CN115745021A - Method for removing residual lithium in high-nickel ternary cathode material - Google Patents
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 109
- 239000010406 cathode material Substances 0.000 title claims abstract description 88
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000007774 positive electrode material Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000010405 anode material Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 21
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 10
- 229910013716 LiNi Inorganic materials 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 4
- 229910018286 SbF 6 Inorganic materials 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 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 relates to a method for removing residual lithium in a high-nickel ternary cathode material. The removing method comprises the following steps: mixing the high nickel ternary anode material with (NH) 4 ) n MF 6 Mixing, and reacting for 4-8 hours at the temperature of 300-500 ℃ and the pressure of-0.07-0.09 MPa to remove residual lithium in the high-nickel ternary cathode material; the high nickel ternary positive electrode material and (NH) 4 ) n MF 6 The mass ratio of (A) to (B) is 100: (0.1 to 0.5); wherein M is Ti, mg, sb, nb, V or Y, and n is 3 or 4. The removing method does not need to consume water resources, reduces the production and manufacturing cost, can effectively reduce the residual lithium content of the high-nickel ternary cathode material, and can also improve the electrical property of the high-nickel ternary cathode material.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a method for removing residual lithium in a high-nickel ternary cathode material.
Background
Because of the advantages of high energy density and low manufacturing cost, the lithium ion ternary cathode material is one of the most popular cathode materials of current battery manufacturers, especially a high-nickel ternary cathode material, and is considered as one of the best cathode materials for developing low-cost high-specific energy density lithium ion batteries. However, the residual lithium in the high-nickel ternary cathode material is high, which affects a series of properties of the material, and especially, excessive residual lithium in the slurry-making and coating process accelerates water absorption and reacts with a binder and a solvent to form jelly-like gel, which affects the processability of the material; in addition, residual lithium accelerates the decomposition of the electrolyte, reduces the interface stability and causes the electrical property of the material to be poor; under the conditions of high temperature and high pressure, the residual lithium is decomposed to produce carbon dioxide, so that the unsafe problems of gas expansion, explosion and the like of the battery are easy to occur. These problems have greatly limited the practical application of high nickel ternary cathode materials.
At present, a common method for reducing lithium residue of a high-nickel ternary cathode material is to wash, dehydrate and dry the high-nickel ternary cathode material, a water washing process consumes a large amount of water resources, and generated waste liquid contains a large amount of impurity ions, mainly Li + 、OH - 、CO 3 2- 、SO 4 2- Some small-particle metal ions and the like can be discharged after being treated to reach the standard, so that the processing cost is obviously increased and materials are wasted; in addition, the crystal surface structure of the washed high-nickel ternary cathode material is damaged to a certain extent, and the moisture in the crystal is difficult to remove, which causes the performance of the high-nickel ternary cathode material to be reduced. For example, the name is a washing method for removing residual alkali on the surface of a positive electrode material, which is characterized in that an aprotic nonpolar solution and water are uniformly mixed and dispersed to obtain a mixed solution, then a ternary material is added into the mixed solution for washing, and then the ternary material is subjected to standing layering, dewatering, filtering and drying to obtain the ternary material for removing the residual alkali on the surface, wherein the standing layering needs a long time, a large amount of water resources are consumed, and the generated wastewater is not required to be treated, so that the processing cost is increased; in addition, after removing the residual lithium, defects may occur on the particle surface of the ternary material, and the specific surface may also be increased, thereby adversely affecting the ternary material.
The name is a ternary material recyclable for lithium ion batteriesThe washing alkali-reducing method comprises the steps of putting a ternary anode material and deionized water into a stirring barrel according to a certain proportion, stirring and washing, washing a filter cake by using a small amount of deionized water after primary solid-liquid separation, and performing solid-liquid separation again to obtain a powder material; and (3) the separated filtrate enters a circulating storage tank, an acidic solution is added to adjust the pH value, the obtained filtrate can be used for treating the next batch of ternary cathode materials, after certain times of circulating treatment, the filtrate is led into a wastewater treatment system, and lithium in the wastewater is recovered through a filtering and evaporating device. The method adjusts pH by adding acidic solution (including sulfuric acid, phosphoric acid, hydrochloric acid, boric acid, acetic acid, oxalic acid, etc.), and introduces relatively large amount of hetero anion such as SO into filtrate 4 2- 、P4O 3 3- And the content of impurities is higher, and the existence of more anions can also influence the dissolution of residual lithium in the ternary material in the circulating use into water, so that the effect of reducing the residual lithium is poor.
