CN113353986A - Rapid preparation method and application of lithium manganate cathode material - Google Patents
Rapid preparation method and application of lithium manganate cathode material Download PDFInfo
- Publication number
- CN113353986A CN113353986A CN202110772739.4A CN202110772739A CN113353986A CN 113353986 A CN113353986 A CN 113353986A CN 202110772739 A CN202110772739 A CN 202110772739A CN 113353986 A CN113353986 A CN 113353986A
- Authority
- CN
- China
- Prior art keywords
- limn
- lithium
- liquid
- lithium manganate
- positive electrode
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1235—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]2-, e.g. Li2Mn2O4, Li2[MxMn2-x]O4
-
- 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
- H01M4/48—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- 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 lithium manganate (LiMn)2O4) A rapid preparation method and application of the anode material. The invention quickly synthesizes LiMn2O4Positive electrode material, LiMn produced by rapid heating2O4Conversion of precursor into LiMn2O4And (3) granules. The spinel of the invention has the same spinel as the anode material synthesized by the traditional method, is beneficial to the extraction and the insertion of lithium ions, and simultaneously, the valence state of manganese ions is consistent with that synthesized by the traditional method. LiMn of the invention2O4The anode material has LiMn synthesized by the traditional method2O4The positive electrode material has almost the same performance without any modified LiMn2O4The first coulombic efficiency of the anode material is 85 percent, the first discharge specific capacity is 120mAh/g, and the first discharge specific capacity is better timesRate capability.
Description
Technical Field
The invention relates to the field of lithium ion battery materials, in particular to lithium manganate (LiMn)2O4) A rapid preparation method and application of the anode material.
Background
At present, lithium ion batteries are widely used in various electronic devices such as mobile phones and computers, wherein the positive electrode material of the lithium ion battery accounts for a large proportion in the battery, but the commonly used raw materials such as lithium manganate and the like and the production cost are high, and along with the continuous improvement of the demand of people on the lithium ion batteries, higher requirements are also put forward on the preparation process and the production cost of the positive electrode material. Reducing the preparation period of the positive electrode material is one of the most important ways to reduce the production cost of lithium batteries. However, the preparation period of the anode material in both laboratories and industries is generally more than ten hours at present, so that the preparation period of the anode material of the lithium battery is long, and much electric power and time are consumed during production, thereby greatly improving the production cost of the lithium battery.
Further, the lithium manganate anode material synthesized by the industrial method has large particle size, which results in small specific surface area and poor rate capability.
Disclosure of Invention
The invention overcomes the defects of the existing LiMn2O4The invention provides lithium manganate (LiMn), which has the defect of long production cycle in the preparation technology of a positive electrode material2O4) A rapid preparation method of a cathode material.
LiMn prepared by the invention2O4The anode material has LiMn synthesized by the traditional method2O4The positive electrode material has almost the same performance (lithium manganate crystals with good crystal forms can be obtained, and lithium ions can be favorably extracted and inserted), such as specific capacity of a battery, and the like, but the preparation time only needs dozens of seconds.
The invention also overcomes the defect that the lithium manganate anode material particles prepared by the traditional industrial technology are large, and compared with the lithium manganate anode material prepared by the existing industrial method, the lithium manganate anode material particles prepared by the invention are reduced by 5-8 times, and are expected to be widely applied to rate-type batteries.
The invention quickly synthesizes LiMn2O4The positive electrode material is granular and has LiMn synthesized by the traditional method2O4The anode material has the same spinel structure, is beneficial to the extraction and the insertion of lithium ions, and simultaneously, the valence state of the manganese ions is consistent with that synthesized by the traditional method. Ultra-fast synthesized LiMn without any modification2O4Positive electrode material and LiMn synthesized by traditional method2O4The positive electrode material has almost the same performance, in the conventional electrolyte, the first coulombic efficiency is 85%, the first discharge specific capacity is 120mAh/g, and meanwhile, the positive electrode material has relatively good rate performance.
The purpose of the invention is realized by the following technical scheme:
a method for rapidly synthesizing a lithium manganate cathode material comprises the following steps: placing a lithium manganate precursor on carbon cloth with two ends connected to a direct-current power supply; electrifying and calcining twice, firstly calcining for the first time, grinding the primary calcined product, and then calcining for the second time to obtain the lithium manganate cathode material; the electrifying current for the first calcination is 8-12A, and the duration is 5-15 s; the electrifying current for the second calcination is 11-17A, and the duration is 10-40 s.
Further, the lithium manganate precursor is prepared by a liquid phase method. The liquid phase method comprises the following steps: completely dissolving lithium acetate and lithium manganate together by using absolute ethyl alcohol to obtain a metal salt solution, and complexing by using a citric acid absolute ethyl alcohol solution as a complexing agent (dropwise adding the metal salt solution and the citric acid solution into the absolute ethyl alcohol simultaneously, and continuously stirring the metal salt solution and the citric acid solution); heating and evaporating the liquid to dryness, transferring the liquid to an oven for drying after the liquid is completely evaporated to dryness, taking out the dried liquid and grinding the dried liquid to fine powder, namely the precursor of the lithium manganate positive electrode material.
In a mixed absolute ethyl alcohol solution (namely a metal salt solution) of lithium acetate and manganese acetate, the concentration of the lithium acetate is 1-3M/L, and the concentration of the manganese acetate is 1-3M/L; the concentration of the citric acid solution is 1-3M/L, and lithium acetate needs to be added in order to prevent the loss of lithium. Most preferably, the concentration of lithium acetate is 1.25M/L and the concentration of manganese acetate is 1.25M/L; the concentration of the aqueous citric acid solution was 1.25M/L, and lithium acetate was added in an amount sufficient to prevent loss of lithium.
In certain embodiments, the complexing is carried out at 75-85 deg.C, most preferably, at 80 deg.C.
The invention also relates to application of the lithium manganate positive electrode material synthesized by the method in preparation of lithium manganate lithium ion batteries.
The invention has the beneficial effects that: the lithium manganate anode material with the size of dozens of nanometers to hundreds of nanometers is prepared by ultra-fast synthesis. The lithium manganate anode material has a layered structure with the same hexagonal system as the lithium manganate anode material synthesized by the traditional method, is beneficial to the extraction and the insertion of lithium ions, and simultaneously, the valence state of manganese ions is positive trivalent as the valence state of manganese ions synthesized by the traditional method. The ultra-fast synthesized lithium manganate positive electrode material without any modification has almost the same performance as the lithium manganate positive electrode material synthesized by the traditional method, in a lithium hexafluorophosphate electrolyte, the first coulombic efficiency is 89%, the first discharge specific capacity is 140mAh/g, the coulombic efficiency is still close to 100% when the lithium hexafluorophosphate electrolyte is circulated for 300 circles at 1C, and the capacity retention rate within 100 circles is still about 90%. The lithium manganate cathode material with small size is expected to be widely applied to rate batteries.
In conclusion, the research work provides a brand new method for rapidly synthesizing the lithium ion battery cathode material.
Drawings
FIG. 1(a) shows the preparation of LiMn according to the invention2O4An XRD pattern spectrum of the anode material;
FIG. 1(b) shows LiMn prepared by a conventional process2O4An XRD pattern spectrum of the anode material;
FIG. 2(a) shows LiMn in the present invention2O4Temperature-time variation curve of thermal shock primary calcination of the positive electrode material;
FIG. 2(b) shows LiMn in the present invention2O4Hot stamping of positive electrode materialsThe temperature-time change curve of the secondary calcination is hit;
FIG. 3 shows LiMn in the present invention2O4A Scanning Electron Microscope (SEM) image of the positive electrode material;
FIG. 4(a) shows the preparation of LiMn according to the present invention2O4A first charge-discharge curve of the material-assembled battery;
FIG. 4(b) is LiMn prepared by conventional process2O4A first charge-discharge curve of a battery assembled by the positive electrode material;
FIG. 4(c) is a diagram of the preparation of LiMn according to the present invention2O4Performance plots of the material assembled cells at different rates.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the following examples, the carbon cloth was 5cm by 2.5cm in size and was obtained from Taiwan carbon technologies, Inc.
Example 1
Ultra-fast synthesis of LiMn2O4The positive electrode material is prepared by the following steps:
step 1, completely dissolving lithium acetate and manganese acetate by using absolute ethyl alcohol (the concentrations of the lithium acetate and the manganese acetate are both 1.25M/L, stirring and dissolving at a certain temperature), and complexing at 80 ℃ by using a citric acid absolute ethyl alcohol solution (the concentration of the citric acid absolute ethyl alcohol solution is 1.25M/L) as a complexing agent. The specific process of the complexation is that the metal salt solution and the citric acid solution are simultaneously dripped into a certain amount of absolute ethyl alcohol (the amount of the absolute ethyl alcohol is 200mL of absolute ethyl alcohol per 0.1M of metal salt), the metal salt solution and the citric acid solution are required to be consistent in amount, the metal salt solution and the citric acid solution are continuously stirred while being dripped, and the liquid is evaporated to dryness by heating after the two solutions are completely dripped. Transferring the liquid into an oven to dry overnight after the liquid is completely evaporated to dryness, taking out the dried liquid and grinding the dried liquid in a mortar to fine powder, namely LiMn2O4Precursor of positive electrode material, and then adding LiMn2O4And (5) storing the precursor in a vacuum drier.
Step 2, preparing LiMn in step 12O4Uniformly spreading the precursor of the anode materialOn a carbon cloth (laying mass is 0.03 g/cm)2) And the power is connected to a direct current power supply and electrified. Electrifying and calcining twice, wherein the electrifying current for primary calcining is 10A, the duration is 10s, then grinding the primary calcined product and then calcining twice, the electrifying current for secondary calcining is 15A, and the duration is 30s, thus obtaining the LiMn2O4And (3) a positive electrode material.
As shown in FIGS. 1(a) and 1(b), the powder X-ray diffraction (XRD) patterns show that ultra-fast preparation of LiMn2O4The anode material has LiMn prepared by the traditional method2O4The positive electrode material has the same XRD pattern and is in a spinel structure. With LiMn2O4Compared with the standard PDF card, the ultra-fast synthesized LiMn2O4The diffraction peak of (2) was consistent therewith.
FIG. 2(a) shows LiMn2O4A schematic diagram of temperature change of the precursor after primary calcination and heating to 650 ℃, heat preservation, cutting off input current and rapid cooling; FIG. 2(b) shows LiMn2O4And (3) a schematic diagram of temperature change of cutting off input current and rapidly cooling after primary calcination and grinding and secondary calcination and heating to 700 ℃ for heat preservation.
Ultra-fast synthesis of LiMn2O4Morphology of the particles, ultra-fast synthesized LiMn, as shown in FIG. 32O4The anode material is particles with the nanometer range from tens to hundreds.
In order to explore ultra-fast synthesized LiMn2O4Electrochemical performance of the cathode material, we further assembled the battery and tested the electrochemical performance, fig. 4(a) is for preparing LiMn2O4LiMn meeting charge-discharge platform of first charge-discharge curve of battery assembled by materials2O4The typical charge and discharge platform of the anode material has a specific discharge capacity of 120mAh/g, and is similar to LiMn prepared by a conventional method2O4The specific discharge capacity of the positive electrode material was substantially the same as that shown in fig. 4 (b). Meanwhile, the initial coulombic efficiency can reach 85 percent, and the method is basically consistent with the battery assembled by the lithium manganate cathode material prepared by the traditional process. FIG. 4(c) is a diagram of the preparation of LiMn according to the present invention2O4Performance plots of the material assembled cells at different rates,it can be seen that the battery exhibited relatively excellent rate performance at different current densities.
Example 2
Ultra-fast synthesis of LiMn2O4The positive electrode material is prepared by the following steps:
step 1, completely dissolving lithium acetate and manganese acetate together by using absolute ethyl alcohol (the concentrations of the lithium acetate and the manganese acetate are both 1M/L, stirring and dissolving at a certain temperature), and complexing at 75 ℃ by using a citric acid absolute ethyl alcohol solution (the concentration of the citric acid absolute ethyl alcohol solution is 1M/L) as a complexing agent. The specific process of the complexation is that the metal salt solution and the citric acid solution are simultaneously dripped into a certain amount of absolute ethyl alcohol (the amount of the absolute ethyl alcohol is 200mL of absolute ethyl alcohol per 0.1M of metal salt), the metal salt solution and the citric acid solution are required to be consistent in amount, the metal salt solution and the citric acid solution are continuously stirred while being dripped, and the liquid is evaporated to dryness by heating after the two solutions are completely dripped. Transferring the liquid into an oven to dry overnight after the liquid is completely evaporated to dryness, taking out the dried liquid and grinding the dried liquid in a mortar to fine powder, namely LiMn2O4Precursor of positive electrode material, and then adding LiMn2O4And (5) storing the precursor in a vacuum drier.
Step 2, preparing LiMn in step 12O4The precursor of the anode material is uniformly paved on carbon cloth (the paving mass is 0.03 g/cm)2) And the power is connected to a direct current power supply and electrified. Electrifying and calcining twice, wherein the electrifying current for the primary calcining is 8A, the duration is 5s, then grinding the primary calcined product and then calcining twice, the electrifying current for the secondary calcining is 11A, and the duration is 10s, thus obtaining the LiMn2O4And (3) a positive electrode material.
The powder X-ray diffraction (XRD) pattern shows that the LiMn is prepared ultrafast2O4The anode material has LiMn prepared by the traditional method2O4The positive electrode material has the same XRD pattern and is in a spinel structure.
By using the test method in the same example 1, the first coulombic efficiency of the lithium cobaltate obtained in this example can reach 88%, and the lithium cobaltate is basically consistent with a battery assembled by a lithium cobaltate positive electrode material prepared by a conventional process. The capacity retention rate of the assembled battery is more than 90% after the battery is cycled for 100 circles, the coulombic efficiency of the assembled battery is still almost 100% after the battery is cycled for 100 circles, and meanwhile, the assembled battery shows relatively excellent rate performance under different current densities.
Example 3
Ultra-fast synthesis of LiMn2O4The positive electrode material is prepared by the following steps:
step 1, completely dissolving lithium acetate and manganese acetate together by using absolute ethyl alcohol (the concentrations of the lithium acetate and the manganese acetate are both 3M/L, stirring and dissolving at a certain temperature), and complexing at 85 ℃ by using a citric acid absolute ethyl alcohol solution (the concentration of the citric acid absolute ethyl alcohol solution is 3M/L) as a complexing agent. The specific process of the complexation is that the metal salt solution and the citric acid solution are simultaneously dripped into a certain amount of absolute ethyl alcohol (the amount of the absolute ethyl alcohol is 200mL of absolute ethyl alcohol per 0.1M of metal salt), the metal salt solution and the citric acid solution are required to be consistent in amount, the metal salt solution and the citric acid solution are continuously stirred while being dripped, and the liquid is evaporated to dryness by heating after the two solutions are completely dripped. Transferring the liquid into an oven to dry overnight after the liquid is completely evaporated to dryness, taking out the dried liquid and grinding the dried liquid in a mortar to fine powder, namely LiMn2O4Precursor of positive electrode material, and then adding LiMn2O4And (5) storing the precursor in a vacuum drier.
Step 2, preparing LiMn in step 12O4The precursor of the anode material is uniformly paved on carbon cloth (the paving mass is 0.03 g/cm)2) And the power is connected to a direct current power supply and electrified. Electrifying and calcining twice, wherein the electrifying current for the primary calcining is 12A, the duration is 15s, then grinding the primary calcined product and then calcining twice, the electrifying current for the secondary calcining is 17A, and the duration is 40s, thus obtaining the LiMn2O4And (3) a positive electrode material.
The powder X-ray diffraction (XRD) pattern shows that the LiMn is prepared ultrafast2O4The anode material has LiMn prepared by the traditional method2O4The positive electrode material has the same XRD pattern and is in a spinel structure.
By using the test method in the same example 1, the first coulombic efficiency of the lithium cobaltate obtained in this example can reach 87%, and the first coulombic efficiency is basically the same as that of a battery assembled by the lithium cobaltate cathode material prepared by the conventional process. The capacity retention rate of the assembled battery is more than 90% after the battery is cycled for 100 circles, the coulombic efficiency of the assembled battery is still almost 100% after the battery is cycled for 100 circles, and meanwhile, the assembled battery shows relatively excellent rate performance under different current densities.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (7)
1. LiMn2O4The rapid preparation method of the cathode material is characterized by comprising the following steps:
placing the lithium manganate precursor on a carbon cloth, and connecting two ends of the carbon cloth to a direct-current power supply; electrifying and calcining twice, firstly calcining for the first time, grinding the primary calcined product, and then calcining for the second time to obtain the lithium manganate cathode material; the electrifying current for the first calcination is about 8-12A, and the duration is 5-15 s; the electrifying current for the second calcination is 11-17A, and the duration is about 10-40 s.
2. The method of claim 1, wherein the lithium manganate precursor is prepared by a liquid phase method.
3. The method of claim 1, wherein the liquid phase process is: completely dissolving lithium acetate and manganese acetate in absolute ethyl alcohol to obtain a metal salt solution, and complexing by using a citric acid absolute ethyl alcohol solution as a complexing agent; heating and evaporating the liquid to dryness, transferring the liquid to an oven for drying after the liquid is completely evaporated to dryness, taking out the dried liquid and grinding the dried liquid to fine powder to obtain the precursor of the lithium manganate positive electrode material.
4. LiMn according to claim 32O4The rapid preparation method of the anode material is characterized in that complexation is carried out at the temperature of 75-85 ℃.
5. LiMn according to claim 32O4The rapid preparation method of the cathode material is characterized in that in the metal salt solution, the concentration of lithium acetate is 0.75-1.5M/L, and the concentration of manganese acetate is 0.75-1.5M/L.
6. LiMn according to claim 32O4The rapid preparation method of the cathode material is characterized in that in the step 3, the concentration of the ethanol solution of the citric acid is 0.75-1.5M/L.
7. LiMn produced by the production method according to any one of claims 1 to 62O4The application of the anode material in the preparation of lithium ion batteries.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110772739.4A CN113353986A (en) | 2021-07-08 | 2021-07-08 | Rapid preparation method and application of lithium manganate cathode material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110772739.4A CN113353986A (en) | 2021-07-08 | 2021-07-08 | Rapid preparation method and application of lithium manganate cathode material |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113353986A true CN113353986A (en) | 2021-09-07 |
Family
ID=77538940
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110772739.4A Pending CN113353986A (en) | 2021-07-08 | 2021-07-08 | Rapid preparation method and application of lithium manganate cathode material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113353986A (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6455303A (en) * | 1987-08-26 | 1989-03-02 | Sumitomo Heavy Industries | Sintering method |
CN104319400A (en) * | 2014-10-11 | 2015-01-28 | 柳州豪祥特科技有限公司 | Preparation method of nano spinel-type lithium manganate |
WO2016122070A1 (en) * | 2015-01-29 | 2016-08-04 | 한국전기연구원 | Method for modifying carbon material electrode surface by current carrying, surface-modified carbon material electrode, and electrochemical capacitor comprising surface-modified carbon material electrode |
CN111477864A (en) * | 2020-04-13 | 2020-07-31 | 山东鲁北国际新材料研究院有限公司 | Preparation method and application of superfine metal bismuth nano material |
-
2021
- 2021-07-08 CN CN202110772739.4A patent/CN113353986A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6455303A (en) * | 1987-08-26 | 1989-03-02 | Sumitomo Heavy Industries | Sintering method |
CN104319400A (en) * | 2014-10-11 | 2015-01-28 | 柳州豪祥特科技有限公司 | Preparation method of nano spinel-type lithium manganate |
WO2016122070A1 (en) * | 2015-01-29 | 2016-08-04 | 한국전기연구원 | Method for modifying carbon material electrode surface by current carrying, surface-modified carbon material electrode, and electrochemical capacitor comprising surface-modified carbon material electrode |
CN111477864A (en) * | 2020-04-13 | 2020-07-31 | 山东鲁北国际新材料研究院有限公司 | Preparation method and application of superfine metal bismuth nano material |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102386381B (en) | Preparation method of nano positive material for lithium ion battery | |
CN105161705B (en) | A kind of lithium manganese phosphate cladding nickel-cobalt lithium manganate cathode material and preparation method thereof | |
CN102738458B (en) | Surface modification method of lithium-rich cathode material | |
CN107403903B (en) | A kind of method of the sol-tgel self-propagating combustion method preparation nickelic positive electrode of ternary | |
CN103956485B (en) | Lithium iron phosphate electrode material of a kind of three-dimensional hierarchical structure and preparation method thereof | |
CN104051724A (en) | Carbon-coated nickel-cobalt lithium manganate positive electrode material and preparation method thereof | |
CN109607505A (en) | A kind of preparation method for the LiFePO4 improving cryogenic property | |
CN108933247B (en) | Method for preparing AZO-coated 523 single-crystal nickel-cobalt-manganese ternary positive electrode material and product | |
CN111430687B (en) | Carbon-coated lithium iron phosphate composite material, preparation method thereof and lithium ion battery | |
CN103346317A (en) | Compound doped and cladded lithium ion cell anode material LiFePO4 and preparation method thereof | |
CN102208618A (en) | Preparation method of lithium ion phosphate used as positive electrode active material | |
CN102208644A (en) | Composite lithium manganese phosphate serving as lithium ion battery anode material and preparation method thereof and lithium ion battery | |
Li et al. | Synthesis and properties of nanostructured LiNi1/3Co1/3Mn1/3O2 as cathode with lithium bis (oxalate) borate-based electrolyte to improve cycle performance in Li-ion battery | |
CN108807899A (en) | A kind of preparation method of multistage spherical vanadium phosphate sodium composite positive pole | |
CN105938905A (en) | Preparation method of nitrogen-enriched doping modified porous carbon materials | |
CN111003733A (en) | Method for preparing high-nickel ternary lithium battery anode material through microwave intelligent frequency conversion second-order sintering | |
Liu et al. | The effect of calcination temperature on combustion preparation of ZnFe2O4 as anode for lithium batteries | |
CN108565427B (en) | Preparation method of carbon/lithium titanate composite material | |
Wu et al. | Study on Li1+ xV3O8 synthesized by microwave sol–gel route | |
Zhou et al. | Hierarchical LiNi 0.5 Mn 1.5 O 4 micro-rods with enhanced rate performance for lithium-ion batteries | |
CN112938952A (en) | Preparation and application of cathode material with two-dimensional structure tungsten trioxide coated with graphene | |
Wu et al. | Structural, morphological and electrochemical characteristics of spinel LiMn2O4 prepared by spray-drying method | |
CN104810519A (en) | Lithium ion battery cathode material rich in lithium and manganese and preparation method thereof | |
Lu et al. | Morphology and electrochemical properties of LiMn2O4 powders derived from the sol–gel route | |
Chen et al. | Electrochemical studies on LiCoO2 surface coated with Y3Al5O12 for lithium-ion cells |
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 |