CN107482183B - Preparation method of nanometer flower-shaped lithium ion battery negative electrode material - Google Patents

Preparation method of nanometer flower-shaped lithium ion battery negative electrode material Download PDF

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CN107482183B
CN107482183B CN201710572806.1A CN201710572806A CN107482183B CN 107482183 B CN107482183 B CN 107482183B CN 201710572806 A CN201710572806 A CN 201710572806A CN 107482183 B CN107482183 B CN 107482183B
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lithium ion
ion battery
cathode material
shaped lithium
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CN107482183A (en
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易健宏
刘警峰
张正富
甘国友
李才巨
鲍瑞
刘意春
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Kunming University of Science and Technology
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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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Abstract

The invention relates to a preparation method of a nanometer flower-shaped lithium ion battery cathode material, belonging to the technical field of lithium ion batteries. Dissolving ammonium metatungstate, nickel oxalate and 1,2,4 triazole into deionized water to prepare a mixed solution, and adjusting the pH value to 1-2 by hydrochloric acid to obtain a precursor solution; reacting the precursor solution at the temperature of 150-180 ℃ for 5-6 days, filtering, washing and drying to obtain precursor powder; and roasting the precursor powder for 2-3 h at the temperature of 500-600 ℃, and cooling to obtain the nano flower-shaped lithium ion battery cathode material. The nano flower-shaped lithium ion battery cathode material prepared by the method has the characteristics of small granularity and good uniformity, and the discharge specific capacity of the assembled battery can reach 1000mA h g‑1And the cycle stability is excellent.

