CN111082045A - Preparation method of hollow material, product and application - Google Patents

Preparation method of hollow material, product and application Download PDF

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Publication number
CN111082045A
CN111082045A CN201911326859.0A CN201911326859A CN111082045A CN 111082045 A CN111082045 A CN 111082045A CN 201911326859 A CN201911326859 A CN 201911326859A CN 111082045 A CN111082045 A CN 111082045A
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Prior art keywords
hollow
solution
zinc
znmn
minutes
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Inventor
崔大祥
赵立敏
张芳
解启飞
邓秉浩
王惠亚
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Shanghai National Engineering Research Center for Nanotechnology 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
    • H01M4/36—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative 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 invention provides a preparation method of a hollow material, a product and application thereof, wherein the molecular formula of the hollow material is ZnMn2O4Any two zinc salts and manganese salts are selected as raw materials to match, such as: zinc chloride, manganese chloride, zinc acetate, manganese acetate, zinc nitrate, manganese nitrate, zinc sulfate, manganese sulfate and the like, and hollow Zn with different shapes can be realized by a one-step hydrothermal methodxMnyCO3Followed by calcination at 650 ℃ for 2 hours to give hollow ZnMn2O4. ZnMn with the hollow structure2O4The lithium ion battery cathode shows good cycle performance, and the specific capacity is kept to be 660 mAh g after 200 cycles under the current of 0.5C‑1。

Description

Preparation method of hollow material, product and application
Technical Field
The invention relates to a preparation method of a hollow material, a product and application thereof. The molecular formula of the hollow material is ZnMn2O4The method is mainly applied to the field of lithium ion battery cathode materials.
Background
The hollow nano material has the advantages of large specific surface area, small density, hollow interior and the like, so the hollow nano material is widely applied to the fields of adsorption, catalysis, supercapacitors, lithium ion batteries and the like.
The lithium ion battery as an efficient energy storage device has the advantages of environmental friendliness, long cycle life, high energy density and the like, and is widely applied to portable electronic equipment. ZnMn2O4As a spinel type metal oxide, has MnO more than that of the conventional one2The oxides have higher theoretical specific capacity, are environment-friendly, have rich reserves on the earth and have low voltage platform. ZnMn compared to cobalt-based metal oxides2O4The material only contains zinc and manganese, is more environment-friendly, and has great attention in the research of lithium ion battery cathode materials.
However, ZnMn2O4The problems of low specific capacity, poor rate capability and cycling stability and the like still exist when the lithium ion battery cathode is applied, which are caused by the inherent poor conductivity of the ionic crystal and the large volume change in the continuous lithiation/delithiation process. Research shows that the hollow material can effectively deal with the volume change of the material caused by lithium ion extraction in the electrochemical reaction. ZnMn2O4When the volume expansion is generated, different particles of the solid structure can be mutually extruded to cause the active material to fall off from the current collector, the hollow structure can gather the volume change at the hollow part, the stress is effectively released, the problems of falling off of the active material and the like caused by the volume expansion are relieved, and the overall cycle life of the battery is prolonged.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a hollow material.
Yet another object of the present invention is to: a hollow material product prepared by the method is provided.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme:
in order to achieve the purpose, the technical scheme of the invention is as follows: a method for preparing a hollow material, in particular to a hollow material,the molecular formula of the hollow material is ZnMn2O4Any two zinc salts and manganese salts are selected as raw materials to be matched, and hollow Zn with different shapes of intermediate products is realized by a one-step hydrothermal methodxMnyCO3Followed by calcination at 650 ℃ for 2 hours to give hollow ZnMn2O4Intermediate product ZnxMnyCO3Morphology and hollow ZnMn obtained after calcination2O4The appearance is the same.
Any two zinc salts and manganese salts are selected as raw materials to match: zinc chloride, manganese chloride, zinc acetate, manganese acetate, zinc nitrate, manganese nitrate, zinc sulfate and manganese sulfate.
