CN112928244A - Lithium ion battery electrode material, preparation method and battery - Google Patents

Lithium ion battery electrode material, preparation method and battery Download PDF

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Publication number
CN112928244A
CN112928244A CN201911232263.4A CN201911232263A CN112928244A CN 112928244 A CN112928244 A CN 112928244A CN 201911232263 A CN201911232263 A CN 201911232263A CN 112928244 A CN112928244 A CN 112928244A
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lithium ion
ion battery
electrode material
reaction
reaction kettle
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唐地源
祝建勋
刘海强
王鹏程
盛杰
李军
于永昕
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Jinan Shengquan Group Share Holding 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/388—Halogens
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • 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 lithium ion battery electrode material, a preparation method and a battery, wherein the method comprises the following steps: putting a solvent and a fluorine source raw material into a reaction kettle; putting the lithium ion battery electrode material into the reaction kettle, and sealing the reaction kettle to perform hydrothermal reaction; and after the reaction is finished, taking out the reaction product from the reaction kettle, and washing and drying the reaction product. The invention adopts a hydrothermal gas phase method process means, the method is simple, effective, green and economic, and the prepared surface-doped modified lithium ion battery electrode material has excellent electrochemical performance and is very suitable to be used as a battery anode material.

Description

Lithium ion battery electrode material, preparation method and battery
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a lithium ion battery electrode material, a preparation method and a battery.
Background
With the increasing severity of the problems of energy crisis, environmental pollution and the like, the sustainable development of new energy becomes an important means for building a low-carbon environment-friendly society. The development of various new energy sources necessarily requires corresponding energy transmission, storage, transformation and other technologies. Currently, the common energy storage modes are mainly classified into five types: mechanical energy storage, electromagnetic energy storage, phase change energy storage, chemical energy storage and electrochemical energy storage. Compared with other modes, the electrochemical energy storage has the advantages of convenience in use, less environmental pollution, no region limitation, no Carnot cycle limitation on energy conversion, high conversion efficiency, high specific energy and specific power and the like. These advantages make it the most widely used energy storage technology.
The electrochemical energy storage mainly comprises a lead-acid battery, a lithium ion battery, a fuel battery and a super capacitor. Lithium ion batteries are one of the most popular electrochemical energy storage technologies at present and are also the fastest-developing technology in recent years. The lithium ion battery developed in the 90 s is one of the most important batteries at present, has high capacity, high specific energy, long cycle life, low self-discharge rate and no memory effect, and can meet the requirements of electric automobiles with higher requirements on volume, service life, power and the like. Therefore, it is considered as a power source with great potential for next generation Electric Vehicles (EVs), Hybrid Electric Vehicles (HEVs), and plug-in hybrid electric vehicles (PHEVs). At present, the key for restricting the rapid development and practical application of the lithium ion battery is the electrode material.
Due to crystal structure, reaction interface, electrolyte and other reasons, capacity attenuation of the electrode material is relatively serious, and cycle life is poor. In addition, the rate capability of the battery is to be further improved to meet the requirements of large-current charging and discharging in special scenes. In order to improve the cycle performance and rate performance of the material, bulk phase doping and surface coating methods are generally adopted for modification. The structural stability of the material can be improved through bulk phase doping, and the cycle performance of the material is further improved. The doping of some elements can improve the electronic conductivity and the lithium ion diffusion coefficient of the material, thereby improving the rate capability of the material. The direct contact between the electrode material and the electrolyte is effectively avoided through surface coating, so that the electrolyte and the side reaction between HF in the electrolyte and the material are inhibited, the interface stability of the battery material is improved, and the stability of the surface structure is improved. Fewer side reactions are beneficial to optimizing the interface of the electrode and electrolyte reaction, and simultaneously, the interface impedance of the electrode is reduced, so that the rate capability of the material is improved.
Although bulk doping can improve the structural stability of the material, the introduction of doping elements, particularly invariable valence elements, reduces the proportion of transition metals in the material for charge compensation, which leads to a reduction in the number of lithium ions that can be deintercalated in the material, resulting in a reduction in the effective reversible capacity of the material.
The surface coating generally adopts oxides, fluorides, phosphates, silicates and the like, the lithium ion diffusion coefficient and the conductivity of the materials are relatively low, and the existence of the materials is not favorable for the transmission of lithium ions and electrons between the surface of the material and an SEI (Solid Electrolyte Interface) film.
Disclosure of Invention
In order to solve the problems of the prior art, an object of the present invention is to provide a method for surface doping modification of an electrode material of a lithium ion battery, which comprises performing F treatment on the surface of the electrode material of the lithium ion battery by using a hydrothermal gas phase method-Doping ofThrough the surface F-The surface of the electrode material of the lithium ion battery is formed with a fluorine-containing protective layer by doping modification, thereby improving the reaction interface of the electrode material of the lithium ion battery and electrolyte and improving the electrochemical performance of the electrode material of the lithium ion battery.