Description

Preparation method of nanometer flower-shaped lithium ion battery negative electrode material
Technical Field
The invention relates to a preparation method of a nanometer flower-shaped lithium ion battery cathode material, belonging to the technical field of lithium ion batteries.
Background
Energy is the life line of the current social development, and the storage and the application of new energy become important research hotspots at present due to the increasingly exhausted fossil fuel and the serious problem of environmental pollution. As an important energy storage system, lithium ion batteries are receiving much attention in the field of new energy technologies. At present, the development of new energy technologies such as electric vehicles and the like puts higher demands on lithium ion batteries, wherein energy density and power density are particularly concerned. The energy density of a lithium ion battery is mainly determined by the energy density of the electrode material. Transition metal oxides have high theoretical specific capacity and specific energy density, and can be used as a preferred material for lithium ion batteries with high specific energy density, so that the transition metal oxides are widely researched and paid attention in recent years.
The nanometer transition metal oxide (MO, M = Co, Ni, Cu, Fe, W) cathode has good lithium storage performance, and many other transition metal oxides such as CuO, Fe2O3、Fe3O4、Co3O4、WO3Etc. can be obtained by conversion reaction
Figure DEST_PATH_IMAGE002
And the capacity of the lithium storage battery is far higher than that of a graphite negative electrode material used in a commercial lithium ion battery. In which WO3Is the most stable oxide of tungsten at normal temperature, has little environmental toxicity, low price and high theoretical specific capacity (693mAh ∙ g-1), is a lithium ion battery cathode material with development potential, however, the block WO is3The conductivity is low, and the volume change is large in the charging and discharging process, so that the multiplying power performance and the cycling stability are poor.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a nanometer flower-shaped lithium ion battery cathode material, namely WO is prepared by taking heteropoly acid of tungsten and nickel as a precursor3The method has the advantages of simple process and low cost, and the obtained lithium ion battery cathode material has small granularity, good uniformity, a nano flower-shaped structure, higher specific discharge capacity and excellent cycle performance.
A preparation method of a nanometer flower-shaped lithium ion battery cathode material comprises the following specific steps:
(1) dissolving ammonium metatungstate, nickel oxalate and 1,2, 4-triazole into deionized water to prepare a mixed solution, and adjusting the pH value to 1-2 by hydrochloric acid to obtain a precursor solution;
(2) reacting the precursor solution obtained in the step (1) at the temperature of 150-180 ℃ for 5-6 days, filtering, washing and drying to obtain precursor powder;
(3) roasting the precursor powder obtained in the step (2) for 2-3 hours at the temperature of 500-600 ℃, and cooling to obtain a nano flower-shaped lithium ion battery cathode material;
in the step (1), the molar ratio of ammonium metatungstate to nickel oxalate to 1,2, 4-triazole is 3 (2-4) to 6-12;
WO prepared by the method of the invention3Carrying out electrochemical performance test on the negative electrode material powder of the/Ni lithium ion battery: mixing WO3Mixing and grinding the negative electrode material powder of the/Ni lithium ion battery, Ketjen black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1 to assemble the CR2025 button cell; and testing the charge and discharge performance after standing for 24 hours.
The invention has the beneficial effects that:
(1) the invention adopts one-step hydrothermal method to obtain heteropoly acid of tungsten and nickel as precursor material, and the heteropoly acid is roasted in air environment to obtain WO3The negative electrode material powder of the/Ni lithium ion battery; the method has simple process and low cost; product WO3The negative electrode material powder of the/Ni lithium ion battery has the advantages of small and uniform granularity, organic combination of tungsten and nickel and the like; the heat preservation time in the roasting process is short, the particles are ensured to be uniform and fine, and the growth of the particles is avoided.
(2) Nano WO3the/Ni lithium ion battery cathode material powder is used for preparing a lithium ion battery, and compared with the traditional cathode material tungsten oxide, the electrochemical performance is improved. In the roasting process, tungsten and nickel are organically combined to form a nano flower-shaped structure, so that the insertion and the separation of lithium ions of the material are further improved, the discharge specific capacity of the battery is increased, and the discharge specific capacity is 1050mA h g-1And the cycle stability is more excellent.
Drawings
FIG. 1 shows the nano-sized WO obtained in example 13Scanning electron microscope images of the/Ni lithium ion battery cathode material powder;
fig. 2 is a charge-discharge curve of the lithium ion battery of example 1;
fig. 3 is a rate performance curve for the lithium ion battery of example 1.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a preparation method of a nanometer flower-shaped lithium ion battery cathode material comprises the following specific steps:
(1) dissolving ammonium metatungstate, nickel oxalate and 1,2, 4-triazole into deionized water to prepare a mixed solution, and adjusting the pH value to 2 by hydrochloric acid to obtain a precursor solution; wherein the molar ratio of ammonium metatungstate to nickel oxalate to 1,2, 4-triazole is 3:2: 6;
(2) transferring the precursor solution obtained in the step (1) to a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 5.2 days at the temperature of 175 ℃, filtering, washing and drying to obtain precursor powder;
(3) roasting the precursor powder obtained in the step (2) for 2 hours at the temperature of 500 ℃, and cooling along with the furnace to obtain the nano flower-shaped WO3a/Ni lithium ion battery cathode material;
and (3) electrochemical performance testing:
the nano WO obtained in this example3Weighing the negative electrode material powder of the/Ni lithium ion battery, Ketjen black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, placing the powder into an agate mortar, dropwise adding a proper amount of N-methyl-2-pyrrolidone (NMP), and uniformly grinding; coating the copper foil on a Cu foil with the thickness of 0.15mm, then placing the copper foil in a vacuum drying oven for drying for 24 hours at the temperature of 80 ℃, and then taking out the pole piece to be used as a negative pole;
the metal lithium sheet is used as a negative electrode and a reference electrode, the polypropylene microporous membrane is used as a diaphragm, and 1mol/LiPF6The + EC/DMC/EMC is electrolyte, and is assembled into a CR2025 stainless steel button cell in a glove box filled with argon and with the moisture content lower than 2 ppm; standing for 24h, and testing the charge and discharge performance of the material;
the nano-WO prepared in this example3The scanning electron microscope picture of the/Ni lithium ion battery cathode material powder is shown in FIG. 1, and from FIG. 1, it can be seen that the nano WO of the embodiment3The negative electrode material of the/Ni lithium ion battery is in a nanometer flower-shaped structure; the nano-WO prepared in this example3The charge-discharge curve of the lithium ion battery prepared from the/Ni lithium ion battery negative electrode material is shown in figure 2, and as can be seen from figure 2, the maximum specific discharge capacity is 1039mA hg-1(ii) a The nano-WO prepared in this example3The rate performance curve of the lithium ion battery prepared from the/Ni lithium ion battery cathode material is shown in fig. 3, and it can be known from fig. 3 that the nano WO of the embodiment3The negative electrode material of the/Ni lithium ion battery has excellent stability under high current density.
Example 2: a preparation method of a nanometer flower-shaped lithium ion battery cathode material comprises the following specific steps:
(1) dissolving ammonium metatungstate, nickel oxalate and 1,2, 4-triazole into deionized water to prepare a mixed solution, and adjusting the pH value to 1.5 by hydrochloric acid to obtain a precursor solution; wherein the molar ratio of ammonium metatungstate to nickel oxalate to 1,2, 4-triazole is 3:3: 8;
(2) transferring the precursor solution obtained in the step (1) into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 5.5 days at the temperature of 170 ℃, filtering, washing and drying to obtain precursor powder;
(3) roasting the precursor powder obtained in the step (2) for 2.5 hours at the temperature of 550 ℃, and cooling along with the furnace to obtain the nano flower-shaped WO3a/Ni lithium ion battery cathode material;
and (3) electrochemical performance testing: assembling a CR2025 button cell according to the method of the embodiment 1, standing for 24h, and testing the charge and discharge performance of the button cell; the nano-WO prepared in this example3The maximum specific discharge capacity of the lithium ion battery prepared from the/Ni lithium ion battery cathode material is 1051mA h g-1。
Example 3: a preparation method of a nanometer flower-shaped lithium ion battery cathode material comprises the following specific steps:
(1) dissolving ammonium metatungstate, nickel oxalate and 1,2, 4-triazole into deionized water to prepare a mixed solution, and adjusting the pH value to 1 by hydrochloric acid to obtain a precursor solution; wherein the molar ratio of ammonium metatungstate to nickel oxalate to 1,2, 4-triazole is 3:4: 10;
(2) transferring the precursor solution obtained in the step (1) to a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 5.0 days at the temperature of 180 ℃, filtering, washing and drying to obtain precursor powder;
(3) roasting the precursor powder obtained in the step (2) for 3.5 hours at the temperature of 600 ℃, and cooling along with the furnace to obtain the nano flower-shaped WO3a/Ni lithium ion battery cathode material;
and (3) electrochemical performance testing: assembling a CR2025 button cell according to the method of the embodiment 1, standing for 24h, and testing the charge and discharge performance of the button cell; the nano-WO prepared in this example3The maximum specific discharge capacity of the lithium ion battery prepared from the/Ni lithium ion battery cathode material is 1028mA h g-1。
Example 4: a preparation method of a nanometer flower-shaped lithium ion battery cathode material comprises the following specific steps:
(1) dissolving ammonium metatungstate, nickel oxalate and 1,2, 4-triazole into deionized water to prepare a mixed solution, and adjusting the pH value to 2 by hydrochloric acid to obtain a precursor solution; wherein the molar ratio of ammonium metatungstate to nickel oxalate to 1,2, 4-triazole is 3:4: 12;
(2) transferring the precursor solution obtained in the step (1) into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, reacting for 6.0 days at the temperature of 150 ℃, filtering, washing and drying to obtain precursor powder;
(3) roasting the precursor powder obtained in the step (2) for 3 hours at the temperature of 600 ℃, and cooling along with the furnace to obtain the nano flower-shaped WO3a/Ni lithium ion battery cathode material;
and (3) electrochemical performance testing: assembling a CR2025 button cell according to the method of the embodiment 1, standing for 24h, and testing the charge and discharge performance of the button cell; the nano-WO prepared in this example3The maximum specific discharge capacity of the lithium ion battery prepared from the/Ni lithium ion battery cathode material is 1014mA h g-1。

