CN114682575B - Method for reducing residual alkali on surface of high-nickel anode material, obtained material and application - Google Patents
Method for reducing residual alkali on surface of high-nickel anode material, obtained material and application Download PDFInfo
- Publication number
- CN114682575B CN114682575B CN202210603107.XA CN202210603107A CN114682575B CN 114682575 B CN114682575 B CN 114682575B CN 202210603107 A CN202210603107 A CN 202210603107A CN 114682575 B CN114682575 B CN 114682575B
- Authority
- CN
- China
- Prior art keywords
- residual alkali
- strong oxidizing
- oxidizing gas
- temperature
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
- B08B7/02—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by distortion, beating, or vibration of the surface to be cleaned
-
- 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
-
- 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 method for reducing residual alkali on the surface of a high-nickel anode material, and an obtained material and application thereof, and belongs to the technical field of lithium battery materials. It includes: vibrating the high-nickel anode material obtained by high-temperature roasting at 20-40 ℃ for 10-60 min in the presence of strong oxidizing gas to reduce residual alkali on the surface of the high-nickel anode material, wherein the strong oxidizing gas is ClO 2 、NO 2 、Cl 2 、Cl 2 O and Cl 2 O 7 One or more of them. The method is a water-free method for washing off residual alkali on the surface of the lithium battery material, and utilizes the characteristic that strong oxidizing substances such as chlorine dioxide can react with alkaline substances to ensure that the ClO is removed 2 The lithium salt reacts with residual alkali on the lithium battery material at a certain temperature to generate an alkali-free lithium salt, so that the residual alkali index is effectively reduced, a useful lithium component is reserved for the lithium battery material, and the lithium salt has an obvious effect on subsequent improvement of the electrochemical performance of the material.
Description
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a method for reducing residual alkali on the surface of a high-nickel anode material, an obtained material and application.
Background
High residual alkali is a problem often faced by lithium battery materials, particularly high nickel materials, and high surface residual alkali is an important cause for deterioration of electrochemical properties of lithium battery materials and deterioration of battery processing technology (homogenization). The problem of high residual alkali of the material is often treated in the current lithium battery material production or due to production batching errors, production equipment abnormity or due to the requirement of material system formula (such as high nickel proportion).
The water washing is a very common process scheme for removing the high residual alkali of the lithium battery material, but the problems of complex process, material electrochemical capacity loss and the like are brought along, so that the rapid and effective reduction of the residual alkali on the surface of the lithium battery material becomes a problem to be solved urgently.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for reducing residual alkali on the surface of a high-nickel cathode material, the obtained material and application.
The invention is realized in the following way:
the invention provides a method for reducing residual alkali on the surface of a high-nickel anode material, which comprises the following steps: vibrating the high-nickel anode material obtained by high-temperature roasting at 20-40 ℃ for 10-60 min in the presence of strong oxidizing gas to reduce residual alkali on the surface of the high-nickel anode material, wherein the strong oxidizing gas is ClO 2 、NO 2 、Cl 2 、Cl 2 O and Cl 2 O 7 One or more of them.
The invention also provides a lithium battery material prepared by the preparation method.
The invention also provides an application of the lithium battery material prepared by the preparation method in a lithium battery.
The invention has the following beneficial effects:
the invention provides a method for reducing residual alkali on the surface of a high-nickel anode material, and an obtained material and application thereof, wherein the method comprises the following steps: carrying out vibration treatment on the high-nickel anode material obtained by high-temperature roasting at the temperature of 20-40 ℃ for 10-60 min in the presence of strong oxidizing gas to reduce residual alkali on the surface of the high-nickel anode material, wherein the strong oxidizing gas is ClO 2 、NO 2 、Cl 2 、Cl 2 O and Cl 2 O 7 One or more of them. The method is a method for removing residual alkali on the surface of the lithium battery material by water-free washing, and utilizes the characteristic that a strong oxidizing substance can react with an alkaline substance to ensure that the material is positive to high nickel at a certain temperatureThe residual alkali on the electrode material reacts to generate an alkali-free lithium salt, so that the residual alkali index is effectively reduced, a useful lithium component is reserved for the lithium battery material, and the material has an obvious effect on subsequent electrochemical performance improvement.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
Fig. 1 is a first-turn charge-discharge curve of example 1 and comparative examples 1, 3, 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention aims to provide a method for reducing residual alkali on the surface of a high-nickel cathode material, the obtained material and application.