The invention provides a method for surface doping modification of an electrode material of a lithium ion battery, which comprises the following steps: putting a solvent and a fluorine source raw material into a reaction kettle; putting the lithium ion battery electrode material into a reaction kettle, and sealing the reaction kettle to perform hydrothermal reaction; and after the reaction is finished, taking out the reaction product from the reaction kettle, and washing and drying the reaction product.
Further, the solvent is selected from one or a mixture of at least two of purified water, ultrapure water, deionized water or distilled water, preferably deionized water; the fluorine source material is a fluorine-containing compound, preferably HF and H2SiF6、NH4H2F3Or NH4One or a mixture of at least two of F, more preferably NH4F。
Further, the lithium ion battery electrode material comprises a lithium-containing compound selected from the group consisting of LiMn2O4、LiNi0.5Mn1.5O4、LiCoO2、LiNi1-x-yCoxMnyO2(0≤x<0.5，0≤y<0.5) or Li4Ti5O12。
Furthermore, the molar ratio of the fluorine source raw material, the solvent and the lithium ion battery electrode material is (50-100): 100-1000): 1000-10000), preferably (50-100): 300-500): 5000, more preferably (50-100): 400:5000, and more preferably 75:400: 5000.
Furthermore, the placing height of the electrode material of the lithium ion battery is higher than that of the fluorine source raw material, and the height difference is 6-16 cm, preferably 11 cm.
Further, the reaction conditions of the hydrothermal reaction include: the reaction temperature is 100-230 ℃, and preferably 180 ℃; the reaction time is 2-10 h, preferably 5 h.
Further, the washing includes: the reaction product was washed with deionized water and absolute ethanol.
Further, 0.40mol of deionized water was added to the hydrothermal reaction kettle, followed by charging 0.075mol of NH4The watch glass of F is arranged at the bottom of the hydrothermal reaction kettle; 5.00mol of LiNi are laid flat0.5Mn1.5O4The watch glass is arranged in a hydrothermal reaction kettle and is about 11cm higher than the watch glass filled with the fluorine source raw material; carefully sealing the hydrothermal reaction kettle, and then placing the hydrothermal reaction kettle in an oven for hydrothermal reaction under the condition of reaction for 5 hours at 180 ℃; the reaction product is washed by deionized water and absolute ethyl alcohol and then dried.
In addition, the invention also provides a lithium ion battery electrode material prepared by using the method.
Further, the electrode material of the lithium ion battery comprises a lithium-containing compound and a fluorine-containing layer doped on the surface of the lithium-containing compound; wherein the fluorine content in the fluorine-containing layer is 80-200ppm, preferably 95-175 ppm, and more preferably 110ppm based on the total amount of the lithium ion battery electrode material. The doping amount of F is not too much or too little, and the excessive doping amount of F can cause the change of a crystal structure, thereby leading to unknown change of electrochemical performance; when the amount of F incorporated is too small, the desired modification effect cannot be obtained.
In addition, the invention also provides a battery, which comprises the lithium ion battery electrode material.
The surface doping modification is carried out on the material, so that the reduction of reversible capacity caused by bulk phase doping modification can be reduced. Meanwhile, the surface doping combines the advantages of bulk phase doping and surface coating, the surface structure of the material and the stability of an electrochemical reaction interface are improved, and the cycle performance of the material can be effectively improved. In addition, the crystal structure of the outer layer material cannot be greatly changed due to surface doping, so that the conductivity and the lithium ion diffusion coefficient of the surface modification layer are basically equivalent to those of a bulk phase, and the influence of surface modification on the transmission of lithium ions and electrons between the surface of the material and an SEI film is further reduced.
In addition, compared with the unmodified lithium ion battery electrode material, the surface doping modification by the common high-temperature solid phase method has no obvious advantage in electrochemical performance, the method adopts a hydrothermal gas phase method process means, the method is simple, effective, green and economical, and the prepared surface doping modified lithium ion battery electrode material has excellent electrochemical performance and is very suitable to be used as the anode material of the battery.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 shows surface F prepared according to example 2-1 of the present disclosure-Doping modified LiMn2O4XRD pattern of (a).
FIG. 2 shows surface F prepared according to example 2-1 of the present disclosure-Doping modified LiMn2O4SEM image 1200 times.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Furthermore, the terms "include" and "have," as well as any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those steps or elements listed, but may alternatively include other steps or elements not listed, or inherent to such process, method, article, or apparatus.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the application. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. It is explicitly and implicitly understood by one skilled in the art that the embodiments described herein can be combined with other embodiments.
