CN111994965B - Preparation method of precursor of LTH-structure ternary cathode material - Google Patents

Preparation method of precursor of LTH-structure ternary cathode material Download PDF

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CN111994965B
CN111994965B CN201910444644.2A CN201910444644A CN111994965B CN 111994965 B CN111994965 B CN 111994965B CN 201910444644 A CN201910444644 A CN 201910444644A CN 111994965 B CN111994965 B CN 111994965B
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胡培
徐杉
史德友
刘航
刘世琦
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Hubei Wanrun New Energy Technology Co Ltd
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    • 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
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Abstract

The invention discloses a preparation method of a precursor of a ternary cathode material with an LTH structure, which is characterized in that the precursor of the ternary cathode material with the LTH structure, which has the advantages of high specific surface area, spherical shape and narrow particle size distribution, is synthesized in a reaction kettle by adopting a uniform precipitation technology. The ternary cathode material prepared by the precursor ensures that the material has excellent physical and electrochemical properties, improves the rate capability of the ternary cathode material, and is beneficial to the industrialization process of power batteries. The method can control the shape and the particle size of the material, is simple and controllable, and is suitable for industrial production.

Description

Preparation method of precursor of LTH-structure ternary cathode material
Technical Field
The invention belongs to the technical field of new energy material preparation, and particularly relates to a preparation method of a precursor of a ternary cathode material with an LTH structure.
Background
As is well known, in the emerging high and new technology of the 2l century, the new energy technology is the first time to come, and the battery industry, as an important component in the technical field of new energy, occupies a great position in the global development of science and technology and economy. In the current battery industry, lithium ion batteries are more and more favored by consumers. The lithium ion battery has the advantages of high specific capacity, high energy density, high charging and discharging efficiency, good safety performance, long cycle life and the like. Electronic products in production and life of people are as small as watches, mobile phones, notebook computers and cameras and as large as electric bicycles and electric automobiles, and used batteries are lithium ion batteries or are evolved from the lithium ion batteries, so that the lithium ion battery has excellent market advantages and application prospects.
The anode material is an important component of the lithium ion battery and a key factor for restricting the energy density of the battery. The lithium ion battery anode material which is industrialized at present is LiCoO 2 The process is mature, the comprehensive performance is good, but the price is high, the toxicity is high, the safety performance is poor, and particularly, the material is unstable when overcharged, reacts with electrolyte and the like.
LiFePO 4 And LiMn 2 O 4 As material of LiCoO 2 The substitute materials of (2) have come into play. LiFePO 4 The high-performance lithium ion battery has excellent thermal stability and cycle performance, but the actual specific capacity is low (less than 150 mAh/g), the working voltage is low, the electronic conductivity is low, the rate capability is poor, and the improvement of the energy density of the battery is limited. LiMn 2 O 4 The cost is low, the safety is good, but the cycle performance, particularly the high-temperature cycle performance, is poor, the structure is unstable, and the ginger-Taylor effect occurs to cause the capacity to be sharply attenuated.
At present, the ternary cathode material nickel-cobalt-manganese (aluminum) oxide system has the advantages of low cost, high specific capacity, high voltage plateau and the like, and is concerned. Power cells for HEVs and PHEVs have power and energy density requirements that are different from those of ternary materials commonly used in consumer electronics. The requirement of meeting the high multiplying power needs to increase the specific surface area of the ternary material and increase the reaction active area, which is contrary to the requirement of the common ternary material. The specific surface area of the ternary material is determined by the BET of the precursor, so that the technical problem to be overcome by the dynamic ternary material is solved by improving the BET of the precursor as much as possible on the premise of keeping the sphericity and a certain tap density of the precursor.
The conventional ternary anode material precursor is usually synthesized by a coprecipitation method, ammonia water is used as a complexing agent, and sodium hydroxide is used as a precipitator, so that pure hydroxide precipitate is obtained. The ternary material prepared by the precursor has high tap density but low rate performance. Because pores are generated by high-temperature sintering, the BET of the material and the ternary carbonate of the material are improvedPrecursors have also attracted attention. However, the material has poor processability and low tap density, and is not a good choice for power batteries. The invention mainly aims to synthesize a precursor [ A ] of a ternary cathode material with a layered hydroxide LTH structure Ⅱ 1-x-y B Ⅱ x C Ⅲ y (OH) 2 ] y+ [CO 3 2- ] y/n While satisfying OH - High tap density and CO provided 3 2- The requirement of high specific surface area is provided, and the rate capability, the cycle performance and the thermal stability of the ternary cathode material are improved by improving the physical and chemical properties of the precursor of the ternary cathode material.
Disclosure of Invention
The invention aims to provide a preparation method of a precursor of a ternary cathode material with an LTH structure, which can improve the rate capability, the cycle performance and the stability of the ternary cathode material, and control the interlayer spacing of LTH by an ion exchange method so as to achieve the purpose of improving the rate capability of the ternary cathode material.
In order to achieve the above purpose, the solution of the invention is:
1) melting one or more than two of soluble nickel salt, soluble ferric salt, soluble zinc salt, soluble manganese salt, soluble cobalt salt, soluble magnesium salt, soluble aluminum salt and soluble chromium salt into water, and adding one or more than two of soluble nickel salt, soluble ferric salt, soluble zinc salt, soluble manganese salt, soluble cobalt salt, soluble magnesium salt, soluble aluminum salt and soluble chromium salt to form a solution S;
2) putting the solution S obtained in the step 1), an alkaline aqueous solution and a settling agent in a reaction kettle, adopting uniform precipitation and stably controlling synthesis process parameters to synthesize a spherical or sphere-like ternary anode material precursor with a chemical formula of [ A ] Ⅱ 1-x-y B Ⅱ x C Ⅲ y (OH) 2 ] y+ [P n- ] y/n ·mH 2 O，P n- Is interlayer anion, m is the number of water molecules with interlayer structure, x is more than 0 and less than 1, y is more than 0 and less than 0.2, carbonate is added for interlayer ion exchange treatment, and the ternary positive electrode is prepared by washing and dryingPrecursor of Material [ A Ⅱ 1-x-y B Ⅱ x C Ⅲ y (OH) 2 ] y+ [CO 3 2- ] y/n 。
The nickel salt, the iron salt, the chromium salt, the cobalt salt, the magnesium salt, the aluminum salt, the zinc salt and the manganese salt are one or more of sulfate, nitrate and chloride, the concentration of the metal salt solution is 1.0-4.0 mol/L, and the molar ratio of divalent metal ions to trivalent metal ions is 4-20.
The alkaline aqueous solution is one or more of NaOH, KOH, LiOH and ammonia water, and the concentration of the alkaline aqueous solution is 1-8 mol/L.
The settling agent is one or more of ammonium bicarbonate, ammonium carbonate, urea and hexamethylenetetramine, and the concentration of the settling agent is 2-10 mol/L.
The uniform precipitation method is characterized in that under the protection of argon, nitrogen or other inert gases, a precipitator is slowly generated in the whole solution through chemical reaction in a reaction kettle, so that the product is uniformly precipitated.
The synthesis process parameters are metal salt solution, alkaline aqueous solution and settling agent solution, the metal salt solution, the alkaline aqueous solution and the settling agent solution are continuously input into the vortex type reaction kettle by using a metering pump, and the PH value is controlled to be 8.0-11.0; the precipitation temperature is 50-90 ℃; the stirring speed of the reaction kettle is 100-500 rpm, and the coprecipitation reaction time is 12-96 hours.
The synthesis process parameter is that the solid content in the reaction process is controlled to be 200-1000 g/L.
The carbonate is added for interlayer ion exchange treatment to convert [ A ] into Ⅱ 1-x-y B Ⅱ x C Ⅲ y (OH) 2 ] y+ [P n- ] y/n ·mH 2 Interlayer anion P in O n- By substitution with carbonate radicals, due to interlayer anions P n- The purity of the material obtained by post sintering is influenced. Transferring the synthesized precursor to an aging tank, adding carbonate with the same mole number as that of the interlayer anions, stirring for 1-5 h, performing solid-liquid separation, washing the obtained solid product with deionized water, and drying to obtain the spherical or spherical-like ternary cathode material precursor.
The carbonate for treating interlayer anions is one or more of ammonium bicarbonate, ammonium carbonate and urea.
The precursor of the ternary cathode material is spherical-like, D50 is 2-40 mu m, and the tap density is more than or equal to 2.20g/cm 3 。
The invention has the advantages that: in a reaction kettle, a uniform precipitation technology is adopted to synthesize the precursor of the ternary cathode material with an LTH structure, high specific surface area, spherical shape and narrow particle size distribution, the process can control the appearance and tap density of the precursor, can control the proportion of divalent metal ions and trivalent metal ions, and ensures that the three metal elements are completely and uniformly mixed. The ternary cathode material prepared by the precursor ensures that the material has excellent physical and electrochemical properties.
The ternary cathode material prepared by the precursor of the ternary cathode material has excellent stability, can improve the high-rate performance of the ternary cathode material, and is beneficial to the industrialization process of power batteries. The method can control the shape and the particle size of the material, is simple and controllable, and is suitable for industrial production.
Drawings
FIG. 1 shows [ Ni ] provided in example 1 of the present invention 0.5 Co 0.3 Mn 0.2 (OH) 2 ] 0.2+ [CO 3 2- ] 0.1 ，[Ni 0.8 Co 0.15 Al 0.05 (OH) 2 ] 0.05+ [CO 3 2- ] 0.025 ，[Ni 0.6 Mn 0.2 Mn 0.2 (OH) 2 ] 0.2+ [CO 3 2- ] 0.1 An X-ray diffraction pattern of a precursor of the ternary cathode material;
FIG. 2 is a drawing showing the results of example 1 of the present invention providing [ Ni ] 0.5 Co 0.3 Mn 0.2 (OH) 2 ] 0.2+ [CO 3 2- ] 0.1 Scanning electron microscopy of the precursor.
Detailed Description
Example 1
Mixing NiSO 4 ，CoSO 4 ，Mn 2 (SO 4 ) 3 According to the molar ratio of Ni: co: mn (Mn)= 5: 3: preparing a nickel-cobalt-manganese mixed aqueous solution according to a proportion of 2, wherein the total concentration is 2.0 mol/L, preparing ammonia-alkali mixed solutions with the concentrations of 3.0mol/L and preparing a urea solution with the concentration of 7.5mol/L, and respectively inputting the nickel-cobalt-manganese salt solution, the ammonia aqueous solution and the urea solution into a reaction kettle with the volume of 50L for reaction by using a metering pump. Because no manganese ions are added, protective gas is not needed in the reaction process. Controlling the temperature of the reaction kettle to be 80 ℃, the pH value to be 8.5, the stirring speed to be 150r/min, controlling the flow of ammonia-soda and urea, and controlling the solid content of feed liquid in the reaction kettle to be 300 g/L. And after 24 hours of reaction, transferring the materials in the reaction kettle to an aging tank, adding an ammonium bicarbonate solution with the concentration of 0.2mol/L, stirring for 1 hour, carrying out solid-liquid separation, washing with deionized water, and drying to obtain the precursor of the spherical ternary cathode material. The morphology is similar to a sphere, the particle size distribution is narrow, the D50 is 20 mu m, the tap density is 2.22g/cm3, and the specific surface area is 0.41 m2/g, as shown in figure 2.
Example 2
Mixing NiSO 4 ，CoSO 4 ，Mn 2 (SO 4 ) 3 According to the molar ratio of Ni: co: al = 8: 1.5: preparing a nickel-cobalt-aluminum mixed aqueous solution according to a proportion of 0.5, wherein the total concentration is 2.5 mol/L, preparing ammonia-base mixed solutions with the concentrations of 4.0mol/L respectively, preparing a hexamethylenetetramine solution with the concentration of 5.0 mol/L, and inputting the nickel-cobalt-aluminum salt solution, the ammonia-base solution and the hexamethylenetetramine solution into a reaction kettle with the volume of 50L respectively by using a metering pump for reaction. Because no manganese ions are added, protective gas is not needed in the reaction process. Controlling the temperature of the reaction kettle at 70 ℃, the pH value at 9, the stirring speed at 180r/min, controlling the flow of ammonia alkali and hexamethylenetetramine, and controlling the solid content of the feed liquid in the reaction kettle at 400 g/L. After 12 hours of reaction, transferring the materials in the reaction kettle to an aging tank, adding a urea solution with the concentration of 0.0625mol/L, stirring for 1.5 hours, carrying out solid-liquid separation, washing with deionized water, and drying to obtain the precursor of the spherical ternary cathode material. The appearance is similar to a sphere, the particle size distribution is narrow, the D50 is 30 mu m, the tap density is 2.25g/cm3, and the specific surface area is 0.45 m 2/g.
Example 3
Mixing NiSO 4 ，CoSO 4 ，Mn 2 (SO 4 ) 3 According to the molar ratio of Ni: mn: mn = 6: 2: preparing a nickel-cobalt-manganese mixed aqueous solution according to a proportion of 2, wherein the total concentration is 1.5 mol/L, preparing ammonia-alkali mixed solutions with the concentrations of 3.0mol/L and preparing a hexamethylenediamine solution with the concentration of 8.0 mol/L, and respectively inputting the nickel-cobalt-manganese salt solution, the ammonia-alkali solution and the hexamethylenediamine solution into a reaction kettle with the volume of 50L for reaction by using a metering pump. Introducing nitrogen for protection, controlling the temperature of the reaction kettle to be 65 ℃, the pH value to be 10, the stirring speed to be 200r/min, controlling the flow of ammonia alkali and hexamethylenediamine, and controlling the solid content of the feed liquid in the reaction kettle to be 250 g/L. And after reacting for 18h, transferring the materials in the reaction kettle to an aging tank, adding a urea solution with the concentration of 0.15mol/L, stirring for 2h, carrying out solid-liquid separation, washing with deionized water, and drying to obtain the precursor of the spherical ternary cathode material. The morphology is similar to a sphere, the particle size distribution is narrow, the D50 is 18 mu m, the tap density is 2.23g/cm3, and the specific surface area is 0.39 m 2/g.
D50, tap density, and specific surface area of the ternary positive electrode material precursors prepared in examples 1 to 3 were measured, respectively, and are shown in table 1.
Table 1 is a materialized performance data table of the embodiment of the invention
Examples Chemical formula (II) D50(μm) Tap density (g/cm) 3) Specific surface area (m) 2 /g)
Example 1 [Ni 0.5 Co 0.3 Mn 0.2 (OH) 2 ] 0.2+ [CO 3 2- ] 0.1 20 2.22 0.41
Example 2 [Ni 0.8 Co 0.15 Al 0.05 (OH) 2 ] 0.05+ [CO 3 2- ] 0.025 30 2.25 0.45
Example 3 [Ni 0.6 Mn 0.2 Mn 0.2 (OH) 2 ] 0.2+ [CO 3 2- ] 0.1 18 2.23 0.39
The particle size distribution of the precursor of the ternary cathode material with the LTH structure is uniform, and the specific surface area of the material is increased and the high-current charge-discharge performance of the material is improved under the condition of ensuring high tap density through the improvement of the material structure.

Claims (5)

1. A precursor of a ternary cathode material with a TLH structure is characterized in that: the precursor of the ternary cathode material is microscopically a ternary layered hydroxide TLH structure with a molecular formula of [ A Ⅱ 1-x-y B Ⅱ x C Ⅲ y (OH) 2 ] y+ [CO 3 2- ] y/n Wherein A is II 、B II And C III Are respectively provided withRepresents divalent and trivalent metal ions; y is the molar ratio n (C) 3+ )/( n(A 2+ )+ n(B 2+ )+ n(C 3+ ))；
Wherein x is more than 0 and less than 1, and y is more than 0 and less than 0.2;
the preparation method of the precursor of the ternary cathode material with the TLH structure comprises the following steps of 1) melting one or more than two of soluble nickel salt, soluble ferric salt, soluble zinc salt, soluble manganese salt, soluble cobalt salt, soluble magnesium salt, soluble aluminum salt and soluble chromium salt into water, adding one or more than two of soluble nickel salt, soluble ferric salt, soluble zinc salt, soluble manganese salt, soluble cobalt salt, soluble magnesium salt, soluble aluminum salt and soluble chromium salt into the water to form a solution S with the concentration of 1.0-4.0 mol/L and the molar ratio of divalent metal ions to trivalent metal ions of 4-20;
2) putting the solution S obtained in the step 1) and an alkaline aqueous solution with the solution concentration of 1-8 mol/L and a settling agent with the solution concentration of 2-10 mol/L into a reaction kettle, and synthesizing a spherical or spheroidal ternary anode material precursor with a chemical formula of [ A ] by adopting uniform precipitation and stably controlling synthesis process parameters Ⅱ 1-x-y B Ⅱ x C Ⅲ y (OH) 2 ] y+ [P n- ] y/n ·mH 2 O，P n- Is interlayer anion, m is the number of water molecules with interlayer structure, x is more than 0 and less than 1, y is more than 0 and less than 0.2, carbonate is added for interlayer ion exchange treatment, and a precursor [ A ] of the ternary cathode material is prepared by washing and drying Ⅱ 1-x-y B Ⅱ x C Ⅲ y (OH) 2 ] y+ [CO 3 2- ] y/n ；
The synthesis process parameters are that a metal salt solution, an alkaline aqueous solution and a settling agent solution are continuously input into a vortex type reaction kettle by a metering pump, and the pH value is controlled to be between 8.0 and 11.0; the precipitation temperature is 50-90 ℃; the stirring speed of the reaction kettle is 100-500 rpm, and the coprecipitation reaction time is 12-96 hours; the solid content in the reaction process is controlled to be 200-1000 g/L;
the precursor D50 of the ternary cathode material is 2-40 mu m, and the tap density is more than or equal to 2.20g/cm 3 ；
The carbonate is added for interlayer ion exchange treatment to convert [ A ] into Ⅱ 1-x-y B Ⅱ x C Ⅲ y (OH) 2 ] y+ [P n- ] y/n ·mH 2 Interlayer anion P in O n- By substitution with carbonate radicals, due to interlayer anions P n- The purity of the material obtained by later sintering is influenced; transferring the synthesized precursor to an aging tank, adding carbonate with the same mole number as that of interlayer anions, stirring for 1-5 h, performing solid-liquid separation, washing the obtained solid product with deionized water, and drying to obtain a spherical-like or spherical-like ternary cathode material precursor; the carbonate for treating interlayer anions is one or more of ammonium bicarbonate, ammonium carbonate and urea.
2. The ternary positive electrode material precursor of the TLH structure of claim 1, wherein: the nickel salt, iron salt, chromium salt, cobalt salt, magnesium salt, aluminum salt, zinc salt and manganese salt are one or more of sulfate, nitrate and chloride.
3. The ternary positive electrode material precursor of the TLH structure according to claim 1, wherein: the alkaline aqueous solution is one or more of NaOH, KOH, LiOH and ammonia water.
4. The ternary positive electrode material precursor of the TLH structure of claim 1, wherein: the settling agent is one or more of ammonium bicarbonate, ammonium carbonate, urea, hexamethylenetetramine and hexamethylenediamine.
5. The ternary positive electrode material precursor of the TLH structure according to claim 1, wherein: the uniform precipitation method is to slowly generate a precipitator in the whole solution through chemical reaction in a reaction kettle under the protection of argon, nitrogen or other inert gases so as to uniformly precipitate a product.
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