CN111403725A - Aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate cathode material and preparation method thereof - Google Patents
Aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate cathode material and preparation method thereof Download PDFInfo
- Publication number
- CN111403725A CN111403725A CN202010333070.4A CN202010333070A CN111403725A CN 111403725 A CN111403725 A CN 111403725A CN 202010333070 A CN202010333070 A CN 202010333070A CN 111403725 A CN111403725 A CN 111403725A
- Authority
- CN
- China
- Prior art keywords
- iron phosphate
- lithium iron
- hafnium
- nitrogen
- cathode material
- 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.)
- Pending
Links
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
-
- 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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The method comprises the steps of mixing and thermally treating four raw materials of a hafnium salt, a lithium source, a phosphorus source and an iron source to prepare hafnium-doped lithium iron phosphate; secondly, putting the lithium iron phosphate precursor into a mixed solution of aluminum nitrate, urea and glucose again for secondary dispersion and mixing and carrying out hydrothermal reaction; and finally, cleaning, drying and calcining the hydrothermal product to prepare the alumina-coated hafnium/nitrogen co-doped lithium iron phosphate anode material, wherein the method has the advantages of simple process steps, short flow, adjustable morphology structure and the like in the aspect of preparing the lithium iron phosphate anode material, and the prepared lithium iron phosphate anode material has obvious advantages in electrochemical properties such as high rate performance, cycle times, energy density and the like, is more stable in performance, low in equipment requirement of the whole route and good in process stability, and has important industrial popularization and application values.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to an aluminum oxide coated nitrogen/aluminum co-doped lithium iron phosphate anode material and a preparation method thereof.
Background
The lithium ion battery has the advantages of high specific energy, high power density, long cycle life and the like, and is widely applied to electric equipment such as electric vehicles, notebook computers, portable cameras and the like. In recent years, special equipment fields such as space flight devices and deep sea diving equipment also put urgent demands on the adoption of lithium ion batteries to provide lasting power output. The lithium ion positive electrode material, which is typically a lithium-containing metal compound of a valence transition, has a decisive influence on the energy density of a lithium ion battery. The currently widely used lithium ion battery anode materials mainly include lithium iron phosphate, nickel cobalt manganese ternary materials, lithium iron manganese phosphate, and other lithium-rich materials. With the continuous upgrading and upgrading of electric automobiles and electronic products and the rapid expansion of the application field, higher requirements are also put forward on the safety and energy density of the lithium ion battery. Therefore, the development of the lithium ion battery anode material with high energy density, good cycle performance, rate discharge performance and safety performance has important significance for equipment manufacture and kinetic energy conversion in China.
Compared with other lithium ion anode materials, the battery formed by using the lithium iron phosphate as the anode material has the outstanding advantages of long service life, low cost and high safety, and has larger market share in the lithium ion battery market. However, at the present stage, the problems are that the ionic conductivity and the electronic conductivity of the lithium iron phosphate are relatively low, and the lithium iron phosphate is only suitable for charging and discharging under a small current density, and the specific capacity is reduced in high-rate charging and discharging, and the short plates hinder the large-scale application of the material in more fields. Aiming at the inherent defects of the lithium iron phosphate material, research and development personnel at home and abroad carry out a great deal of modification research on the lithium iron phosphate material to improve the conductivity of the lithium iron phosphate. The most important modification is that sodium ion doping is carried out at the site where the iron ions are located, so that the ionic conductivity and the electronic conductivity can be greatly improved simultaneously. Another modification strategy adopted by the method is to introduce a carbon component with extremely excellent conductivity and lower commercial cost into the lithium iron phosphate, and the specific implementation methods include graphene coating, three-dimensional carbon loading, porous carbon skeleton linking and the like, which all play a certain role in improving the performance.
Although a few modification methods have been developed at the present stage, the prepared lithium iron phosphate material cannot meet the requirements of industrialization in terms of energy density, cycle performance, rate discharge performance and the like, and production cost. The modified lithium iron phosphate with better performance, lower manufacturing cost and more controllable process conditions and the prepared material structure needs further research and development.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention aims to provide the preparation method of the aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate cathode material, which has the advantages of simple preparation process, good process repeatability, controllable product organization structure, high energy density and long cycle life. The invention provides a method for further optimizing the synthesis and performance of a lithium iron phosphate material by using an occupying doping mode, and the method is realized by the following technical scheme.