The invention provides a method for surface doping modification of an electrode material of a lithium ion battery, which comprises the following steps: putting a solvent and a fluorine source raw material into a reaction kettle; putting the lithium ion battery electrode material into a reaction kettle, and sealing the reaction kettle to perform hydrothermal reaction; and after the reaction is finished, taking out the reaction product from the reaction kettle, and washing and drying the reaction product.
Further, the solvent is selected from one or a mixture of at least two of purified water, ultrapure water, deionized water or distilled water, preferably deionized water; the fluorine source material is a fluorine-containing compound, preferably HF and H2SiF6、NH4H2F3Or NH4One or a mixture of at least two of F, more preferably NH4F。
Further, the lithium ion battery electrode material comprises a lithium-containing compound selected from the group consisting of LiMn2O4、LiNi0.5Mn1.5O4、LiCoO2、LiNi1-x-yCoxMnyO2(0≤x<0.5，0≤y<0.5) or Li4Ti5O12。
Furthermore, the molar ratio of the fluorine source raw material, the solvent and the lithium ion battery electrode material is (50-100): 100-1000): 1000-10000), preferably (50-100): 300-500): 5000, more preferably (50-100): 400:5000, and more preferably 75:400: 5000.
Furthermore, the placing height of the electrode material of the lithium ion battery is higher than that of the fluorine source raw material, and the height difference is 6-16 cm, preferably 11 cm.
Further, the reaction conditions of the hydrothermal reaction include: the reaction temperature is 100-230 ℃, and preferably 180 ℃; the reaction time is 2-10 h, preferably 5 h.
Further, the washing includes: the reaction product was washed with deionized water and absolute ethanol.
The main purpose of washing the reaction product is to remove the reaction productThe impurities in the reaction product can further improve the purity of the reaction product, and the drying treatment is carried out after the impurities are removed so as to remove the solvent such as ethanol, deionized water and the like to obtain the final product, namely the surface F-Doping modified lithium ion battery electrode material.
In the present invention, the final product obtained is F in HF obtained by decomposing the fluorine source raw material-O substituted for surface of electrode material of lithium ion battery2-Thereby realizing the doping modification of the surface of the electrode material of the lithium ion battery and obtaining the surface F-Doping modified lithium ion battery electrode material.
In the following experiments, the information on the source and purity of the main raw materials used is shown in table 1.
Table 1: the source and purity of the main raw materials
Chemical formula (II) Source Purity of
NH4F Beijing GmbH chemical reagent of national drug group Analytical purity
LiCoO2 HEFEI KEJING MATERIALS TECHNOLOGY Co.,Ltd. ＞99％
LiMn2O4 Laboratory self-control ＞99％
Li4Ti5O12 HEFEI KEJING MATERIALS TECHNOLOGY Co.,Ltd. ＞99％
LiNi0.5Mn1.5O4 HEFEI KEJING MATERIALS TECHNOLOGY Co.,Ltd. ＞99％
Examples 1 to 1
0.40mol of deionized water was added to the hydrothermal reaction kettle, which was then charged with 0.075mol of NH4And the watch glass of the F is arranged at the bottom of the hydrothermal reaction kettle. Will be tiled with 5.00mol LiCoO2The watch glass of (a) was placed in the hydrothermal reaction kettle about 11cm above the watch glass containing the fluorine source material. Carefully sealing the hydrothermal reaction kettle, and then placing the hydrothermal reaction kettle in an oven for hydrothermal reaction under the condition of reaction for 5 hours at 180 ℃. After the reaction is finished, washing the reaction product by deionized water and absolute ethyl alcohol, and then drying.
X-ray powder diffraction (XRD) analysis showed that the resulting product was a pure phase LiCoO with a space group of R-3m2No distinct hetero-phase peak (not shown) is seen; from Scanning Electron Microscope (SEM) analysis, it was found that hydrothermal vapor phase surface doping modification did not significantly change its topographical features (not shown); the ICP-AES test results showed that the F content in the prepared material was 100 ppm.
The product obtained in example 1-1 was used as a positive electrode material, and assembled into an experimental lithium ion button cell in an argon-protected glove box, and charge and discharge tests were performed at different rates, and the discharge test results are shown in "example 1-1" in table 2.
Examples 1 to 2
0.40mol of deionized water was added to the hydrothermal reaction kettle, followed by charging 0.02mol of NH4And the watch glass of the F is arranged at the bottom of the hydrothermal reaction kettle. Will be tiled with 2.66mol LiCoO2The watch glass of (a) was placed in the hydrothermal reaction kettle about 8cm above the watch glass containing the fluorine source material. The hydrothermal reaction kettle is carefully sealed and then placed in an oven for hydrothermal reaction, and the hydrothermal reaction condition is that the hydrothermal reaction is carried out for 8 hours at 230 ℃. After the reaction is finished, washing the reaction product by deionized water and absolute ethyl alcohol, and then drying.