In order to achieve the above object of the present invention, the following technical solutions are adopted.
In a first aspect, an embodiment of the present invention provides a method for reducing alkali residue on a surface of a high nickel cathode material, including: carrying out vibration treatment on the high-nickel anode material obtained by high-temperature roasting at the temperature of 20-40 ℃ for 10-60 min in the presence of strong oxidizing gas to reduce residual alkali on the surface of the high-nickel anode material, wherein the strong oxidizing gas is ClO 2 、NO 2 、Cl 2 、Cl 2 O and Cl 2 O 7 One or more of them.
The high nickel anode material has a higher residual alkali content on the surface due to a lower sintering temperature, the residual alkali content on the surface of the high nickel anode material which is usually just sintered is about thousands to ten thousand, and the residual alkali content on the surface of the high nickel anode material is increased along with the increase of the nickel content, so that the high nickel anode material is easy to damp and absorb water in the air, the viscosity of the material is increased and even jelly-shaped during size mixing, and the processing difficulty is higher; and the residual alkaline substances on the surface of the high-nickel anode material can bring water into the battery, so that the loss of the battery is large, side reaction is easy to occur, the internal resistance of the battery is increased, the performance of the battery is reduced, and the battery can be expanded.
At present, the general method for reducing the residual alkali on the surface of the high-nickel anode material precursor is to uniformly mix deionized water and the high-nickel anode material according to a certain proportion, and considering that the solubility of the residual alkali at a low temperature is higher than the normal temperature, the residual alkali floating on the surface of the high-nickel anode material is generally dissolved in water as much as possible by stirring at a low temperature of 5-10 ℃, then the filtration is carried out, and the filter element is dried to remove the water in the high-nickel anode material, so that the purpose of reducing the residual alkali is achieved; however, in the washing process, the low-temperature washing control is complex, the cost is high, and the residual alkali dissolved in the normal-temperature filtration can return to the high-nickel cathode material, so that the washing effect is reduced.
To the present problem such as the technology that adopts the washing to get rid of lithium electricity material high residual alkali is loaded down with trivial details, material electrochemical capacity loss, the inventor pioneered provide a washing-free scheme to high residual alkali lithium electricity material, it includes: carrying out vibration treatment on the high-nickel anode material obtained by high-temperature roasting at the temperature of 20-40 ℃ for 10-60 min in the presence of a strong oxidizing substance to reduce residual alkali on the surface of the high-nickel anode material, wherein the strong oxidizing substance is ClO 2 、NO 2 、Cl 2 、Cl 2 O and Cl 2 O 7 One or more of them. Although in the usual case, Cl 2 O 7 Is colorless and volatile oily liquid, but is due to Cl 2 O 7 Is extremely easy to volatilize, and can be changed into gas for use by utilizing the characteristic that the volatile gas is in a gas state.
Using a strongly oxidizing substance as ClO 2 By way of example, using ClO 2 The lithium battery material obtained by high-temperature firing is treated by gas, so that the content of the lithium battery material can be effectively reducedThe reason for the residual alkali on the surface of the low-lithium battery material is as follows: ClO 2 Has strong oxidizing power in the +4 valence state, can perform oxidation-reduction reactions with a plurality of organic and inorganic compounds, and chlorine dioxide gas is extremely soluble in water and has the solubility about 5 times that of chlorine gas. The concentration of chlorine dioxide in the liquid phase at 25 ℃ equilibration was 23 times that in the gas phase. In contrast to the hydrolysis of chlorine in water, chlorine dioxide cannot be hydrolyzed to any significant amount in water, but instead remains in solution as a dissolved gas. The lithium battery material with high residual alkali on the surface generally increases along with the increase of the nickel content, so that the high-nickel cathode material is very easy to be affected with moisture and absorb water in the air, and the ClO can be greatly improved 2 Adsorption capacity of gas on the surface of high-nickel anode material, ClO 2 Disproportionation reaction can rapidly occur in alkaline solution to generate the mixture of chlorite and chlorate. And in order to further increase the reaction rate, the high-nickel cathode material is subjected to vibration treatment at a certain temperature, wherein the reaction is as follows:
2LiOH + 2ClO 2 →LiClO 2 + LiClO 3 + H 2 O
therefore, the embodiment of the invention provides a brand-new method for removing the residual alkali on the surface of the lithium battery material, the residual alkali on the surface is reduced by converting a gaseous substance into a low-alkalinity substance through the reaction of the gaseous substance and the residual alkali on the surface of the lithium battery material instead of removing the residual alkali through water washing, a useful lithium component is reserved for the lithium battery material while the index of the residual alkali is effectively reduced, and the material has an obvious effect on subsequent electrochemical performance improvement.
