof.
Claims (1)
1. the preparation method of the sulphur/nickel cobalt manganese oxidate for lithium electrode material of a metallic cover, it is characterized in that: by mechanical ball milling mix sulphur/nickel cobalt manganese oxidate for lithium, then depositing metal oxide, alcohol reduction, oven dry, obtain the sulphur/nickel cobalt manganese oxidate for lithium electrode material of metallic cover; Sulphur accounts for 65 ~ 90% of electrode material gross mass, and nickel cobalt manganese oxidate for lithium accounts for 3 ~ 20% of electrode material gross mass, and clad metal accounts for 7 ~ 15% of electrode material gross mass; Metal be copper, silver, tungsten, gold one or two kinds; . a kind of preparation method of sulphur/nickel cobalt manganese oxidate for lithium electrode material of metallic cover, it comprises the following steps:
1) sulphur, nickel cobalt manganese oxidate for lithium is weighed by a certain percentage; Argon gas atmosphere, mechanical ball milling 2 ~ 20h;
2) step 1 product be dispersed in soluble metal salt solution and add surfactant, stirring 1 ~ 10h; Then slowly drip aqueous slkali, stir 2 ~ 5h; Filtering drying, 60 ~ 120 DEG C leave standstill 1 ~ 10h, obtain sulphur/nickel cobalt manganese oxidate for lithium electrode material that metal oxide is coated;
Wherein, the slaine of solubility is the copper of solubility, silver, tungsten, the inorganic salts of gold or the one of organic salt; The mol ratio of alkali and slaine controls 1.05 ~ 5; Alkali is the one of NaOH, potassium hydroxide, calcium hydroxide, barium hydroxide, ammoniacal liquor;
3) sulphur coated for metal oxide/nickel cobalt manganese oxidate for lithium electrode material atmosphere protection is heated to 60 ~ 120 DEG C, passes into the alcohol vapor of C1 ~ C4; Reduction obtains the sulphur/nickel cobalt manganese oxidate for lithium electrode material of metallic cover;
Wherein, the mol ratio of alcohol and oxide controls 1.05 ~ 5.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108428866A (en) * | 2018-03-06 | 2018-08-21 | 昆明理工大学 | A kind of method that in-situ reducing cladding metal improves electrode capacity |
| CN109786701A (en) * | 2018-12-29 | 2019-05-21 | 桂林电器科学研究院有限公司 | Modified LiNi0.8Co0.1Mn0.1O2The preparation method and product and battery of tertiary cathode material |
Citations (3)
| 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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Patent Citations (3)
| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108428866A (en) * | 2018-03-06 | 2018-08-21 | 昆明理工大学 | A kind of method that in-situ reducing cladding metal improves electrode capacity |
| 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 |
| CN109786701A (en) * | 2018-12-29 | 2019-05-21 | 桂林电器科学研究院有限公司 | Modified LiNi0.8Co0.1Mn0.1O2The preparation method and product and battery of tertiary cathode material |
| 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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