CN114927682A - LiNi ternary material for increasing high nickel content x Co y Mn 1-x-y O 2 Method for cycling stability and safety of anode material - Google Patents
LiNi ternary material for increasing high nickel content x Co y Mn 1-x-y O 2 Method for cycling stability and safety of anode material Download PDFInfo
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Abstract
The invention discloses a method for improving high-nickel ternary LiNi x Co y Mn 1‑x‑y O 2 The method for the cycling stability and safety of the cathode material. Organic acid is used as modifier, and a large amount of H is enriched in organic acid molecules + And high nickel ternary LiNi x Co y Mn 1‑x‑y O 2 Li in residual alkali on surface of positive electrode material + Ion exchange is carried out, organic acid solvent is uniformly adhered to the surface of the material, and then high-temperature roasting is carried out in inert atmosphere to obtain carbon-coated high-nickel ternary LiNi x Co y Mn 1‑x‑y O 2 And (3) a positive electrode material. The method of the invention effectively reduces the high-nickel ternary LiNi x Co y Mn 1‑x‑y O 2 The surface residual alkali amount of the anode material prevents the side reaction of the material and the electrolyte interface, relieves the crystal lattice oxygen precipitation of the material in the circulation process, and enables the material to show excellent circulation stability and safety.
Description
Technical Field
The invention relates to a method for improving high-nickel ternary LiNi x Co y Mn 1-x-y O 2 A method for the cycling stability and safety of a positive electrode material belongs to the field of preparation of positive electrode materials of lithium ion batteries.
Background
High energy density is an important requirement for industrial application of lithium ion batteries, and the positive electrode material is considered as a bottleneck for increasing energy density. Currently, common commercial positive electrode materials (e.g., LiCoO) 2 、LiFePO 4 And LiMn 2 O 4 ) High nickel ternary LiNi with limited specific capacity x Co y Mn 1-x-y O 2 (1>x.gtoreq.0.5, e.g. LiNi 0.6 Co 0.2 Mn 0.2 O 2 ，LiNi 0.7 Co 0.1 Mn 0.2 O 2 ，LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) Layered metal oxides due to their higher reversible specific capacity (-200 mAh g -1 ) And operating voltages (-3.8V) are becoming one of the most promising candidates and drawing more and more attention. However, high nickel ternary LiNi x Co y Mn 1-x-y O 2 The poor cycle stability and safety of the cathode material inhibit the commercial development thereof.
Resulting in a high nickel ternary LiNi x Co y Mn 1-x-y O 2 The reasons for poor cycling stability and safety of the cathode material mainly include the following three aspects: (1) lithium remaining on the surface of the material is easy to react with CO in air 2 And H 2 O reacts to form Li 2 CO 3 And LiOH (i.e. surface residual alkali),Li 2 CO 3 can cause the material to generate serious flatulence during high-temperature storage, and LiOH can react with LiPF in electrolyte 6 Reacting to generate HF corrosion material; (2) li extracted from high-nickel material under same potential + Higher than that of the low-nickel material, so that Ni is in the composition 4+ Relatively high content of Ni 4+ Has strong reduction tendency and is easy to generate Ni 4+ To Ni 3+ In order to keep charge balance, oxygen ions in material crystal lattices can generate oxidation reaction to generate oxygen to be discharged; (3) ni of material unstable in charging process 4+ The method is easy to have strong side reaction with electrolyte, which causes the dissolution of metal ions in the material, causes the instability of the main structure of the material and is accompanied with the generation of more byproducts.
For high nickel ternary LiNi x Co y Mn 1-x-y O 2 The anode material is subjected to modification treatment such as doping and coating or is improved from a synthesis process (such as adding a washing step of a product), so that the problems can be effectively solved, and the performance of the material is improved. However, these methods have certain limitations, such as doping and coating modification of the material, which can effectively alleviate the precipitation of lattice oxygen during the circulation process of the material, prevent the side reaction between the material interface and the electrolyte, and stabilize the main structure of the material, but cannot remove the residual alkali remaining on the surface of the material; the water washing step of the material is added, so that the residual alkali amount on the surface of the material can be effectively reduced, but the precipitation of lattice oxygen and the side reaction of the material and an electrolyte interface in the circulating process of the material cannot be relieved. Therefore, it is required to develop a method for improving high-nickel ternary LiNi x Co y Mn 1-x-y O 2 The method for the cycling stability and safety of the cathode material.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for improving high-nickel ternary LiNi x Co y Mn 1-x-y O 2 A method for cycling stability and safety of a positive electrode material, which method aims to solve the following two problems: (1) inhibiting side reaction at material and electrolyte interface and preventing material main body knotCollapse of structure to increase high nickel ternary LiNi x Co y Mn 1-x-y O 2 Cycling stability of the positive electrode material; (2) reduce the surface residual alkali amount of the material and relieve the precipitation of lattice oxygen of the material in the circulating process, thereby improving the nickel-rich ternary LiNi x Co y Mn 1-x-y O 2 Safety of the positive electrode material.
In order to realize the purpose of the invention, the following technical scheme is adopted:
1. high-nickel-content ternary LiNi-lifting catalyst x Co y Mn 1-x-y O 2 A method for cycling stability and safety of a positive electrode material, comprising the steps of:
(1) according to the stoichiometric ratio of Ni to Co to Mn to x: y: 1-x-y respectively weighing nickel salt, cobalt salt and manganese salt with corresponding mass to prepare mixed metal salt solution as reaction raw material, NaOH solution as precipitator and NH 3 ·H 2 Taking O solution as a complexing agent, and adopting a parallel flow mode to mix the prepared mixed metal salt solution, NaOH solution and NH 3 ·H 2 Conveying the O solution to a reaction kettle with continuous stirring for coprecipitation reaction, and synthesizing Ni by controlling reaction temperature, ammonia-mixed metal salt feeding molar ratio, pH value, stirring speed and reaction time in the reaction process x Co y Mn 1-x-y (OH) 2 Precursor, the whole process of coprecipitation reaction is carried out under the protection of nitrogen atmosphere; ni to be synthesized subsequently x Co y Mn 1-x-y (OH) 2 The precursor and lithium salt are mixed evenly and are roasted in two steps in air or oxygen atmosphere to obtain the high-nickel ternary LiNi x Co y Mn 1-x-y O 2 A positive electrode material;
(2) the high nickel ternary LiNi prepared by the method is x Co y Mn 1-x-y O 2 Dispersing the positive electrode material in organic acid solvent or organic acid/water mixed solvent, stirring to make H in organic acid molecule + And high nickel ternary LiNi x Co y Mn 1-x-y O 2 Li in residual alkali on surface of positive electrode material + Carrying out ion exchange, and simultaneously enabling the organic acid solvent to be uniformly adhered to the surface of the material; then by washingWashing and centrifuging to remove redundant organic acid solvent on the surface of the material, and drying to obtain the high-nickel ternary LiNi subjected to organic acid treatment x Co y Mn 1-x-y O 2 A positive electrode material; finally, the high nickel ternary LiNi after organic acid treatment x Co y Mn 1-x-y O 2 Placing the anode material in a tubular furnace, and roasting in an inert atmosphere to obtain carbon-coated high-nickel ternary LiNi x Co y Mn 1-x-y O 2 A positive electrode material; wherein 1 is>x≥0.5，0.5>y>0。
In one embodiment of the present invention, 1> x ≧ 0.5. For example, x is 0.5, 0.52, 0.54, 0.56, 0.58, 0.6, 0.62, 0.64, 0.65, 0.66, 0.68, 0.7, 0.72, 0.74, 0.75, 0.76, 0.78, 0.8, 0.82, 0.84, 0.85, 0.86, 0.88, 0.9, 0.92, 0.94, 0.96, 0.98, or 0.99.
In one embodiment of the invention, 0.5> y > 0. For example, y is 0.02, 0.04, 0.06, 0.08, 0.1, 0.12, 0.14, 0.16, 0.18, 0.2, 0.22, 0.24, 0.26, 0.28, 0.3, 0.32, 0.34, 0.36, 0.38, 0.4, 0.42, 0.44, 0.46, 0.48, 0.49, or 0.499.
Further, in the step (1), the total metal concentration of the nickel-cobalt-manganese mixed metal salt solution is 0.5-3 mol/L, the concentration of NaOH solution is 8-12 mol/L, and NH is added 3 ·H 2 The concentration of the O solution is 3-6 mol/L.
In one embodiment of the invention, the total metal concentration of the nickel-cobalt-manganese mixed metal salt solution is 0.5-3 mol/L. For example, the concentration of the nickel cobalt manganese mixed metal salt solution is 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 or 3 mol/L.
In one embodiment of the invention, the concentration of the NaOH solution is 8-12 mol/L. For example, the concentration of the NaOH solution is 8, 8.2, 8.4, 8.6, 8.8, 9, 9.2, 9.4, 9.6, 9.8, 10, 10.2, 10.4, 10.6, 10.8, 11, 11.2, 11.4, 11.6, 11.8 or 12 mol/L.
In one embodiment of the invention, NH 3 ·H 2 The concentration of the O solution is 36 mol/L. For example, the NH 3 ·H 2 The concentration of the O solution is 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4, 5.6, 5.8 or 6.0 mol/L.
Further, in the step (1), the coprecipitation reaction temperature is 45-70 ℃, and the feeding molar ratio of ammonia to the mixed metal salt is 2.5: 4-3.5: 4, the pH value is 10-12, the stirring speed is 400-1500 rpm, and the reaction time is 20-50 h. For example, the coprecipitation reaction temperature is 45, 50, 55, 60, 65, 70 ℃. For example, the co-precipitation reaction ammonia and mixed metal salt feed molar ratio is 2.5: 4. 2.6: 4. 2.7: 4. 2.8: 4. 2.9: 4. 3.0: 4. 3.1: 4. 3.2: 4. 3.3: 4. 3.4: 4 or 3.5: 4. for example, the co-precipitation reaction pH is 10, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, or 12. For example, the co-precipitation reaction time is 20, 25, 30, 35, 40, 45 or 50 h.
Further, in the step (1), Ni is synthesized x Co y Mn 1-x-y (OH) 2 The whole process of the precursor is carried out under the protection of nitrogen atmosphere.
Further, in the step (1), the Ni x Co y Mn 1-x-y (OH) 2 The stoichiometric ratio of the mixed precursor and lithium salt is 1: 1.02-1: 1.10. for example, the Ni x Co y Mn 1-x-y (OH) 2 The stoichiometric ratio of the mixed precursor and lithium salt is 1: 1.02, 1: 1.03, 1: 1.04, 1:1.05, 1: 1.06, 1:1.07, 1: 1.08, 1: 1.09 or 1: 1.10.
further, in the step (1), the two-step firing includes a first firing and a second firing.
Further, in the step (1), in the two-step roasting, the first-step roasting temperature is 350-550 ℃, the first-step roasting time is 2-8 hours, the second-step roasting temperature is 700-900 ℃, the second-step roasting time is 12-24 hours, and the heating rates of the first-step roasting and the second-step roasting are both 2-6 ℃/min. For example, the first step firing temperature is 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540 or 550 ℃, and the first step firing time is 2, 3, 4, 5, 6, 7 or 8 hours. For example, the second step firing temperature is 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890 or 900 ℃, and the second step firing time is 12, 14, 16, 18, 20, 22, or 24 hours. The heating rate of the first-step roasting and the second-step roasting is 2, 3, 4, 5 or 6 ℃/min.
Further, in the step (2), the solution used for washing is deionized water, and the number of washing is 2-5.
Further, in the step (2), the rotating speed of the centrifugation is 2000-8000 rpm, and the centrifugation times are 2-5.
Further, in the step (2), the drying temperature is 40-120 ℃, and the drying time is 6-48 h.
Further, in the step (2), the temperature in roasting is 300-600 ℃, the roasting time is 1-6 h, and the roasting temperature rise rate is 2-6 ℃/min. For example, the firing temperature is 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590 or 600 ℃, the firing time is 1, 2, 3, 4, 5 or 6 hours, and the firing ramp rate is 2, 3, 4, 5 or 6 ℃/min.
Specifically, step (1) comprises mixing, in a stoichiometric ratio Ni: Co: Mn ═ x: y: 1-x-y (1)>x≥0.5，0.5>y>0) Respectively weighing NiSO with corresponding mass 4 ·6H 2 O、CoSO 4 ·7H 2 O and MnSO 4 ·H 2 O is prepared into mixed metal salt solution with the total metal concentration of 0.5-3 mol/L, and then NaOH with the concentration of 8-12 mol/L is used as a precipitator and NH with the concentration of 3-6 mol/L 3 ·H 2 Taking O as a complexing agent, and mixing the prepared mixed metal salt solution, NaOH solution and NH in a parallel flow mode 3 ·H 2 Conveying the O solution to a reaction kettle with continuous stirring for coprecipitation reaction, wherein the reaction temperature is controlled to be 45-70 ℃ in the reaction process, and the feeding ratio of ammonia to the metal in the mixed metal salt is 2.5: 4 to 3.5: 4, the pH value is 10-12, the stirring speed is 400-1500 rpm, and the reaction time is 20-50 h x Co y Mn 1-x-y (OH) 2 Precursor, the whole process of coprecipitation reaction is carried out under the protection of nitrogen atmosphere; followed by synthesis of Ni x Co y Mn 1-x-y (OH) 2 The precursor and lithium salt are mixed according to the stoichiometric ratio of 1: 1.02-1: 1.10, uniformly mixing, then roasting in air or oxygen atmosphere in two steps, firstly heating to 350-550 ℃ at a heating rate of 2-6 ℃/min, carrying out heat preservation treatment for 2-8 h, then heating to 700-900 ℃ at a heating rate of 2-6 ℃/min, carrying out heat preservation treatment for 12-24 h, and finally naturally cooling to room temperature to obtain the high-nickel ternary LiNi x Co y Mn 1-x-y O 2 And (3) a positive electrode material.
And in the lithium mixing step, the lithium salt is one or more of lithium oxide, lithium carbonate, lithium acetate, lithium nitrate, lithium oxalate and lithium hydroxide.
Specifically, the step (2) comprises the step of mixing the high-nickel ternary LiNi prepared by the method x Co y Mn 1-x-y O 2 Dispersing the positive electrode material in organic acid solvent or organic acid/water mixed solvent, stirring, and allowing the positive electrode material to pass through H in organic acid molecules + And high nickel ternary LiNi x Co y Mn 1-x-y O 2 Li in residual alkali on surface of positive electrode material + Carrying out ion exchange, and simultaneously enabling the organic acid to be uniformly adhered to the surface of the material; and then washing the material with deionized water for 2-5 times, centrifuging the material for 2-5 times at a rotating speed of 2000-8000 rpm to remove redundant organic acid solvent on the surface of the material, and drying the material at 40-120 ℃ for 6-48 h to obtain the organic acid-treated high-nickel ternary LiNi x Co y Mn 1-x-y O 2 A positive electrode material; finally, the high nickel ternary LiNi treated by organic acid x Co y Mn 1-x-y O 2 Placing the positive electrode material in a tube furnace, heating to 300-600 ℃ at a heating rate of 2-6 ℃/min under the atmosphere of nitrogen or argon, and carrying out heat preservation treatment for 1-6 h to obtain the carbon-coated high-nickel ternary LiNi x Co y Mn 1-x-y O 2 And (3) a positive electrode material.
In the present invention, the term "organic acid/water mixed solvent" refers to a mixed solvent formed by mixing an organic acid and water.
In the present invention, the feed mole ratio of ammonia to mixed metal salt refers to the ratio of the number of moles of ammonia in the feed to the total number of moles of metal salt in the mixed metal salt.
The organic acid is one of lactic acid, oleic acid, linolenic acid and arachidonic acid.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a method for improving high-nickel ternary LiNi x Co y Mn 1-x-y O 2 The method for improving the circulation stability and safety of the anode material adopts organic acid as a modifier and provides rich H in organic acid molecules + And high nickel ternary LiNi x Co y Mn 1-x-y O 2 Li in residual alkali on surface of positive electrode material + Ion exchange is carried out, organic acid is uniformly adhered to the surface of the material, and then high-temperature roasting is carried out in inert atmosphere to obtain carbon-coated high-nickel ternary LiNi x Co y Mn 1-x-y O 2 And (3) a positive electrode material. The method of the invention effectively reduces the high-nickel ternary LiNi x Co y Mn 1-x-y O 2 The surface residual alkali amount of the anode material relieves the precipitation of lattice oxygen of the material in the circulation process and prevents the side reaction of the material and the electrolyte interface, so that the high-nickel ternary LiNi x Co y Mn 1-x-y O 2 The cycle stability and the safety of the anode material are greatly improved.
Drawings
FIG. 1 is a high nickel ternary LiNi prepared according to example 1 of the present invention 0.8 Co 0.1 Mn 0.1 O 2 XRD pattern of the positive electrode material;
FIG. 2 is a carbon-coated high-nickel ternary LiNi prepared in example 1 of the present invention 0.8 Co 0.1 Mn 0.1 O 2 XRD pattern of the positive electrode material;
FIG. 3 shows Ni prepared in example 1 of the present invention 0.8 Co 0.1 Mn 0.1 (OH) 2 Precursor (a) and high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 Positive electrode material (b), lactic acid modified high nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 A positive electrode material (c) and carbon-coated high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 FESEM image of positive electrode material (d);
FIG. 4 is a high nickel ternary LiNi prepared according to example 1 of the present invention 0.8 Co 0.1 Mn 0.1 O 2 Positive electrode material and carbon-coated high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle performance diagram of the positive electrode material;
FIG. 5 is a high nickel ternary LiNi prepared according to example 1 of the present invention 0.8 Co 0.1 Mn 0.1 O 2 Positive electrode material and carbon-coated high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 DSC curve of the positive electrode material;
FIG. 6 is a high nickel ternary LiNi prepared according to example 1 of the present invention 0.8 Co 0.1 Mn 0.1 O 2 Positive electrode material (a), (b) and carbon-coated high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 FESEM images of the cathode materials (c), (d) after 100 cycles.
Detailed Description
The following examples are given for the detailed implementation and the specific operation procedures, but the scope of the present invention is not limited to the following examples.
Example 1:
according to the stoichiometric ratio of Ni to Co to Mn being 0.8: 0.1: 0.1 respectively weighing NiSO with corresponding mass 4 ·6H 2 O、CoSO 4 ·7H 2 O and MnSO 4 ·H 2 O is prepared into mixed metal salt solution with the total volume of 7L and the total metal concentration of 2 mol/L. Then NaOH with the concentration of 10mol/L is used as a precipitator, NH with the concentration of 5mol/L 3 ·H 2 O is taken as a complexing agent, and the prepared mixed metal salt solution, NaOH solution and NH are mixed in a parallel flow mode 3 ·H 2 Conveying the O solution to a 20L reaction kettle which is continuously stirred for coprecipitation reactionThe reaction is carried out at a temperature of 60 ℃ by controlling the reaction temperature so that the molar ratio of ammonia to the feed of the mixed metal salt (where the molar ratio of ammonia to the feed of the mixed metal salt is defined as the ratio of the number of moles of ammonia in the feed to the total number of moles of the metal salt in the mixed metal salt) is 3: 4, the pH value is 11.2, the stirring speed is 600rpm, and the reaction time is 35h to synthesize Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Precursor, the whole process of coprecipitation reaction is carried out under the protection of nitrogen atmosphere; followed by synthesis of Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Precursors with Li 2 CO 3 Uniformly mixing the components according to the stoichiometric ratio of 1:1.05, then roasting the mixture in two steps under the oxygen atmosphere, firstly heating the mixture to 450 ℃ at the heating rate of 2 ℃/min, carrying out heat preservation treatment for 6 hours, then heating the mixture to 750 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation treatment for 15 hours, and finally naturally cooling the mixture to room temperature to obtain the high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 And (3) a positive electrode material.
10g of the high nickel ternary LiNi prepared as described above was charged 0.8 Co 0.1 Mn 0.1 O 2 The cathode material is dispersed in 300mL of lactic acid/water with the volume ratio of 2: 1 for 2 hours, passing through H in lactic acid molecules + And high nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 Li in residual alkali on surface of positive electrode material + Ion exchange is carried out, and simultaneously, the lactic acid solvent is uniformly adhered to the surface of the material; then washing the material with deionized water for 3 times, centrifuging the material for 3 times at the rotating speed of 6000rpm to remove the redundant lactic acid solvent on the surface of the material, and drying the material at 80 ℃ for 12 hours to obtain the lactic acid modified high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 A positive electrode material; finally, modifying the lactic acid to obtain the high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 Placing the anode material in a tubular furnace, heating to 500 ℃ at a heating rate of 4 ℃/min in a nitrogen atmosphere, and carrying out heat preservation treatment for 2h to obtain the carbon-coated high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 And (3) a positive electrode material.
FIGS. 1 and 2 are the high nickel ternary LiNi prepared in example 1, respectively 0.8 Co 0.1 Mn 0.1 O 2 Positive electrode material and carbon-coated high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 XRD pattern of anode material, it can be seen that both materials can be indexed to typical layered alpha-NaFeO 2 The structure, space group is R _3_ m, belonging to the hexagonal system. In addition, the (018)/(110) and (006)/(012) peaks of both materials showed more pronounced splitting, and the (003)/(104) peak showed greater peak intensity ratios (both greater than 1.2), indicating that the materials had better lamellar structures and lower degrees of lithium-nickel intergrowth before and after modification, and further confirming that the modification process did not cause damage to the crystalline structure of the materials. In addition, in fig. 2, a characteristic peak corresponding to carbon does not appear, which may be caused by a low carbon coating amount.
FIG. 3 shows Ni prepared in example 1 of the present invention 0.8 Co 0.1 Mn 0.1 (OH) 2 Precursor, high nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 Positive electrode material and lactic acid modified high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 Positive electrode material and carbon-coated high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 FESEM image of positive electrode material. From the figure, Ni can be seen 0.8 Co 0.1 Mn 0.1 (OH) 2 The precursor is a secondary spherical particle consisting of primary flaky particles, and the diameter of the secondary spherical particle is about 8 mu m (a); high-nickel ternary LiNi obtained after high-temperature roasting 0.8 Co 0.1 Mn 0.1 O 2 The original sphericity of the anode material is still maintained, and the morphology is not damaged (b); after lactic acid treatment, high nickel ternary LiNi can be seen 0.8 Co 0.1 Mn 0.1 O 2 A layer of lactic acid solvent (c) is uniformly adhered to the surface of the anode material, and the anode material is placed in an inert atmosphere for high-temperature roasting to obtain carbon-coated high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 The shape and the size of the anode material are compared with original high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 There was no significant difference in the positive electrode material, however the material surface became slightly hazy due to the carbon coating (d).
The high nickel ternary LiNi prepared in the embodiment 1 of the invention 0.8 Co 0.1 Mn 0.1 O 2 Positive electrode material and carbon-coated high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode material is fully mixed with acetylene black and polyvinylidene fluoride according to the mass ratio of 8:1:1, the mixture is mixed into paste, the paste is uniformly coated on an aluminum foil, the coating thickness is 100 mu m, the paste is dried at 80 ℃, rolled and sheared into a positive electrode sheet with the diameter of 12mm, and the positive electrode sheet is dried in vacuum for standby. A2032 button cell is prepared by using a metal lithium sheet as a cathode and a Cellgard 2400 type polypropylene membrane as a diaphragm in an argon glove box, and then a constant voltage and constant current charge and discharge test is carried out on the button cell at 25 ℃.
FIG. 4 is a high nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 Positive electrode material and carbon-coated high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle performance of the positive electrode material at a current density of 0.5C. As can be seen from the figure, carbon-coated high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 The initial discharge capacity of the positive electrode material was 189.1mAh g -1 Higher than high nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 180.8mAh g of positive electrode material -1 . In addition, with the increase of the number of cycle times, the carbon-coated high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 The discharge capacity of the anode material decays slowly, and after 100 cycles of charge and discharge tests, the discharge capacity still has 170.5mAh g -1 The attenuation rate of the capacity per circle is only 0.09%; in contrast, high nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 The capacity attenuation rate per circle of the anode material is as high as 0.21 percent (143.3mAh g) -1 ). Electrochemical test results show that the lactic acid modification treatment can effectively improve the high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycling stability of the positive electrode material.
The thermal stability of the positive electrode material is one of very important factors, especially in a fully charged state, in view of the safety of the battery. Based on this, we will 2032 button cellAnd disassembling, taking out the cathode material inside, and performing DSC test so that the DSC result can simulate actual heat dissipation. FIG. 5 is a high nickel ternary LiNi prepared according to example 1 of the present invention 0.8 Co 0.1 Mn 0.1 O 2 Positive electrode material and carbon-coated high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 DSC curve of the positive electrode material. It can be seen from the figure that high nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode material has an exothermic peak at 228.1 ℃, and in contrast, the carbon-coated high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 The exothermic peak of the positive electrode material was shifted up to 242.2 ℃. In addition, compared to high nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 Carbon-coated high-nickel ternary LiNi as anode material 0.8 Co 0.1 Mn 0.1 O 2 The heat release amount of the positive electrode material is also significantly reduced. DSC test result proves that lactic acid modification treatment effectively improves high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 The thermal stability of the positive electrode material, thereby improving the safety thereof.
FIG. 6 is a high nickel ternary LiNi prepared according to example 1 of the present invention 0.8 Co 0.1 Mn 0.1 O 2 Positive electrode material and carbon-coated high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 FESEM images of the cathode material after 100 cycles. As can be seen from the graph, after 100 charge-discharge cycle tests at a current density of 0.5C, the high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 The morphology of the positive electrode material is severely damaged (a), (b); in contrast, carbon-coated high-nickel ternary LiNi 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode material has little change in morphology (c), (d) in long-term cycling tests. This demonstrates that high nickel ternary LiNi is present after lactic acid modification 0.8 Co 0.1 Mn 0.1 O 2 The carbon coating layer formed on the surface of the anode material effectively isolates the side reaction of the active material and the electrolyte interface, and prevents the dissolution of transition metal ions, thereby improving the structural stability of the material.
Example 2:
according to the stoichiometric ratio of Ni to Co to Mn being 0.7: 0.1: 0.2 separately weighing NiSO with corresponding mass 4 ·6H 2 O、CoSO 4 ·7H 2 O and MnSO 4 ·H 2 O is prepared into mixed metal salt solution with the total volume of 6L and the total metal concentration of 2mol/L, and then NaOH with the concentration of 10.5mol/L is used as a precipitator and NH with the concentration of 4mol/L 3 ·H 2 Taking O as a complexing agent, and mixing the prepared mixed metal salt solution, NaOH solution and NH in a parallel flow mode 3 ·H 2 Conveying the O solution into a continuous stirring reaction kettle for coprecipitation reaction, wherein the reaction temperature is controlled to be 55 ℃, and the feeding molar ratio of ammonia to mixed metal salt (the feeding molar ratio of ammonia to mixed metal salt refers to the ratio of the mole number of the ammonia in the feeding to the total mole number of the metal salt in the mixed metal salt) is 3.2: 4, pH value of 11, stirring speed of 800rpm and reaction time of 30h for synthesizing Ni 0.7 Co 0.1 Mn 0.2 (OH) 2 Precursor, the whole process of coprecipitation reaction is carried out under the protection of nitrogen atmosphere; followed by synthesis of Ni 0.7 Co 0.1 Mn 0.2 (OH) 2 Uniformly mixing the precursor and LiOH according to the stoichiometric ratio of 1:1.07, then roasting in an oxygen atmosphere in two steps, firstly heating to 480 ℃ at the heating rate of 2 ℃/min, carrying out heat preservation treatment for 6h, then heating to 780 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation treatment for 16h, and finally naturally cooling to room temperature to obtain the high-nickel ternary LiNi 0.7 Co 0.1 Mn 0.2 O 2 And (3) a positive electrode material.
10g of the high nickel ternary LiNi prepared above was added 0.7 Co 0.1 Mn 0.2 O 2 Dispersing the positive electrode material in 150mL of oleic acid solvent, stirring for 1.5H, and passing through H in oleic acid molecules + And high nickel ternary LiNi 0.7 Co 0.1 Mn 0.2 O 2 Li in residual alkali on surface of positive electrode material + Carrying out ion exchange, and simultaneously enabling the oleic acid solvent to be uniformly adhered to the surface of the material; then removing the redundant oleic acid solvent on the surface of the material by washing 3 times with deionized water and centrifuging 3 times at the rotating speed of 4500rpm, and drying for 10h at 90 ℃ to obtain oleic acidTreated high nickel ternary LiNi 0.7 Co 0.1 Mn 0.2 O 2 A positive electrode material; finally, the oleic acid treated high-nickel ternary LiNi 0.7 Co 0.1 Mn 0.2 O 2 Placing the anode material in a tubular furnace, heating to 450 ℃ at a heating rate of 3 ℃/min under a nitrogen atmosphere, and carrying out heat preservation treatment for 2.5h to obtain the carbon-coated high-nickel ternary LiNi 0.7 Co 0.1 Mn 0.2 O 2 And (3) a positive electrode material.
Example 3:
according to the stoichiometric ratio of Ni, Co and Mn being 0.6: 0.2: 0.2 separately weighing NiSO with corresponding mass 4 ·6H 2 O、CoSO 4 ·7H 2 O and MnSO 4 ·H 2 O is prepared into mixed metal salt solution with the total volume of 8L and the total metal concentration of 2mol/L, and then NaOH with the concentration of 12mol/L is used as a precipitator and NH with the concentration of 3mol/L 3 ·H 2 O is taken as a complexing agent, and the prepared mixed metal salt solution, NaOH solution and NH are mixed in a parallel flow mode 3 ·H 2 Conveying the O solution into a continuous stirring reaction kettle for coprecipitation reaction, wherein the reaction temperature is controlled to be 65 ℃ during the reaction, the feeding molar ratio of ammonia to mixed metal salt (the feeding molar ratio of ammonia to mixed metal salt refers to the ratio of the number of moles of ammonia in feeding to the total number of moles of metal salt in mixed metal salt) is 2.8: 4, pH value of 10.8, stirring speed of 1000rpm and reaction time of 40h for synthesizing Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 Precursor, the whole process of coprecipitation reaction is carried out under the protection of nitrogen atmosphere; followed by synthesis of Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 Precursors with Li 2 CO 3 Uniformly mixing the components according to the stoichiometric ratio of 1:1.05, then roasting the mixture in two steps under the air atmosphere, firstly heating the mixture to 500 ℃ at the heating rate of 2 ℃/min, carrying out heat preservation treatment for 5 hours, then heating the mixture to 800 ℃ at the heating rate of 2 ℃/min, carrying out heat preservation treatment for 12 hours, and finally naturally cooling the mixture to room temperature to obtain the high-nickel ternary LiNi 0.6 Co 0.2 Mn 0.2 O 2 And (3) a positive electrode material.
20g of the high nickel ternary LiNi prepared above was charged 0.8 Co 0.1 Mn 0.1 O 2 Dispersing the positive electrode material in 400mL of linolenic acid solvent, stirring for 3H, and allowing the positive electrode material to pass through H in linolenic acid molecules + And high nickel ternary LiNi 0.6 Co 0.2 Mn 0.2 O 2 Li in residual alkali on surface of positive electrode material + Ion exchange is carried out, and meanwhile, the linolenic acid solvent is uniformly adhered to the surface of the material; then washing with deionized water for 3 times, centrifuging at 5000rpm for 3 times to remove the redundant linolenic acid solvent on the surface of the material, and drying at 110 ℃ for 8h to obtain linolenic acid-treated high-nickel ternary LiNi 0.6 Co 0.2 Mn 0.2 O 2 A positive electrode material; finally, linolenic acid treated high-nickel ternary LiNi 0.6 Co 0.2 Mn 0.2 O 2 Placing the anode material in a tube furnace, heating to 400 ℃ at the heating rate of 2 ℃/min under the argon atmosphere, and carrying out heat preservation treatment for 3h to obtain the carbon-coated high-nickel ternary LiNi 0.6 Co 0.2 Mn 0.2 O 2 And (3) a positive electrode material.
The above description is only exemplary of the present invention and should not be taken as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (11)
1. High-nickel-content ternary LiNi lifting method x Co y Mn 1-x-y O 2 The method for cycling stability and safety of the cathode material is characterized by comprising the following steps:
(1) according to the stoichiometric ratio of Ni to Co to Mn to x: y: 1-x-y respectively weighing nickel salt, cobalt salt and manganese salt with corresponding mass to prepare mixed metal salt solution as reaction raw material, NaOH solution as precipitator and NH 3 ·H 2 Taking O solution as a complexing agent, and adopting a parallel flow mode to mix the prepared mixed metal salt solution, NaOH solution and NH 3 ·H 2 Conveying the O solution to a reaction kettle with continuous stirring for coprecipitation reaction, and synthesizing Ni by controlling reaction temperature, ammonia-mixed metal salt feeding molar ratio, pH value, stirring speed and reaction time in the reaction process x Co y Mn 1-x-y (OH) 2 Precursor, the whole process of coprecipitation reaction is carried out under the protection of nitrogen atmosphere; ni to be synthesized subsequently x Co y Mn 1-x-y (OH) 2 The precursor and lithium salt are mixed evenly and are roasted in two steps in air or oxygen atmosphere to obtain the high-nickel ternary LiNi x Co y Mn 1-x-y O 2 A positive electrode material;
(2) the high nickel ternary LiNi prepared by the method is x Co y Mn 1-x-y O 2 Dispersing the positive electrode material in organic acid solvent or organic acid/water mixed solvent, stirring to make H in organic acid molecule + And high nickel ternary LiNi x Co y Mn 1-x-y O 2 Li in residual alkali on surface of positive electrode material + Carrying out ion exchange, and simultaneously enabling the organic acid solvent to be uniformly adhered to the surface of the material; then washing and centrifuging to remove redundant organic acid solvent on the surface of the material, and drying to obtain the high-nickel ternary LiNi after organic acid treatment x Co y Mn 1-x-y O 2 A positive electrode material; finally, the high nickel ternary LiNi after organic acid treatment x Co y Mn 1-x-y O 2 Placing the anode material in a tubular furnace, and roasting in an inert atmosphere to obtain carbon-coated high-nickel ternary LiNi x Co y Mn 1-x-y O 2 A positive electrode material; wherein 1 is>x≥0.5，0.5>y>0。
2. The method of claim 1, wherein: in the step (1), the total metal concentration of the nickel-cobalt-manganese mixed metal salt solution is 0.5-3 mol/L, the concentration of NaOH solution is 8-12 mol/L, and NH is added 3 ·H 2 The concentration of the O solution is 3-6 mol/L;
preferably, the nickel salt is NiSO 4 ·6H 2 O；
Preferably, the cobalt salt is CoSO 4 ·7H 2 O；
Preferably, the manganese salt is MnSO 4 ·H 2 O。
3. The method of claim 1, wherein: in the step (1), the coprecipitation reaction temperature is 45-70 ℃, and the feeding molar ratio of ammonia to mixed metal salt is 2.5: 4-3.5: 4, the pH value is 10-12, the stirring speed is 400-1500 rpm, and the reaction time is 20-50 h.
4. The method of claim 1, wherein: in the step (1), the whole process of the coprecipitation reaction is carried out under the protection of a nitrogen atmosphere.
5. The method of claim 1, wherein: in the step (1), the lithium salt is one or more of lithium oxide, lithium carbonate, lithium acetate, lithium nitrate, lithium oxalate and lithium hydroxide.
6. The method of claim 1, wherein: in the step (1), the Ni x Co y Mn 1-x-y (OH) 2 The stoichiometric ratio of the mixed precursor and lithium salt is 1: 1.02-1: 1.10.
7. the method of claim 1, wherein: in the step (1), in the two-step roasting, the roasting temperature of the first step is 350-550 ℃, the roasting time is 2-8 hours, the roasting temperature of the second step is 700-900 ℃, the roasting time is 12-24 hours, and the heating rate of the two-step roasting is 2-6 ℃/min.
8. The method of claim 1, wherein: in the step (2), the organic acid is one of lactic acid, oleic acid, linolenic acid and arachidonic acid.
9. The method of claim 1, wherein: in the step (2), the solution used for washing is deionized water, and the washing times are 2-5 times; the rotating speed of the centrifugation is 2000-8000 rpm, and the centrifugation times are 2-5; the drying temperature is 40-120 ℃, and the drying time is 6-48 h.
10. The method of claim 1, wherein: in the step (2), the inert atmosphere is one of nitrogen or argon.
11. The method of claim 1, wherein: in the step (2), the temperature in roasting is 300-600 ℃, the roasting time is 1-6 h, and the roasting temperature rise rate is 2-6 ℃/min.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208624A (en) * | 2011-04-29 | 2011-10-05 | 武汉大学 | Method for preparing carbon-coated LiFePO4 anode material by using low-temperature solid-phase method |
| CN108448069A (en) * | 2017-11-23 | 2018-08-24 | 山东省科学院能源研究所 | A kind of nickelic modification of lithium ion battery anode material method |
| CN109360983A (en) * | 2018-10-29 | 2019-02-19 | 合肥国轩高科动力能源有限公司 | A kind of nickelic tertiary cathode material of modification and its preparation method and application |
| CN109728279A (en) * | 2018-12-29 | 2019-05-07 | 桂林电器科学研究院有限公司 | The surface treatment method and product and battery of a kind of nickelic tertiary cathode material |
| CN109728277A (en) * | 2018-12-29 | 2019-05-07 | 桂林电器科学研究院有限公司 | The method and product and battery be surface-treated to nickelic tertiary cathode material |
| CN111916693A (en) * | 2020-06-28 | 2020-11-10 | 南昌大学 | Method for preparing organic matter coated high-nickel cathode material |
| CN112216830A (en) * | 2020-10-13 | 2021-01-12 | 厦门大学 | Layered positive electrode material improved by organic acid and preparation method |
-
2022
- 2022-05-18 CN CN202210542496.XA patent/CN114927682A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208624A (en) * | 2011-04-29 | 2011-10-05 | 武汉大学 | Method for preparing carbon-coated LiFePO4 anode material by using low-temperature solid-phase method |
| CN108448069A (en) * | 2017-11-23 | 2018-08-24 | 山东省科学院能源研究所 | A kind of nickelic modification of lithium ion battery anode material method |
| CN109360983A (en) * | 2018-10-29 | 2019-02-19 | 合肥国轩高科动力能源有限公司 | A kind of nickelic tertiary cathode material of modification and its preparation method and application |
| CN109728279A (en) * | 2018-12-29 | 2019-05-07 | 桂林电器科学研究院有限公司 | The surface treatment method and product and battery of a kind of nickelic tertiary cathode material |
| CN109728277A (en) * | 2018-12-29 | 2019-05-07 | 桂林电器科学研究院有限公司 | The method and product and battery be surface-treated to nickelic tertiary cathode material |
| CN111916693A (en) * | 2020-06-28 | 2020-11-10 | 南昌大学 | Method for preparing organic matter coated high-nickel cathode material |
| CN112216830A (en) * | 2020-10-13 | 2021-01-12 | 厦门大学 | Layered positive electrode material improved by organic acid and preparation method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116177625A (en) * | 2023-04-19 | 2023-05-30 | 新乡天力锂能股份有限公司 | Method for reducing residual alkali on surface of nickel-based positive electrode material and application thereof |
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