In an alternative embodiment, the molar ratio of Li to the strongly oxidizing gas in the high nickel cathode material is 1: 1.
In an alternative embodiment, the vibration treatment has an amplitude of 1mm to 3mm and a frequency of 20Hz to 40 Hz.
In an alternative embodiment, the vibration process comprises the steps of: placing the high-nickel anode material in a reaction container, reducing the pressure of the reaction container to be below 0.01MPa, introducing mixed gas of strong oxidizing gas with the volume concentration of 1% -10% into the reaction container, keeping the pressure of the reaction container to be below 0.05MPa, and carrying out vibration treatment.
In an alternative embodiment, the mixed gas of the strong oxidizing gas is a mixed gas of the strong oxidizing gas and a non-oxidizing gas. If the gaseous chlorine dioxide is unstable, the gaseous chlorine dioxide is easily decomposed into oxygen and chlorine by heat or light to cause explosion; explosion can also occur when encountering substances that promote oxidation, such as organic matter. The chlorine dioxide gas is safe when diluted to the concentration below 10 percent (V/V) by air.
In an alternative embodiment, the method further comprises: and after stopping vibration, cooling the temperature to room temperature, taking out the material, and directly using the material as a battery anode material or using the material as the battery anode material after heat treatment.
In an alternative embodiment, the temperature of the heat treatment is 300 ℃ to 600 ℃ for 3h to 6 h.
Using strong oxidizing gas as ClO 2 For example, the material after the vibration treatment is cooled to room temperature is continuously subjected to high-temperature secondary combustion to enable the previous ClO 2 LiClO generated by reaction with residual alkali on the surface of high-nickel cathode material 3 Further decomposing at high temperature to form LiCl and releasing oxygen, wherein the released oxygen can further improve the surface oxidation state of the nickel cathode material, and the residual trace LiCl is also a commonly used additive in the electrolyte and does not adversely affect the performance of the material. The reactions involved are as follows:
2LiClO 3 →2LiCl + 3O 2
in a second aspect, the embodiment of the invention also provides a lithium battery material prepared according to the preparation method.
In a third aspect, the embodiment of the invention also provides an application of the lithium battery material prepared by the preparation method in a lithium battery.
The features and properties of the present invention are described in further detail below with reference to examples.
The embodiment of the invention provides a method for effectively reducing alkali residues on the surface of a lithium battery material, which takes strong oxidizing gas as ClO 2 For example, the specific steps are as follows:
(1) placing the high-residual-alkali lithium battery material in a closed container with a vibration function, and reducing the pressure to be below 0.01 MPa;
(2) the ClO with the proportion of 1 percent to 10 percent is adopted 2 Introducing the mixed gas into a container, and keeping the pressure of the container below 0.05 MPa;
(3) adjusting the temperature to 20-40 ℃, starting the furnace to carry out vibration treatment for 10-60 min, setting the amplitude to be 1-3 mm and the frequency to be 20-40 Hz;
(4) determining ClO according to the residual alkali value of the target product 2 The specific calculation mode is Li: ClO 2 1:1 (molar ratio), where Li represents lithium as residual base; if limited by container ClO 2 The ClO in the container can be supplemented in batches when the feeding amount exceeds the concentration specified in the step 2 2 When the concentration is reduced to about 25% of the initial concentration, the supplement is carried out.
(5) Stopping vibrating, introducing oxygen to restore the pressure of the container to normal pressure, cooling the temperature to room temperature, and taking out to obtain a target product;
(6) the processed material can be directly used as a battery anode material, and can also be used as the battery anode material after further heat treatment.
