CN109860549B - Preparation method of shell-core structure binary carbonate anode material - Google Patents
Preparation method of shell-core structure binary carbonate anode material Download PDFInfo
- Publication number
- CN109860549B CN109860549B CN201910064452.9A CN201910064452A CN109860549B CN 109860549 B CN109860549 B CN 109860549B CN 201910064452 A CN201910064452 A CN 201910064452A CN 109860549 B CN109860549 B CN 109860549B
- Authority
- CN
- China
- Prior art keywords
- carbonate
- manganese
- reaction kettle
- nickel
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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 application provides a preparation method of a shell-core structure binary carbonate anode material, and belongs to the technical field of lithium ion battery anode materials. The application solves the technical problem that the bimetal carbonate with hierarchical structure is used as the cathode material due to the restriction of the carbonate synthesis method and the like. The method comprises the following steps: 1. uniformly dispersing graphite oxide into deionized water, adding manganese acetate and nickel acetate, and dropwise adding urea solution while stirring after complete dissolution; 2. stirring after the dripping is finished, pouring the mixture into a reaction kettle, sealing the reaction kettle, placing the reaction kettle in an oven for heating reaction, washing the reaction kettle to be neutral by deionized water after the reaction is finished, and freeze-drying the reaction kettle to obtain the anode material. The mixed bimetallic carbonate with the shell-core structure prepared by the application has excellent electrochemical performance and rate capability.
Description
Technical Field
The application belongs to the technical field of lithium ion battery cathode materials; relates to a preparation method of a shell-core structure binary carbonate anode material; specifically, the nickel-doped manganese carbonate@manganese-doped nickel carbonate/graphene three-phase composite material for the negative electrode of the lithium ion battery is prepared by a one-step method.
Background
With the development of social technology, the practical use of power automobiles and portable electronic devices has advanced, and lithium ion secondary batteries are required to have higher power density and energy density. Currently, commercial lithium ion battery cathode material graphite has lower specific capacity (372 mAhg -1 ) And potential safety hazards, cannot meet higher power demands. Transition group carbonates due to their higher specific capacity (1000+mAhg -1 Is 3 times of the specific capacity of the graphite anode material for the commercial lithium ion battery at present).
When manganese carbonate is used as a negative electrode material of a lithium ion battery, the specific capacity and the cycling stability of active substances are greatly lost due to low conductivity and volume change generated in the electrochemical lithium intercalation/deintercalation process, namely volume expansion and the like in the charge and discharge process.
The current research shows that the comprehensive electrochemical performance of the transition carbonate can be effectively improved by designing and adjusting the components and the structure of the anode material.
At present, researches show that the electron conductivity of carbonate can be improved, the conductivity of the material can be improved, and the electrochemical performance can be promoted by doping the bimetal element. Although the conductivity of the composite material can be improved by adopting element doping, and meanwhile, the structural collapse of the electrode material can be restrained by the synergistic effect of different elements. The doping elements which are green and environment-friendly, rich in reserves and good in conductivity are selected, so that the method has important significance for pushing the practical application of the electrode. Meanwhile, in order to further improve the electrochemical activity of the active substance, the micro/nano material with the grading/hetero-structure is prepared through ingenious micro/nano structure design, so that the volume expansion of the material in the electrochemical process can be effectively slowed down, and the electrochemical circulation capacity of the material is enhanced. However, due to the limitations of the carbonate synthesis method, the heterostructure design of carbonates has been a difficult problem, namely, the hierarchical structure design of bimetallic carbonates is difficult, which limits the practical development of the bimetallic carbonates.
Disclosure of Invention
The application aims to solve the technical problem that the bimetal carbonate with the hierarchical structure is used as the anode material due to the limitation of a carbonate synthesis method and the like, and provides a preparation method of a shell-core structure binary carbonate anode material.
In order to solve the technical problems, the preparation method of the shell-core structure binary carbonate anode material is completed through the following steps:
uniformly dispersing graphite oxide into deionized water, adding manganese acetate and nickel acetate, and dropwise adding urea solution while stirring after the manganese acetate and the nickel acetate are completely dissolved;
and step two, stirring for 10 to 30 minutes after the dripping is finished, pouring the mixture into a reaction kettle, sealing the reaction kettle, placing the reaction kettle in an oven for heating reaction, washing the reaction kettle with deionized water to be neutral after the reaction is finished, and freeze-drying the reaction kettle to obtain the anode material.
Further defined, in step one, 100mg to 200mg of graphite oxide is uniformly dispersed into 70mL of deionized water.
Further limiting that the total addition amount of the manganese acetate and the nickel acetate in the first step is 1mmol to 5mmol; wherein, the molar ratio of manganese acetate to nickel acetate is (0.25:0.75) - (0.75:0.25).
Further defined, step one said urea solution is formulated by dissolving 15mmol urea into 10mL deionized water.
Further limited, in the second step, heating and reacting for 13-20 hours at 150-200 ℃.
The method utilizes nickel carbonate and graphene to modify manganese carbonate, and synthesizes manganese-doped nickel carbonate-coated nickel-doped manganese carbonate shell-core structure microparticles (Ni-MnCO) through a one-step hydrothermal method 3 @Mn-NiCO 3 ) The application obtains a bimetal carbonate/graphene composite material with a shell-core structure, wherein the shell structure is nickel-doped manganese carbonate, the core structure is manganese-doped nickel carbonate, and the nickel-doped manganese carbonate@manganese-doped nickel carbonate/graphene ternary composite material is formed after the bimetal carbonate/graphene composite material is compounded with graphene. The application synthesizes the carbonate material with the shell-core structure. For Ni-MnCO of the present application 3 @Mn-NiCO 3 Electrochemical performance tests of the RGO composite material show that the composite material with the shell-core structure can show high specific capacity and excellent rate performance and can also withstand longer cycle in the rapid charge and discharge process. The Ni element in the anode material prepared by the method is mainly distributed in the shell layer, and the Mn element is mainly distributed in the core.
When the structure of the application is used as a negative electrode, the volume expansion can be effectively relieved in the charge and discharge process due to the characteristic of the hierarchical structure of the shell and the core, and the cycle performance can be enhanced. Meanwhile, due to the existence of the bimetallic element, the electron state density of different metal cations is different, and the activation energy of electron transmission between different metal ions is lower, so that the electron transmission is promoted and the intrinsic conductivity of the material is improved due to the synergistic effect between the bimetallic element and the metal cations.
The method is simple and easy to operate.
Drawings
FIG. 1 is an XRD pattern of a negative electrode material and a manganese carbonate/graphene composite material prepared by different proportions of manganese acetate and nickel acetate;
FIG. 2 is a scanning photograph and a surface scanning photograph of the anode material prepared in example 1;
FIG. 3 is a line scan photograph of the negative electrode material prepared in example 1;
FIG. 4 is a graph showing the ratio performance of manganese acetate to nickel acetate to produce a negative electrode material and a manganese carbonate/graphene composite material;
FIG. 5 is a graph comparing cycle performance of a negative electrode material and a manganese carbonate/graphene composite material prepared from different ratios of manganese acetate to nickel acetate;
FIG. 6 is a CV curve of a negative electrode material and a manganese carbonate/graphene composite material prepared by different ratios of manganese acetate and nickel acetate; in FIG. 6, (a) NM@MN/RGO-1, (b) NM@MN/RGO-2, (c) NM@MN/RGO-3, (d) MnCO 3 RGO, 1st, 2nd3 rd 4th represents the number of reaction turns, and represents a first turn, a second turn, a third turn and a fourth turn respectively;
FIG. 7 is a cycle performance curve (a) 2Ag for the negative electrode material NM@MN/RGO-2 prepared in example 2 -1 ；(b)5Ag -1 。
Detailed Description
Example 1:
the preparation method of the shell-core structure binary carbonate anode material in the embodiment is completed through the following steps:
step one, adding 160mg of graphite oxide into 70mL of deionized water, carrying out ultrasonic treatment for 30min, mechanically stirring for 30min, uniformly dispersing the graphite oxide into the deionized water, adding 3mmol of manganese acetate and nickel acetate (the molar ratio is 0.75:0.25), and dropwise adding a urea solution while stirring after complete dissolution, wherein the urea solution is prepared by dissolving 15mmol of urea into 10mL of deionized water. The method comprises the steps of carrying out a first treatment on the surface of the
Stirring for 30min after the dripping is finished, pouring the mixture into a reaction kettle, sealing the reaction kettle, heating the reaction kettle in an oven at 180 ℃ for 15h, washing the reaction kettle with deionized water to be neutral after the reaction is finished, and freeze-drying the reaction product to obtain the negative electrode material, wherein the negative electrode material is marked as NM@MN/RGO-1.
Example 2:
the preparation method of the shell-core structure binary carbonate anode material in the embodiment is completed through the following steps:
adding 160mg of graphite oxide into 70mL of deionized water, carrying out ultrasonic treatment for 30min, mechanically stirring for 30min, uniformly dispersing the graphite oxide into the deionized water, adding 3mmol of manganese acetate and nickel acetate (the molar ratio is 0.50:0.50), and dropwise adding a urea solution while stirring after complete dissolution, wherein the urea solution is prepared by dissolving 15mmol of urea into 10mL of deionized water;
stirring for 30min after the dripping is finished, pouring the mixture into a reaction kettle, sealing the reaction kettle, heating the reaction kettle in an oven at 180 ℃ for 15h, washing the reaction kettle with deionized water to be neutral after the reaction is finished, and freeze-drying the reaction product to obtain the negative electrode material, wherein the negative electrode material is marked as NM@MN/RGO-2.
Example 3:
the preparation method of the shell-core structure binary carbonate anode material in the embodiment is completed through the following steps:
adding 160mg of graphite oxide into 70mL of deionized water, carrying out ultrasonic treatment for 30min, mechanically stirring for 30min, uniformly dispersing the graphite oxide into the deionized water, adding 3mmol of manganese acetate and nickel acetate (the molar ratio is 0.25:0.75), and dropwise adding a urea solution while stirring after complete dissolution, wherein the urea solution is prepared by dissolving 15mmol of urea into 10mL of deionized water;
stirring for 30min after the dripping is finished, pouring the mixture into a reaction kettle, sealing the reaction kettle, heating the reaction kettle in an oven at 180 ℃ for 15h, washing the reaction kettle with deionized water to be neutral after the reaction is finished, and freeze-drying the reaction product to obtain the negative electrode material, wherein the negative electrode material is marked as NM@MN/RGO-3.
Comparative example:
the preparation method of the shell-core structure binary carbonate anode material in the embodiment is completed through the following steps:
step one, adding 160mg of graphite oxide into 70mL of deionized water, carrying out ultrasonic treatment for 30min, mechanically stirring for 30min, uniformly dispersing the graphite oxide into the deionized water, adding 3mmol of manganese acetate, and dropwise adding urea solution while stirring after complete dissolution, wherein the urea solution is prepared by dissolving 15mmol of urea into 10mL of deionized water.
Stirring for 30min after the dripping is finished, pouring the mixture into a reaction kettle, sealing the reaction kettle, heating the reaction kettle in an oven at 180 ℃ for reaction for 15h, washing the reaction kettle with deionized water to be neutral after the reaction is finished, and freeze-drying the reaction product to obtain a negative electrode material, namely MnCO 3 /RGO。
The properties of the obtained products of examples 1 to 3 and comparative examples were tested and the results are shown in FIGS. 1 to 7:
as can be seen from FIG. 1, the products obtained in examples 1 to 3 and comparative example were two phases of manganese carbonate and nickel carbonate, and it can be seen from an enlarged view of peaks that manganese carbonate is not pure manganese carbonate but Ni element is doped therein so that the peak position is shifted, while nickel carbonate is not pure nickel carbonate but peaks are shifted to a low angle due to the doping of Mn.
As can be seen from fig. 2 and 3, ni element is mainly distributed in the shell layer and Mn element is mainly distributed in the core.
As can be seen from FIGS. 4 and 5, the cycle performance and the multiplying power of the products obtained in examples 1 to 3 and comparative example were improved.
The CV curves of the composites prepared by the comparative examples 1-3 and comparative example methods, as well as the manganese carbonate/graphene composites (fig. 6), can be found that carbonates with bimetallic have more redox reaction pairs, indicating greater electrochemical deactivation.
By subjecting the product of example 2 to a large current long cycle, the results are shown in FIG. 7, and it can be found that it shows a higher specific capacity and also better stability.
Claims (5)
1. The preparation method of the shell-core structure binary carbonate anode material is characterized by comprising the following steps of:
uniformly dispersing graphite oxide into deionized water, adding manganese acetate and nickel acetate, and dropwise adding urea solution while stirring after the manganese acetate and the nickel acetate are completely dissolved;
stirring after the dripping is finished, pouring the mixture into a reaction kettle, sealing the reaction kettle, placing the reaction kettle in an oven for heating reaction, washing the reaction kettle with deionized water to be neutral after the reaction is finished, and freeze-drying the reaction kettle to obtain a negative electrode material;
in the first step, 100-200 mg of graphite oxide is uniformly dispersed into 70mL deionized water, the total addition amount of manganese acetate and nickel acetate is 3mmol, and the molar ratio of manganese acetate to nickel acetate is 0.50:0.50;
wherein the core structure is nickel-doped manganese carbonate, the shell structure is manganese-doped nickel carbonate, and the manganese-doped nickel carbonate is compounded with graphene;
the anode material is composed of two phases of manganese carbonate and nickel carbonate, wherein the manganese carbonate is not pure manganese carbonate, but Ni element is doped in the manganese carbonate; meanwhile, nickel carbonate is not pure nickel carbonate, and Mn is doped in the nickel carbonate, wherein Ni element is mainly distributed in a shell layer, and Mn element is mainly distributed in a core; the negative electrode material is ellipsoidal micrometer particles.
2. The method according to claim 1, wherein the urea solution is prepared by dissolving 15mmol of urea in 10mL deionized water.
3. The preparation method according to claim 1, wherein the stirring is performed for 10min to 30min after the dropping in the first step is completed.
4. The preparation method according to claim 1, wherein in the second step, the reaction is performed under heating at 150-200 ℃ for 13-20 hours.
5. The process according to claim 1, wherein the reaction is carried out in step two by heating at 180℃to 15 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910064452.9A CN109860549B (en) | 2019-01-23 | 2019-01-23 | Preparation method of shell-core structure binary carbonate anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910064452.9A CN109860549B (en) | 2019-01-23 | 2019-01-23 | Preparation method of shell-core structure binary carbonate anode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109860549A CN109860549A (en) | 2019-06-07 |
| CN109860549B true CN109860549B (en) | 2023-08-18 |
Family
ID=66895965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910064452.9A Active CN109860549B (en) | 2019-01-23 | 2019-01-23 | Preparation method of shell-core structure binary carbonate anode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109860549B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005285572A (en) * | 2004-03-30 | 2005-10-13 | Nikko Materials Co Ltd | Precursor for lithium-ion secondary battery anode material, its manufacturing method, and manufacturing method of anode material using it |
| CN104538623A (en) * | 2015-01-20 | 2015-04-22 | 河北工业大学 | Preparation method for sphere-like lithium nickel manganese oxide positive electrode material |
| CN105244501A (en) * | 2015-09-25 | 2016-01-13 | 湖北工程学院 | Active substance precursor nickel manganese carbonate of lithium ion battery electrode |
| CN105304901A (en) * | 2015-09-25 | 2016-02-03 | 北京理工大学 | Nickel-carbonate-doped manganese-carbonate-based anode material for lithium ion battery and preparation method |
| CN107394178A (en) * | 2017-08-02 | 2017-11-24 | 中国石油大学(华东) | A kind of sodium-ion battery negative pole cobalt carbonate/graphene composite material and preparation method and application |
| CN108439474A (en) * | 2018-03-12 | 2018-08-24 | 南京信息工程大学 | A kind of lithium battery high-performance Ni doping MnCO3The preparation method of negative material |
-
2019
- 2019-01-23 CN CN201910064452.9A patent/CN109860549B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005285572A (en) * | 2004-03-30 | 2005-10-13 | Nikko Materials Co Ltd | Precursor for lithium-ion secondary battery anode material, its manufacturing method, and manufacturing method of anode material using it |
| CN104538623A (en) * | 2015-01-20 | 2015-04-22 | 河北工业大学 | Preparation method for sphere-like lithium nickel manganese oxide positive electrode material |
| CN105244501A (en) * | 2015-09-25 | 2016-01-13 | 湖北工程学院 | Active substance precursor nickel manganese carbonate of lithium ion battery electrode |
| CN105304901A (en) * | 2015-09-25 | 2016-02-03 | 北京理工大学 | Nickel-carbonate-doped manganese-carbonate-based anode material for lithium ion battery and preparation method |
| CN107394178A (en) * | 2017-08-02 | 2017-11-24 | 中国石油大学(华东) | A kind of sodium-ion battery negative pole cobalt carbonate/graphene composite material and preparation method and application |
| CN108439474A (en) * | 2018-03-12 | 2018-08-24 | 南京信息工程大学 | A kind of lithium battery high-performance Ni doping MnCO3The preparation method of negative material |
Non-Patent Citations (1)
| Title |
|---|
| One-step hydrothermal method synthesis of core shell LiNi0.5Mn1.5O4 spinel cathodes for Li-ion batteries;Liu Yuanzhuang 等;《JOURNAL OF POWER SOURCES》;20140123;第256卷;第66-71页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109860549A (en) | 2019-06-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20220376235A1 (en) | Composite Negative Electrode Material and Method for Preparing Composite Negative Electrode Material, Negative Electrode Plate of Lithium Ion Secondary Battery, and Lithium Ion Secondary Battery | |
| Lu et al. | Core-shell materials for advanced batteries | |
| CN104885269B (en) | Anode active material for lithium secondary battery, lithium secondary battery including same, and method for manufacturing anode active material | |
| CN111564612B (en) | High-thermal-conductivity and high-electrical-conductivity lithium battery positive electrode material and preparation method thereof | |
| CN107732172B (en) | Lithium ion battery cathode material and preparation method thereof | |
| CN104157854A (en) | Preparation method for ternary positive electrode material of graphene composite lithium ion battery | |
| CN105336941A (en) | High-voltage LiNixCoyMnzM(1-x-y-z)O2 cathode material, preparation method thereof, cathode and battery | |
| CN109411733A (en) | Modified anode material for lithium-ion batteries of compound coating and preparation method thereof, anode and lithium ion battery | |
| CN104167540A (en) | Negative electrode active material and preparation method thereof and lithium ion battery | |
| CN104766959B (en) | A preparing method of a Li(Ni0.8Co0.1Mn0.1)O2 ternary material | |
| CN108658119B (en) | Method for preparing copper sulfide nanosheet and compound thereof by low-temperature vulcanization technology and application | |
| CN107910532A (en) | A kind of preparation method of graphene coated nickle cobalt lithium manganate composite material | |
| CN104332619A (en) | Polypyrrole- coated full-gradient cathode material and preparation method thereof | |
| CN109449379A (en) | A kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material and the preparation method and application thereof | |
| CN106887575A (en) | A kind of cobalt acid zinc/graphene composite negative pole and preparation method thereof and lithium ion battery | |
| CN105390682A (en) | Preparation method for lithium iron phosphate microsphere/three-dimensional graphene composite electrode material and application of composite electrode material | |
| JP2019016484A (en) | Negative electrode for all solid-state battery and all solid-state battery including the same | |
| CN104852040A (en) | Preparation method of lithium nickel manganese oxide anode material for high-rate lithium ion battery | |
| Seo et al. | Multi-Doped (Ga, B) Li [Ni0. 885Co0. 100Al0. 015] O2 Cathode | |
| CN109411706B (en) | Modified working electrode and preparation method thereof | |
| CN112186166B (en) | Molybdenum/cobalt oxide-carbon composite material and preparation method thereof, lithium ion battery negative electrode piece and lithium ion battery | |
| CN112331852B (en) | Nitrogen self-doped carbon-coated silicon monoxide negative electrode material and preparation method and application thereof | |
| CN109860549B (en) | Preparation method of shell-core structure binary carbonate anode material | |
| CN108899473B (en) | High-performance flexible lithium secondary battery positive electrode and preparation method thereof | |
| CN108682842B (en) | Y-doped CaMnO3Coated ternary positive electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |