CN115959719B - Treatment method of positive electrode material precursor slurry and positive electrode material prepared by same - Google Patents
Treatment method of positive electrode material precursor slurry and positive electrode material prepared by same Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 74
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 66
- 239000002002 slurry Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000012065 filter cake Substances 0.000 claims abstract description 73
- 238000005406 washing Methods 0.000 claims abstract description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims abstract description 16
- 238000007873 sieving Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000003599 detergent Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 4
- 238000000975 co-precipitation Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000002425 crystallisation Methods 0.000 claims description 17
- 230000008025 crystallization Effects 0.000 claims description 17
- 239000010405 anode material Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 10
- 230000007480 spreading Effects 0.000 claims description 9
- 238000003892 spreading Methods 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 239000012716 precipitator Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 19
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 21
- 239000000463 material Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000011572 manganese Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- -1 C 2 H 5 OH Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of lithium batteries, and particularly relates to a method for treating a precursor slurry of a positive electrode material and the positive electrode material prepared by the method. The positive electrode material precursor slurry treatment method comprises the following steps: and conveying the precursor slurry of the positive electrode material into a filter press, pressurizing and filtering to obtain a filter cake, introducing low-pressure steam and oxygen-containing gas to filter-press again, and finally washing with a detergent and pure water, drying and sieving to obtain the precursor of the positive electrode material. According to the invention, the precursor slurry of the positive electrode material is conveyed into a filter press to be pressurized and filtered into a filter cake, and meanwhile, low-pressure steam and oxygen-containing gas are introduced, so that the solid on the surface of the filter cake is subjected to micro-oxidation, particles in the filter cake are further increased to be contacted with oxygen under the action of a certain pressure, the micro-oxidation of the particles is promoted at a certain temperature, the pore channel structure among the particles in the filter cake is further increased to a certain extent, and finally, the specific surface area of the whole precursor of the positive electrode material can be increased, so that the defect that the specific surface area does not reach the index requirement is overcome.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a method for treating a precursor slurry of a positive electrode material and the positive electrode material prepared by the method.
Background
The layered transition metal oxide in the lithium ion positive electrode material has excellent multiplying power and cycle performance, so that the lithium ion positive electrode material is widely applied to the fields of electric automobiles, portable power supplies, large-scale energy storage and the like. Among the preparation methods, the preparation method of preparing the precursor of the positive electrode material by coprecipitation and then high-temperature solid-phase sintering of lithium salt is adopted by most enterprises due to the characteristics of uniform components, low cost, suitability for large-scale production and the like. Among these, the preparation of the precursor of the positive electrode material is an intermediate with higher technical difficulty and customization requirement, and the positive electrode material for the power battery has more severe requirements on the quality of the precursor. Therefore, the production of the positive electrode material precursor is an enterprise that needs to take strict care of each process of product production, both from the viewpoint of quality and cost control. However, because of the numerous parameters involved, there is a certain difficulty in achieving accurate regulation and control of the index in the coprecipitation crystallization process and directly achieving the requirements, and the manner of regulating and controlling the index by the treatment means of the cathode material precursor slurry is relatively small.
As one of the main indexes of the production of the positive electrode material precursor, the regulation and control of the specific surface area is a core technology of a production enterprise, and the situation that the specific surface area is not up to standard is unavoidable in the core coprecipitation crystallization process due to the influence of uncontrollable factors such as an initial process, equipment and the like, so that the production yield is influenced, and the production cost is greatly increased.
The publication No. CN113003616A discloses a method for improving the specific surface area of a precursor of a positive electrode material, which comprises the following steps: spin-drying the obtained filter cake by a centrifuge after crystallization is finished, (secondly) leaching the filter cake by using NaOH solution, (thirdly) washing the filter cake by pure water, and (fourthly) putting the obtained filter cake into a reaction kettle again, adding the NaOH solution for stirring, introducing oxygen for a long time for stirring, and repeating the washing step again until a finished product is obtained. The method is long in time consumption, complex in operation, more in equipment and not suitable for large-scale production.