Therefore, the problems that the effect of reducing the residual lithium of the high-nickel ternary cathode material is poor, the water consumption is high and the electrical property of the material is negatively influenced by the conventional method need to be solved.
Disclosure of Invention
The invention aims to overcome the problems of poor effect, high water consumption and negative influence on the electrical property of the high-nickel ternary cathode material in the conventional method for reducing the residual lithium of the high-nickel ternary cathode material, and provides a method for removing the residual lithium in the high-nickel ternary cathode material. The removing method does not need to consume water resources, reduces the production and manufacturing cost, can effectively reduce the residual lithium content of the high-nickel ternary cathode material, and can also improve the electrical property of the high-nickel ternary cathode material.
The above purpose of the invention is realized by the following technical scheme:
a method for removing residual lithium in a high-nickel ternary cathode material comprises the following steps:
mixing the high nickel ternary anode material with (NH) 4 ) n MF 6 Mixing, and reacting for 4-8 hours at the temperature of 300-500 ℃ and under the pressure of-0.07-0.09 MPa to finish the removal of residual lithium in the high-nickel ternary cathode material;
the high nickel ternary positive electrode material and (NH) 4 ) n MF 6 The mass ratio of (A) to (B) is 100: (0.1-0.5);
wherein M is Ti, mg, sb, nb, V or Y, and n is 3 or 4.
Through multiple researches, the inventor of the invention finds that the high-nickel ternary cathode material is mixed with (NH) 4 ) n MF 6 The high-nickel ternary cathode material is mixed and reacts under specific reaction conditions, residual lithium in the high-nickel ternary cathode material can be effectively removed, the processing performance of the material is improved, and the electrical performance (discharge first effect and discharge specific capacity) of the obtained high-nickel ternary cathode material is not reduced and is improved to a certain extent compared with the high-nickel ternary cathode material before the residual lithium is removed. The reason is that: under specific temperature and pressure, (NH) 4 ) n MF 6 Can react with residual lithium (including lithium carbonate and lithium hydroxide) on the surface of the high-nickel ternary cathode material particles, and NH 4 + Can react with OH-and CO 3 2- Combined to form NH 3 ·H 2 O and (NH) 4 ) 2 CO 3 And NH 3 H 2 O and (NH) 4 ) 2 CO 3 Further decomposed into NH 3 、CO 2 And H 2 O, thereby realizing effective removal of residual lithium; and (NH) 4 ) n MF 6 MF in 6 n- Li capable of reacting with residual lithium + Reaction to give compound Li n MF 6 ,Li n MF 6 The material has good conductivity, on one hand, the conductivity of the material can be improved, on the other hand, the material can be filled between grain boundaries of the high-nickel ternary cathode material and the surfaces of particles after being generated, and the particle surface defects of the high-nickel ternary cathode material are effectively modified, so that the electrical property of the high-nickel ternary cathode material is improved.
In addition, the removing method does not need to consume water resources, does not generate wastewater, not only effectively reduces the production cost of enterprises, but also conforms to the development concept of environmental protection.
The removing method does not need to consume water resources, reduces the production and manufacturing cost, can effectively reduce the residual lithium content of the high-nickel ternary cathode material, and can improve the electrical property of the high-nickel ternary cathode material.
The removal method is suitable for the high-nickel ternary cathode material commonly used in the field.
Preferably, the high-nickel ternary cathode material is LiNi x Co y Mn 1-x-y O 2 Or LiNi x Co y Al 1-x-y O 2 Wherein x is more than or equal to 0.80 and less than 1, and y is more than 0 and less than or equal to 0.20.