X-ray powder diffraction (XRD) analysis showed that the resulting product was a pure phase LiCoO with a space group of R-3m2No distinct hetero-phase peak (not shown) is seen; from Scanning Electron Microscope (SEM) analysis, it was found that hydrothermal vapor phase surface doping modification did not significantly change its topographical features (not shown); the ICP-AES test results showed that the F content in the prepared material was 150 ppm.
The product obtained in example 1-2 was used as a positive electrode material, and assembled into an experimental button lithium ion battery in an argon-protected glove box, and charge and discharge tests were performed at different rates, and the discharge test results are shown in "example 1-2" in table 2.
Comparative examples 1 to 1
This comparative example was prepared with unmodified LiCoO2The lithium ion battery is assembled as a positive electrode material to test electrochemical performance.
Unmodified LiCoO2As a positive electrode material, an experimental button type lithium ion battery is assembled in an argon protective glove box, charge and discharge tests are carried out at different multiplying powers, and the results of the discharge tests are shown as 'comparative example 1-1' in table 2.
Comparative examples 1 to 2
This comparative example used a conventional high temperature solid phase method to prepare surface F-Doping modified LiCoO2Material and doped LiCoO obtained by the preparation2The lithium ion battery is assembled as a positive electrode material to test electrochemical performance.
100.0000g LiCoO2And 0.0300g NH4And F, placing the mixture in a high-speed mixer for high-speed mixing. After mixing well, the resulting mixture was placed in a sagger for heat treatment. The heat treatment temperature is 400 ℃ for reaction for 3h, the heating rate is 2 ℃/min, and finally the prepared product is washed and dried to obtain the final product.
The ICP-AES test results showed that the F content in the prepared material was 100 ppm. The obtained final product is used as a positive electrode material and assembled into an experimental button lithium ion battery in an argon protective glove box, charge and discharge tests are carried out at different multiplying powers, and the results of the discharge tests are shown in 'comparative examples 1-2' in table 2.
Example 2-1
0.40mol of deionized water was added to the hydrothermal reaction kettle, which was then charged with 0.075mol of NH4And the watch glass of the F is arranged at the bottom of the hydrothermal reaction kettle. 5.00mol of LiMn will be flatly laid2O4The watch glass of (a) was placed in the hydrothermal reaction kettle about 11cm above the watch glass containing the fluorine source material. Carefully sealing the hydrothermal reaction kettle, and then placing the hydrothermal reaction kettle in an oven for hydrothermal reaction under the condition of reaction for 5 hours at 180 ℃. After the reaction is finished, washing the reaction product by deionized water and absolute ethyl alcohol, and then drying.
FIG. 1 shows surface F prepared according to example 2-1 of the present disclosure-Doping modified LiMn2O4As shown in FIG. 1, wherein surface F-Doping modified LiMn2O4The lower part of the XRD spectrum of the crystal is marked with LiMn2O4XRD standard peak position of (A), X-ray powder diffraction (XRD) analysis shows that the obtained product is pure-phase LiMn with space group Fd3m2O4No distinct hetero-phase peak is observed.
FIG. 2 shows surface F prepared according to example 2-1 of the present disclosure-Doping modified LiMn2O4The 1200 x SEM image, as shown in fig. 2, shows that the hydrothermal vapor phase surface doping modification did not significantly change its morphological characteristics from Scanning Electron Microscope (SEM) analysis.
The ICP-AES test results showed that the F content in the prepared material was 95 ppm.
The product obtained in example 2-1 was used as a positive electrode material, and was assembled into an experimental lithium ion button cell in an argon-protected glove box, and charge and discharge tests were performed at different rates, and the results of the discharge tests are shown in "example 2-1" in table 2.
Examples 2 to 2
0.40mol of deionized water was added to the hydrothermal reaction kettle, followed by charging 0.02mol of NH4And the watch glass of the F is arranged at the bottom of the hydrothermal reaction kettle. 2.66mol of LiMn will be flatly laid2O4The watch glass of (a) was placed in the hydrothermal reaction kettle about 8cm above the watch glass containing the fluorine source material. The hydrothermal reaction kettle is carefully sealed and then placed in an oven for hydrothermal reaction, and the hydrothermal reaction condition is that the hydrothermal reaction is carried out for 8 hours at 230 ℃. After the reaction is finished, washing the reaction product by deionized water and absolute ethyl alcohol, and then drying.
X-ray powder diffraction (XRD) analysis showed that the resulting product was pure phase LiMn with space group Fd3m2O4No distinct hetero-phase peak (not shown) is seen; from Scanning Electron Microscope (SEM) analysis, it was found that hydrothermal vapor phase surface doping modification did not significantly change its topographical features (not shown); the ICP-AES test results showed that the F content in the prepared material was 145 ppm.
The product obtained in example 2-2 was used as a positive electrode material, and was assembled into an experimental button lithium ion battery in an argon-protected glove box, and charge and discharge tests were performed at different rates, and the results of the discharge tests are shown in "example 2-2" in table 2.
Comparative example 2-1
This comparative example uses unmodified LiMn2O4The lithium ion battery is assembled as a positive electrode material to test electrochemical performance.
Mixing unmodified LiMn2O4As a positive electrode material, an experimental button type lithium ion battery is assembled in an argon protective glove box, charge and discharge tests are carried out at different multiplying powers, and the results of the discharge tests are shown as a comparative example 2-1 in a table 2.
Comparative examples 2 to 2
This comparative example used a conventional high temperature solid phase method to prepare surface F-Doping modified LiMn2O4Material and preparation of the obtained doped LiMn2O4The lithium ion battery is assembled as a positive electrode material to test electrochemical performance.
100.0000g LiMn2O4And 0.0195g NH4F is arranged atHigh speed mixing is carried out in a high speed mixer. After mixing well, the resulting mixture was placed in a sagger for heat treatment. The heat treatment temperature is 400 ℃ for reaction for 3h, the heating rate is 2 ℃/min, and finally the prepared product is washed and dried to obtain the final product.
The ICP-AES test results showed that the F content in the prepared material was 105 ppm. The obtained final product is used as a positive electrode material and assembled into an experimental button lithium ion battery in an argon protective glove box, charge and discharge tests are carried out at different multiplying powers, and the results of the discharge tests are shown in 'comparative example 2-2' in table 2.
Example 3-1
0.40mol of deionized water was added to the hydrothermal reaction kettle, which was then charged with 0.075mol of NH4And the watch glass of the F is arranged at the bottom of the hydrothermal reaction kettle. Will be tiled with 5.00mol Li4Ti5O12The watch glass of (a) was placed in the hydrothermal reaction kettle about 11cm above the watch glass containing the fluorine source material. Carefully sealing the hydrothermal reaction kettle, and then placing the hydrothermal reaction kettle in an oven for hydrothermal reaction under the condition of reaction for 5 hours at 180 ℃. After the reaction is finished, washing the reaction product by deionized water and absolute ethyl alcohol, and then drying.
X-ray powder diffraction (XRD) analysis showed that the resulting product was a pure phase Li with space group Fd3m4Ti5O12No distinct hetero-phase peak (not shown) is seen; from Scanning Electron Microscope (SEM) analysis, it was found that hydrothermal vapor phase surface doping modification did not significantly change its topographical features (not shown); the ICP-AES test results showed that the F content in the prepared material was 110 ppm.
The product obtained in example 3-1 was used as a positive electrode material, and was assembled into an experimental lithium ion button cell in an argon-protected glove box, and charge and discharge tests were performed at different rates, and the results of the discharge tests are shown in "example 3-1" in table 2.
Examples 3 to 2
0.40mol of deionized water was added to the hydrothermal reaction kettle, followed by charging 0.02mol of NH4And the watch glass of the F is arranged at the bottom of the hydrothermal reaction kettle. Will be tiled with 2.66mol Li4Ti5O12The watch glass of (a) was placed in the hydrothermal reaction kettle about 8cm above the watch glass containing the fluorine source material. The hydrothermal reaction kettle is carefully sealed and then placed in an oven for hydrothermal reaction, and the hydrothermal reaction condition is that the hydrothermal reaction is carried out for 8 hours at 230 ℃. After the reaction is finished, washing the reaction product by deionized water and absolute ethyl alcohol, and then drying.
X-ray powder diffraction (XRD) analysis showed that the resulting product was a pure phase Li with space group Fd3m4Ti5O12No distinct hetero-phase peak (not shown) is seen; from Scanning Electron Microscope (SEM) analysis, it was found that hydrothermal vapor phase surface doping modification did not significantly change its topographical features (not shown); the ICP-AES test results showed that the F content in the prepared material was 170 ppm.
The product obtained in example 3-2 was used as a positive electrode material, and was assembled into an experimental button lithium ion battery in an argon-protected glove box, and charge and discharge tests were performed at different rates, and the results of the discharge tests are shown in "example 3-2" in table 2.
Comparative example 3-1
This comparative example uses unmodified Li4Ti5O12The lithium ion battery is assembled as a positive electrode material to test electrochemical performance.
Unmodified Li4Ti5O12As a positive electrode material, an experimental button type lithium ion battery is assembled in an argon protective glove box, charge and discharge tests are carried out at different multiplying powers, and the results of the discharge tests are shown as a comparative example 3-1 in a table 2.