Disclosure of Invention
The invention aims to solve the technical problem of how to further improve the specific surface area of the positive electrode material precursor in the post-treatment process under the condition that the specific surface area of the positive electrode material precursor does not reach the standard in the prior art.
The invention solves the technical problems by the following technical means:
a method for treating a precursor slurry of a positive electrode material comprises the following steps:
and (3) conveying the anode material precursor slurry after the coprecipitation crystallization reaction is finished to a filter press, pressurizing and filtering to obtain a filter cake, simultaneously introducing low-pressure steam and oxygen-containing gas for filter pressing again, and finally washing the filter cake by using a detergent and pure water, drying and sieving to obtain the anode material precursor.
The beneficial effects are that: the method comprises the steps of conveying the anode material precursor slurry after the coprecipitation crystallization is finished to a filter press, pressurizing and filtering the anode material precursor slurry to form a filter cake with a certain thickness, introducing low-pressure steam and oxygen-containing gas at the same time to enable solid on the surface of the filter cake to generate micro-oxidation, further increasing particles in the filter cake to contact with oxygen under the action of a certain pressure, enabling the particles to be micro-oxidized at a certain temperature so as to increase the pore channel structures among the particles in the filter cake to a certain extent, and finally increasing the specific surface area of the whole anode material precursor particle, thereby overcoming the defect that the specific surface area in the coprecipitation crystallization process does not reach the index requirement.
Preferably, the positive electrode material precursor slurry is a mixture of cobalt-manganese-containing hydroxide, a precipitant thereof and a complexing agent.
Preferably, the filter press is one of a closed chamber filter press, a vertical filter press, a belt filter press, and a membrane filter press.
Preferably, the filter cake obtained has a thickness of 1-5cm.
Preferably, the low pressure in the low pressure steam is 0.2-0.4Mpa; the treatment time is 10-30min.
Preferably, the oxygen content of the introduced oxygen-containing gas is 20% -100%.
Preferably, the detergent is KOH, naOH, C 2 H 5 OH、Na 2 CO 3 One or more mixed solutions of the solutions; the concentration of the detergent is 0.1-1.5mol/L, and the temperature of the detergent is 25-80 ℃.
Preferably, the pH of the washing water obtained after the washing treatment with pure water is 8.5 to 9.5.
Preferably, the drying temperature is 80-140 ℃, so that the moisture is less than 0.8wt% and the spreading thickness is 1-4cm.
The invention also provides a positive electrode material, which is obtained by mixing the positive electrode material precursor prepared by the method with a lithium source, sintering, crushing and sieving.
The invention has the advantages that: (1) According to the invention, slurry after coprecipitation crystallization is conveyed into a filter press, pressurized and filtered to form a filter cake with a certain thickness, low-pressure steam is introduced into the filter cake, and oxygen-containing gas is continuously introduced into the filter cake, so that under the action of a certain pressure, the existence of pores in the filter cake can be ensured, the contact of particles in the filter cake with oxygen is further increased, the micro-oxidation of the particles is promoted at a certain temperature, the pore channel structure among the particles in the filter cake is further increased to a certain extent, and finally, the specific surface area of the precursor particles of the whole positive electrode material can be increased, thereby overcoming the defect that the specific surface area in the coprecipitation crystallization process does not reach the index requirement.
(2) The invention can enlarge the internal structure of the particles by higher temperature treatment to a certain extent, optimize the crystal structure of the precursor material, and simultaneously ensure that the morphology, chemical index and tap density of the material are not obviously changed.
(3) The invention has simple treatment, can improve the material yield of the production line and reduce the production waste.
Drawings
FIG. 1 is a scanning electron microscope image of a positive electrode material precursor in the crystallization step of example 1;
FIG. 2 is a scanning electron microscope image of the positive electrode material precursor after post-treatment in example 1;
FIG. 3 is a scanning electron microscope image of the positive electrode material prepared in example 1;
fig. 4 is a normal temperature cycle chart of the button half cell of the positive electrode material prepared in example 1 under the condition of 2.8-4.45V.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Ni is a precursor of a positive electrode material with the particle diameter of 8.0-12.0 mu m 0.8 Co 0.1 Mn 0.1 (OH) 2 Coprecipitation ofAfter the reaction is finished, the method comprises the following steps:
according to the slurry obtained after the prepared coprecipitation crystallization reaction, conveying a certain volume of slurry into a closed filter press, and filtering out supernatant under pressure to obtain a 1cm filter cake sample;
a sample of the filter cake was taken and placed in an oven at 125 c to provide less than 0.8wt% moisture.
The tap density TD of the obtained sample was measured to be 1.90g/m using a tap densitometer 3 The BET of the sample was measured to be 7.91 square meters per gram using a surface area meter and the morphology of the sample was measured using a scanning electron microscope and is shown in FIG. 1.
The method for treating the precursor slurry of the positive electrode material is used for improving the specific surface area of the precursor of the positive electrode material and comprises the following steps of:
1. further compressing the filter cake for 10min by using low-pressure steam of 0.2Mpa, and simultaneously introducing oxygen-containing gas, wherein the oxygen content in the oxygen-containing gas is 20%, and the temperature in the filter press is kept to be less than 130 ℃;
2. preparing 0.1mol/LNaOH solution, heating to 80 ℃, and washing the filter cake in a filter press according to the amount of consuming 15L of sodium hydroxide per kilogram of filter cake;
3. according to the consumption of 30L of pure water per kilogram of filter cake, eluting the filter cake by using pure water at 25 ℃ until the PH of the obtained washing liquid is between 8.5 and 9.5, and stopping washing;
4. spreading the filter cake to a thickness of 2-3cm, and putting the filter cake into an oven to be dried at 80 ℃ to ensure that the water content is less than 0.8wt%;
5. the resulting material was sieved.
The tap density TD of the resulting sample was 1.88g/m using a tap densitometer 3 The BET of the sample was measured to be 11.41 square meters per gram using a surface area meter, and the morphology of the sample was measured using a scanning electron microscope and is shown in FIG. 2.
The molar ratio of the obtained treated positive electrode material precursor to lithium hydroxide is 1:1.07, sintering for 15 hours at 885 ℃ in oxygen atmosphere, crushing and sieving to obtain the anode material, wherein the morphology of the anode material is shown in figure 3.
The obtained positive electrode material is assembled into 2032 button half battery, and the capacity retention rate is 92% under normal temperature 1C charge and discharge for 50 times under 2.8-4.45V voltage, as shown in figure 4.
Example 2
Ni is a precursor of positive electrode material with the particle diameter of 2.5-4.0 mu m 0.8 Co 0.1 Mn 0.1 (OH) 2 After the coprecipitation reaction is completed, the following steps are used for treatment:
according to the slurry obtained after the prepared coprecipitation crystallization reaction, conveying a certain volume of slurry into a closed filter press, and filtering out supernatant under pressure to obtain a 5cm filter cake sample;
a sample of the filter cake was taken and placed in an oven at 125 c to provide less than 0.8wt% moisture.
The tap density TD of the obtained sample was measured to be 1.60g/m using a tap densitometer 3 The resulting sample was tested with a surface area meter for BET of 11.60 square meters per gram.
The method for treating the precursor slurry of the positive electrode material is used for improving the specific surface area of the precursor of the positive electrode material and comprises the following steps of:
1. further compressing the filter cake for 30min by using low-pressure steam of 0.4Mpa, and simultaneously introducing oxygen-containing gas, wherein the oxygen content in the oxygen-containing gas is 100%, and the temperature in the filter press is kept to be less than 130 ℃;
2. preparing a solution with the concentration of 1.5mol/LKOH, washing a filter cake in a filter press according to the amount of consuming 15 liters of potassium hydroxide per kilogram of precursor at the temperature of 25 ℃;
3. according to the consumption of 30L of pure water per kilogram of precursor, washing the filter cake by pure water at 25 ℃ until the PH of the obtained washing liquid is 8.5-9.5, and stopping washing;
4. spreading the filter cake to a thickness of 2-3cm, and putting the filter cake into a baking oven to be dried at 140 ℃ so that the water content is less than 0.8wt%;
5. the resulting material was sieved.
The tap density TD of the obtained sample was measured to be 1.58g/m using a tap densitometer 3 The resulting sample was tested using a surface area meter for a BET of 14.32 square meters per gram.
The molar ratio of the obtained treated positive electrode material precursor to lithium hydroxide is 1:1.07, sintering for 15 hours at 885 ℃ in oxygen atmosphere, and crushing and sieving to obtain the anode material.
Example 3
Ni is a precursor of a positive electrode material with the particle diameter of 8.0-12.0 mu m 0.6 Co 0.2 Mn 0.2 (OH) 2 After the coprecipitation reaction is completed, the following steps are used for treatment:
according to the slurry obtained after the prepared coprecipitation crystallization reaction, conveying a certain volume of slurry into a closed filter press, and filtering out supernatant under pressure to obtain a 1.5cm filter cake sample;
a sample of the filter cake was taken and placed in an oven at 125 c to provide less than 0.8wt% moisture.
The tap density TD of the obtained sample was measured using a tap densitometer to be 2.05g/m 3 The resulting sample was tested with a surface area meter for BET of 8.68 square meters per gram.
The method for treating the precursor slurry of the positive electrode material is used for improving the specific surface area of the precursor of the positive electrode material and comprises the following steps of:
1. further compressing the filter cake for 30min by using low-pressure steam of 0.3Mpa, and simultaneously introducing oxygen-containing gas, wherein the oxygen content in the oxygen-containing gas is 50%, and the temperature in the filter press is kept to be less than 130 ℃;
2. the concentration of the preparation is 0.2mol/LNa 2 CO 3 The solution, at 35℃and 15 liters of Na per kg of precursor 2 CO 3 Washing the filter cake in a filter press;
3. according to the consumption of 30L of pure water per kilogram of precursor, washing the filter cake by pure water at 25 ℃ until the PH of the obtained washing liquid is between 8.5 and 9.5, and stopping washing;
4. spreading the filter cake to a thickness of 1-3cm, and putting the filter cake into a baking oven to be dried at 125 ℃ to ensure that the water content is less than 0.8wt%;
5. the resulting material was sieved.
The tap density TD of the obtained sample was measured to be 1.98g/m using a tap densitometer 3 The resulting sample was tested using a surface area meter for a BET of 12.32 square meters per gram.
The molar ratio of the obtained treated positive electrode material precursor to lithium hydroxide is 1:1.07, sintering for 15 hours at 885 ℃ in oxygen atmosphere, and crushing and sieving to obtain the anode material.
Example 4
Ni is a precursor of positive electrode material with the particle diameter of 2.5-4.0 mu m 0.6 Co 0.2 Mn 0.2 (OH) 2 After the co-precipitation reaction is completed, the following steps are used for treatment:
according to the slurry obtained after the prepared coprecipitation crystallization reaction, conveying a certain volume of slurry into a closed filter press, and filtering out supernatant under pressure to obtain a 3cm filter cake;
a sample of the filter cake was taken and placed in an oven at 125 c to provide less than 0.8wt% moisture.
The tap density TD of the obtained sample was 1.63g/m by using a tap densitometer 3 The resulting sample was tested with a surface area meter for a BET of 15.10 square meters per gram.
The method for treating the precursor slurry of the positive electrode material is used for improving the specific surface area of the precursor of the positive electrode material and comprises the following steps of:
1. further compressing the filter cake for 20min by using low-pressure steam of 0.2Mpa, and simultaneously introducing oxygen-containing gas, wherein the oxygen content in the oxygen-containing gas is 80%, and the temperature in the filter press is kept to be less than 130 ℃;
2. the concentration of the preparation is 0.2mol/LC 2 H 5 OH solution at 50℃and 15 liters of C per kg of precursor 2 H 5 The amount of OH washes the filter cake in the filter press;
3. according to the consumption of 30L of pure water per kilogram of precursor, washing the filter cake by pure water at 25 ℃ until the PH of the obtained washing liquid is between 8.5 and 9.5, and stopping washing;
4. spreading the filter cake to a thickness of 2-4cm, and putting the filter cake into a baking oven to be dried at 125 ℃ to ensure that the water content is less than 0.8wt%;
5. the resulting material was sieved.
The tap density TD of the obtained sample was measured to be 1.57g/m using a tap densitometer 3 The resulting sample was tested using a surface area meter for BET of 20.52 square meters per gram.
The molar ratio of the obtained treated positive electrode material precursor to lithium hydroxide is 1:1.07, sintering for 15 hours at 885 ℃ in oxygen atmosphere, and crushing and sieving to obtain the anode material.
Comparative example 1
Ni is a precursor of a positive electrode material with the particle diameter of 8.0-12.0 mu m 0.8 Co 0.1 Mn 0.1 (OH) 2 After the coprecipitation reaction is completed, the following steps are used for treatment:
according to the slurry obtained after the prepared coprecipitation crystallization reaction, conveying a certain volume of slurry into a closed filter press, and filtering out supernatant under pressure to obtain a 1.5cm filter cake sample;
a sample of the filter cake was taken and placed in an oven at 125 c to provide less than 0.8wt% moisture.
The tap density TD of the resulting sample was 1.88g/m using a tap densitometer 3 The resulting sample was tested with a surface area meter for BET of 8.74 square meters per gram.
Washing the filter cake sample by the following steps:
1. preparing a solution with the temperature of 80 ℃ and the concentration of 0.2mol/LNaOH, and washing a filter cake sample in a filter press according to the amount of consuming 15L of 0.2mol/LNaOH per kilogram of precursor;
2. according to the consumption of 30L of pure water per kilogram of precursor, washing a filter cake sample by using pure water at 25 ℃ until the PH of the obtained washing liquid is between 8.5 and 9.5, and stopping washing;
3. spreading the filter cake sample to a thickness of 2-3cm, and putting the filter cake sample into an oven to be dried at 125 ℃ to ensure that the water content is less than 0.8wt%;
4. the resulting material was sieved.
The tap density TD of the resulting sample was 1.85g/m using a tap densitometer 3 The resulting sample was tested with a surface area meter for BET of 8.33 square meters per gram.
The molar ratio of the obtained treated positive electrode material precursor to lithium hydroxide is 1:1.07, sintering for 15 hours at 885 ℃ in oxygen atmosphere, and crushing and sieving to obtain the anode material.
Comparative example 2
Ni is a precursor of positive electrode material with the particle diameter of 2.5-4.0 mu m 0.6 Co 0.2 Mn 0.2 (OH) 2 After the coprecipitation reaction is completed, useThe method comprises the following steps:
according to the slurry obtained after the prepared coprecipitation crystallization reaction, conveying a certain volume of slurry into a closed filter press, and filtering out supernatant under pressure to obtain a 1.5cm filter cake sample;
a sample of the filter cake was taken and placed in an oven at 125 c to provide less than 0.8wt% moisture.
The tap density TD of the obtained sample was measured to be 1.55g/m using a tap densitometer 3 The resulting sample was tested using a surface area meter for a BET of 17.30 square meters per gram.
Washing the filter cake sample by the following steps:
1. preparing a solution with the temperature of 80 ℃ and the concentration of 0.2mol/LNaOH, and washing a filter cake sample in a filter press according to the amount of consuming 15L of 0.2mol/LNaOH per kilogram of precursor;
2. according to the consumption of 30L of pure water per kilogram of precursor, washing the filter cake by pure water at 25 ℃ until the PH of the obtained washing liquid is between 8.5 and 9.5, and stopping washing;
3. spreading the filter cake to a thickness of 2-3cm, and drying in a drying oven at 125 ℃ to make the water content less than 0.8wt%;
4. the resulting material was sieved.
The tap density TD of the obtained sample was measured to be 1.60g/m using a tap densitometer 3 The resulting sample was tested using a surface area meter for a BET of 17.12 square meters per gram.