Preferably, said (NH) 4 ) n MF 6 Is (NH) 4 ) 3 VF 6 、(NH 4 ) 4 MgF 6 、(NH 4 ) 3 SbF 6 、(NH 4 ) 3 NbF 6 、(NH 4 ) 4 TiF 6 Or (NH) 4 ) 3 YF 6 。
More preferably, the (NH) 4 ) n MF 6 Is (NH) 4 ) 3 VF 6 Or (NH) 4 ) 3 YF 6 One or two of them.
Preferably, the mixing is performed in a blender.
More preferably, the rotating speed of the mixer is 300-500 rpm.
Preferably, the mixing time is 10 to 30min.
Preferably, the reaction is carried out in a coulter dryer.
More preferably, the coulter dryer is in communication with a waste disposal device for collecting gases generated during the reaction.
NH generated in the reaction process can be treated by communicating with a waste treatment device 3 、CO 2 The gas is collected and treated, so that the pollution to the environment is avoided.
Preferably, the residual lithium is at least one of lithium carbonate or lithium hydroxide.
Compared with the prior art, the invention has the beneficial effects that:
the removing method does not need to consume water resources, reduces the production and manufacturing cost, can effectively reduce the residual lithium content of the high-nickel ternary cathode material, and can also improve the electrical property of the high-nickel ternary cathode material.
Drawings
Fig. 1 is an SEM image of the high nickel ternary positive electrode material of example 1 before removal of residual lithium;
fig. 2 is an SEM image of the high nickel ternary positive electrode material of example 1 after removal of residual lithium.
Detailed Description
In order to more clearly and completely describe the technical scheme of the invention, the invention is further described in detail by the specific embodiments, and it should be understood that the specific embodiments described herein are only used for explaining the invention, and are not used for limiting the invention, and various changes can be made within the scope defined by the claims of the invention.
Example 1
The embodiment provides a method for removing residual lithium in a high-nickel ternary cathode material, which comprises the following steps of:
100kg of high-nickel ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 And 0.3kg (NH) 4 ) 3 VF 6 Adding into a mixer, and mixing for 20 minutes at the rotating speed of 400 r/min to obtain a mixture. And then putting the mixture into a coulter dryer, heating to 400 ℃, pumping negative pressure to the coulter dryer to enable the pressure in the coulter dryer to be-0.08 MPa, and reacting for 6 hours at 400 ℃ and-0.08 MPa to finish the removal of residual lithium in the high-nickel ternary cathode material. The coulter dryer and the waste gas treatment device are used for collecting and treating gas generated in the reaction process.
Example 2
The embodiment provides a method for removing residual lithium in a high-nickel ternary cathode material, which comprises the following steps:
100kg of high-nickel ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 And 0.1kg (NH) 4 ) 3 VF 6 Adding into a mixer, and mixing for 20 minutes at the rotating speed of 400 r/min to obtain a mixture. Then mixing the mixturePutting the materials into a coulter dryer, heating to 400 ℃, pumping negative pressure to the coulter dryer to enable the pressure in the coulter dryer to be-0.08 MPa, and reacting for 6 hours at 400 ℃ and-0.08 MPa to finish the removal of residual lithium in the high-nickel ternary cathode material. The coulter dryer and the waste gas treatment device are used for collecting and treating gas generated in the reaction process.
Example 3
The embodiment provides a method for removing residual lithium in a high-nickel ternary cathode material, which comprises the following steps:
100kg of high-nickel ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 And 0.5kg (NH) 4 ) 3 VF 6 Adding into a mixer, and mixing for 20 minutes at the rotating speed of 400 r/min to obtain a mixture. And then putting the mixture into a coulter dryer, heating to 400 ℃, pumping negative pressure to the coulter dryer to enable the pressure in the coulter dryer to be-0.08 MPa, and reacting for 6 hours at 400 ℃ and-0.08 MPa to finish the removal of residual lithium in the high-nickel ternary cathode material. The coulter dryer and the waste gas treatment device are used for collecting and treating gas generated in the reaction process.
Example 4
The embodiment provides a method for removing residual lithium in a high-nickel ternary cathode material, which comprises the following steps of:
100kg of high-nickel ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 And 0.1kg (NH) 4 ) 3 VF 6 Adding into a mixer, and mixing for 20 minutes at the rotating speed of 400 r/min to obtain a mixture. And then putting the mixture into a coulter dryer, heating to 300 ℃, pumping negative pressure to the coulter dryer to enable the pressure in the coulter dryer to be-0.07 MPa, and reacting for 4 hours at the temperature of 300 ℃ and the pressure of-0.07 MPa to finish the removal of residual lithium in the high-nickel ternary cathode material. The coulter dryer and the waste gas treatment device are used for collecting and treating gas generated in the reaction process.
Example 5
The embodiment provides a method for removing residual lithium in a high-nickel ternary cathode material, which comprises the following steps:
100kg of high-nickel ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 And 0.1kg (NH) 4 ) 3 VF 6 Adding into a mixer, and mixing for 20 minutes at the rotating speed of 400 rpm to obtain a mixture. And then putting the mixture into a coulter dryer, heating to 500 ℃, pumping negative pressure to the coulter dryer to enable the pressure in the coulter dryer to be-0.09 MPa, and reacting for 8 hours at 500 ℃ and-0.09 MPa to finish the removal of residual lithium in the high-nickel ternary cathode material. The coulter dryer and the waste gas treatment device are used for collecting and treating gas generated in the reaction process.
Example 6
The embodiment provides a method for removing residual lithium in a high-nickel ternary cathode material, which is basically the same as that in embodiment 1, except that: will be (NH) 4 ) 3 VF 6 By replacement with an equivalent amount of (NH) 4 ) 4 MgF 6 。
Example 7
The embodiment provides a method for removing residual lithium in a high-nickel ternary cathode material, which is basically the same as that in embodiment 1, except that: will be (NH) 4 ) 3 VF 6 By replacement with an equivalent amount of (NH) 4 ) 3 SbF 6 、。
Example 8
The embodiment provides a method for removing residual lithium in a high-nickel ternary cathode material, which is basically the same as that in embodiment 1, except that: will be (NH) 4 ) 3 VF 6 By replacement with an equivalent amount of (NH) 4 ) 3 NbF 6 、。
Example 9
This example provides a method for removing residual lithium in a high-nickel ternary cathode material, which is substantially the same as that in example 1, except that: will be (NH) 4 ) 3 VF 6 By replacement with an equivalent amount of (NH) 4 ) 4 TiF 6 。
Example 10
The embodiment provides a method for removing residual lithium in a high-nickel ternary cathode material, which is basically the same as that in embodiment 1, except that: will be (NH) 4 ) 3 VF 6 By replacement of (NH) by an equivalent amount 4 ) 3 YF 6 。
Example 11
This example provides a method for removing residual lithium in a high-nickel ternary cathode material, which is substantially the same as that in example 1, except that: reacting LiNi 0.8 Co 0.1 Mn 0.1 O 2 Substitution with LiNi in equivalent amounts 0.8 Co 0.1 Al 0.1 O 2 。
Comparative example 1
This comparative example provides a method for removing residual lithium from a high-nickel ternary positive electrode material, which is substantially the same as example 1, except that: (NH) 4 ) 3 VF 6 The amount of (B) is 0.05kg.
Comparative example 2
This comparative example provides a method for removing residual lithium from a high-nickel ternary positive electrode material, which is substantially the same as example 1, except that: (NH) 4 ) 3 VF 6 The amount of (B) was 0.6kg.
Comparative example 3
This comparative example provides a method for removing residual lithium from a high nickel ternary positive electrode material, which is substantially the same as example 1, except that: the temperature is raised to 200 ℃ and the reaction is carried out at 200 ℃.
Comparative example 4
This comparative example provides a method for removing residual lithium from a high nickel ternary positive electrode material, which is substantially the same as example 1, except that: the temperature is raised to 600 ℃, and the reaction is carried out at the temperature of 600 ℃.
Comparative example 5
The comparative example provides a method for removing residual lithium in a high-nickel ternary cathode material, which is basically the same as that in example 1, except that: the pressure in the coulter dryer is-0.06 MPa, and the reaction is carried out under the condition of-0.06 MPa.
Comparative example 6
The comparative example provides a method for removing residual lithium in a high-nickel ternary cathode material, which is basically the same as that in example 1, except that: the pressure in the coulter dryer is-0.10 MPa, and the reaction is carried out under the condition of-0.10 MPa.
Comparative example 7
The comparative example provides a method for removing residual lithium in a high-nickel ternary cathode material, which is basically the same as that in example 1, except that: the reaction time was 3 hours.
Comparative example 8
This comparative example provides a method for removing residual lithium from a high nickel ternary positive electrode material, which is substantially the same as example 1, except that: the reaction time was 9 hours.
Performance test
SEM scanning is performed on the high-nickel ternary positive electrode material before and after removing the residual lithium in example 1, and the results are shown in fig. 1 and fig. 2, where fig. 1 is an SEM image of the high-nickel ternary positive electrode material before removing the residual lithium, and fig. 2 is an SEM image of the high-nickel ternary positive electrode material after removing the residual lithium. As can be seen from FIG. 2, li was filled between the grain boundaries and the surface of the high-nickel ternary positive electrode material particles from which residual lithium was removed n MF 6 (Li 3 VF 6 ) The surface defects of the particles of the material are effectively modified, so that the electrical property of the high-nickel ternary cathode material is effectively improved. SEM images of the high nickel ternary cathode material after removing residual lithium of examples 2 to 11 are similar to those of the high nickel ternary cathode material after removing residual lithium of example 1.
Residual lithium (Li) of the high-nickel ternary positive electrode material before removal of residual lithium and the high-nickel ternary positive electrode materials after removal of residual lithium of each example and comparative example 2 CO 3 And LiOH) content, and the discharge first effect and specific discharge capacity of the button cell prepared from the material. Wherein:
1. and testing residual lithium of the high-nickel ternary cathode material by using a hydrochloric acid standard solution and a potentiometric titration method.
2. The button cell prepared from the high-nickel ternary cathode material comprises the following steps:
preparing a high-nickel ternary positive electrode material, a conductive agent carbon black and a binder PVDF (polyvinylidene fluoride) in a mass ratio of 90 to 5, uniformly mixing the prepared slurry, coating the mixture on an aluminum foil to prepare a positive electrode plate, and placing the positive electrode plate in a glove box by taking a metal lithium plate as a negative electrode, taking Celgard2300 as a diaphragm and 1mol/L LiPF (lithium ion power) 1 6 DMC (volume ratio 1. And the charge-discharge test selects the high-nickel ternary cathode material with the voltage of 3.0-4.3V and the current density of 0.2C/0.2C to test the electrical property.
Wherein, the high nickel ternary positive electrode materials before removing residual lithium in the embodiments 1-10 and the comparative examples 1-8 are LiNi of the same batch 0.8 Co 0.1 Mn 0.1 O 2 Before removing residual lithium, the high-nickel ternary positive electrode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 Li of (2) 2 CO 3 The content is 5061ppm, the LiOH content is 5516ppm, the first discharge efficiency is 82.6 percent, and the specific discharge capacity is 188.7mAh/g.
High nickel ternary positive electrode material LiNi before removal of residual lithium of example 11 0.8 Co 0.1 Al 0.1 O 2 Li of (2) 2 CO 3 5213ppm, 5862ppm LiOH, 82.4% first discharge efficiency and 187.6mAh/g specific discharge capacity.
The test results of the residual lithium content of the high-nickel ternary cathode material with the residual lithium removed, and the discharge first efficiency and specific discharge capacity of the button cell prepared from the material are shown in table 1.
Table 1 results of performance test of high nickel ternary cathode material after removing residual lithium in each example and comparative example
As can be seen from examples 1 to 11 in table 1, the method for removing residual lithium in the high-nickel ternary cathode material of the present invention can effectively remove the residual lithium content in the high-nickel ternary cathode material, and can improve the electrical properties of the high-nickel ternary cathode material. Specifically, the Li of the high-nickel ternary cathode material treated by the removing method is Li 2 CO 3 The content can be reduced to below 1851ppm, the LiOH content is reduced to below 3231ppm, and meanwhile, the discharge first effect can be improved to above 86.3 percent, and the discharge specific capacity is improved to above 196.5 mAh/g.