Zn prepared from different zinc salts and manganese saltsxMnyCO3And ZnMn2O4The shapes are different, but the shapes are all hollow structures, hollow rings, hollow spheres, hollow cakes and hollow cubes.
In the present invention, Zn is an intermediate productxMnyCO3Also has a hollow structure, the subsequent calcination does not cause the collapse of the hollow structure, the appearance is not obviously changed before and after the calcination, and the hollow annular ZnxMnyCO3Corresponding hollow ring ZnMn after calcination2O3Hollow spherical ZnxMnyCO3Corresponding hollow spherical ZnMn after calcination2O4。
The invention provides a hollow ZnMn2O4The preparation method comprises the following specific steps:
a. taking 0.05 mmol of zinc chloride and 0.1 mmol of manganese acetate, dissolving the two salts in 0.2 ml of deionized water, and stirring for 10 minutes to obtain a solution a;
b. adding the solution a into 50 ml of diethylene glycol, and stirring for 10 minutes to obtain a solution b;
c. adding 0.8g of ammonium bicarbonate into the solution b, stirring for 40 minutes, and carrying out ultrasonic treatment for 30 minutes by an ultrasonic machine to obtain a turbid solution c;
d. adding the turbid solution c into a 50 ml hydrothermal reaction kettle, and preserving the heat at 180 ℃ for 12 hours;
e. centrifuging, washing with deionized water for many times,drying to obtain' hollow ZnxMnyCO3”；
f. The above-mentioned "hollow Zn" is mixedxMnyCO3Calcining at 650 ℃ for 2 hours to obtain hollow ZnMn2O4”。
The invention also provides a hollow ZnMn2O4The preparation method comprises the following specific steps:
a. taking 0.05 mmol of zinc nitrate and 0.1 mmol of manganese sulfate, dissolving the two salts in 0.2 ml of deionized water, and stirring for 10 minutes to obtain a solution a;
b. adding the solution a into 50 ml of diethylene glycol, and stirring for 10 minutes to obtain a solution b;
c. adding 0.8g of ammonium bicarbonate into the solution b, stirring for 40 minutes, and carrying out ultrasonic treatment for 30 minutes by an ultrasonic machine to obtain a turbid solution c;
d. adding the turbid solution c into a 50 ml hydrothermal reaction kettle, and preserving the heat at 180 ℃ for 12 hours;
e. centrifuging, washing with deionized water for multiple times, and drying to obtain "hollow ZnxMnyCO3”；
f. The above-mentioned "hollow Zn" is mixedxMnyCO3Calcining at 650 ℃ for 2 hours to obtain hollow ZnMn2O4”。
The invention also provides another hollow ZnMn2O4The preparation method comprises the following specific steps:
a. taking 0.05 mmol of zinc nitrate and 0.1 mmol of manganese sulfate, dissolving the two salts in 0.2 ml of deionized water, and stirring for 10 minutes to obtain a solution a;
b. adding the solution a into 50 ml of diethylene glycol, and stirring for 10 minutes to obtain a solution b;
c. adding 0.8g of ammonium bicarbonate into the solution b, stirring for 40 minutes, and carrying out ultrasonic treatment for 30 minutes by an ultrasonic machine to obtain a turbid solution c;
d. adding the turbid solution c into a 50 ml hydrothermal reaction kettle, and preserving the heat at 180 ℃ for 12 hours;
e. centrifuging, washing with deionized water for multiple times, and drying to obtain "hollow ZnxMnyCO3”；
f. The above-mentioned "hollow Zn" is mixedxMnyCO3Calcining at 650 ℃ for 2 hours to obtain hollow ZnMn2O4”。
The invention provides a hollow ZnMn2O4Prepared according to any one of the methods described above.
The invention provides a hollow ZnMn2O4The lithium ion battery can be used as a negative electrode.