The obtained treated positive electrode material precursor material and lithium hydroxide are mixed according to a molar ratio of 1:1.07, sintering for 15 hours at 885 ℃ in oxygen atmosphere, crushing and sieving to obtain the anode material.
Comparative example 3
Ni is a precursor of a positive electrode material with the particle diameter of 8.0-12.0 mu m 0.6 Co 0.2 Mn 0.2 (OH) 2 After the coprecipitation reaction is completed, the following steps are used for treatment:
according to the slurry obtained after the prepared coprecipitation crystallization reaction, conveying a certain volume of slurry into a closed filter press, and filtering out supernatant under pressure to obtain a 1.5cm filter cake sample;
a sample of the filter cake was taken and placed in an oven at 125 c to provide less than 0.8wt% moisture.
The tap density of the sample obtained was measured to be 1.97g/m using a tap densitometer 3 The resulting sample was tested with a surface area meter for BET of 6.32 square meters per gram.
The filter cake samples were treated by the following steps:
spreading the filter cake sample to a thickness of 2-3cm, and putting the filter cake sample into an oven to be dried at 125 ℃ to ensure that the water content is less than 0.8wt%; the resulting material was sieved.
The tap density TD of the obtained sample was 1.91g/m using a tap densitometer 3 The resulting sample was tested with a surface area meter for BET of 6.59 square meters per gram.
The molar ratio of the obtained treated positive electrode material precursor to lithium hydroxide is 1:1.07, sintering for 15 hours at 885 ℃ in oxygen atmosphere, and crushing and sieving to obtain the anode material.
Table 1 shows the test data for the samples obtained for the examples and comparative examples:
TABLE 1
As can be seen from table 1:
the specific surface area of the embodiment 1-3 treated by the method is further improved, the tap density is basically unchanged, and the scanning electron microscope result shows that the morphology change before and after the treatment is not obvious, so that the structure is not changed. The effect of increasing the specific surface area is not obvious in comparative examples 1 to 2 only by washing. As can be seen from comparative example 3, the index of the material directly dried without the washing treatment was not substantially changed.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. The method for treating the precursor slurry of the positive electrode material is characterized by comprising the following steps of:
delivering the anode material precursor slurry after the coprecipitation crystallization reaction to a filter press, carrying out pressurized filtration to obtain a filter cake, then simultaneously introducing low-pressure steam and oxygen-containing gas for carrying out filter pressing again, and finally washing the filter cake by using a detergent and pure water, drying and sieving to obtain an anode material precursor;
the pressure of the low-pressure steam is 0.2-0.4Mpa; the treatment time is 10-30min; the oxygen content of the oxygen-containing gas is 20% -100%; the detergent is KOH, naOH, C 2 H 5 OH、Na 2 CO 3 One or more mixed solutions of the solutions; the concentration of the detergent is 0.1-1.5mol/L, and the temperature of the detergent is 25-80 ℃.
2. The positive electrode material precursor slurry treatment method according to claim 1, characterized in that: the positive electrode material precursor slurry is a mixture of hydroxide containing cobalt and manganese, a precipitator thereof and a complexing agent.
3. The positive electrode material precursor slurry treatment method according to claim 1, characterized in that: the filter press is one of a closed chamber filter press, a vertical filter press, a belt filter press and a membrane filter press.
4. The positive electrode material precursor slurry treatment method according to claim 1, characterized in that: the thickness of the obtained filter cake is 1-5cm.
5. The positive electrode material precursor slurry treatment method according to claim 1, characterized in that: the pH value of the washing water obtained after the pure water washing treatment is 8.5-9.5.
6. The positive electrode material precursor slurry treatment method according to claim 1, characterized in that: the drying temperature is 80-140 ℃, the moisture is less than 0.8wt%, and the spreading thickness is 1-4cm.
7. A positive electrode material precursor prepared by the positive electrode material precursor slurry treatment method according to any one of claims 1 to 6, characterized in that: and mixing the positive electrode material precursor with a lithium source, sintering, crushing and sieving to obtain the positive electrode material.
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