Comparative example 1 (NH) 4 ) 3 VF 6 The residual lithium removal effect is poor due to too low dosage, and certain residual lithium exists on the surface of the high-nickel ternary cathode material and the generated Li 3 VF 6 Relatively few, the electrical performance of the material is improved to a limited extent; comparative example 2 (NH) 4 ) 3 VF 6 Too much amount of (NH) is used, although the effect of removing residual lithium is better, the amount is too much 4 ) 3 VF 6 Do not participate in the reaction, and (NH) 4 ) 3 VF 6 The existence of the nickel-based composite material has negative influence on the high-nickel ternary cathode material, so that the electrical property of the high-nickel ternary cathode material is improved to a limited extent; the temperature of comparative example 3 is too low, the reaction is not sufficient enough, and the removal of residual lithium and the improvement of electrical property are relatively poor; the temperature of comparative example 4 was too high and the improvement of the electrical properties was limited, probably due to (NH) 4 ) 3 VF 6 The lithium ion battery can react with matrix lithium < + > of the high-nickel ternary cathode material to generate negative influence on the high-nickel ternary cathode material; the negative pressure of the comparative example 5 is too small, the generated gases such as carbon dioxide and the like can be effectively discharged, and the reaction is insufficient; the effects of removing residual lithium and improving electrical performance of the material are limited, and the negative pressure of comparative example 6 is too large, and part of small particles (NH) 4 ) 3 VF 6 Small-particle high-nickel ternary cathode materials can be pumped away, the reaction is insufficient, and the particle size distribution of the high-nickel ternary cathode materials can be changed to a certain degree, so that the electrical property improvement effect is poor; the reaction time of comparative example 7 was too short, and the effects of removing residual lithium and improving electrical properties were relatively poor; the reaction time of comparative example 8 was too long and the improvement of the electrical properties was limited, which may be due to (NH) 4 ) 3 VF 6 Matrix lithium Li capable of being mixed with high-nickel ternary cathode material + The reaction occurs, and the negative effect is generated on the high-nickel ternary cathode material.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A method for removing residual lithium in a high-nickel ternary cathode material is characterized by comprising the following steps:
mixing the high nickel ternary anode material with (NH) 4 ) n MF 6 Mixing, and reacting for 4-8 hours at the temperature of 300-500 ℃ and the pressure of-0.07-0.09 MPa to remove residual lithium in the high-nickel ternary cathode material;
the high-nickel ternary positive electrode material and (NH) 4 ) n MF 6 The mass ratio of (A) to (B) is 100: (0.1-0.5);
wherein M is Ti, mg, sb, nb, V or Y, and n is 3 or 4.
2. The removal method of claim 1, wherein the high-nickel ternary positive electrode material is LiNi x Co y Mn 1-x- y O 2 Or LiNi x Co y Al 1-x-y O 2 Wherein x is more than or equal to 0.80 and less than 1, and y is more than 0 and less than or equal to 0.20.
3. The removal method according to claim 1, wherein the (NH) is 4 ) n MF 6 Is (NH) 4 ) 3 VF 6 、(NH 4 ) 4 MgF 6 、(NH 4 ) 3 SbF 6 、(NH 4 ) 3 NbF 6 、(NH 4 ) 4 TiF 6 Or (NH) 4 ) 3 YF 6 One or more of (a).
4. The removing method according to claim 3, wherein the removing step is carried out by a vacuumIn the (NH) mentioned 4 ) n MF 6 Is (NH) 4 ) 3 VF 6 Or (NH) 4 ) 3 YF 6 One or two of them.
5. The removal method of claim 1, wherein the mixing is performed in a blender.
6. The removal method of claim 5, wherein the mixer is rotated at a speed of 300 to 500 rpm.
7. The removal method according to claim 1, wherein the mixing time is 10 to 30min.
8. The removal method of claim 1, wherein the reaction is carried out in a coulter dryer.
9. The removal method as claimed in claim 8, wherein the coulter dryer is in communication with a waste disposal device for collecting gases generated during the reaction.
10. The removal method of claim 1, wherein the residual lithium is at least one of lithium carbonate or lithium hydroxide.
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