CN115286051B - Quaternary positive electrode precursor and preparation method and application thereof - Google Patents
Quaternary positive electrode precursor and preparation method and application thereof Download PDFInfo
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- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
- C01G45/1257—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing lithium, e.g. Li2MnO3, Li2[MxMn1-xO3
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention provides a quaternary positive electrode precursor, and a preparation method and application thereof. The surface of the quaternary positive electrode precursor is covered with MnOOH, and the chemical general formula of the quaternary positive electrode precursor is Ni x Co y Mn 1‑x‑y‑z M z (OH) 2 The @ MnOOH is more than or equal to 0.7 and less than or equal to 1.0, the y is more than or equal to 0.01 and less than or equal to 0.2,0.001, the z is more than or equal to 0.003, and M is transition metal. The invention forms a quaternary precursor structure through doping elements, and carries out surface coating on MnOOH, and after the anode material is prepared, the surface of the anode material can beObtaining Li 2 MnO 3 The material can inhibit the phase change from H2 to H3, protect the active positive electrode material from being influenced by electrolyte, provide certain reversible capacity for the material, improve the ionic conductivity of the material, reduce the electrochemical polarization of the material in the charge and discharge process, and finally improve the cycle performance and discharge capacity of the material, especially the cycle performance under high voltage.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a quaternary positive electrode precursor, a preparation method and application thereof.
Background
As an efficient and environment-friendly energy storage system, a lithium ion battery has a long cycle life and high safety, and is a key point which must be satisfied in the application of the lithium ion battery in the field. Generally, the quaternary positive electrode material prepared by the quaternary precursor has better cycle performance and safety performance than ternary materials. The conventional quaternary precursor is often obtained by uniformly doping another element in the preparation process of the ternary precursor, and the introduction of the fourth element can reduce the mixed discharge of lithium and nickel, so that the electrochemical performance of the lithium ion battery is improved. However, when these materials are subjected to long-term cycling at a high cut-off voltage, microcracks are formed at grain boundaries due to lattice expansion and phase transition, and thus Solid Electrolyte Interface (SEI) films are also formed in the bulk of the materials, consuming a large amount of active lithium ions, and eventually exhibiting rapid decay of the cycling capacity of the battery.
CN111874958A discloses a wet synthesis method of NCMA high nickel quaternary precursor. According to the method, NCMA quaternary precursor solid micro-crystal nucleus is synthesized in a first reaction kettle, and the quaternary precursor solid micro-crystal nucleus is promoted to continuously grow to a certain granularity in a second reaction kettle; the first reaction kettle adopts an upper-layer feeding mode to continuously produce the NCMA quaternary precursor solid micro-crystal nucleus, and the second reaction kettle adopts an upper-layer and lower-layer feeding mode to promote continuous growth of the NCMA quaternary precursor solid micro-crystal nucleus. In the washing process, the NCMA quaternary precursor is washed by mixed alkali solution of sodium carbonate and sodium hydroxide with a certain concentration, na can be washed to be less than 50ppm, and sulfur can be reduced to be less than 800 ppm.
The preparation method of the in-situ doped high-nickel cathode material of CN112174224A comprises the following steps: (1) Preparing a spherical NCM ternary precursor from soluble salts of nickel, cobalt and manganese, a doping agent A and ammonia water with a certain concentration according to a certain proportion; (2) Uniformly mixing the precursor and a lithium source, performing primary sintering at 800-950 ℃, and then performing jaw breaking, roller pair, crushing and sieving to obtain a monocrystal high-nickel material; (3) And (3) carrying out dry coating on the primary sintering material and a certain amount of coating agent B, then carrying out secondary sintering under the oxygen-enriched condition, wherein the sintering temperature is 550-750 ℃, and crushing and sieving to obtain the high-nickel single crystal NCM ternary positive electrode material.
The doping of elements is performed in the precursor preparation process in the above documents, and although the performance of the cathode material can be improved to a certain extent, when the cathode material is cycled for a long time under high cut-off voltage, microcracks caused at grain boundaries due to lattice expansion and phase change are easy to occur, so that the cycle performance of the battery is affected.
Therefore, how to effectively improve the cycle performance of the quaternary positive electrode precursor under high cut-off voltage is a technical problem to be solved.
Disclosure of Invention
The invention aims to provide a quaternary positive electrode precursor, and a preparation method and application thereof. The anode precursor provided by the invention forms a quaternary precursor structure through doping elements, and carries out surface coating on MnOOH, so that the anode precursor is preparedAfter the positive electrode material is prepared, li can be obtained on the surface of the positive electrode material 2 MnO 3 The material can inhibit the phase change from H2 to H3, protect the active positive electrode material from being influenced by electrolyte, provide certain reversible capacity for the material, improve the ionic conductivity of the material, reduce the electrochemical polarization of the material in the charge-discharge process, and finally improve the cycle performance and discharge capacity of the material, especially the cycle performance under high voltage.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a quaternary positive electrode precursor, the quaternary positive electrode precursor is coated with MnOOH, and the quaternary positive electrode precursor has a chemical formula of Ni x Co y Mn 1-x-y-z M z (OH) 2 And @ MnOOH, wherein x is more than or equal to 0.7 and less than or equal to 1.0, y is more than or equal to 0.01 and less than or equal to 0.2,0.001, z is more than or equal to 0.003, and M is a transition metal.
For example, x may be 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 0.98, etc., y may be 0.01, 0.03, 0.05, 0.08, 0.1, 0.13, 0.15, 0.18, 0.2, etc., and z may be 0.001, 0.0015, 0.002, 0.0025, 0.003, etc.
In the chemical formula of the invention, the @ is coated.
The anode precursor provided by the invention forms a quaternary precursor structure through doping elements, and is subjected to surface coating with MnOOH, so that after the anode precursor is prepared into an anode material, li can be obtained on the surface of the anode material 2 MnO 3 The phase change of the material from H2 to H3 can be inhibited, the active positive electrode material is protected from being influenced by electrolyte, certain reversible capacity can be provided for the material, the ionic conductivity of the material can be improved, the electrochemical polarization of the material in the charge and discharge process is reduced, and the improvement can finally improve the cycle performance and discharge capacity of the material.
That is, the crystal nucleus formed by doping metal and nickel cobalt manganese can effectively stabilize the structure of the material, thereby improving the stability of the quaternary material; meanwhile, the MnOOH coated on the surface of the material is calcined to form Li 2 MnO 3 Not only can provide certain reversible capacity for materials, but alsoThe ionic conductivity of the material can be improved, the electrochemical polarization of the material in the charge-discharge process can be reduced, the active positive electrode material can be protected from being influenced by electrolyte, the phase change of the material from H2 to H3 can be inhibited, and further, the material has better cycle performance in a high voltage (2.8-4.6V) range.
The positive electrode precursor provided by the invention has the advantages that if MnOOH coating is not carried out, the problem of rapid decay of reversible capacity of the battery can occur along with the increase of cycle times in a high voltage (2.8-4.6V) range, and if manganese hydroxide or manganese oxide coating is carried out, the effective improvement of the cycle performance of the battery under high voltage can not be realized.
Preferably, the molar amount of Mn in the MnOOH is 2-6%, e.g., 2%, 2.3%, 2.5%, 2.8%, 3%, 3.3%, 3.5%, 3.8%, 4%, 4.3%, 4.5%, 4.8%, 5%, 5.3%, 5.5%, 5.8%, or 6%, etc., of the total molar amount of metal in the quaternary positive electrode precursor.
In the invention, excessive molar quantity of MnOOH can lead to nickel-lithium rearrangement of the quaternary material core layer, thereby reducing the reversible capacity of the battery, while excessive molar quantity can influence the protection effect of the quaternary material core layer.
Preferably, the M comprises any one or a combination of at least two of Al, mg, zn, ti, zr or W.
In a second aspect, the present invention provides a method for preparing the quaternary positive electrode precursor according to the first aspect, the method comprising the steps of:
(1) The mixed salt solution of nickel, cobalt and manganese, the metal salt solution containing M, the precipitant solution and the first complexing agent solution are added into the base solution in parallel to carry out coprecipitation reaction, and after the average particle size of the product reaches the target particle size, the reaction is stopped;
(2) And (2) adding a manganese salt solution, an oxidant solution, an alkali solution and a second complexing agent solution into the solution after stopping the reaction in the step (1) in parallel flow, and continuing the reaction in a protective atmosphere to obtain the quaternary positive electrode precursor.
According to the preparation method provided by the invention, the four-element precursor is obtained by directly doping and coating in the precursor coprecipitation stage, compared with doping and coating after calcination, the preparation process of the anode material can be simplified, the energy consumption in material preparation can be reduced, meanwhile, in the later coating process, the atmosphere is strictly controlled to be a protective atmosphere, and a certain amount of oxidant is added in the precipitation coating process, so that the in-situ coating of MnOOH is finally realized.
In the preparation process, if the oxidant is not added in the step (2), the coating of MnOOH cannot be realized, and if the coating is not carried out in a protective atmosphere and is carried out in air or oxygen atmosphere, mn can be obtained 3 O 4 And MnO 2 The coating layer can not realize in-situ coating of MnOOH.
Preferably, the feeding speed of the mixed salt solution of nickel, cobalt and manganese in the step (1) is 8-200L/h, such as 8L/h, 10L/h, 30L/h, 50L/h, 80L/h, 100L/h, 130L/h, 150L/h, 180L/h or 200L/h, etc.
Preferably, the feeding rate of the M-containing metal salt solution of step (1) is 2 to 20L/h, for example 2L/h, 3L/h, 4L/h, 5L/h, 6L/h, 7L/h, 8L/h, 9L/h, 10L/h, 11L/h, 12L/h, 13L/h, 14L/h, 15L/h, 16L/h, 17L/h, 18L/h, 19L/h or 20L/h, etc.
Preferably, the feed rate of the precipitant solution of step (1) is 2 to 20L/h, e.g. 2L/h, 3L/h, 4L/h, 5L/h, 6L/h, 7L/h, 8L/h, 9L/h, 10L/h, 11L/h, 12L/h, 13L/h, 14L/h, 15L/h, 16L/h, 17L/h, 18L/h, 19L/h or 20L/h etc.
Preferably, the first complexing agent solution of step (1) is fed at a rate of 0.5 to 5L/h, for example 0.5L/h, 1L/h, 2L/h, 3L/h, 4L/h or 5L/h, etc.
Preferably, the concentration of the mixed salt solution of nickel, cobalt and manganese in the step (1) is 0.5-4 mol/L, for example 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L or 4mol/L, etc.
Preferably, the concentration of the M-containing metal salt solution in step (1) is 5 to 20mmol/L, for example 5mmol/L, 6mmol/L, 7mmol/L, 8mmol/L, 9mmol/L, 10mmol/L, 11mmol/L, 12mmol/L, 13mmol/L, 14mmol/L, 15mmol/L, 16mmol/L, 17mmol/L, 18mmol/L, 19mmol/L or 20mmol/L, etc.
Preferably, the concentration of the precipitant solution in step (1) is 2 to 15mol/L, for example 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L, 14mol/L or 15mol/L, etc.
Preferably, the concentration of the first complexing agent solution of step (1) is 4 to 12mol/L, e.g. 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L or 12mol/L, etc.
Preferably, the concentration of complexing agent in the base liquid of step (1) is 0 to 2mol/L, for example 0mol/L, 0.3mol/L, 0.5mol/L, 0.8mol/L, 1mol/L, 1.3mol/L, 1.5mol/L, 1.8mol/L or 2mol/L, etc.
Preferably, the complexing agent in the first complexing agent solution comprises any one or a combination of at least two of hydrazine hydrate, ammonia water or oxalic acid.
Preferably, the temperature of the coprecipitation reaction in step (1) is 40 to 80 ℃, for example 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or the like.
Preferably, the pH of the coprecipitation reaction of step (1) is 9.5 to 12.5, for example 9.5, 10, 10.5, 11, 11.5, 12 or 12.5, etc.
Preferably, the atmosphere of the coprecipitation reaction in step (1) is a protective atmosphere.
Preferably, the pH of the base liquid of step (1) is between 9.5 and 12.5, e.g. 9.5, 10, 10.5, 11, 11.5, 12 or 12.5, etc.
Preferably, the target particle size in step (1) is 3 to 15. Mu.m, for example 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm, etc.
In the invention, the target particle diameter is too small, so that the coating thickness is too low to play a role in protection, and if the target particle diameter is too large, the coating thickness is too high, so that the reversible capacity of the battery is reduced.
Preferably, the feeding rate of the manganese salt solution in step (2) is 8 to 200L/h, for example 8L/h, 10L/h, 30L/h, 50L/h, 80L/h, 100L/h, 130L/h, 150L/h, 180L/h or 200L/h, etc.
Preferably, the oxidant solution of step (2) is fed at a rate of 4 to 100L/h, for example 4L/h, 10L/h, 20L/h, 30L/h, 40L/h, 50L/h, 60L/h, 70L/h, 80L/h, 90L/h or 100L/h, etc.
Preferably, the alkali solution in step (2) is fed at a rate of 2 to 20L/h, for example 2L/h, 5L/h, 8Lh, 10L/h, 13L/h, 15L/h, 18L/h or 20L/h, etc.
Preferably, the second complexing agent solution of step (2) is fed at a rate of 0.5 to 5L/h, for example 0.5L/h, 1L/h, 2L/h, 3L/h, 4L/h or 5L/h, etc.
Preferably, the manganese salt in the manganese salt solution in step (2) comprises any one or a combination of at least two of chloride, sulfate, nitrate or acetate.
Preferably, the oxidizing agent in the oxidizing agent solution in step (2) comprises hydrogen peroxide.
Preferably, the complexing agent in the second complexing agent solution of step (2) comprises any one or a combination of at least two of hydrazine hydrate, ammonia water or oxalic acid.
Preferably, the molar ratio of manganese in the manganese salt solution to the oxidant in the oxidant solution in step (2) is (1.9-2.1): 1, e.g. 1.9:1, 1.95:1, 2:1, 2.05:1 or 2.1:1, etc.
In the present invention, too small a ratio of manganese in the manganese salt solution to the molar amount of the oxidizing agent in the oxidizing agent solution, i.e., too small manganese, results in further oxidation of Mn to Mn 3 O 4 And MnO 2 While too large a molar ratio, the coating layer forms a large amount of Mn (OH) 2 。
Preferably, the concentration of manganese ions in the manganese salt solution in step (2) is 0.5 to 4mol/L, for example 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L or 4mol/L, etc.
In the invention, the concentration of manganese ions in the manganese salt solution is too small, which can lead to yield reduction and cost increase, is unfavorable for large-scale production, and the coating effect is influenced by too high concentration.
Preferably, the concentration of the oxidant solution in step (2) is 0.5 to 4mol/L, for example 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L or 4mol/L, etc.
In the invention, the concentration of the oxidant solution is too small, which is unfavorable for industrial large-scale production, while the too high concentration can influence the oxidation of local manganese into Mn 3 O 4 And MnO 2 。
Preferably, the concentration of the alkaline solution in step (2) is 2 to 15mol/L, for example 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L, 14mol/L or 15mol/L, etc.
Preferably, the concentration of the second complexing agent solution of step (2) is 4 to 12mol/L, for example 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L or 12mol/L, etc.
Preferably, the temperature of the coprecipitation reaction in step (2) is 40 to 80 ℃, for example 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃.
Preferably, the pH of the coprecipitation reaction of step (2) is 9.5 to 12.5, for example 9.5, 10, 10.5, 11, 11.5, 12 or 12.5, etc.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) The mixed salt solution of nickel, cobalt and manganese, the metal salt solution containing M, the precipitant solution and the first complexing agent solution are added into the base solution in parallel, the pH value is kept to be 9.5-12.5 under the protective atmosphere, the coprecipitation reaction is carried out at the temperature of 40-80 ℃, and the reaction is stopped after the average grain diameter of the product reaches the target grain diameter of 3-15 mu M;
(2) Adding a manganese salt solution, an oxidant solution, an alkali solution and a second complexing agent solution into the solution after stopping the reaction in the step (1) in parallel, wherein the molar weight ratio of manganese in the manganese salt solution to oxidant in the oxidant solution is (1.9-2.1): 1, keeping the pH value at 9.5-12.5 in a protective atmosphere, and continuing the reaction at the temperature of 40-80 ℃ to obtain the quaternary positive electrode precursor;
wherein the feeding speed of the mixed salt solution of nickel, cobalt and manganese in the step (1) is 8-200L/h, the feeding speed of the metal salt solution containing M in the step (1) is 2-20L/h, the feeding speed of the precipitant solution in the step (1) is 2-20L/h, and the feeding speed of the first complexing agent solution in the step (1) is 0.5-5L/h; the feeding speed of the manganese salt solution in the step (2) is 8-200L/h, the feeding speed of the oxidant solution in the step (2) is 4-100L/h, the feeding speed of the alkali solution in the step (2) is 2-20L/h, and the feeding speed of the second complexing agent solution in the step (2) is 0.5-5L/h.
In a third aspect, the present invention provides a positive electrode material, which is obtained by mixing and sintering the quaternary positive electrode precursor according to the first aspect and a lithium source, wherein the surface of the positive electrode material is coated with Li 2 MnO 3 。
In the invention, the MnOOH coated on the surface of the precursor is sintered by mixing lithium sources to form Li 2 MnO 3 The active positive electrode material can be protected from electrolyte, can inhibit phase change from H2 to H3, can provide certain reversible capacity for the material, improves the ionic conductivity of the material, reduces electrochemical polarization of the material in the charge-discharge process, and can finally improve the cycle performance and discharge capacity of the positive electrode material.
The process of preparing the positive electrode material from the precursor is a conventional technical means, namely the precursor and a lithium source are directly mixed and sintered, the sintering can be primary sintering or secondary sintering, the adaptability adjustment can be carried out according to the actual situation, and the selection of the lithium source is a conventional technical means, such as lithium hydroxide or lithium carbonate.
In a fourth aspect, the present invention also provides a lithium ion battery comprising the positive electrode material according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) The anode precursor provided by the invention forms a quaternary precursor structure through doping elements, and is subjected to surface coating with MnOOH, so that after the anode precursor is prepared into an anode material, li can be obtained on the surface of the anode material 2 MnO 3 Can inhibit phase change of the material from H2 to H3, protect the active positive electrode material from electrolyte, and provide the materialThe ionic conductivity of the material can be improved by a certain reversible capacity, the electrochemical polarization of the material in the charge and discharge process is reduced, the improvement can finally improve the cycle performance and discharge capacity of the material, especially the cycle performance under high voltage, the button cell prepared by the precursor provided by the invention has the discharge capacity retention rate of 88.7% or more after the precursor is cycled for 300 circles under 0.1C in a discharge interval of 2.8-4.3V, and the discharge capacity retention rate of 84.7% or more after the precursor is cycled for 300 circles under 0.1C in a high-voltage discharge interval of 2.8-4.6V; further, the molar quantity of the manganese salt and the oxidant is regulated, the discharge capacity retention rate is above 90.1% after 300 circles of circulation are carried out at 0.1 ℃, and the discharge capacity retention rate is still above 88.3% after 300 circles of circulation are carried out at 0.1 ℃ in a high-voltage discharge interval of 2.8-4.6V.
(2) According to the preparation method provided by the invention, the four-element precursor is obtained by directly doping and coating in the precursor coprecipitation stage, compared with doping and coating after calcination, the preparation process of the anode material can be simplified, the energy consumption in material preparation can be reduced, meanwhile, in the later coating process, the atmosphere is strictly controlled to be a protective atmosphere, and the oxidizing agent is added in the precipitation coating process, so that the in-situ coating of MnOOH is finally realized.
Drawings
Fig. 1 is an SEM image of the quaternary positive electrode precursor provided in example 1.
Fig. 2 is an SEM image of a cut surface of the quaternary positive electrode precursor provided in example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a quaternary positive electrode precursor, the surface of which is coated with MnOOH, and the chemical formula of the quaternary positive electrode precursor is Ni 0.799 Co 0.1 Mn 0.1 Mg 0.001 (OH) 2 @MnOOH, wherein the coated metal Mn occupies the quaternary precursorThe molar proportion of total metals is 5%.
The preparation method of the precursor comprises the following steps:
(1) First stage reaction: mixing salt solution with total concentration of metal ion of 2mol/L (nickel cobalt manganese mol ratio of 8:1:1), 20mmol/L MgSO 4 The solution, 10mol/L sodium hydroxide solution and 8mol/L ammonia water are added into the base solution with pH value of 11.6 and ammonia concentration of 0.5mol/L in parallel flow; in the process of parallel flow addition, the feeding speed of the mixed salt solution of nickel, cobalt and manganese is 32L/h, mgSO 4 The feeding speed of the solution is 8L/h, the pH value of the reaction system is controlled to be between 11.5 and 11.7 by controlling the flow rates of the precipitant and the complexing agent solution, the concentration of ammonia water in the reaction process is controlled to be between 0.40 and 0.50mol/L, the coprecipitation reaction is carried out at the reaction temperature of 58 ℃ under the protection of nitrogen, the reaction is carried out for 60 hours, the average grain diameter reaches 8 mu m, and the reaction of the first stage is stopped;
(2) The second stage reaction: adding 1mol/L manganese sulfate solution containing metal ions, 1mol/L hydrogen peroxide (the molar ratio of manganese in manganese sulfate to hydrogen peroxide is 2.0:1), 10mol/L sodium hydroxide solution and 8mol/L ammonia water into the mixed solution after the first-stage reaction in parallel; in the parallel flow adding process, the feeding speed of the manganese sulfate solution is 32L/h, the feeding speed of the oxidant is 16L/h, the pH value of a reaction system is controlled to be 11.3-11.5, the concentration of a complexing agent is controlled to be 0.40-0.50 mol/L by controlling the flow of the precipitant and the complexing agent solution, the coprecipitation reaction is carried out at the reaction temperature of 58 ℃ under the protection of nitrogen, the reaction is carried out for 6h, the average particle size reaches 8.5 mu m, and the second-stage reaction is stopped.
(3) Post-treatment of the product: and after the reaction is finished, centrifugally washing a product of the coprecipitation reaction, and drying at 100 ℃ for 24 hours to obtain the quaternary positive electrode precursor.
Fig. 1 shows an SEM image of the quaternary positive electrode precursor provided in example 1, fig. 2 shows an SEM image of a cut surface of the quaternary positive electrode precursor provided in example 1, and as can be seen in conjunction with fig. 1 and fig. 2, the quaternary precursor prepared in this example has a good sphericity, a uniform size, fine primary particles on the surface, and the cut surface SEM image also shows that the quaternary precursor is tightly packed.
Example 2
The embodiment provides a quaternary positive electrode precursor, the surface of which is coated with MnOOH, and the chemical formula of the quaternary positive electrode precursor is Ni 0.897 Co 0.05 Mn 0.05 Zn 0.003 (OH) 2 The molar ratio of coated metal Mn to total metal in the quaternary precursor is 2 percent.
The preparation method of the precursor comprises the following steps:
(1) First stage reaction: mixing mixed salt solution with total concentration of metal ions of 0.5mol/L (nickel cobalt manganese mol ratio of 90:5:5) and ZnSO with concentration of 5mmol/L 4 The solution, 15mol/L sodium hydroxide solution and 12mol/L oxalic acid are added into the base solution with the pH value of 10.9 and the oxalic acid concentration of 0.35mol/L in parallel flow; in the parallel flow adding process, the feeding speed of the mixed salt solution of nickel, cobalt and manganese is 8L/h, znSO 4 The feeding speed of the solution is 2L/h, the pH value of the reaction system is controlled to be between 10.8 and 11.0, the oxalic acid concentration is controlled to be between 0.3 and 0.4mol/L by controlling the flow of the precipitant and complexing agent solution, the coprecipitation reaction is carried out at the reaction temperature of 80 ℃ under the protection of nitrogen, the reaction is carried out for 120 hours, the average grain diameter reaches 15 mu m, and the reaction of the first stage is stopped;
(2) The second stage reaction: adding manganese chloride solution with the concentration of metal ions of 0.5mol/L, hydrogen peroxide with the concentration of metal ions of 0.5mol/L (the mol ratio of manganese in manganese sulfate to hydrogen peroxide is 2.05:1), sodium hydroxide solution with the concentration of 15mol/L and oxalic acid with the concentration of 12mol/L into the mixed solution after the first-stage reaction, wherein the feeding speed of the manganese chloride solution is 8.2L/h, the feeding speed of the oxidant is 4L/h, controlling the pH value of a reaction system to be between 10.8 and 11.0 and the concentration of oxalic acid to be between 0.3 and 0.4mol/L by controlling the flow of a precipitator and a complexing agent solution, performing coprecipitation reaction at the reaction temperature of 80 ℃ under the protection of nitrogen, reacting for 2.4 hours, and stopping the second-stage reaction, wherein the average particle size reaches 15.2 mu m;
(3) Post-treatment of the product: and after the reaction is finished, centrifugally washing a product of the coprecipitation reaction, and drying at 80 ℃ for 24 hours to obtain the quaternary positive electrode precursor.
Example 3
The embodiment provides a quaternary positive electrode precursor, the surface of which is covered with MnOOH, and the chemical formula Ni of the quaternary positive electrode precursor 0.9185 Co 0.05 Mn 0.03 W 0.0015 (OH) 2 The molar ratio of coated metal Mn to total metal in the quaternary precursor is 6 percent.
The preparation method of the precursor comprises the following steps:
(1) First stage reaction: adding mixed salt solution with total concentration of metal ions of 4mol/L (molar ratio of nickel to cobalt to manganese of 92:5:3), ammonium tungstate solution with concentration of 20mmol/L, sodium hydroxide solution with concentration of 12mol/L and ammonia water with concentration of 10mol/L into base solution with pH value of 11.9 and ammonia concentration of 2.0mol/L in parallel flow; in the parallel flow adding process, the feeding speed of the mixed salt solution of nickel, cobalt and manganese is 200L/h, the feeding speed of the ammonium tungstate solution is 20L/h, the pH value of a reaction system is controlled to be 11.8-12.0, the concentration of a complexing agent is controlled to be 1.8-2.0 mol/L by controlling the flow of a precipitator and the complexing agent solution, the coprecipitation reaction is carried out at the reaction temperature of 40 ℃ under the protection of nitrogen, the reaction is carried out for 30h, the average grain diameter reaches 3 mu m, and the first-stage reaction is stopped;
(2) The second stage reaction: adding 4mol/L manganese sulfate solution containing metal ions, 4mol/L hydrogen peroxide (the molar ratio of manganese in manganese sulfate to hydrogen peroxide is 1.95:1), 12mol/L sodium hydroxide solution and 10mol/L ammonia water into the mixed solution after the first-stage reaction in parallel. In the parallel flow adding process, the feeding speed of the manganese sulfate solution is 195L/h, the feeding speed of the oxidant is 100L/h, the pH value of a reaction system is controlled to be 11.8-12.0, the concentration of a complexing agent is controlled to be 1.8-2.0 mol/L by controlling the flow of the precipitant and the complexing agent solution, the coprecipitation reaction is carried out at the reaction temperature of 40 ℃ under the protection of nitrogen, the reaction is carried out for 1.8h, the average particle size reaches 3.2 mu m, and the second-stage reaction is stopped;
(3) Post-treatment of the product: and after the reaction is finished, centrifugally washing a product of the coprecipitation reaction, and drying at 150 ℃ for 24 hours to obtain the quaternary positive electrode precursor.
Example 4
The difference between this example and example 1 is that the molar ratio of manganese in the manganese sulfate to hydrogen peroxide in step (2) of this example is 1.85:1.
The remaining preparation methods and parameters were consistent with example 1.
Example 5
The difference between this example and example 1 is that the molar ratio of manganese in the manganese sulfate to hydrogen peroxide in step (2) of this example is 2.15:1.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 1
The difference between this comparative example and example 1 is that this comparative example was not subjected to step (2).
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 2
The difference between this comparative example and example 1 is that the atmosphere in step (2) of this comparative example is an air atmosphere.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 3
The difference between this comparative example and example 1 is that hydrogen peroxide was not added in step (2) of this comparative example.
The remaining preparation methods and parameters were consistent with example 1.
The quaternary positive electrode precursors provided in examples 1-5 and comparative examples 1-3 were fully mixed with lithium hydroxide in a molar ratio of 1.00:1.08, sintered in a tube furnace under oxygen flow, pre-sintered at 480 ℃ for 5 hours, then calcined at 800 ℃ for 15 hours at high temperature, and ground and sieved to obtain a quaternary positive electrode material.
The obtained positive electrode material was prepared into a positive electrode sheet (80 wt% of positive electrode material, 10wt% of conductive carbon black, 10wt% of pvdf), and the positive electrode sheet and the metallic lithium sheet were assembled into a CR2032 button cell at 25C, and then the cycle performance test was performed at 0.1C in the ranges of 2.8 to 4.3V and 2.8 to 4.6V, respectively, and the test results are shown in table 1.
TABLE 1
As is clear from the data of examples 1 and 4 and 5, the molar ratio of manganese to the oxidizing agent in the manganese salt is too small, that is, the MnOOH is excessively oxidized, or the molar ratio is too large, and a part of divalent Mn is not oxidized, which is unfavorable for forming a good MnOOH coating layer on the surface, thereby resulting in a decrease in cycle performance of the battery.
From the data of example 1 and comparative example 1, it is apparent that the conventional 811 high nickel positive electrode material prepared in comparative example 1 has a discharge capacity retention rate of 81.4% after 300 cycles at 0.1C in a discharge interval of 2.8 to 4.3V, and a discharge capacity retention rate of only 68.4% after 300 cycles at 0.1C in a high voltage discharge interval of 2.8 to 4.6V. Therefore, the cycle performance of the lithium ion battery prepared by the quaternary coating doping precursor is superior to that of a conventional high-nickel ternary battery. In particular, in a high-voltage discharge region of 2.8-4.6V, the cycle performance of the lithium ion battery prepared by the quaternary coating doping precursor is improved more remarkably.
From the data results of example 1 and comparative example 2, it is apparent that the MnOOH coating layer cannot be obtained without performing the coating under a protective atmosphere, and thus the improvement of the reversible capacity and cycle performance of the battery cannot be achieved.
From the data of example 1 and comparative example 3, it is apparent that the oxidation agent was not added during the coating, and the MnOOH coating was not obtained, thereby affecting the reversible capacity and cycle performance of the material.
The anode precursor provided by the invention forms a quaternary precursor structure through doping elements, and is subjected to surface coating with MnOOH, so that after the anode precursor is prepared into an anode material, li can be obtained on the surface of the anode material 2 MnO 3 The phase change of the material from H2 to H3 can be inhibited, the active positive electrode material is protected from being influenced by electrolyte, a certain reversible capacity can be provided for the material, the ion conductivity of the material can be improved, and the electrochemical polarization of the material in the charge and discharge process can be reducedThe improvement can finally improve the cycle performance and discharge capacity of the material, especially the cycle performance under high voltage, the discharge capacity retention rate of the button cell prepared by the precursor provided by the invention is above 88.7% after the button cell is cycled for 300 circles under 0.1C in a discharge interval of 2.8-4.3V, and the discharge capacity retention rate of the button cell is still above 84.7% after the button cell is cycled for 300 circles under 0.1C in a high-voltage discharge interval of 2.8-4.6V; further regulating the molar quantity of the manganese salt and the oxidant, wherein the discharge capacity retention rate is above 90.1% after 300 circles of circulation are performed at 0.1 ℃, and the discharge capacity retention rate is still above 88.3% after 300 circles of circulation are performed at 0.1 ℃ in a high-voltage discharge interval of 2.8-4.6V; doping and coating are directly carried out at the coprecipitation stage of the precursor to obtain a quaternary precursor, compared with doping and coating after calcination, the preparation process of the anode material can be simplified, the energy consumption in the preparation of the material can be reduced, meanwhile, in the later coating process, the atmosphere is strictly controlled to be a protective atmosphere, and an oxidant is added in the precipitation coating process, so that the in-situ coating of MnOOH is finally realized.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (36)
1. A quaternary positive electrode precursor is characterized in that MnOOH is coated on the surface of the quaternary positive electrode precursor, and the chemical formula of the quaternary positive electrode precursor is Ni x Co y Mn 1-x-y-z M z (OH) 2 And @ MnOOH, wherein x is more than or equal to 0.7 and less than or equal to 1.0, y is more than or equal to 0.01 and less than or equal to 0.2,0.001, z is more than or equal to 0.003, and M is a transition metal.
2. The quaternary positive electrode precursor according to claim 1, wherein the molar amount of Mn in the MnOOH is 2-6% of the total molar amount of metal in the quaternary positive electrode precursor.
3. The quaternary positive electrode precursor according to claim 1, wherein M comprises any one or a combination of at least two of Al, mg, zn, ti, zr or W.
4. A method of preparing the quaternary positive electrode precursor according to any one of claims 1-3, comprising the steps of:
(1) The mixed salt solution of nickel, cobalt and manganese, the metal salt solution containing M, the precipitant solution and the first complexing agent solution are added into the base solution in parallel to carry out coprecipitation reaction, and after the average particle size of the product reaches the target particle size, the reaction is stopped;
(2) And (2) adding a manganese salt solution, an oxidant solution, an alkali solution and a second complexing agent solution into the solution after stopping the reaction in the step (1) in parallel flow, and continuing the reaction in a protective atmosphere to obtain the quaternary positive electrode precursor.
5. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the feeding speed of the mixed salt solution of nickel, cobalt and manganese in the step (1) is 8-200L/h.
6. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the feeding rate of the metal salt solution containing M in the step (1) is 2-20L/h.
7. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the feeding rate of the precipitant solution in step (1) is 2-20 l/h.
8. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the feeding speed of the first complexing agent solution in the step (1) is 0.5-5 l/h.
9. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the concentration of the nickel-cobalt-manganese mixed salt solution in the step (1) is 0.5-4 mol/L.
10. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the concentration of the metal salt solution containing M in the step (1) is 5-20 mmol/L.
11. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the concentration of the precipitant solution in the step (1) is 2-15 mol/L.
12. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the concentration of the first complexing agent solution in the step (1) is 4-12 mol/L.
13. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the concentration of the complexing agent in the base solution in the step (1) is 0-2 mol/L.
14. The method of claim 4, wherein the complexing agent in the first complexing agent solution comprises any one or a combination of at least two of hydrazine hydrate, ammonia water, and oxalic acid.
15. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the temperature of the coprecipitation reaction in step (1) is 40-80 ℃.
16. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the pH value of the coprecipitation reaction in step (1) is 9.5 to 12.5.
17. The method of claim 4, wherein the atmosphere of the coprecipitation reaction in step (1) is a protective atmosphere.
18. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the pH value of the base solution in the step (1) is 9.5 to 12.5.
19. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the target particle diameter in the step (1) is 3-15 μm.
20. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the feeding speed of the manganese salt solution in the step (2) is 8-200L/h.
21. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the feeding rate of the oxidant solution in the step (2) is 4-100 l/h.
22. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the feeding speed of the alkaline solution in the step (2) is 2-20L/h.
23. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the feeding rate of the second complexing agent solution in the step (2) is 0.5-5 l/h.
24. The method of claim 4, wherein the manganese salt in the manganese salt solution in step (2) comprises any one or a combination of at least two of chloride, sulfate, nitrate, and acetate.
25. The method of claim 4, wherein the oxidant in the oxidant solution in step (2) comprises hydrogen peroxide.
26. The method of claim 4, wherein the complexing agent in the second complexing agent solution of step (2) comprises any one or a combination of at least two of hydrazine hydrate, ammonia water, and oxalic acid.
27. The method of claim 4, wherein the molar ratio of manganese in the manganese salt solution to the oxidant in the oxidant solution in step (2) is 1.9-2.1.
28. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the concentration of manganese ions in the manganese salt solution in the step (2) is 0.5-4 mol/L.
29. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the concentration of the oxidant solution in the step (2) is 0.5-4 mol/L.
30. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the concentration of the alkaline solution in the step (2) is 2-15 mol/L.
31. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the concentration of the second complexing agent solution in the step (2) is 4-12 mol/L.
32. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the temperature of the coprecipitation reaction in step (2) is 40-80 ℃.
33. The method for preparing a quaternary positive electrode precursor according to claim 4, wherein the pH value of the coprecipitation reaction in step (2) is 9.5 to 12.5.
34. The method of preparing a quaternary positive electrode precursor according to claim 4, comprising the steps of:
(1) The mixed salt solution of nickel, cobalt and manganese, the metal salt solution containing M, the precipitant solution and the first complexing agent solution are added into the base solution in parallel, the pH value is kept to be 9.5-12.5 under the protective atmosphere, the coprecipitation reaction is carried out at the temperature of 40-80 ℃, and the reaction is stopped after the average grain diameter of the product reaches the target grain diameter of 3-15 mu M;
(2) Adding a manganese salt solution, an oxidant solution, an alkali solution and a second complexing agent solution into the solution after stopping the reaction in the step (1) in parallel, wherein the molar weight ratio of manganese in the manganese salt solution to oxidant in the oxidant solution is (1.9-2.1): 1, keeping the pH value at 9.5-12.5 in a protective atmosphere, and continuing the reaction at the temperature of 40-80 ℃ to obtain the quaternary positive electrode precursor;
wherein the feeding speed of the mixed salt solution of nickel, cobalt and manganese in the step (1) is 8-200L/h, the feeding speed of the metal salt solution containing M in the step (1) is 2-20L/h, the feeding speed of the precipitant solution in the step (1) is 2-20L/h, and the feeding speed of the first complexing agent solution in the step (1) is 0.5-5L/h; the feeding speed of the manganese salt solution in the step (2) is 8-200L/h, the feeding speed of the oxidant solution in the step (2) is 4-100L/h, the feeding speed of the alkali solution in the step (2) is 2-20L/h, and the feeding speed of the second complexing agent solution in the step (2) is 0.5-5L/h.
35. A positive electrode material obtained by mixing and sintering the quaternary positive electrode precursor according to any one of claims 1 to 3 with a lithium source, wherein the surface of the positive electrode material is coated with Li 2 MnO 3 。
36. A lithium ion battery comprising the positive electrode material of claim 35.
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