Example 1
The embodiment provides a lithium battery cathode material, and a preparation method thereof is as follows:
mixing the ternary material LiNi 0.83 Co 0.11 Mn 0.06 O 2 Placing in a vacuum container, discharging gas in pores of the ternary material, adjusting the temperature in the vacuum container to 30 deg.C, vibrating at amplitude of 2mm and frequency of 30Hz, and introducing 10% ClO 2 Mixed gas, ClO 2 The content of (b) and the molar ratio of lithium in the residual alkali are 1:1, and the vibration treatment is carried out for 30 min.
Stopping vibration, introducing oxygen to restore the pressure of the container to normal pressure, cooling to room temperature, and taking out the target product.
Subsequently, the mixture was further heat-treated at 300 ℃ for 4 hours.
Example 2
The embodiment provides a lithium battery cathode material, and a preparation method thereof is as follows:
mixing the ternary material LiNi 0.83 Co 0.11 Mn 0.06 O 2 Placing in a vacuum container to discharge gas in the pores of the ternary material, adjusting the temperature in the vacuum container to 30 deg.C, vibrating at amplitude of 1mm and frequency of 40Hz, and introducing 5% ClO 2 Mixed gas ClO 2 The content of (b) and the molar ratio of lithium in the residual alkali are 1:1, and the vibration treatment is carried out for 30 min.
Stopping vibration, introducing oxygen to restore the pressure of the container to normal pressure, cooling to room temperature, and taking out the target product.
Subsequently, the mixture was further heat-treated at 500 ℃ for 5 hours.
Example 3
The embodiment provides a lithium battery positive electrode material, and a preparation method thereof comprises the following steps:
mixing the ternary material LiNi 0.83 Co 0.11 Mn 0.06 O 2 Placing in a vacuum container to discharge gas in the pores of the ternary material, adjusting the temperature in the vacuum container to 30 deg.C, vibrating at an amplitude of 3mm and a frequency of 20Hz, and introducing 1% ClO 2 Mixed gas ClO 2 The content of (b) and the molar ratio of lithium in the residual alkali are 1:1, and the vibration treatment is carried out for 30 min.
Stopping vibrating, introducing oxygen to restore the pressure of the container to normal pressure, cooling to room temperature, and taking out the target product.
Subsequently, the mixture was further heat-treated at 600 ℃ for 3 hours.
Example 4
The embodiment provides a lithium battery positive electrode material, and a preparation method thereof comprises the following steps:
mixing the ternary material LiNi 0.83 Co 0.11 Mn 0.06 O 2 Placing in a vacuum container to discharge gas in the pores of the ternary material, adjusting the temperature in the vacuum container to 30 deg.C, vibrating at amplitude of 2mm and frequency of 30Hz, and introducing 1% ClO 2 Mixed gas ClO 2 The content of (b) and the molar ratio of lithium in residual alkali are 1:1, and vibration treatment is carried out for 30 min.
Stopping vibration, introducing oxygen to restore the pressure of the container to normal pressure, cooling to room temperature, and taking out the target product.
Subsequently, the mixture was further heat-treated at 300 ℃ for 4 hours.
Example 5
The embodiment provides a lithium battery cathode material, and a preparation method thereof is as follows:
mixing the ternary material LiNi 0.83 Co 0.11 Mn 0.06 O 2 Placing in a vacuum container to discharge gas in the pores of the ternary material, adjusting the temperature in the vacuum container to 30 deg.C, vibrating at amplitude of 2mm and frequency of 30Hz, and introducing 10% Cl 2 Mixed gas of O, Cl 2 The molar ratio of the O content to the lithium in the residual alkali is 1:1, and the vibration treatment is carried out for 30 min.
Stopping vibration, introducing oxygen to restore the pressure of the container to normal pressure, cooling to room temperature, and taking out the target product.
Subsequently, the mixture was further heat-treated at 300 ℃ for 4 hours.
Comparative example 1
This comparative example differs from example 1 in that: the residual alkali on the surface is directly removed by adopting a water washing mode, and the rest conditions are the same.
Comparative example 2
Similar to the procedure of example 1, except that: the temperature of the vibration treatment was 80 ℃ and the rest of the conditions were the same.
Comparative example 3
Similar to the procedure of example 1, except that: the amplitude was set to 5mm and the frequency was set to 60Hz, the rest of the conditions being the same.