The product of the invention has a hollow structure of ZnMn2O4The lithium ion battery cathode shows good cycle performance, and the specific capacity is kept to be 660 mAh g after 200 cycles under the current of 0.5C-1。
Drawings
FIG. 1 shows "hollow ZnMn" synthesized in example 2 of the present invention2O4"SEM picture of;
FIG. 2 shows "hollow ZnMn" synthesized in example 2 of the present invention2O4"cycle performance map of;
FIG. 3 shows "hollow ZnMn" synthesized in example 3 of the present invention2O4"SEM picture of;
FIG. 4 shows "hollow ZnMn" synthesized in example 4 of the present invention2O4"SEM image of.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the scope of the present invention is not limited to these examples.
Example 1:
hollow Zn prepared by one-step hydrothermal methodxMnyCO3The preparation method comprises the following steps:
a. taking 0.05 mmol of zinc chloride and 0.1 mmol of manganese acetate, dissolving the two salts in 0.2 ml of deionized water, and stirring for 10 minutes to obtain a solution a;
b. adding the solution a into 50 ml of diethylene glycol, and stirring for 10 minutes to obtain a solution b;
c. adding 0.8g of ammonium bicarbonate into the solution b, stirring for 40 minutes, and carrying out ultrasonic treatment for 30 minutes by an ultrasonic machine to obtain a turbid solution c;
d. adding the turbid solution c into a 50 ml hydrothermal reaction kettle, and preserving the heat at 180 ℃ for 12 hours;
e. centrifuging, washing with deionized water for multiple times, and drying to obtain "hollow ZnxMnyCO3”。
Example 2
Hollow ZnMn2O4The zinc salt and the manganese salt are matched to realize the hollow Zn of the intermediate product by a one-step hydrothermal methodxMnyCO3And then calcined at 650 ℃ for 2 hours to obtain hollow ZnMn2O4The preparation method comprises the following steps:
a, taking 0.05 mmol of zinc chloride and 0.1 mmol of manganese acetate, dissolving the two salts in 0.2 ml of deionized water, and stirring for 10 minutes to obtain a solution a;
b. adding the solution a into 50 ml of diethylene glycol, and stirring for 10 minutes to obtain a solution b;
c. adding 0.8g of ammonium bicarbonate into the solution b, stirring for 40 minutes, and carrying out ultrasonic treatment for 30 minutes by an ultrasonic machine to obtain a turbid solution c;
d. adding the turbid solution c into a 50 ml hydrothermal reaction kettle, and preserving the heat at 180 ℃ for 12 hours;
e. centrifuging, washing with deionized water for multiple times, and drying to obtain "hollow ZnxMnyCO3”；
f. The above-mentioned "hollow Zn" is mixedxMnyCO3Calcining at 650 ℃ for 2 hours to obtain hollow ZnMn2O4"," hollow ZnMn2O4"is shown in FIG. 1; synthetic hollow ZnMn2O4"the cycle performance is shown in FIG. 2.
Example 3
Hollow ZnMn2O4Similar to example 2, the preparation method comprises the following steps:
a. taking 0.05 mmol of zinc acetate and 0.1 mmol of manganese nitrate, dissolving the two salts in 0.2 ml of deionized water, and stirring for 10 minutes to obtain a solution a;
b. adding the solution a into 50 ml of diethylene glycol, and stirring for 10 minutes to obtain a solution b;
c. adding 0.8g of ammonium bicarbonate into the solution b, stirring for 40 minutes, and carrying out ultrasonic treatment for 30 minutes by an ultrasonic machine to obtain a turbid solution c;
d. adding the turbid solution c into a 50 ml hydrothermal reaction kettle, and preserving the heat at 180 ℃ for 12 hours;
e. centrifuging, washing with deionized water for multiple times, and drying to obtain "hollow ZnxMnyCO3”；
f. The above-mentioned "hollow Zn" is mixedxMnyCO3Calcining at 650 ℃ for 2 hours to obtain hollow ZnMn2O4". Synthetic hollow ZnMn2O4"is shown in FIG. 3.
Example 4
Hollow ZnMn2O4Similar to example 2, the preparation method comprises the following steps:
a. taking 0.05 mmol of zinc nitrate and 0.1 mmol of manganese sulfate, dissolving the two salts in 0.2 ml of deionized water, and stirring for 10 minutes to obtain a solution a;
b. adding the solution a into 50 ml of diethylene glycol, and stirring for 10 minutes to obtain a solution b;
c. adding 0.8g of ammonium bicarbonate into the solution b, stirring for 40 minutes, and carrying out ultrasonic treatment for 30 minutes by an ultrasonic machine to obtain a turbid solution c;
d. adding the turbid solution c into a 50 ml hydrothermal reaction kettle, and preserving the heat at 180 ℃ for 12 hours;
e. centrifuging, washing with deionized water for multiple times, and drying to obtain "hollow ZnxMnyCO3”；
f. The above-mentioned "hollow Zn" is mixedxMnyCO3Calcining at 650 ℃ for 2 hours to obtain hollow ZnMn2O4". Synthetic hollow ZnMn2O4"is shown in FIG. 4.

Claims (7)

1. A preparation method of a hollow material, wherein the molecular formula of the hollow material is ZnMn2O4The method is characterized in that any two zinc salts and manganese salts are selected as raw materials to be matched, and the method is realized through a one-step hydrothermal methodIntermediate product hollow Zn with different shapesxMnyCO3Followed by calcination at 650 ℃ for 2 hours to give hollow ZnMn2O4Intermediate product ZnxMnyCO3Morphology and hollow ZnMn obtained after calcination2O4The appearance is the same.
2. The method for producing a hollow material according to claim 1, wherein: the raw materials are selected from any two zinc salts and manganese salts: the zinc salt is: one of zinc chloride, zinc acetate, zinc nitrate and zinc sulfate, and the manganese salt matched with the zinc chloride, the zinc acetate, the zinc nitrate and the zinc sulfate is as follows: one of manganese chloride, manganese acetate, manganese nitrate and manganese sulfate; intermediate Zn prepared by matching different zinc salts and manganese saltsxMnyCO3And ZnMn2O4All are hollow structures, but the shapes are different, and are as follows: hollow ring shape, hollow sphere shape, hollow cake shape or hollow cube shape.
3. The method for preparing the hollow material according to claim 1 or 2, which is characterized by comprising the following specific steps:
a. taking 0.05 mmol of zinc chloride and 0.1 mmol of manganese acetate, dissolving the two salts in 0.2 ml of deionized water, and stirring for 10 minutes to obtain a solution a;
b. adding the solution a into 50 ml of diethylene glycol, and stirring for 10 minutes to obtain a solution b;
c. adding 0.8g of ammonium bicarbonate into the solution b, stirring for 40 minutes, and performing ultrasonic treatment for 30 minutes to obtain a turbid solution c;
d. adding the turbid solution c into a 50 ml hydrothermal reaction kettle, and preserving the heat at 180 ℃ for 12 hours;
e. centrifuging, washing with deionized water for multiple times, and drying to obtain hollow ZnxMnyCO3；
f. The hollow Zn is preparedxMnyCO3Calcining at 650 ℃ for 2 hours to obtain hollow ZnMn2O4。
4. Hollow ZnMn according to claim 1 or 22O4The preparation method is characterized by comprising the following specific steps:
a. taking 0.05 mmol of zinc nitrate and 0.1 mmol of manganese sulfate, dissolving the two salts in 0.2 ml of deionized water, and stirring for 10 minutes to obtain a solution a;
b. adding the solution a into 50 ml of diethylene glycol, and stirring for 10 minutes to obtain a solution b;
c. adding 0.8g of ammonium bicarbonate into the solution b, stirring for 40 minutes, and carrying out ultrasonic treatment for 30 minutes by an ultrasonic machine to obtain a turbid solution c;
d. adding the turbid solution c into a 50 ml hydrothermal reaction kettle, and preserving the heat at 180 ℃ for 12 hours;
e. centrifuging, washing with deionized water for multiple times, and drying to obtain intermediate hollow ZnxMnyCO3；
f. The hollow Zn is preparedxMnyCO3Calcining at 650 ℃ for 2 hours to obtain hollow ZnMn2O4。
5. The method for preparing the hollow material according to claim 1 or 2, which is characterized by comprising the following specific steps:
a. taking 0.05 mmol of zinc nitrate and 0.1 mmol of manganese sulfate, dissolving the two salts in 0.2 ml of deionized water, and stirring for 10 minutes to obtain a solution a;
b. adding the solution a into 50 ml of diethylene glycol, and stirring for 10 minutes to obtain a solution b;
c. adding 0.8g of ammonium bicarbonate into the solution b, stirring for 40 minutes, and carrying out ultrasonic treatment for 30 minutes by an ultrasonic machine to obtain a turbid solution c;
d. adding the turbid solution c into a 50 ml hydrothermal reaction kettle, and preserving the heat at 180 ℃ for 12 hours;
e. centrifuging, washing with deionized water for multiple times, and drying to obtain intermediate hollow ZnxMnyCO3；
f. The hollow Zn is preparedxMnyCO3Calcining at 650 ℃ for 2 hours to obtain hollow ZnMn2O4。
6. A hollow material with molecular formula of ZnMn2O4Characterized by being prepared according to the method of any one of claims 1 to 5.
7. Use of the hollow material according to claim 6 as a negative electrode in a lithium ion battery.
CN201911326859.0A 2019-12-20 2019-12-20 Preparation method of hollow material, product and application Pending CN111082045A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102082270A (en) * 2010-12-03 2011-06-01 南开大学 Manganese spinel nano material as well as preparation method and application of manganese spinel nano material
CN104037402A (en) * 2014-06-19 2014-09-10 合肥国轩高科动力能源股份公司 Method for preparing hollow nickle-manganese composite oxide balls
US20170092932A1 (en) * 2015-09-24 2017-03-30 Samsung Electronics Co., Ltd. Composite electrode active material, electrode and lithium battery including the composite electrode active material, and method of preparing the composite electrode active material
CN108400324A (en) * 2018-03-07 2018-08-14 华南师范大学 A kind of lithium ion battery negative material zinc manganate nanometer rods and preparation method thereof
CN108467066A (en) * 2018-04-08 2018-08-31 淮北师范大学 A kind of porous micro-nano structure ZnMn of rice-shaped2O4Lithium ion battery negative material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102082270A (en) * 2010-12-03 2011-06-01 南开大学 Manganese spinel nano material as well as preparation method and application of manganese spinel nano material
CN104037402A (en) * 2014-06-19 2014-09-10 合肥国轩高科动力能源股份公司 Method for preparing hollow nickle-manganese composite oxide balls
US20170092932A1 (en) * 2015-09-24 2017-03-30 Samsung Electronics Co., Ltd. Composite electrode active material, electrode and lithium battery including the composite electrode active material, and method of preparing the composite electrode active material
CN108400324A (en) * 2018-03-07 2018-08-14 华南师范大学 A kind of lithium ion battery negative material zinc manganate nanometer rods and preparation method thereof
CN108467066A (en) * 2018-04-08 2018-08-31 淮北师范大学 A kind of porous micro-nano structure ZnMn of rice-shaped2O4Lithium ion battery negative material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
WEIWEI ZHOU等: "Template-Free Fabrication of Graphene-wrapped Mesoporous ZnMn2O4 Nanorings as Anode Materials for Lithium-Ion Batteries", 《NANOTECHNOLOGY》 *
杨天博: "锂离子电池负极材料ZnM2O4(M=Mn,Fe)的合成、改性与电化学性能研究", 《中国优秀博硕士学位论文全文数据库(博士)工程科技II辑》 *

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