A method for preparing an aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate anode material comprises the following specific steps:
step 1: weighing hafnium salt, a lithium source, a phosphorus source and an iron source according to a certain molar ratio at room temperature, adding the hafnium salt, the lithium source, the phosphorus source and the iron source into deionized water, dispersing and stirring to prepare a dispersion liquid;
step 2: performing rotary evaporation and tubular furnace calcination treatment on the dispersion liquid obtained in the step 1 to obtain a lithium iron phosphate precursor;
and step 3: putting the lithium iron phosphate precursor obtained in the step 2 into a mixed solution of aluminum nitrate, urea and glucose again, and quickly stirring for a certain time;
and 4, step 4: carrying out hydrothermal treatment on the dispersion liquid formed in the step 3 to form sol and washing the sol with deionized water;
and 5: and (4) performing freeze drying and high-temperature calcination on the product obtained after washing in the step (4) to obtain the aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate cathode material.
Preferably, the hafnium salt of step 1 is generally HfCl4，Hf(NO3)4The amount of hafnium in the produced hafnium-doped lithium iron phosphate material is controlled to be below 5 at percent; the lithium source is one or more of lithium hydroxide, lithium carbonate and lithium hydrogen phosphate generally; the iron source is one or more of ferrous sulfate, ferric phosphate, ferric oxide, ferric chloride and ferric acetate; the molar ratio of the lithium source to the phosphorus source to the iron source is (1-1.5): 1: 1. the stirring time is generally 10-15 hours and the stirring speed is 800-.
Preferably, the rotary evaporation temperature in step 2 is 50-80 ℃. The heat treatment atmosphere is inert atmosphere, such as Ar gas, N2Gas, He gas and the like, the heat treatment temperature is 500-800 ℃, the heat treatment time is 5-10 hours, and the heating rate is selected between 1-10 ℃/min.
Preferably, the mass ratio of the lithium iron phosphate precursor to the mixed solution of aluminum nitrate, urea and glucose is 1: (2-4), the molar ratio of the aluminum nitrate to the urea to the glucose is 0.1:5:1, the stirring time of the mixed solution is 10-24 hours, and the stirring speed is 800-1000 revolutions per minute.
Preferably, the hydrothermal treatment equipment in the step 4 adopts a stainless steel jacket to wrap a polytetrafluoroethylene lining, the reaction temperature is between 150 ℃ and 200 ℃, and the reaction time is 5-20 hours; the washing times of the deionized water are 3-5 times, and the rotating speed of centrifugally collecting the products in the washing process is 8000-15000 r/min.
Preferably, the freeze-drying parameters in step 5 are: freezing at-40-50 deg.C, and drying for 15-25 hr. The high-temperature calcination temperature is 200-500 ℃, the calcination time is 2-5 hours, and the calcination atmosphere is one or more than two of nitrogen, argon and oxygen.
The beneficial effect of this application does:
the method obtains the aluminum oxide coated nitrogen/aluminum co-doped lithium iron phosphate cathode material, has low cost, simple equipment requirement and short preparation flow, has the advantages of other preparation methods adopting concentrated acid or high-pressure equipment, and specifically comprises the following steps:
step 1 the present invention creatively adopts an in-situ solid phase nitrogen doping mode to modify lithium iron phosphate sites. The urea will slowly decompose to release NH during the heat treatment process3Active NH3Can coordinate with Fe ions to form FeNxThe sites effectively change the electron cloud state and the energy state density around the Fe atomic nucleus, and effectively improve the ion conductivity and the electron conductivity of the lithium iron phosphate material, thereby improving the electrochemical performance. Meanwhile, the adopted urea has low manufacturing cost and few harmful products, and represents great economic value and environmental protection value in the aspect of modifying the lithium iron phosphate cathode material.
Step 2, the invention adopts the process of firstly synthesizing sodium-doped lithium iron phosphate and then carrying out aluminum coating and N doping, and the route can well promote the formation of a lithium iron phosphate/aluminum oxide core-shell structure, thereby not only maintaining the original olivine structure of the lithium iron phosphate and realizing the replacement of sodium ions at an iron site, but also well realizing the uniform doping and coating of other elements, effectively avoiding the segregation and aggregation of doping elements in the heat treatment process, forming a channel more beneficial to the conduction of lithium ions, reducing the resistance, and further promoting the stability and the high efficiency of the synthesized anode material. Through subsequent doping, aluminum and nitrogen elements can be doped into the cavities in the olivine structure more uniformly, so that the conductivity of the olivine structure is improved well, and the charge-discharge rate performance of the prepared anode material is improved.
Step 3, the rotary evaporation adopted by the invention can well ensure that all the dispersed components are still in a uniformly mixed state while the dispersion liquid volatilizes, and the condition of uneven component distribution after the heat treatment process caused by segregation is avoided. The freeze drying can fully ensure that a transmission channel in the sample is not closed on the premise that the sample is dried, and the structural characteristics of the material are kept as much as possible.
Drawings
Fig. 1 is a charge and discharge curve of the lithium iron phosphate-based material of example 1;
FIG. 2 is a cycle curve for the lithium iron phosphate-based material of example 1;
fig. 3 is a surface topography of a material of a lithium iron phosphate-based material.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
The preparation method disclosed by the invention is simple in preparation process, high in effective product yield, and the doped and coated modified lithium iron phosphate-based material has the characteristics of easily controllable particle size and morphology, good uniformity, good batch consistency and good stability, and can simultaneously meet the comprehensive requirements of the battery on the electrochemical performance and the processing performance of the material. Firstly, mixing and thermally treating four raw materials of a hafnium salt, a lithium source, a phosphorus source and an iron source to prepare hafnium-doped lithium iron phosphate; secondly, putting the lithium iron phosphate precursor into a mixed solution of aluminum nitrate, urea and glucose again for secondary dispersion and mixing and carrying out hydrothermal reaction; and finally, cleaning, drying and calcining the hydrothermal product to prepare the aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate cathode material. The method has the advantages of simple process steps, short flow, adjustable morphology structure and the like in the aspect of preparing the lithium iron phosphate cathode material, the prepared lithium iron phosphate cathode material has obvious advantages in electrochemical properties such as high rate performance, cycle times, energy density and the like, the performance is more stable, the requirement on equipment in the whole route is low, the process stability is good, and the method has important industrial popularization and application values.
Example 1
Weighing Hf (NO) at room temperature according to a molar ratio of 0.1:1:1:13)4Adding lithium carbonate, diammonium phosphate and ferrous sulfate heptahydrate into deionized water, dispersing and stirring to prepare a dispersion liquid, wherein the stirring time is selected to be 10 hours,the stirring rate was 1500 rpm. The obtained dispersion was evaporated to dryness by rotary evaporation at 70 ℃ and 100 rpm. And then, calcining the dried mixture in a tubular furnace at 500 ℃ for 10 hours at the heating rate of 1 ℃/min to obtain the lithium iron phosphate precursor. And putting the obtained lithium iron phosphate precursor into a mixed solution of aluminum nitrate, urea and glucose again, wherein the molar ratio of the aluminum nitrate to the urea to the glucose is 0.1:5:1, the ratio of the mass of the lithium iron phosphate precursor to the sum of the mass of the aluminum nitrate to the sum of the mass of the urea to the mass of the glucose is 1:2, the rapid stirring speed is 1200 r/min, and the stirring time is selected to be 8 hours. Transferring the formed dispersion liquid to a polytetrafluoroethylene hydrothermal reaction kettle for hydrothermal synthesis treatment, wherein the synthesis temperature is 150 ℃, the reaction time is 15h, and the formed sol is washed for 3 times by deionized water. And finally, carrying out freeze drying and high-temperature calcination on the washed product, wherein the freeze drying temperature is-40 ℃, the time duration is 24 hours, the calcination temperature is 200 ℃, the time duration is 5 hours, and finally obtaining the aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate cathode material.
Example 2
Weighing HfCl at room temperature according to the molar ratio of 0.2:1:1:14And adding lithium nitrate, diammonium phosphate and ferrous sulfate heptahydrate into deionized water, dispersing and stirring to prepare a dispersion liquid, wherein the stirring time is selected to be 20 hours, and the stirring speed is 900 revolutions per minute. The obtained dispersion was evaporated to dryness by rotary evaporation at 70 ℃ and 100 rpm. And then, calcining the dried mixture in a tubular furnace at 600 ℃ for 8 hours at the heating rate of 2 ℃/min to obtain the lithium iron phosphate precursor. And putting the obtained lithium iron phosphate precursor into a mixed solution of aluminum nitrate, urea and glucose again, wherein the molar ratio of the aluminum nitrate to the urea to the glucose is 0.15:5:1, the ratio of the mass of the lithium iron phosphate precursor to the sum of the mass of the aluminum nitrate to the sum of the mass of the urea to the glucose is 1:2, the rapid stirring speed is 1000 revolutions per minute, and the stirring time is selected to be 10 hours. Transferring the formed dispersion liquid to a polytetrafluoroethylene hydrothermal reaction kettle for hydrothermal synthesis treatment, wherein the synthesis temperature is 180 ℃, the reaction time is 10h,the formed sol was washed 3 times with deionized water. And finally, carrying out freeze drying and high-temperature calcination on the washed product, wherein the freeze drying temperature is-40 ℃, the time duration is 24 hours, the calcination temperature is 300 ℃, the time duration is 4 hours, and finally obtaining the aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate cathode material.
Example 3
Weighing HfCl at room temperature according to the molar ratio of 0.15:1:1:14Adding lithium nitrate, phosphoric acid and ferric trichloride into deionized water, dispersing and stirring to prepare a dispersion liquid, wherein the stirring time is 20 hours, and the stirring speed is 900 revolutions per minute. The obtained dispersion was evaporated to dryness by rotary evaporation at 70 ℃ and 100 rpm. And then, calcining the dried mixture in a tubular furnace at 700 ℃ for 5 hours at the heating rate of 3 ℃/min to obtain the lithium iron phosphate precursor. And putting the obtained lithium iron phosphate precursor into a mixed solution of aluminum nitrate, urea and glucose again, wherein the molar ratio of the aluminum nitrate to the urea to the glucose is 0.15:6:1.5, the ratio of the mass of the lithium iron phosphate precursor to the sum of the mass of the aluminum nitrate to the sum of the mass of the urea to the mass of the glucose is 1:2, the rapid stirring speed is 1000 revolutions per minute, and the stirring time is selected to be 10 hours. Transferring the formed dispersion liquid to a polytetrafluoroethylene hydrothermal reaction kettle for hydrothermal synthesis treatment, wherein the synthesis temperature is 200 ℃, the reaction time is 6 hours, and the formed sol is washed for 3 times by deionized water. And finally, carrying out freeze drying and high-temperature calcination on the washed product, wherein the freeze drying temperature is-40 ℃, the time duration is 24 hours, the calcination temperature is 500 ℃, the time duration is 2 hours, and finally obtaining the aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate cathode material.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A method for preparing an aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate anode material comprises the following specific steps:
step 1: weighing hafnium salt, a lithium source, a phosphorus source and an iron source according to a certain molar ratio at room temperature, adding the hafnium salt, the lithium source, the phosphorus source and the iron source into deionized water, dispersing and stirring to prepare a dispersion liquid;
step 2: performing rotary evaporation and tubular furnace calcination treatment on the dispersion liquid obtained in the step 1 to obtain a lithium iron phosphate precursor;
and step 3: putting the lithium iron phosphate precursor obtained in the step 2 into a mixed solution of aluminum nitrate, urea and glucose again, and quickly stirring for a certain time to form a dispersion liquid;
and 4, step 4: carrying out hydrothermal treatment on the dispersion liquid obtained in the step 3 to form sol, and washing the sol with deionized water;
and 5: and (4) performing freeze drying and high-temperature calcination on the product obtained after washing in the step (4) to obtain the aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate cathode material.
2. The method for preparing the alumina-coated hafnium/nitrogen co-doped lithium iron phosphate cathode material according to claim 1, wherein the hafnium salt in step 1 is HfCl4Or Hf (NO)3)4The hafnium salt comprises less than 5 at% of hafnium, one or more of lithium hydroxide, lithium carbonate and lithium hydrogen phosphate is used as a lithium source, one or more of ferrous sulfate, ferric phosphate, ferric oxide, ferric chloride and ferric acetate is used as an iron source, and the molar ratio of the lithium source to the phosphorus source to the iron source is (1-1.5): 1: 1.
3. the method for preparing an alumina-coated hafnium/nitrogen co-doped lithium iron phosphate cathode material as claimed in claim 1, wherein the stirring time in step 1 is 10-15 hours, and the stirring speed is 800-1500 rpm.
4. The method for preparing the aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate cathode material according to claim 1, wherein the method comprisesThe rotary evaporation temperature in the step 2 is 50-80 ℃, the heat treatment atmosphere in the rotary evaporation is inert atmosphere, and the inert gas is Ar gas and N gas2Gas and He gas, the heat treatment temperature is 500-.
5. The method for preparing the aluminum oxide-coated hafnium/nitrogen co-doped lithium iron phosphate cathode material according to claim 1, wherein the mass ratio of the lithium iron phosphate precursor to the mixed solution of aluminum nitrate, urea and glucose in the step 3 is 1: (2-4), wherein the molar ratio of the aluminum nitrate to the urea to the glucose is 0.1:5: 1.
6. The method for preparing an alumina-coated hafnium/nitrogen co-doped lithium iron phosphate cathode material as claimed in claim 1, wherein the stirring time of the mixed solution in step 3 is 10-24 hours, and the stirring speed is 800-1000 rpm.
7. The method for preparing an alumina-coated hafnium/nitrogen co-doped lithium iron phosphate cathode material as claimed in claim 1, wherein the hydrothermal treatment device in step 4 is formed by wrapping a polytetrafluoroethylene lining with a stainless steel jacket, the reaction temperature is between 150 ℃ and 200 ℃, and the reaction time is 5-20 hours.
8. The method for preparing an alumina-coated hafnium/nitrogen co-doped lithium iron phosphate cathode material as claimed in claim 1, wherein the number of times of rinsing with deionized water is 3-5, and the sol is centrifugally moved during rinsing to collect the product, wherein the centrifugal speed is 8000-.
9. The method for preparing the aluminum oxide-coated hafnium/nitrogen co-doped lithium iron phosphate cathode material according to claim 1, wherein the freeze-drying parameters in the step 5 are as follows: freezing at-40-50 deg.C, and drying for 15-25 hr.
10. The method for preparing the alumina-coated hafnium/nitrogen co-doped lithium iron phosphate cathode material as claimed in claim 1, wherein the high temperature calcination temperature in step 5 is 200-500 ℃, the calcination time is 2-5 hours, and the calcination atmosphere is one or more of nitrogen, argon and oxygen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010333070.4A CN111403725A (en) | 2020-04-24 | 2020-04-24 | Aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate cathode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010333070.4A CN111403725A (en) | 2020-04-24 | 2020-04-24 | Aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate cathode material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111403725A true CN111403725A (en) | 2020-07-10 |
Family
ID=71429799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010333070.4A Pending CN111403725A (en) | 2020-04-24 | 2020-04-24 | Aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate cathode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111403725A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112490427A (en) * | 2020-11-30 | 2021-03-12 | 湖北亿纬动力有限公司 | Cathode material and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101212049A (en) * | 2007-12-21 | 2008-07-02 | 中国科学院上海硅酸盐研究所 | Anode material made of doped lithium-iron phosphate active material and carbon and method for producing the same |
| US20090155689A1 (en) * | 2007-12-14 | 2009-06-18 | Karim Zaghib | Lithium iron phosphate cathode materials with enhanced energy density and power performance |
| CN101645504A (en) * | 2008-08-07 | 2010-02-10 | 赵兵 | Method for preparing lithium iron phosphate of anode material of lithium ion battery |
| CN103579597A (en) * | 2012-07-24 | 2014-02-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Cathode material lithium titanate composite material of lithium ion secondary battery and preparation method of the material |
| CN104577128A (en) * | 2013-10-10 | 2015-04-29 | 无锡星波能源科技有限公司 | Alumina coating method of lithium ion battery positive electrode material |
| CN110316711A (en) * | 2019-05-29 | 2019-10-11 | 合肥国轩高科动力能源有限公司 | Method for preparing precursor of lithium iron phosphate positive electrode material by liquid phase method |
| CN110511036A (en) * | 2019-07-25 | 2019-11-29 | 东莞材料基因高等理工研究院 | A kind of submicron order aluminum oxynitride ceramic powder and preparation method thereof |
-
2020
- 2020-04-24 CN CN202010333070.4A patent/CN111403725A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090155689A1 (en) * | 2007-12-14 | 2009-06-18 | Karim Zaghib | Lithium iron phosphate cathode materials with enhanced energy density and power performance |
| CN101212049A (en) * | 2007-12-21 | 2008-07-02 | 中国科学院上海硅酸盐研究所 | Anode material made of doped lithium-iron phosphate active material and carbon and method for producing the same |
| CN101645504A (en) * | 2008-08-07 | 2010-02-10 | 赵兵 | Method for preparing lithium iron phosphate of anode material of lithium ion battery |
| CN103579597A (en) * | 2012-07-24 | 2014-02-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Cathode material lithium titanate composite material of lithium ion secondary battery and preparation method of the material |
| CN104577128A (en) * | 2013-10-10 | 2015-04-29 | 无锡星波能源科技有限公司 | Alumina coating method of lithium ion battery positive electrode material |
| CN110316711A (en) * | 2019-05-29 | 2019-10-11 | 合肥国轩高科动力能源有限公司 | Method for preparing precursor of lithium iron phosphate positive electrode material by liquid phase method |
| CN110511036A (en) * | 2019-07-25 | 2019-11-29 | 东莞材料基因高等理工研究院 | A kind of submicron order aluminum oxynitride ceramic powder and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112490427A (en) * | 2020-11-30 | 2021-03-12 | 湖北亿纬动力有限公司 | Cathode material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108511714B (en) | Transition metal phosphide-carbon composite material and preparation method and application thereof | |
| CN112151804A (en) | Prussian blue analogue-based carbon-coated transition metal oxide and preparation method and application thereof | |
| CN104752718B (en) | A kind of LiMnxFe1‑xPO4Positive electrode active materials and preparation method thereof | |
| CN102104143A (en) | Hydrothermal synthesis method of composite material for high-performance power battery | |
| CN102311109A (en) | Method for preparing LiFePO4/C composite cathode material by continuous reaction | |
| CN104577072A (en) | Preparation method of graphene-oxide-based MoO2 high-performance electrode material of lithium/sodium ion battery | |
| CN115020855A (en) | Recycling method of waste lithium iron phosphate battery | |
| CN115132981A (en) | Binary doped iron-based fluorophosphate sodium ion positive electrode material and preparation method thereof | |
| CN112038640A (en) | Porous carbon coated ternary positive electrode material and preparation method thereof | |
| CN112786865A (en) | MoS2Preparation method and application of quasi-quantum dot/nitrogen-sulfur co-doped biomass carbon composite nano material | |
| CN115954443A (en) | Preparation method of carbon-coated silicon-copper alloy negative electrode material of lithium ion battery | |
| CN109671937B (en) | In-situ synthesis method of transition metal oxide/graphene composite material | |
| CN114242972A (en) | Nickel-rich high-voltage sodium ion battery positive electrode material and preparation method and application thereof | |
| CN112614999A (en) | Preparation method of aluminum oxide coated lithium iron phosphate cathode material | |
| CN117577830A (en) | Ferric sodium pyrophosphate material, and preparation method and application thereof | |
| CN113044890A (en) | Cathode material, preparation method thereof and lithium ion battery | |
| CN110137472B (en) | Preparation method of composite positive electrode material | |
| CN116854141A (en) | Manganous oxide polyhedral material for water-based zinc ion battery and preparation method thereof | |
| CN111403725A (en) | Aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate cathode material and preparation method thereof | |
| CN108023079B (en) | Mixed transition metal borate anode material and preparation method thereof | |
| CN114105145B (en) | Carbon-coated three-dimensional porous silicon anode material and preparation method and application thereof | |
| CN116190591A (en) | Preparation method of modified material modified lithium iron manganese phosphate material | |
| CN102263248B (en) | Method for preparing carbon coated nanometer LiFePO4 | |
| CN115275151A (en) | Vanadium disulfide/titanium carbide composite material and preparation method and application thereof | |
| CN111952569B (en) | Silicon oxide-based negative electrode material for lithium ion battery 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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230403 Address after: 277800 No. x6699, Guangming Road, high tech Zone, Zaozhuang City, Shandong Province (north of the junction of Guangming Road and Huaxin Road) Applicant after: Shandong Jinggong Electronic Technology Co.,Ltd. Address before: 277800 west side of Fuyuan 5th Road, Zaozhuang high tech Zone, Zaozhuang City, Shandong Province Applicant before: Shandong Seiko Electronic Technology Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 277800 No. x6699, Guangming Road, high tech Zone, Zaozhuang City, Shandong Province (north of the junction of Guangming Road and Huaxin Road) Applicant after: Shandong Jinggong Electronic Technology Co.,Ltd. Address before: 277800 west side of Fuyuan 5th Road, Zaozhuang high tech Zone, Zaozhuang City, Shandong Province Applicant before: Shandong Seiko Electronic Technology Co.,Ltd. |
|
| CI02 | Correction of invention patent application | ||
| CI02 | Correction of invention patent application |
Correction item: Applicant|Address Correct: Shandong Seiko Electronic Technology Co.,Ltd.|277800 west side of Fuyuan 5th Road, Zaozhuang high tech Zone, Zaozhuang City, Shandong Province False: Shandong Jinggong Electronic Technology Co.,Ltd.|277800 No. x6699, Guangming Road, high tech Zone, Zaozhuang City, Shandong Province (north of the junction of Guangming Road and Huaxin Road) Number: 15-02 Volume: 39 |