Comparative example 4
Similar to the procedure of example 1, except that: ClO 2 The content of (b) and the molar ratio of lithium in the residual alkali are 1:5, and the rest conditions are the same.
Comparative example 5
Similar to the procedure of example 1, except that: the vibration treatment time was 5min, and the rest conditions were the same.
Test results
For the positive electrode materials obtained in examples 1 to 5 and comparative examples 1 to 5, the alkali content of the materials was measured by referring to "measurement of pH of aqueous pigment suspension GB/T1717" and "measurement of sodium hydroxide and sodium carbonate content for industrial use in GBT 4348.1-2013", and the results are shown in Table 1.
TABLE 1
As can be seen from table 1: the method in the embodiment 1-5 can effectively reduce the residual alkali content on the surface of the high nickel material. Comparative example 1 adopts the traditional alkali-reducing manner by water washing, and although the alkali residue on the surface of the material can be eluted, the alkali residue on the surface of the material is obviously reduced, the surface state is changed due to the sensitivity of high nickel to water and the water immersion treatment in the water washing process, so that the cycle performance of the material is obviously reduced. In comparative examples 2 to 5, however, the residual alkali content on the surface of the material could not be effectively reduced by using experimental conditions different from those of the examples of the present invention.
In addition, the ternary material, the conductive carbon black Super P and the adhesive PVDF which are obtained in the embodiment and the comparative example are prepared into the pole piece according to the mass ratio of 90: 5. The specific process is as follows: PVDF was added to NMP and stirred to dissolve in the NMP to form a dope. Adding the glue solution, conductive carbon black Super P and the ternary material into a defoaming machine together to prepare battery slurry; uniformly coating the slurry on an aluminum foil on a coating machine to prepare a pole piece, wherein the density of a single-side surface is controlled to be 8-12mg/cm 2 And drying the left and the right for preparing the battery.
The button cell testing method comprises the following steps: and (3) putting the single-side coated pole piece into a vacuum drying oven at the temperature of 105 ℃ for vacuum drying for 12 hours, taking out the pole piece, and rolling the pole piece on a rolling machine for later use. The cell assembly was carried out in an argon-filled glove box with an electrolyte of 1M LiPF6 EC: DEC: DMC 1: 1:1 (volume ratio), and the metal lithium sheet is a counter electrode. The battery model is as follows: 2025.
testing in a battery test cabinet:
1) testing specific capacity, charging to 4.3V at 0.1C constant current, and standing for 5 min; and discharging at constant current of 0.1C to 3.0V, wherein the discharge specific capacity is the specific capacity of the ternary material.
2) Performing high-temperature cycle performance test, namely after the test of 1) is finished, charging to 4.3V by adopting a 1C constant current in a constant temperature box at 25 ℃, and standing for 5 min; discharging to 3.0V at constant current of 0.2C; the above steps were then repeated again for 50 cycles.
The lithium batteries assembled by using the ternary materials prepared in examples 1 to 5 and comparative examples 1 to 5 were subjected to performance tests, and the results thereof are shown in table 2.
TABLE 2
| Performance of battery | |
| Example 1 | The initial discharge specific capacity is 219 mAh/g, and the capacity retention rate is more than or equal to 98 percent after 50 cycles at 25 DEG C |
| Example 2 | The initial discharge specific capacity is 215 mAh/g, and the capacity retention rate is more than or equal to 92 percent after the circulation for 100 times at the temperature of 25 DEG C |
| Example 3 | The initial discharge specific capacity is 214 mAh/g, and the capacity retention rate is more than or equal to 98 percent after 50 cycles at 25 DEG C |
| Example 4 | The initial discharge specific capacity is 216 mAh/g, and the capacity retention rate is more than or equal to 93 percent after 100 times of circulation at 25 DEG C |
| Example 5 | Initial discharge specific capacity 219 mAh/g, 25 DEG CThe capacity retention rate is more than or equal to 98 percent after 50 times of next circulation |
| Comparative example 1 | The initial discharge specific capacity is 203 mAh/g, and the capacity retention rate is about 90 percent after 50 times of circulation at 25 DEG C |
| Comparative example 2 | The initial discharge specific capacity is 205 mAh/g, and the capacity retention rate is about 88 percent after 50 times of circulation at 25 DEG C |
| Comparative example 3 | The initial discharge specific capacity is 198 mAh/g, and the capacity retention rate is about 90 percent after 50 times of circulation at 25 DEG C |