Comparative examples 3 to 2
This comparative example used a conventional high temperature solid phase method to prepare surface F-Doping modified Li4Ti5O12Materials and doped Li obtained by the preparation4Ti5O12The lithium ion battery is assembled as a positive electrode material to test electrochemical performance.
100.0000g of Li4Ti5O12And 0.0195g NH4And F, placing the mixture in a high-speed mixer for high-speed mixing. After mixing well, the resulting mixture was placed in a sagger for heat treatment. Temperature of heat treatmentReacting for 3h at 400 ℃, heating at the speed of 2 ℃/min, and finally washing and drying the prepared product to obtain the final product.
The ICP-AES test results showed that the F content in the prepared material was 105 ppm. The obtained final product is used as a positive electrode material and assembled into an experimental button lithium ion battery in an argon protective glove box, charge and discharge tests are carried out at different multiplying powers, and the results of the discharge tests are shown in a comparative example 3-2 in a table 2.
Example 4
0.40mol of deionized water was added to the hydrothermal reaction kettle, which was then charged with 0.075mol of NH4And the watch glass of the F is arranged at the bottom of the hydrothermal reaction kettle. 5.00mol of LiNi are laid flat0.5Mn1.5O4The watch glass of (a) was placed in the hydrothermal reaction kettle about 11cm above the watch glass containing the fluorine source material. Carefully sealing the hydrothermal reaction kettle, and then placing the hydrothermal reaction kettle in an oven for hydrothermal reaction under the condition of reaction for 5 hours at 180 ℃. After the reaction is finished, washing the reaction product by deionized water and absolute ethyl alcohol, and then drying.
X-ray powder diffraction (XRD) analysis showed that the resulting product was a pure phase LiNi with space group Fd3m0.5Mn1.5O4No distinct hetero-phase peak (not shown) is seen; from Scanning Electron Microscope (SEM) analysis, it was found that hydrothermal vapor phase surface doping modification did not significantly change its topographical features (not shown); the ICP-AES test results showed that the F content in the prepared material was 110 ppm.
The product obtained in example 4 was used as a positive electrode material, and assembled into an experimental button lithium ion battery in an argon-protected glove box, and charge and discharge tests were performed at different rates, and the discharge test results are shown in "example 4" in table 2.
Comparative example 4-1
This comparative example was prepared from unmodified LiNi0.5Mn1.5O4The lithium ion battery is assembled as a positive electrode material to test electrochemical performance.
Subjecting unmodified LiNi0.5Mn1.5O4As a positive electrode material, is assembled in an argon-protected glove boxThe experimental button lithium ion battery was subjected to charge and discharge tests at different rates, and the results of the discharge tests are shown in "comparative example 4-1" in table 2.
Comparative examples 4 to 2
This comparative example used a conventional high temperature solid phase method to prepare surface F-Doping modified LiNi0.5Mn1.5O4Materials and the preparation of the resulting doped LiNi0.5Mn1.5O4The lithium ion battery is assembled as a positive electrode material to test electrochemical performance.
100.0000g of LiNi0.5Mn1.5O4And 0.0195g NH4And F, placing the mixture in a high-speed mixer for high-speed mixing. After mixing well, the resulting mixture was placed in a sagger for heat treatment. The heat treatment temperature is 400 ℃ for reaction for 3h, the heating rate is 2 ℃/min, and finally the prepared product is washed and dried to obtain the final product.
The ICP-AES test results showed that the F content in the prepared material was 105 ppm. The obtained final product is used as a positive electrode material and assembled into an experimental button lithium ion battery in an argon protective glove box, charge and discharge tests are carried out at different multiplying powers, and the results of the discharge tests are shown in a comparative example 4-2 in the table 2.
Comparative examples 4 to 3
This comparative example also used LiNi0.5Mn1.5O4As the starting materials, but the ratios used were not in the above (50 to 100): 100 to 1000): 1000 to 10000, and the ratio used was 15:1000:7500, which was taken as comparative example 4-3.
2.00mol of deionized water was added to the hydrothermal reaction kettle, which was then charged with 0.03mol of NH4And the watch glass of the F is arranged at the bottom of the hydrothermal reaction kettle. Lay flat with 15.00mol LiNi0.5Mn1.5O4The watch glass of (a) was placed in the hydrothermal reaction kettle about 11cm above the watch glass containing the fluorine source material. Carefully sealing the hydrothermal reaction kettle, and then placing the hydrothermal reaction kettle in an oven for hydrothermal reaction under the condition of reaction for 5 hours at 180 ℃. After the reaction is finished, washing the reaction product by deionized water and absolute ethyl alcohol, and then drying.
X-ray powder diffraction (XRD) analysis showed that the resulting product was a pure phase LiNi with space group Fd3m0.5Mn1.5O4No distinct hetero-phase peak (not shown) is seen; from Scanning Electron Microscope (SEM) analysis, it was found that hydrothermal vapor phase surface doping modification did not significantly change its topographical features (not shown); the ICP-AES test results showed that the F content in the prepared material was 15 ppm.
The product prepared in the comparative example 4-3 is used as a positive electrode material, and is assembled into an experimental button type lithium ion battery in an argon protective glove box, and the charge and discharge tests are carried out at different multiplying powers, and the discharge test result is shown as the comparative example 4-3 in the table 2.
Table 2 discharge test results of each example and comparative example
Figure BDA0002303880200000131
Figure BDA0002303880200000141
As can be seen from examples 1-1, 1-2, 1-1 and 1-2 of Table 2, the surfaces F prepared in examples 1-1 and 1-2-Doping modified LiCoO2Electrochemical performance of the assembled battery was superior to that of the unmodified LiCoO of comparative example 1-12Electrochemical performance of assembled cell and surface F prepared in comparative examples 1-2-Doping modified LiCoO2Electrochemical performance of the assembled cell; the difference in electrochemical properties between the assembled batteries of comparative examples 1-1 and 1-2 is not large, and the surface F prepared in example 1-1-Doping modified LiCoO2Assembled cell is superior to surface F prepared in examples 1-2-Doping modified LiCoO2Electrochemical performance of the assembled cell.
As can be seen from example 2-1, example 2-2, comparative example 2-1 and comparative example 2-2 of Table 2, the surfaces F prepared in example 2-1 and example 2-2-Doping modified LiMn2O4Electrochemistry of assembled batteriesUnmodified LiMn having better performance than comparative example 2-12O4Electrochemical performance of assembled cell and surface F prepared in comparative example 2-2-Doping modified LiMn2O4Electrochemical performance of the assembled cell; the difference in electrochemical properties between the assembled batteries of comparative example 2-1 and comparative example 2-2 was not large, and the surface F prepared in example 2-1-Doping modified LiMn2O4Assembled cell is superior to surface F prepared in example 2-2-Doping modified LiMn2O4Electrochemical performance of the assembled cell.
As can be seen from example 3-1, example 3-2, comparative example 3-1 and comparative example 3-2 of Table 2, the surface F prepared in example 3-1-Doping modified Li4Ti5O12The electrochemical performance of the assembled cell is significantly better than that of surface F prepared in example 3-2-Doping modified Li4Ti5O12The electrochemical performance of the assembled battery is better than that of the unmodified Li of the comparative example 3-14Ti5O12Electrochemical Properties of assembled Battery and surface F prepared in comparative example 3-2-Doping modified Li4Ti5O12The electrochemical properties of the assembled cells were not much different from those of the assembled cells of comparative examples 3-1 and 3-2 d.
As can be seen from example 4, comparative example 4-1, comparative example 4-2 and comparative example 4-3 of Table 2, surface F prepared in example 4-Doping modified LiNi0.5Mn1.5O4The electrochemical performance of the assembled cell was significantly superior to that of the unmodified LiNi of comparative example 4-10.5Mn1.5O4Assembled cell and surface F prepared in comparative example 4-2-Doping modified LiNi0.5Mn1.5O4The electrochemical performance of the assembled cell is better than that of the surface F prepared in comparative examples 4-3-Doping modified LiNi0.5Mn1.5O4The electrochemical properties of the assembled cells were not much different from those of the assembled cells of comparative examples 4-1 and 4-2.
As can be seen from the results of the ICP-AES tests of comparative examples 4-3, use of fluorineSource material, solvent and LiNi0.5Mn1.5O4In a molar ratio of (50-100): (100-1000): out of (1000-10000), and a surface F prepared by hydrothermal gas phase method-Doping modified LiNi0.5Mn1.5O4F of (A)-The incorporation was only 15ppm, significantly less F than in examples 4 and comparative examples 4-2-The mixing amount is as follows. This resulted in the surface F prepared in comparative examples 4-3-Doping modified LiNi0.5Mn1.5O4The electrochemical performance of the assembled cell is even inferior to that of unmodified LiNi0.5Mn1.5O4Electrochemical performance of the assembled cell.
Further, as can be seen from example 4 and comparative examples 4 to 3 of Table 2, comparative examples 4 to 3 produced surface F-Doping modified LiNi0.5Mn1.5O4The electrochemical performance of (A) is significantly inferior to that of the surface F prepared in example 4-Doped LiNi0.5Mn1.5O4The electrochemical performance of (2).
From the foregoing, preferred F is prepared using a hydrothermal gas phase process-Surface F of the doping amount-The electrochemical performance of the doped modified lithium ion battery electrode material is obviously superior to that of the surface F prepared by a high-temperature solid phase method-Doped modified lithium ion battery electrode materials and unmodified lithium ion battery electrode materials. And surface F prepared by high-temperature solid-phase method-Compared with the unmodified lithium ion battery electrode material, the doped modified lithium ion battery electrode material has small difference of electrochemical properties.
It can be seen that the surface F prepared using the hydrothermal gas phase method provided by the present invention has a capacity retention (maintained at 91% or more) after 50 cycles and 100 cycles at a discharge rate of 0.5C and 2C, and a capacity retention after 50 cycles and 100 cycles at a rate of 1C-The doped modified lithium ion battery electrode material shows better results. Due to trace amount of water contained in the electrolyte and LiPF in the electrolyte6HF is generated by reaction, the HF can generate obvious corrosion effect on the electrode material, and a protective layer containing fluorine is formed on the surface of the electrode material after the F is doped, and the protective layer is doped with other elements (such as S)Compared with the fluorine-containing protective layer, the fluorine-containing protective layer has relatively better corrosion resistance to HF, and after multiple cycles under the same condition, the capacity retention rate of other elements (such as S) surface doping modified materials after the cycles is reduced rapidly and is only about 85%, and relatively speaking, the capacity retention rate of F surface doping modified lithium ion battery electrode materials after the multiple cycles is higher.
The above data show that the hydrothermal gas phase synthesis of surface F provided by the present invention-Doping modified LiCoO2、LiMn2O4、Li4Ti5O12And LiNi0.5Mn1.5O4The cathode material is used for assembling a battery, and has excellent electrochemical performance.
It should be understood that the above examples are only for clearly illustrating the present application and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of this invention may be made without departing from the spirit or scope of the invention.

Claims (10)

1. A method of making an electrode material for a lithium ion battery, comprising the steps of:
putting a solvent and a fluorine source raw material into a reaction kettle;
putting the lithium ion battery electrode material into the reaction kettle, and sealing the reaction kettle to perform hydrothermal reaction;
and after the reaction is finished, taking out the reaction product from the reaction kettle, and washing and drying the reaction product.
2. The method according to claim 1, wherein the solvent is selected from one or a mixture of at least two of purified water, ultrapure water, deionized water or distilled water, preferably deionized water;
the fluorine source raw material is a fluorine-containing compound, preferably HF and H2SiF6、NH4H2F3Or NH4One or a mixture of at least two of F, more preferably NH4F；
The lithium ion battery electrode material comprises a lithium-containing compound selected from LiMn2O4、LiNi0.5Mn1.5O4、LiCoO2、LiNi1-x-yCoxMnyO2(0≤x<0.5，0≤y<0.5) or Li4Ti5O12。
3. The method according to claim 1 or 2, wherein the molar ratio of the fluorine source raw material, the solvent and the lithium ion battery electrode material is 50-100: 100-1000: 1000-10000, preferably 50-100: 300-500: 5000, more preferably 50-100: 400:5000, and more preferably 75:400: 5000.
4. The method according to claim 1 or 2, wherein the lithium ion battery electrode material is placed at a height higher than that of the fluorine source raw material, and the height difference is 6-16 cm, preferably 11 cm.
5. The method according to claim 1 or 2, characterized in that the reaction conditions of the hydrothermal reaction comprise:
the reaction temperature is 100-230 ℃, and preferably 180 ℃;
the reaction time is 2-10 h, preferably 5 h.
6. The method according to claim 1 or 2, wherein the washing comprises: the reaction product was washed with deionized water and absolute ethanol.
7. The method of claim 6,
0.40mol of deionized water was added to the hydrothermal reaction kettle, which was then charged with 0.075mol of NH4The watch glass of F is arranged at the bottom of the hydrothermal reaction kettle;
will be tiled with 5.00mol LiNi0.5Mn1.5O4The watch glass is arranged in a hydrothermal reaction kettle and is about 11cm higher than the watch glass filled with the fluorine source raw material;
carefully sealing the hydrothermal reaction kettle, and then placing the hydrothermal reaction kettle in an oven for hydrothermal reaction under the condition of reaction for 5 hours at 180 ℃;
the reaction product is washed by deionized water and absolute ethyl alcohol and then dried.
8. A lithium ion battery electrode material prepared by the method of any one of claims 1 to 7.
9. The lithium ion battery electrode material is characterized by comprising a lithium-containing compound and a fluorine-containing layer doped on the surface of the lithium-containing compound; wherein, the fluorine content in the fluorine-containing layer is 80-200ppm based on the total amount of the lithium ion battery electrode material.
10. A battery comprising the lithium ion battery electrode material of claim 8 or 9.
CN201911232263.4A 2019-12-05 2019-12-05 Lithium ion battery electrode material, preparation method and battery Pending CN112928244A (en)

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