Claims (2)

1. A preparation method of a nanometer flower-shaped lithium ion battery cathode material is characterized by comprising the following specific steps:
(1) dissolving ammonium metatungstate, nickel oxalate and 1,2, 4-triazole into deionized water to prepare a mixed solution, and adjusting the pH value to 1-2 by hydrochloric acid to obtain a precursor solution;
(2) reacting the precursor solution obtained in the step (1) at the temperature of 150-180 ℃ for 5-6 days, filtering, washing and drying to obtain precursor powder;
(3) and (3) roasting the precursor powder obtained in the step (2) for 2-3 hours at the temperature of 500-600 ℃, and cooling to obtain the nano flower-shaped lithium ion battery cathode material.
2. The method for preparing the nano flower-shaped lithium ion battery negative electrode material according to claim 1, is characterized in that: in the step (1), the molar ratio of ammonium metatungstate to nickel oxalate to 1,2, 4-triazole is 3 (2-4) to 6-12.
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CN108417788B (en) * 2018-01-29 2020-08-25 昆明理工大学 Preparation method of chromium and silver bimetal doped nano tungsten oxide @ porous carbon negative electrode material
CN112758990A (en) * 2020-11-09 2021-05-07 中国科学院合肥物质科学研究院 Preparation method and application of transition metal nitride lithium ion battery cathode material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105271419A (en) * 2015-09-30 2016-01-27 南京理工大学 Preparation method of tungstic oxide nanosheet self-assembled micro-nano flower-balls
CN105948129A (en) * 2016-06-12 2016-09-21 南昌航空大学 Controllable synthesis method for different nanocrystalline types of WO3 and application of method to wastewater
CN106430313A (en) * 2016-09-26 2017-02-22 安阳师范学院 Hollow flower-clump-shaped hierarchically-structured gas-sensitive WO3 material, synthesizing method and application
CN106611847A (en) * 2017-01-13 2017-05-03 昆明理工大学 Preparation method of titanium-doped nano tungsten oxide negative electrode material
CN106654245A (en) * 2017-01-13 2017-05-10 昆明理工大学 Preparation method of cobalt-doped nano tungsten oxide negative electrode material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105271419A (en) * 2015-09-30 2016-01-27 南京理工大学 Preparation method of tungstic oxide nanosheet self-assembled micro-nano flower-balls
CN105948129A (en) * 2016-06-12 2016-09-21 南昌航空大学 Controllable synthesis method for different nanocrystalline types of WO3 and application of method to wastewater
CN106430313A (en) * 2016-09-26 2017-02-22 安阳师范学院 Hollow flower-clump-shaped hierarchically-structured gas-sensitive WO3 material, synthesizing method and application
CN106611847A (en) * 2017-01-13 2017-05-03 昆明理工大学 Preparation method of titanium-doped nano tungsten oxide negative electrode material
CN106654245A (en) * 2017-01-13 2017-05-10 昆明理工大学 Preparation method of cobalt-doped nano tungsten oxide negative electrode material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Hierarchical WO3 flowers comprising porous single-crystalline nanoplates show enhanced lithium storage and photocatalysis;Yongcai Qiu等;《Nano Res.》;20121019;第5卷(第11期);摘要，图2 *

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