| Comparative example 4 | The initial specific capacity is 197 mAh/g, and the capacity retention rate is more than or equal to 90 percent after 50 times of circulation at 25 DEG C |
| Comparative example 5 | The initial specific capacity is 189 mAh/g, and the capacity retention rate is about 80 percent after the circulation for 100 times at the temperature of 25 DEG C |
As can be seen from table 2: lithium batteries assembled by the ternary materials prepared in examples 1-5 have better electrical performance indexes than lithium batteries assembled by the ternary materials prepared in comparative examples 1-5. And direct use of gas phase ClO 2 Compared with the manner of reducing residual alkali in comparative example 1, the manner of directly adopting water washing is adopted, lithium in the material can be washed away, so that the material is poor in lithium, the performance of the final material is improved limitedly, and the specific capacity index is slightly low. Comparative example 2 ClO caused by excessively high temperature of the vibration treatment 2 Decomposition, which in turn results in poor residual alkali reducing properties. Comparative example 3 has the problem that the integrity of the particles of the material is influenced due to overhigh vibration frequency and amplitude, so that the electricity of the material is generatedThe chemical properties are degraded. ClO in comparative example 4 2 The content is low, so that the surface residual alkali cannot be sufficiently reduced, a large amount of residual alkali still exists on the surface, and the electrochemical performance is influenced. The shaking time in comparative example 5 was too short, resulting in insufficient conversion of residual alkali into low-alkali substances and a serious capacity loss.
Comparison of rate performance of example 1 with comparative examples 1, 3 and 4 is shown in fig. 1, and too little ClO using conventional water washing 2 And too severe vibration frequencies, all have a detrimental effect on the rate performance of the material: comparative example 1 the traditional washing method leads to the excessive consumption of lithium on the surface of the material, and the rate performance of the material is affected; comparative example 3 too high amplitude and frequency, resulting in a fracture of the morphology of the material secondary sphere; comparative example 4 insufficient amount of ClO 2 The reduction of surface residual alkali is limited, which has negative influence on the improvement of the rate capability of the material.
In summary, the embodiments of the present invention provide a method for effectively reducing alkali residues on a surface of a lithium battery material, and the obtained material and application thereof, including: carrying out vibration treatment on the high-nickel anode material obtained by high-temperature roasting at the temperature of 20-40 ℃ for 10-60 min in the presence of strong oxidizing gas to reduce residual alkali on the surface of the high-nickel anode material, wherein the strong oxidizing gas is ClO 2 、NO 2 、Cl 2 、Cl 2 O and Cl 2 O 7 One or more of them. The method is a water-free method for washing away residual alkali on the surface of the lithium battery material, and makes use of the characteristic that strong oxidizing gas such as chlorine dioxide can react with alkaline substances to ensure that the ClO is 2 The lithium salt reacts with residual alkali on the lithium battery material at a certain temperature to generate an alkaline-free lithium salt, so that the residual alkali index is effectively reduced, a useful lithium component is reserved for the lithium battery material, and the lithium salt has an obvious effect on subsequent improvement of electrochemical properties of the material.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for reducing residual alkali on the surface of a high-nickel cathode material is characterized by comprising the following steps: carrying out vibration treatment on the high-nickel anode material obtained by high-temperature roasting at the temperature of 20-40 ℃ for 10-60 min in the presence of strong oxidizing gas to reduce residual alkali on the surface of the high-nickel anode material, wherein the strong oxidizing gas is ClO 2 、NO 2 、Cl 2 、Cl 2 O and Cl 2 O 7 The amplitude of the vibration treatment is 1mm-3mm, and the frequency is 20Hz-40 Hz.
2. The method according to claim 1, wherein the molar ratio of Li in the high nickel cathode material to the strong oxidizing gas is 1: 1.
3. The method of claim 1, wherein the vibration process comprises the steps of: and placing the high-nickel anode material in a reaction container, reducing the pressure of the reaction container to be below 0.01MPa, introducing mixed gas containing strong oxidizing gas into the reaction container, keeping the pressure of the reaction container to be below 0.05MPa, and carrying out vibration treatment.
4. The method according to claim 3, wherein the mixed gas containing the strong oxidizing gas is a mixed gas containing a volume fraction of the strong oxidizing gas of 1% to 10%, and the mixed gas is a mixed gas containing the strong oxidizing gas and a non-oxidizing gas.
5. The method of claim 3, further comprising: and after stopping vibration, introducing oxygen to restore the pressure of the container to normal pressure, taking out the container after the temperature of the material is cooled to room temperature, and directly using the material as a battery anode material or using the material as the battery anode material after heat treatment.
6. The method according to claim 5, wherein the material is subjected to heat treatment at a temperature of 300 ℃ to 600 ℃ for 3h to 6 h.
7. A lithium electrical material prepared according to the method of any one of claims 1-6.
8. Use of a lithium battery material prepared according to the method of any one of claims 1 to 6 as a lithium battery material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210603107.XA CN114682575B (en) | 2022-05-31 | 2022-05-31 | Method for reducing residual alkali on surface of high-nickel anode material, obtained material and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210603107.XA CN114682575B (en) | 2022-05-31 | 2022-05-31 | Method for reducing residual alkali on surface of high-nickel anode material, obtained material and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114682575A CN114682575A (en) | 2022-07-01 |
| CN114682575B true CN114682575B (en) | 2022-08-23 |
Family
ID=82131191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210603107.XA Active CN114682575B (en) | 2022-05-31 | 2022-05-31 | Method for reducing residual alkali on surface of high-nickel anode material, obtained material and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114682575B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103700838A (en) * | 2013-12-24 | 2014-04-02 | 安徽理工大学 | Preparation method and product of ionic double-doped lithium nickel manganese oxide material, and lithium ion battery |
| CN109402387A (en) * | 2018-10-16 | 2019-03-01 | 湖南行者环保科技有限公司 | Microwave high-temperature leaching device |
| CN111453779A (en) * | 2020-04-15 | 2020-07-28 | 蜂巢能源科技有限公司 | Method for reducing residual alkali content on surface of positive electrode material and application thereof |
| CN111573731A (en) * | 2020-04-26 | 2020-08-25 | 上海大学 | Vanadium-based positive electrode material of water-based zinc ion battery and preparation method and application thereof |
| CN113394390A (en) * | 2020-03-11 | 2021-09-14 | 中国石油化工股份有限公司 | Method for reducing alkali residue of high-nickel ternary material of lithium ion battery |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7282296B2 (en) * | 2002-10-15 | 2007-10-16 | Polyplus Battery Company | Ionically conductive composites for protection of active metal anodes |
| WO2011089958A1 (en) * | 2010-01-21 | 2011-07-28 | 住友金属鉱山株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery, method for producing same, and nonaqueous electrolyte secondary battery using same |
| JP5149927B2 (en) * | 2010-03-05 | 2013-02-20 | 株式会社日立製作所 | Positive electrode material for lithium secondary battery, lithium secondary battery, and secondary battery module using the same |
| CN102263258A (en) * | 2010-08-10 | 2011-11-30 | 中信国安盟固利动力科技有限公司 | Positive electrode material of high voltage lithium battery |
| CN102628351B (en) * | 2012-03-28 | 2014-10-29 | 中国石油大学(华东) | Experimental device and method for thick oil water thermal-catalytic cracking under effect of low frequency vibration waves |
| WO2014074504A1 (en) * | 2012-11-06 | 2014-05-15 | Cornell University | Carbon dioxide assisted metal-oxygen battery and related method |
| CN103964384B (en) * | 2013-01-24 | 2017-04-12 | 高砂热学工业株式会社 | Chlorine dioxide gas generation system and chlorine dioxide gas decomposer |
| CN104201378B (en) * | 2014-09-12 | 2017-04-12 | 中信国安盟固利电源技术有限公司 | Method for preparing high-nickel ternary cathode material of lithium ion battery |
| CN105810929A (en) * | 2014-12-31 | 2016-07-27 | 北京当升材料科技股份有限公司 | Treatment method for reducing residual alkalis on surface of high nickel material |
| CN108376777A (en) * | 2018-02-27 | 2018-08-07 | 贵州丕丕丕电子科技有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof that surface is modified |
| CN111430683A (en) * | 2020-01-17 | 2020-07-17 | 蜂巢能源科技有限公司 | Cobalt-free cathode material of lithium ion battery, preparation method of cobalt-free cathode material and lithium ion battery |
| CN111370664B (en) * | 2020-03-18 | 2022-04-29 | 溧阳中科海钠科技有限责任公司 | Method for reducing residual alkali content on surface of layered positive electrode material of sodium-ion battery and application |
| CN212142684U (en) * | 2020-05-14 | 2020-12-15 | 辽宁石化职业技术学院 | Vibration counterweight heat insulation ring for chemical experiment glassware |
| CN112499696B (en) * | 2020-11-30 | 2023-01-13 | 蜂巢能源科技有限公司 | Method for reducing residual alkali content of high-nickel material and low-residual alkali high-nickel material prepared by method |
| CN113793922A (en) * | 2021-07-30 | 2021-12-14 | 蜂巢能源科技有限公司 | Method for reducing residual alkali of lithium battery positive electrode material |
-
2022
- 2022-05-31 CN CN202210603107.XA patent/CN114682575B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103700838A (en) * | 2013-12-24 | 2014-04-02 | 安徽理工大学 | Preparation method and product of ionic double-doped lithium nickel manganese oxide material, and lithium ion battery |
| CN109402387A (en) * | 2018-10-16 | 2019-03-01 | 湖南行者环保科技有限公司 | Microwave high-temperature leaching device |
| CN113394390A (en) * | 2020-03-11 | 2021-09-14 | 中国石油化工股份有限公司 | Method for reducing alkali residue of high-nickel ternary material of lithium ion battery |
| CN111453779A (en) * | 2020-04-15 | 2020-07-28 | 蜂巢能源科技有限公司 | Method for reducing residual alkali content on surface of positive electrode material and application thereof |
| CN111573731A (en) * | 2020-04-26 | 2020-08-25 | 上海大学 | Vanadium-based positive electrode material of water-based zinc ion battery and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114682575A (en) | 2022-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107452948B (en) | Prussian blue composite lithium ion battery ternary cathode material and preparation method thereof | |
| CN112531158B (en) | High-nickel ternary single crystal material and preparation method thereof | |
| CN108134069A (en) | A kind of composite modifying method of anode material for lithium-ion batteries | |
| CN108987683A (en) | A kind of preparation method of carbon coating tertiary cathode material | |
| CN111653767B (en) | Washing process and preparation method of high-nickel polycrystalline ternary cathode material | |
| CN111916701B (en) | Coated positive electrode material and preparation method and application thereof | |
| CN109461892A (en) | A kind of composite anode material for lithium ion battery and preparation method thereof | |
| CN115498171A (en) | High-nickel ternary cathode material and preparation method and application thereof | |
| CN115064670A (en) | Preparation method of doped coated modified sodium nickel manganese oxide cathode material | |
| CN114956206A (en) | Pre-oxidation method of high-nickel ternary material precursor and obtained precursor material | |
| CN113582254A (en) | Layered positive electrode material and preparation method and application thereof | |
| CN113506874A (en) | One-step doped coating modified NCM ternary cathode material and preparation method thereof | |
| CN113871613A (en) | High-nickel ternary nickel cobalt lithium manganate cathode material and preparation method thereof | |
| CN111293286A (en) | Coating modified lithium ion battery anode material and preparation method thereof | |
| CN109850949B (en) | Preparation method of lithium-rich lithium manganate cathode material for lithium ion battery | |
| CN112510192A (en) | Positive electrode slurry and application thereof | |
| CN114682575B (en) | Method for reducing residual alkali on surface of high-nickel anode material, obtained material and application | |
| CN115477325B (en) | Preparation method and application of bismuth-based negative electrode material | |
| CN113206250B (en) | Semiconductor cathode material and preparation method thereof | |
| CN105720261B (en) | A kind of preparation method of carbon coating high-tap density composite positive pole | |
| CN109686945B (en) | Method for preparing carbon-coated tin-based composite material through low-temperature self-activation | |
| CN112349892A (en) | Coating modified high-nickel cathode material and preparation method and application thereof | |
| CN114682567B (en) | Wet surface treatment method of high-nickel anode material, obtained material and application | |
| CN113745500B (en) | Preparation method of high-nickel ternary positive electrode material | |
| CN111293285A (en) | Coating modified lithium ion battery anode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |