CN109378453A - A kind of cobaltosic oxide lithium ion battery negative material of the high circulation performance of nanoscale core-shell structure - Google Patents
A kind of cobaltosic oxide lithium ion battery negative material of the high circulation performance of nanoscale core-shell structure Download PDFInfo
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- CN109378453A CN109378453A CN201811114047.5A CN201811114047A CN109378453A CN 109378453 A CN109378453 A CN 109378453A CN 201811114047 A CN201811114047 A CN 201811114047A CN 109378453 A CN109378453 A CN 109378453A
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- shell structure
- cobaltosic oxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of methods of cobaltosic oxide for preparing nanoscale core-shell structure, it is to stir five water cobalt nitrates and 2-methylimidazole respectively to dissolution, then it is mixed 6 hours by the two, then drying is washed with water and methanol, then by presoma, 500oC is calcined 3 hours in Muffle furnace, then with sulphur powder in tube furnace, 350oC is calcined 3 hours under the atmosphere of nitrogen.Present invention process process is simple, and raw material is cheap and easy to get, it is easy to accomplish industrialized production.The cobaltosic oxide of nanoscale core-shell structure prepared by the present invention is used for lithium ion battery negative material, with excellent chemical property, under high current density and long circulating number, and capacity also with higher.This method gives preparation high performance lithium ionic cell cathode material of new generation and provides new visual angle, has very big application value.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, the in particular to preparation method of nuclear shell structure nano grade material,
Belong to new material technology field.
Background technique
The world today, the energy source use that lithium ion battery has been used as one kind important is in various mancarried electronic aids, such as pen
Remember on this computer, mobile phone, digital camera etc. and electric car.Lithium ion battery is proposed again with the development of science and technology
New requirement, needs higher cycle life, higher energy density, better high rate performance at higher current densities.
However commercial graphite electrode is not able to satisfy high specific capacity and higher high rate performance, many due to its low specific capacity
Application aspect is all restricted.Therefore, present people are exploring lithium ion battery negative material of new generation.Transiting metal oxidation
There is object high theoretical specific capacity to be concerned by people.
The organic matter that the present invention passes through metal-organic framework is presoma, then calcines in Muffle furnace and four oxygen are made
Change three cobalts, then in a nitrogen atmosphere, the cobaltosic oxide that nanoscale core-shell structure is made is reacted with sulphur powder, for preparation a new generation
Lithium ion battery negative material provides a kind of new thinking.
Summary of the invention
The preparation method of the cobaltosic oxide lithium ion battery negative material of nanoscale core-shell structure of the present invention, specifically
Include the following steps:
(1) a certain amount of five water cobalt nitrate is weighed respectively and 2-methylimidazole is dissolved in deionized water, stirs a timing respectively
Between to dissolve, certain time is then mixed;
(2) the mixing turbid for reacting certain time is subjected to centrifuge washing, then dried;
(3) presoma after drying is calcined in Muffle furnace high temperature, obtains cobaltosic oxide;
(4) obtained cobaltosic oxide and sulphur powder are mixed, is calcined in tube furnace, obtains nanoscale nucleocapsid cobaltosic oxide.
0.45 gram of five water cobalt nitrate and 2-methylimidazole are weighed in step (1) respectively, is dissolved separately in 3 milliliters and 20 milliliters
In deionized water.30 minutes are stirred respectively to dissolving, and then two solution are mixed 6 hours.
It is carried out centrifuge washing 3 times in step (2) with water and methanol.
Step is calcined in Muffle furnace in (3), and 500oC, heating rate 5oC/min are increased in 100 minutes, and heat preservation 3 is small
When.
It in step (4) in tube furnace, in a nitrogen atmosphere, is reacted with sulphur powder, 350 oC is increased in 100 minutes, risen
Warm 3.5 oC/min of rate keeps the temperature 3 hours.
Detailed description of the invention
The X-ray diffractogram of Fig. 1 nanoscale core-shell structure cobaltosic oxide.
The TEM photo of Fig. 2 nanoscale core-shell structure cobaltosic oxide.
The cyclic voltammetry curve figure of Fig. 3 nanoscale core-shell structure cobaltosic oxide.
Fig. 4 nanoscale core-shell structure cobaltosic oxide and commercialization cobaltosic oxide particle are in 10000mA g-1Current density
Under, the cyclical stability comparison diagram after 5000 circulations.
Fig. 5 nanoscale core-shell structure cobaltosic oxide is in 3000mA g-1Current density under, the 1st circulation, the 500th follow
Charging and discharging curve under ring, the 1000th circulation, the 1500th circulation, the 2500th circulation.
Fig. 6 nanoscale core-shell structure cobaltosic oxide and commercialization cobaltosic oxide particle 100,500,800,1000,2000,
3000、5000mAh g-1Current density under multiplying power comparison diagram.
Specific embodiment
Present invention will be further explained below with reference to specific examples.Example is merely to illustrate the present invention rather than limitation
The scope of the present invention.It should also be understood that those skilled in the art can be to this after having read content set forth in the present invention
Invention makes various changes or modifications, and these equivalent forms also fall within the scope of the appended claims of the present application.
Example
The synthesis of nanoscale core-shell structure cobaltosic oxide
It weighs 0.45 gram of five water cobalt nitrate to be dissolved in 3 ml deionized waters, forms solution A to dissolution within stirring 30 minutes;Weigh 5
Gram methylimidazole is dissolved in 20 milliliters of deionized water, and stirring 30 minutes to dissolution forms solution B.Next by solution A
It is mixed 6 hours with solution B.Then the turbid deionized water and methanol of reacting 6 hours are carried out centrifuge washing 3 times.It will
Resulting precipitating is put into 60oC in vacuum oven, 12 hours dry.Obtained presoma is put into Muffle furnace and is forged
It burns, 500oC, heating rate 5oC/min is raised in 100 minutes, keep the temperature 3 hours.After reaction, room temperature is naturally cooled to.So
It afterwards in tube furnace, is reacted under the atmosphere of nitrogen with sulphur powder, raised 350oC in 100 minutes, 3.5 oC/min of heating rate,
Heat preservation 3 hours, can be obtained the cobaltosic oxide of nanoscale core-shell structure.
It is lithium ion battery negative material that the cobaltosic oxide of nanoscale core-shell structure, which is applied,
1. the preparation of electrode material
With electronic balance weighing weigh a certain amount of above-mentioned steps prepared by nanoscale core-shell structure cobaltosic oxide, then press
Conductive agent (acetylene black) and binder (carboxymethyl cellulose) are weighed according to the ratio of 7:2:1, ball milling is carried out, the mud of formation is used
Scraper is uniformly coated on copper foil, and 60oC is dried 12 hours in a vacuum drying oven, and being then cut into diameter with slicer is 12 millis
Rice round copper sheet, is assembled into button cell in glove box.
2. electrochemical property test
Cyclical stability test has been carried out by the battery that blue electric battery test system (CT 2001A) assembles.In 5000 mA g-1Cyclical stability test has been carried out under high current density, can also keep 210mAh g after circulation 5000 times-1Capacity.?
10000 mA g-1Stable circulation test has been carried out under high current density, can also keep 177mAh g after circulation 5000 times-1
Capacity.
Cyclic voltammetry curve test has been carried out by electrochemical workstation (occasion China CHI 660E).First lap aoxidizes
The position of reduction peak is freeed in 2.13V or so in 0.76V or so in the position at peak.Second circle is substantially completely weighed to the 5th circle
It closes, only the positional shift of the oxidation peaks of rear four circle arrives 1.13V or so, and reduction peak is in 2.13V.
Claims (5)
1. a kind of preparation method of the cobaltosic oxide of nanoscale core-shell structure, it is characterised in that: with five water cobalt nitrates and 2- first
Base imidazoles is prepared as a raw material.
2. a kind of preparation method of the cobaltosic oxide of nanoscale core-shell structure as described in claim 1, it is characterised in that: claim
It takes 0.45 gram of five water cobalt nitrate to be dissolved in 3 milliliters of deionized water, forms solution A to dissolving within stirring 30 minutes;Weigh 5 grams of 2-
Methylimidazole is dissolved in 20 milliliters of deionized water, forms solution B to dissolving within stirring 30 minutes.Then by solution A and B solution
It is mixed 6 hours.Then methanol and deionized water centrifuge washing 3 times are used, obtained presoma is placed in a vacuum drying oven
60oC is 12 hours dry.
3. a kind of preparation method of the cobaltosic oxide of nanoscale core-shell structure as described in claim 1, it is characterised in that: will
Presoma after drying is placed in Muffle furnace, and 500oC is calcined under conditions of temperature programmed control, and the heating-up time 100 minutes, heating
Rate 5oC/min, soaking time: 3 hours.It later in tube furnace, reacts, heats up with sulphur powder 350oC under the atmosphere of nitrogen
Time 100 minutes, heating rate 3.5oC, soaking time 3 hours.Deng room temperature is naturally cooled to after having calcined, nucleocapsid can be obtained
The cobaltosic oxide of structure.
4. a kind of preparation method of the cobaltosic oxide of nanoscale core-shell structure as described in claim 1, it is characterised in that: obtain
Within the scope of the 50~100nm of partial size for obtaining the cobaltosic oxide of core-shell structure.
5. a kind of preparation method of the cobaltosic oxide of nanoscale core-shell structure as described in claim 1, it is characterised in that: will
The material is applied to find in lithium ion battery, and during lithium ion is deviate from and is embedded in, core-shell structure has good slow
The effect for rushing structural volume expansion makes it have high capacity and preferable cyclical stability under high current density.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109967093A (en) * | 2019-04-17 | 2019-07-05 | 齐鲁工业大学 | The preparation method of catalyst is precipitated in a kind of spherical shape cobalt disulfide/carbon composite highly effective oxygen |
CN110246700A (en) * | 2019-07-30 | 2019-09-17 | 哈尔滨工业大学 | A kind of preparation method of multi-layer core-shell oxide/sulfide heterojunction structure electrode material |
CN110350157A (en) * | 2019-06-12 | 2019-10-18 | 东南大学 | Sheet zinc cobalt sulfide composite material and preparation and application based on MOFs |
CN111180700A (en) * | 2020-01-06 | 2020-05-19 | 山东大学 | Preparation method of N-doped Co nanocluster/N-doped porous carbon/S composite material for high-performance potassium-sulfur battery positive electrode |
CN114335515A (en) * | 2021-12-06 | 2022-04-12 | 上海大学 | Preparation method of carbon-coated cobalt disulfide sodium ion battery cathode material |
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CN101928044A (en) * | 2009-10-13 | 2010-12-29 | 济南大学 | Preparation method of nano cobaltosic oxide used for negative electrode material of lithium ion battery |
CN106025236A (en) * | 2016-07-21 | 2016-10-12 | 陕西科技大学 | S-SnO2/Ti3C2 two-dimensional nano lithium ion battery cathode material and preparation method thereof |
CN106298255A (en) * | 2016-08-16 | 2017-01-04 | 中南大学 | A kind of hollow sub-microsphere with multilamellar cobalt sulfide/cobalt oxide shell and its preparation method and application |
CN106952743A (en) * | 2017-03-07 | 2017-07-14 | 常州大学 | The preparation and its application of a kind of cobaltosic oxide/carbon@molybdenum disulfide core-shell materials |
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Patent Citations (4)
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CN101928044A (en) * | 2009-10-13 | 2010-12-29 | 济南大学 | Preparation method of nano cobaltosic oxide used for negative electrode material of lithium ion battery |
CN106025236A (en) * | 2016-07-21 | 2016-10-12 | 陕西科技大学 | S-SnO2/Ti3C2 two-dimensional nano lithium ion battery cathode material and preparation method thereof |
CN106298255A (en) * | 2016-08-16 | 2017-01-04 | 中南大学 | A kind of hollow sub-microsphere with multilamellar cobalt sulfide/cobalt oxide shell and its preparation method and application |
CN106952743A (en) * | 2017-03-07 | 2017-07-14 | 常州大学 | The preparation and its application of a kind of cobaltosic oxide/carbon@molybdenum disulfide core-shell materials |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109967093A (en) * | 2019-04-17 | 2019-07-05 | 齐鲁工业大学 | The preparation method of catalyst is precipitated in a kind of spherical shape cobalt disulfide/carbon composite highly effective oxygen |
CN110350157A (en) * | 2019-06-12 | 2019-10-18 | 东南大学 | Sheet zinc cobalt sulfide composite material and preparation and application based on MOFs |
CN110246700A (en) * | 2019-07-30 | 2019-09-17 | 哈尔滨工业大学 | A kind of preparation method of multi-layer core-shell oxide/sulfide heterojunction structure electrode material |
CN111180700A (en) * | 2020-01-06 | 2020-05-19 | 山东大学 | Preparation method of N-doped Co nanocluster/N-doped porous carbon/S composite material for high-performance potassium-sulfur battery positive electrode |
CN111180700B (en) * | 2020-01-06 | 2021-06-22 | 山东大学 | Preparation method of N-doped Co nanocluster/N-doped porous carbon/S composite material for high-performance potassium-sulfur battery positive electrode |
CN114335515A (en) * | 2021-12-06 | 2022-04-12 | 上海大学 | Preparation method of carbon-coated cobalt disulfide sodium ion battery cathode material |
CN114335515B (en) * | 2021-12-06 | 2023-09-15 | 上海大学 | Preparation method of carbon-coated cobalt sodium disulfide ion battery anode material |
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