WO2021129108A1 - 空心结构碳酸盐二元前驱体及其制备方法和应用 - Google Patents

空心结构碳酸盐二元前驱体及其制备方法和应用 Download PDF

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WO2021129108A1
WO2021129108A1 PCT/CN2020/123616 CN2020123616W WO2021129108A1 WO 2021129108 A1 WO2021129108 A1 WO 2021129108A1 CN 2020123616 W CN2020123616 W CN 2020123616W WO 2021129108 A1 WO2021129108 A1 WO 2021129108A1
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precursor
salt
mol
mixed metal
metal salt
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French (fr)
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任海朋
万江涛
车金柱
张勇杰
张宁
陈婷婷
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蜂巢能源科技有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L50/00—Electric propulsion with power supplied within the vehicle
    • B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
    • B60L50/60—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by batteries
    • B60L50/64—Constructional details of batteries specially adapted for electric vehicles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present disclosure relates to the field of lithium batteries, for example, to a hollow-structure carbonate binary precursor and a preparation method and application thereof.
  • LiCoO 2 LiCoO 2
  • LiNiO 2 LiMnO 2
  • spinel LiMn 2 O 4 LiCoO 2
  • LiCoO 2 has a high specific capacity, a high and stable discharge platform and good cycle performance, but cobalt resources are scarce, cobalt is expensive, and toxic, which causes great environmental pollution.
  • LiNiO 2 has the same structure of NaFeO 2 as LiCoO 2 and has the characteristics of high specific capacity, the synthesis conditions of LiNiO 2 are harsh, the thermal stability is poor, and it is prone to decomposition at higher temperatures. The product is easy to absorb water, and it is not easy to carry out a large amount of commercial production.
  • Spinel LiMn 2 O 4 is resistant to overcharge and has good safety performance, but poor cycle performance, high temperature (above 55°C) capacity decays quickly, and relatively low theoretical specific capacity (148mAh/g), making it difficult to prepare pure single-phase products , And the spinel structure is unstable during charging and discharging.
  • LiMnO 2 is a thermodynamically unstable system, and although the undoped m-LiMnO 2 can obtain a first charge specific capacity as high as 270mAh/g, the specific capacity decays very severely during the first charge and discharge, and almost only half of the capacity can be maintained. . This is because the structure of m-LiMnO 2 begins to transform into a spinel structure in the first cycle, and almost completely transforms into a spinel phase after a few cycles.
  • ternary materials have developed rapidly due to the integration of all the advantages of these three materials, and low-cobalt and cobalt-free cathode materials are more likely to become an important development direction in the future, so high-quality high-nickel low-cobalt three
  • the development of meta precursors and cathode materials has become a hot spot.
  • many manufacturers generally use hydroxide precursors as raw materials and lithium salts to mix and sinter them into ternary cathode materials, while carbonate ternary precursors and their cathode materials have relatively little or no research.
  • carbon has been reported.
  • a large part of the salt ternary precursor materials have some problems, such as uneven particle size distribution, poor sphericity, and inability to continuous production.
  • the present disclosure provides a hollow-structure carbonate binary precursor and a preparation method and application thereof.
  • a hollow-structure carbonate binary precursor is provided, the chemical formula of the precursor is Ni x Mn (1-x) CO 3 , wherein x is 0.55 to 0.92, such as 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9 or 0.92, etc.
  • the hollow-structure carbonate binary precursor has the advantages of controllable particle size, uniform particle size distribution, high sphericity, excellent electrochemical performance and energy density.
  • the ammonia system can be produced stably, especially in the non-ammonia system, no ammonia-containing wastewater is produced, which is environmentally friendly.
  • the hollow structure carbonate binary precursor does not contain metal cobalt, which is better than the existing ternary nickel, cobalt, and manganese The precursor not only reduces the cost of raw materials, but also does not cause environmental pollution.
  • the positive electrode material prepared by using the precursor has higher specific capacity, excellent cycle performance and electrochemical discharge performance.
  • the nickel content in the precursor is too high, the mixed lithium and nickel in the obtained positive electrode material will be serious, resulting in poor cycle performance of the lithium battery loaded. If the nickel content in the precursor is too low, the precursor is prepared The lithium battery capacity of the positive electrode material will become lower.
  • the precursor layer has a thickness of 2 to 3 ⁇ m, such as 2.0 ⁇ m, 2.1 ⁇ m, 2.2 ⁇ m, 2.3 ⁇ m, 2.4 ⁇ m, 2.5 ⁇ m, 2.6 ⁇ m, 2.7 ⁇ m, 2.8 ⁇ m, 2.9 ⁇ m, or 3.0 ⁇ m Wait.
  • the thickness of the precursor layer is 2 to 3 ⁇ m. If the thickness of the precursor layer is too high, the electrolyte penetration in the lithium battery loaded with the positive electrode material prepared by the precursor will deteriorate, and the lithium ion The transmission distance becomes longer, resulting in poor battery performance. If the thickness of the precursor layer is too low, the shell layer will be destroyed during the lithium ion transmission process in the lithium battery loaded with the cathode material prepared by the precursor, and the battery cycle Performance will be greatly reduced.
  • the precursor particle size is 8-15 ⁇ m, for example, 8 ⁇ m, 8.5 ⁇ m, 9 ⁇ m, 9.5 ⁇ m, 10 ⁇ m, 10.5 ⁇ m, 11 ⁇ m, 11.5 ⁇ m, 12 ⁇ m, 12.5 ⁇ m, 13 ⁇ m, 13.5 ⁇ m, 14 ⁇ m, 14.5 ⁇ m or 15 ⁇ m etc.
  • the particle size described in an embodiment of the present disclosure is an average particle size.
  • a method for preparing the precursor including:
  • Pre-precipitating agent is added to the reaction kettle, and then with stirring, a part of the mixed metal salt, the precipitating agent and strong acid are added to the reaction kettle for co-precipitation reaction, so as to obtain preformed particles;
  • a precipitating agent is first added to the reactor, and then the mixed metal salt containing soluble nickel salt and soluble manganese salt, the precipitating agent and a strong acid are added to the reactor for co-precipitation reaction to obtain small particles
  • the strong acid in the prefabricated particles as the seed crystal continuously reacts with the carbonate precipitate formed in the seed crystal to obtain a hollow structure
  • the particles are finally washed, dehydrated, and dried and sieved to remove iron.
  • the above-mentioned binary salt with hollow spherical structure, controllable particle size, uniform particle size distribution, high sphericity, excellent electrochemical performance and energy density can be prepared.
  • the precursor which can be produced stably in both the ammonia system and the ammonia-free system, especially in the ammonia-free system, no ammonia-containing wastewater is produced, which is environmentally friendly, and the hollow structure carbonate binary precursor does not contain metal cobalt Compared with the existing ternary nickel-cobalt-manganese precursor, it not only reduces the raw material cost, but also does not cause environmental pollution.
  • the positive electrode material prepared by the precursor obtained by this method has higher specific capacity and excellent cycle performance and Electrochemical discharge performance.
  • metal cobalt is not added in the process of preparing the precursor. Compared with the existing ternary nickel-cobalt-manganese precursor, it not only reduces the raw material cost, but also does not cause environmental pollution. The precursor prepared by the application still has excellent electrochemical performance and energy density.
  • step (2) provided by an embodiment of the present disclosure, a precipitating agent is added to the reactor in advance, and then a part of the mixed metal salt, the precipitating agent, and a strong acid are simultaneously added to the reactor for co-precipitation reaction with stirring to obtain a precipitating reaction. Create particles.
  • the precipitant is added to the reaction kettle in advance, and then the mixed metal salt, precipitant and strong acid are added to ensure that the precipitant preferentially reacts with the mixed metal salt to obtain precipitation particles coated with strong acid, that is, prefabricated particles coated with strong acid are obtained.
  • the strong acid in the prefabricated particles as the seed crystals continuously react with the carbonate precipitate formed in the seed crystals to obtain hollow structured particles.
  • step (3) with stirring, the mixed metal salt and precipitating agent are added to the above-mentioned reaction kettle for obtaining preformed particles, so that the mixed metal salt and precipitating agent are on the surface of the preformed particles obtained above.
  • Co-precipitation reaction occurs. Due to the addition of strong acid in the pre-granulation process, the obtained pre-formed particles contain strong acid. In the process of co-precipitation reaction with small-diameter pre-formed particles as seeds, the pre-formed particles are used as seeds.
  • the medium-strong acid continuously reacts with the carbonate precipitate formed in the seed crystal to obtain the reacted liquid containing hollow structure particles.
  • step (4) provided by an embodiment of the present disclosure, along with stirring, the reacted material obtained in step (3) overflows to the aging tank and mixed with detergent to obtain a washed material.
  • the detergent used in this process is a detergent commonly used in the art, for example, sodium hydroxide solution, and it should be noted that those skilled in the art can choose the stirring speed and the amount of detergent added according to actual needs, as long as It suffices that part of the sodium and sulfur in the material after the reaction can be removed.
  • step (5) the once-washed material obtained in step (4) is dehydrated once to obtain the once-dehydrated material.
  • the first-time dehydration can be dehydrated by a centrifuge, and the obtained once-dehydrated material contains water The rate is not higher than 10wt%.
  • step (6) the primary dehydrated material obtained in step (5) is subjected to secondary washing and then dehydrated, so as to obtain the secondary dehydrated material.
  • Use pure water to wash the material after the primary dehydration for a second time to further remove impurities such as sodium and sulfur in the material after the primary dehydration and those skilled in the art can choose the amount of pure water, stirring speed and time according to actual needs, as long as The washing can be achieved until the sodium and sulfur content is qualified, and the dehydration process also adopts centrifuge dehydration, and the water content of the obtained secondary dehydration material is not higher than 10wt%.
  • the soluble nickel salt and the soluble manganese salt are (0.55-0.92): (0.08-0.45), such as 0.55:0.45, according to the molar ratio of nickel to manganese. 0.6:0.4, 0.7:0.3, 0.8:0.2, 0.9:0.1 or 0.92:0.08, etc.
  • the concentration of the soluble nickel salt and the soluble manganese salt are independently 1 to 2 mol/L, such as 1.0 mol/L, 1.1 mol/L, and 1.1 mol/L. mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L, 1.9mol/L or 2.0mol/L, etc.
  • the soluble nickel salt is at least one selected from nickel chloride and nickel sulfate.
  • the soluble manganese salt is at least one selected from manganese chloride and manganese sulfate.
  • step (2) based on 1L of the reactor, the content of the precipitating agent is pre-added 2-10g, for example, 2g, 3g, 4g, 5g, 6g, 7g, 8g, 9g or 10g Wait.
  • the precipitant added in advance is too high, the crystal nuclei produced will agglomerate, resulting in poorer sphericity of the precursor obtained later, and if the content of precipitant added in advance is too low, the resulting crystal nuclei will agglomerate. If the particle size of the crystal nucleus is too large, the amount of nucleation will decrease. At the same time, the hollow particle size of the precursor prepared in the later stage will also become larger and the wall thickness will become thinner, which will affect the battery performance of the positive electrode material prepared with the precursor. Bad effect.
  • the rotation speed of the stirring is 200-500 rpm, such as 200 rpm, 250 rpm, 300 rpm, 350 rpm, 400 rpm, 450 rpm, or 500 rpm.
  • step (2) the mixed metal, the precipitant and the strong acid are added to the reaction kettle in a molar ratio of 1: (2.5-5): (0.1-1) , Such as 1:2.5:0.1, 1:3:0.2, 1:3.5:0.5, 1:4:0.7, or 1:5:1, etc.
  • the molar ratio of the mixed metal, the precipitant, and the strong acid is 1: (2.5-5): (0.1-1). If the molar ratio of the three is too high, it will cause precursors Poor sphericity, resulting in low tap density, and if the molar ratio of the three is too high, the particle size of the hollow structure precursor obtained in the later reaction process will become larger, and the shell layer will become thinner. The battery cycle performance of the positive electrode material has such a bad influence.
  • the strong acid is hydrochloric acid, sulfuric acid or nitric acid.
  • the concentration of the strong acid is 0.1-1 mol/L, for example, 0.1 mol/L, 0.2 mol/L, 0.3 mol/L, 0.4 mol/L, 0.5 mol/L , 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1mol/L, etc.
  • the concentration of the strong acid is 0.1-1 mol/L. If the concentration of the strong acid is too high, the precursor shell will be destroyed, and if the concentration of the strong acid is too low, the inner hollow will be carved during the later reaction process. The eclipse is incomplete and cannot achieve a completely hollow structure.
  • the precipitating agent is at least one selected from sodium carbonate, ammonium carbonate, ammonium bicarbonate, or ammonia.
  • the concentration of the sodium carbonate is 1 to 2 mol/L, such as 1.0 mol/L, 1.1 mol/L, 1.2 mol/L, 1.3 mol/L, 1.4 mol/L, 1.5 mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L, 1.9mol/L or 2.0mol/L etc.
  • the concentration of the ammonium carbonate is 2-6 mol/L, such as 2.0 mol/L, 2.5 mol/L, 3.0 mol/L, 3.5 mol/L, 4.0 mol/L, 4.5 mol/L, 5.0mol/L, 5.5mol/L or 6.0mol/L etc.
  • the concentration of the ammonium bicarbonate is 1-7 mol/L, for example, 1 mol/L, 2 mol/L, 3 mol/L, 4 mol/L, 5 mol/L, 6 mol/L or 7 mol/L.
  • the concentration of the ammonia water is 0.2 to 1.5 mol/L, such as 0.2 mol/L, 0.3 mol/L, 0.4 mol/L, 0.5 mol/L, 0.6 mol/L, 0.7 mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L or 1.5mol/L, etc.
  • the temperature of the co-precipitation reaction is 30 to 80°C, for example, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C , 70°C, 75°C or 80, etc.; time is 0.1-5h, such as 0.1h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h.
  • the particle size of the prefabricated particles is 0.5-3 ⁇ m, such as 0.5 ⁇ m, 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 2.5 ⁇ m, or 3 ⁇ m.
  • the particle size of the prefabricated particles is 0.5-3 ⁇ m. If the particle size of the obtained prefabricated particles is too low, the precipitation growth in the later reaction process will be too slow, the reaction time will be lengthened, and the final hollow range of the precursor will be reduced. However, if the obtained prefabricated particle size is too high, the hollow area during the later preparation of the precursor will expand, and the thickness of the obtained precursor shell will become smaller.
  • step (3) the molar ratio of the preformed particles, the mixed metal salt and the precipitating agent is (2 ⁇ 3): (1.01 ⁇ 1.5): (2.02 ⁇ 3.02) , Such as 2:1.01:2.02, 2.3:1.1:2.1, 2.5:1.3:2.5, 2.7:1.3:2.7 or 3:1.5:3.02, etc.
  • the stirring speed is 700-1000 rpm, such as 700 rpm, 750 rpm, 800 rpm, 850 rpm, 900 rpm, 950 rpm or 1000 rpm, etc.; the temperature is 50-70° C., such as 50° C., 55° C.
  • the pH of the post-liquid is 8 to 9.5, such as 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4 or 9.5;
  • the solid of the post-reaction liquid The content is 10-30% by weight, such as 10% by weight, 12% by weight, 14% by weight, 16% by weight, 18% by weight, 20% by weight, 22% by weight, 24% by weight, 26% by weight, 28% by weight, or 30% by weight.
  • the pH is 8 to 9.5. If the pH of the liquid after the reaction is too high, the precipitates cannot agglomerate into spheres, but are loose aggregates of small particles. If the pH of the liquid after the reaction is too low, The agglomeration of the precipitates is severe, and the precursors produced have different morphologies.
  • a method for preparing a positive electrode material which includes:
  • the precursor material is the binary precursor described in an embodiment or a binary precursor obtained by the method described in an embodiment.
  • An embodiment of the present disclosure provides a method for preparing a cathode material by pre-sintering the above-mentioned carbonate binary precursor with a spherical structure, uniform particle size distribution, and excellent electrochemical performance, and then performing primary sintering and secondary sintering.
  • pre-sintering causes the carbonate binary precursor to decompose
  • the first sintering process ensures that the carbonate binary precursor is completely decomposed to obtain oxides
  • the second sintering allows lithium ions to migrate into the interior of the precursor to prepare A positive electrode material with high specific capacity, excellent cycle performance and electrochemical discharge performance.
  • the pre-sintering temperature is 400-500°C, such as 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, 490°C, or 500°C, etc.; time is 2-6h, such as 2h, 2.5h, 3.0h, 3.5h, 4.0h, 4.5h, 5.0h, 5.5h or 6.0h, etc.
  • the molar ratio of the pre-calcined material to the lithium salt is 1:(1.02 ⁇ 1.08), for example, 1:1.02, 1:1.03, 1:1.04, 1 :1.05, 1:1.06, 1:1.07 or 1:1.08, etc.
  • the temperature of the primary sintering is 700-850°C, and the time is 8-20h, such as 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h etc.
  • the temperature of the secondary sintering is 580-650°C, such as 580°C, 590°C, 600°C, 610°C, 620°C, 630°C, 640°C, or 650°C Etc.; time is 8-12h, such as 8.0h, 8.5h, 9.0h, 9.5h, 10.0h, 10.5h, 11.0h, 11.5h or 12.0h.
  • the present disclosure provides a positive electrode material in one embodiment, and the positive electrode material is prepared by the method described in one embodiment.
  • the positive electrode material provided by an embodiment of the present disclosure has a relatively high specific capacity and excellent cycle performance and electrochemical discharge performance.
  • An embodiment of the present disclosure provides a lithium battery having the cathode material described in an embodiment.
  • the lithium battery provided by an embodiment of the present disclosure has high specific energy and long cycle life.
  • the present disclosure provides an automobile, and the automobile has the lithium battery described in an embodiment.
  • the car provided by an embodiment of the present disclosure is loaded with the above-mentioned lithium battery with high specific energy and long cycle life, and has excellent endurance.
  • Fig. 1 is a schematic flow chart of a method for preparing a hollow-structured carbonate binary precursor according to an embodiment of the present disclosure
  • FIG. 2 is a schematic flow chart of a method for preparing a cathode material according to an embodiment of the present disclosure
  • Figure 3 is a scanning electron micrograph of a hollow-structure carbonate binary precursor prepared in an embodiment of the present disclosure
  • FIG. 4 is a scanning electron micrograph of a cross-section of a hollow-structure carbonate binary precursor prepared in an embodiment of the present disclosure.
  • the present disclosure provides a hollow-structure carbonate binary precursor with a chemical formula of Ni x Mn (1-x) CO 3 , where x is 0.55 to 0.92.
  • the hollow structure carbonate binary precursor has the advantages of controllable particle size, uniform particle size distribution, high sphericity, excellent electrochemical performance and energy density. It can be stably produced in both ammonia and non-ammonia systems, especially in Under the ammonia-free system, no ammonia-containing wastewater is produced, which is environmentally friendly.
  • the hollow-structure carbonate binary precursor does not contain metal cobalt. Compared with the existing ternary nickel-cobalt-manganese precursor, it not only reduces the raw material cost, but also does not Environmental pollution will occur.
  • the positive electrode material prepared by using the precursor has higher specific capacity, excellent cycle performance and electrochemical discharge performance. If the nickel content in the precursor is too high, the mixed lithium and nickel in the obtained positive electrode material will be serious, resulting in poor cycle performance of the lithium battery loaded. If the nickel content in the precursor is too low, the precursor is prepared The lithium battery capacity of the positive electrode material will become lower.
  • the thickness of the above-mentioned precursor layer is 2 to 3 ⁇ m. If the thickness of the precursor layer is too high, the electrolyte penetration in the lithium battery loaded with the positive electrode material prepared by the precursor will become worse, and the lithium ion transmission distance will become longer, resulting in the deterioration of battery performance.
  • the particle size of the precursor is 8-15 ⁇ m.
  • the present disclosure provides a method for preparing the above-mentioned hollow structure carbonate binary precursor. As shown in Figure 1, the method specifically includes the following steps:
  • S100 Mixing soluble nickel salt and soluble manganese salt to obtain mixed metal salt.
  • the soluble nickel salt is at least one selected from nickel chloride and nickel sulfate; the soluble manganese salt is at least one selected from manganese chloride and manganese sulfate.
  • the concentration of soluble nickel salt and soluble manganese salt is independently 1 ⁇ 2mol/L, and the molar ratio of soluble nickel salt and soluble manganese salt is (0.55 ⁇ 0.92): (0.08 ⁇ 0.45) according to the molar ratio of nickel to manganese. );
  • the precipitating agent is at least one selected from sodium carbonate, ammonium carbonate, ammonium bicarbonate or ammonia, the concentration of sodium carbonate is 1-2 mol/L, the concentration of ammonium carbonate is 2-6 mol/L, and the concentration of ammonium bicarbonate is 1 ⁇ 7mol/L, the concentration of ammonia water is 0.2 ⁇ 1.5mol/L.
  • the strong acid is hydrochloric acid, sulfuric acid or nitric acid.
  • the concentration of the strong acid is 0.1 ⁇ 1mol/L.
  • the speed of the stirring process is 200 ⁇ 500rpm.
  • the molar ratio of the mixed metal, precipitation agent and strong acid is 1:(2.5 ⁇ 5):(0.1 ⁇ 1 ) Put it into the reactor.
  • the temperature of co-precipitation reaction is 30 ⁇ 80°C, and the time is 0.1 ⁇ 5h.
  • the obtained prefabricated particles have a particle size of 0.5-3 ⁇ m;
  • step S300 With stirring, add the mixed metal salt and the precipitating agent to the reaction kettle where the prefabricated particles are obtained in step S200, so that the mixed metal salt and the precipitating agent undergo a co-precipitation reaction on the surface of the prefabricated particles obtained above, and the prefabricated particles are mixed.
  • the pH of the liquid after the reaction is controlled to be 8 to 9.5, the co-precipitation reaction time is 10 to 20 hours, and the solid content in the obtained liquid after the reaction is 10 to 30 wt%, for example, 10 wt%, 11 wt%...29 wt%, 30 wt%.
  • the precipitant and the mixed metal salt are the same as step S200;
  • step S400 Accompanied by stirring, the reacted material obtained in step S300 overflows to the aging tank and mixed with detergent to obtain the washed material, and the stirring time is 0.1-5h;
  • step S500 Dehydrate the once-washed material obtained in step S400 once to obtain the once-dehydrated material, and use a centrifuge for the first-time dehydration, and the moisture content of the obtained material after the first-time dehydration is not higher than 10wt%;
  • step S600 Use pure water to perform secondary washing and dehydration on the primary dehydrated material obtained in step S500 to obtain the secondary dehydrated material, and remove impurities such as sodium and sulfur in the primary dehydrated material.
  • the dehydration process uses a centrifuge to dehydrate. The water content of the material after the secondary dehydration is not higher than 10wt%.
  • the present disclosure provides a method for preparing a positive electrode material. As shown in FIG. 2, the method includes the following steps:
  • the carbonate binary precursor prepared in the above embodiment is pre-fired at 400-500° C. for 2-6 hours to decompose the hollow structure carbonate precursor to obtain an oxide precursor pre-fired material.
  • Sb The pre-fired material obtained by Sa and the lithium salt are mixed for primary sintering, so that the carbonate precursor is fully decomposed to obtain the primary sintered material.
  • the lithium salt is at least one selected from the group consisting of lithium hydroxide and lithium carbonate, and the precursor
  • the molar ratio of the bulk material to the lithium salt is 1: (1.02 ⁇ 1.08), the temperature of the primary sintering is 700 ⁇ 850°C, and the time is 8 ⁇ 20h.
  • the primary sintered material obtained by Sb is crushed and then sintered for the second time, so that the lithium salt migrates into the interior of the precursor to obtain the cathode material.
  • the second sintering is 580 ⁇ 650°C, the time is 8 ⁇ 12h.
  • the present disclosure provides a positive electrode material prepared by the preparation method provided in the foregoing embodiment.
  • the present disclosure provides a lithium battery having the cathode material provided in the above embodiment.
  • the present disclosure provides an automobile having the lithium battery provided in the above embodiment.
  • the method for preparing the hollow structure carbonate binary precursor is as follows:
  • step (3) Using the above-mentioned pre-granulation as the bottom liquid, controlling the rotation speed at 800-1000 rpm, and the temperature at 55°C, add the mixed metal salt and precipitating agent to the reaction kettle.
  • the mixed metal salt and precipitating agent are the same as in step (2).
  • the molar ratio of particle-making, mixed metal salt and precipitant is 2:1.01:2.02, the pH of the control system is 8.5, and the reaction is carried out for 50 hours to obtain a post-reaction liquid with a solid content of 10.5 wt%;
  • the secondary dehydrated material obtained above is dried and then sieved to remove iron to obtain a hollow structure carbonate binary precursor with a particle size of 10 ⁇ m and a layer thickness of 5-7 ⁇ m.
  • the chemical formula of the precursor is Ni 0.88 Mn 0.12 CO 3 .
  • the method of preparing the cathode material is as follows:
  • Figure 3 is a scanning electron micrograph of a hollow-structure carbonate binary precursor material prepared in an embodiment of the present disclosure. It can be seen from Figure 3 that the precursor material obtained by this method has a spherical structure, uniform particle size distribution, and uses Laser particle size analyzer detected the particle size distribution of the precursor and found that the particle size distribution was uniform.
  • Figure 4 is a scanning electron micrograph of a hollow structure carbonate binary precursor prepared in an embodiment of the present disclosure. It can be seen from Figure 4 that the precursor material obtained by this method has a hollow structure, and the precursor sodium detected at the same time The content is less than 300ppm, and the sulfur content is less than 1000ppm.
  • the obtained cathode material is assembled with EC/DMC (ethylene carbonate/dimethyl carbonate) electrolyte, lithium hexafluorophosphate content is 1.0mol/L, and the electrochemical performance is measured.
  • the obtained product has a 0.1C gram capacity of 209-215mAh/g, an initial effect of 92.5%, and a 50-week cycle capacity retention rate of 98.5%.
  • the method for preparing the hollow structure carbonate binary precursor is as follows:
  • step (3) Using the above-mentioned pre-granulation as the bottom liquid, controlling the speed at 800-1000 rpm, and the temperature at 60°C, add the mixed metal salt and precipitating agent to the reaction kettle.
  • the mixed metal salt and precipitating agent are the same as in step (2).
  • the molar ratio of particle-making, mixed metal salt and precipitating agent is 2.2:1.2:2.4, the pH of the control system is 9, and the reaction is 30h to obtain a post-reaction liquid with a solid content of 20.5wt%;
  • the secondary dehydrated material obtained above is dried and then sieved to remove iron to obtain a hollow structure carbonate binary precursor with a particle size of 10 ⁇ m and a layer thickness of 6.0-7.7 ⁇ m.
  • the chemical formula of the precursor is Ni 0.92 Mn 0.08 CO 3 .
  • the method of preparing the cathode material is as follows:
  • the precursor material prepared in an embodiment of the present disclosure has a spherical structure and uniform particle size distribution, and the particle size distribution of the precursor is detected by a laser particle size analyzer, and the particle size distribution is further found to be uniform.
  • the detected precursor sodium content is less than 300 ppm, and the sulfur content is less than 1000ppm.
  • the cathode material obtained was assembled (using EC/DMC electrolyte, lithium hexafluorophosphate content of 1.0mol/L) and the electrochemical performance was tested.
  • the 0.1C gram capacity of the product was 205 ⁇ 210mAh/g, and the first effect was 88.5%.
  • the 50-week cycle capacity retention rate is 94.6%.
  • the method for preparing the hollow structure carbonate binary precursor is as follows:
  • the secondary dehydrated material obtained above is dried and then sieved to remove iron to obtain a hollow structure carbonate binary precursor with a particle size of 8 ⁇ m and a layer thickness of 3-5 ⁇ m.
  • the chemical formula of the precursor is Ni 0.83 Mn 0.17 CO 3 .
  • the method of preparing the cathode material is as follows:
  • the precursor material prepared in an embodiment of the present disclosure has a spherical structure and uniform particle size distribution, and the particle size distribution of the precursor is detected by a laser particle size analyzer, and the particle size distribution is further found to be uniform.
  • the detected precursor sodium content is less than 300 ppm, and the sulfur content is less than 1000ppm, at the same time, the cathode material obtained was assembled (using EC/DMC electrolyte, lithium hexafluorophosphate content 1.0mol/L) and the electrochemical performance was tested.
  • the 0.1C gram capacity of the product was 208 ⁇ 213mAh/g/g, the first effect 88.6%, and the 50-week cycle capacity retention rate was 95.2%.
  • the method for preparing the hollow structure carbonate binary precursor is as follows:
  • the secondary dehydrated material obtained above is dried and then sieved to remove iron to obtain a hollow structure carbonate binary precursor with a particle size of 8 ⁇ m and a layer thickness of 2 to 2.5 ⁇ m.
  • the chemical formula of the precursor is Ni 0.55 Mn 0.45 CO 3 .
  • the method of preparing the cathode material is as follows:
  • the precursor material prepared in an embodiment of the present disclosure has a spherical structure and uniform particle size distribution, and the particle size distribution of the precursor is detected by a laser particle size analyzer, and the particle size distribution is further found to be uniform.
  • the detected precursor sodium content is less than 300 ppm, and the sulfur content is less than 1000ppm.
  • the cathode material obtained was assembled (using EC/DMC electrolyte, lithium hexafluorophosphate content of 1.0mol/L) and the electrochemical performance was tested.
  • the 0.1C gram capacity of the product was 160 ⁇ 165mAh/g, and the first effect was 92%.
  • the 50-week cycle capacity retention rate is 98%.
  • the method for preparing the hollow structure carbonate binary precursor is as follows:
  • the secondary dehydrated material obtained above is dried and then sieved to remove iron to obtain a hollow structure carbonate binary precursor with a particle size of 15 ⁇ m and a layer thickness of 2.5-3 ⁇ m.
  • the chemical formula of the precursor is Ni 0.92 Mn 0.08 CO 3 .
  • the method of preparing the cathode material is as follows:
  • the precursor material prepared in an embodiment of the present disclosure has a spherical structure and uniform particle size distribution, and the particle size distribution of the precursor is detected by a laser particle size analyzer, and the particle size distribution is further found to be uniform.
  • the detected precursor sodium content is less than 300 ppm, and the sulfur content is less than 1000ppm, at the same time, the obtained cathode material was assembled (using EC/DMC electrolyte, lithium hexafluorophosphate content of 1.0mol/L) and tested the electrochemical performance.
  • the 0.1C gram capacity of the product is 210 ⁇ 215mAh/g, and the first effect is 90.6% , And the 50-week cycle capacity retention rate is 94.2%.

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Abstract

一种空心结构碳酸盐二元前驱体及其制备方法和应用，所述前驱体化学式为Ni xMn (1-x)CO 3，其中，x为0.55～0.92。该空心结构碳酸盐二元前驱体具有粒度可控且粒度分布均匀、球形度高、电化学性能和能量密度优异的优势。

Description

空心结构碳酸盐二元前驱体及其制备方法和应用 技术领域
本公开涉及锂电池领域，例如涉及一种空心结构碳酸盐二元前驱体及其制备方法和应用。
背景技术
目前，随着能源科技的快速发展，锂离子电池在社会的各个方面得到了广泛的应用，而其三元正极材料的研究受到了社会的广泛关注。目前，比较成熟的二次锂离子电池正极材料有LiCoO 2、LiNiO 2、LiMnO 2以及尖晶石型LiMn 2O 4。其中LiCoO 2具有比容量高、高且平稳的放电平台及良好的循环性能，但钴资源匮乏，钴价昂贵，且有毒性，对环境污染较大。而LiNiO 2虽然与LiCoO 2同样具有NaFeO 2结构，且具有比容量高的特点，但LiNiO 2的合成条件苛刻，热稳定性差，并且在较高温度下易发生分解，同时合成过程及合成后的产物容易吸水，不易进行大量的商业化生产。尖晶石型LiMn 2O 4耐过充、安全性能好，但循环性能差，高温(55℃以上)容量衰减快，理论比容量相对较低(148mAh/g)，难以制备纯净的单相产物，而且充放电时尖晶石结构不稳定。LiMnO 2是热力学不稳定体系，而且未经掺杂的m-LiMnO 2虽然能获得高达270mAh/g的首次充电比容量，但在首次充放电时比容量衰减非常严重，几乎只有一半的容量能够保持。这是由于m-LiMnO 2的结构在首次循环中就开始转变为尖晶石结构，几个循环后就几乎完全转化为尖晶石相。
近年来，三元材料由于集合了这三者材料的所有优势而得到了迅速发展，而低钴和无钴正极材料更有可能成为未来一个重要的发展方向，所以高品质的高镍低钴三元前驱体及正极材料的开发成为了热点。目前，众多厂家普遍采用 氢氧化物前驱体作为原料与锂盐混合烧结成三元正极材料，而碳酸盐三元前驱体及其正极材料的研究相对较少或者没有，同时已经报道出来的碳酸盐三元前驱体材料很大一部分存在一些问题，如粒度分布不均、球形度差、无法连续生产等。
因此，现有的锂电池前驱体材料有待进一步探究。
发明内容
本公开提供一种空心结构碳酸盐二元前驱体及其制备方法和应用。
本公开在一实施例中提供一种空心结构碳酸盐二元前驱体，所述前驱体化学式为Ni xMn (1-x)CO 3，其中，x为0.55～0.92，例如0.55、0.6、0.65、0.7、0.75、0.8、0.85、0.9或0.92等。
本公开提供的一实施例中，所述空心结构碳酸盐二元前驱体具有粒度可控且粒度分布均匀、球形度高、电化学性能和能量密度优异的优势，其在有氨体系和无氨体系均可稳定生产，特别是在无氨体系下，没有含氨废水产生，对环境友好，同时该空心结构碳酸盐二元前驱体不含金属钴，较现有的三元镍钴锰前驱体不仅降低了原料成本，而且不会产生环境污染，另外采用该前驱体制备得到的正极材料具有较高的比容量以及优异的循环性能和电化学放电性能。如果前驱体中镍含量过高，则得到的正极材料中锂镍混排严重，导致其装载该锂电池的循环性能变差，而如果前驱体中镍含量过低，则采用该前驱体制备的正极材料的锂电池容量会变低。
在一实施例中，所述前驱体层厚为2～3μm，例如2.0μm、2.1μm、2.2μm、2.3μm、2.4μm、2.5μm、2.6μm、2.7μm、2.8μm、2.9μm或3.0μm等。
在本公开提供的一实施例中，前驱体层厚为2～3μm，如果前驱体层厚过高，则在装载该前驱体制备的正极材料的锂电池中电解液渗透会变差，锂离子传输距离变长，导致电池性能变差，而如果前驱体层厚过低，则在装载该前驱体制备的正极材料的锂电池中锂离子传输过程中，壳层会遭到破坏，电池的循环性能会极大下降。
在一实施例中，所述前驱体粒径为8～15μm，例如8μm、8.5μm、9μm、9.5μm、10μm、10.5μm、11μm、11.5μm、12μm、12.5μm、13μm、13.5μm、14μm、14.5μm 或15μm等。
本公开一实施例所述的粒径为平均粒径。
本公开在一实施例中提供了一种制备所述前驱体的方法，包括：
(1)将可溶性镍盐和可溶性锰盐进行混合，以便得到混合金属盐；
(2)在反应釜中预先加入沉淀剂，然后伴随着搅拌，将所述混合金属盐的一部分、所述沉淀剂和强酸加入反应釜中进行共沉淀反应，以便得到预造粒子；
(3)伴随着搅拌，向所述反应釜中加入所述混合金属盐的另一部分和所述沉淀剂，使得所述混合金属盐和所述沉淀剂在所述预造粒子表面发生共沉淀反应，以便得到反应后液；
(4)伴随着搅拌，将所述反应后料与洗涤剂混合，以便得到一次洗涤后料；
(5)将所述一次洗涤后料进行一次脱水，以便得到一次脱水后料；
(6)伴随着搅拌，将所述一次脱水后料进行二次洗涤后脱水，以便得到二次脱水后料；
(7)将所述二次脱水后料干燥后筛分除铁，以便得到空心结构碳酸盐二元前驱体。
本公开提供的一实施例中，首先在反应釜中预先加入沉淀剂，然后将含有可溶性镍盐和可溶性锰盐的混合金属盐与沉淀剂和强酸加入反应釜中进行共沉淀反应，得到小粒径的预造粒子，再向反应釜中加入混合金属盐和沉淀剂，即以小粒径的预造粒子为晶种进行共沉淀反应，由于预造粒过程强酸的加入，使得得到的预造粒子中含有强酸，在以小粒径的预造粒子为晶种进行共沉淀反应过程中，作为晶种的预造粒子中强酸与晶种内形成的碳酸盐沉淀不断反应，从而得到空心结构颗粒，最后经后续的洗涤、脱水以及干燥筛分除铁工序，即可制备得到上述具有空心球形结构、粒度可控且粒度分布均匀、球形度高、电化学性能和能量密度优异的二元盐前驱体，其在有氨体系和无氨体系均可稳定生产，特别是在无氨体系下，没有含氨废水产生，对环境友好，同时该空心结构碳酸盐二元前驱体不含金属钴，较现有的三元镍钴锰前驱体不仅降低了原料成本，而且不会产生环境污染，另外采用该方法得到的前驱体制备得到的正极材料具有较高的比容量以及优异的循环性能和电化学放电性能。
本公开一实施例提供的步骤(1)中，在制备前驱体过程中不加入金属钴，较现有的三元镍钴锰前驱体不仅降低了原料成本，而且不会产生环境污染，同 时本申请最终制备得到的前驱体仍然具有优异的电化学性能和能量密度。
本公开一实施例提供的步骤(2)中，在反应釜中预先加入沉淀剂，然后伴随着搅拌，将混合金属盐的一部分、沉淀剂和强酸同时加入反应釜中进行共沉淀反应，得到预造粒子。预先在反应釜中加入沉淀剂，然后再加入混合金属盐和沉淀剂和强酸，保证了沉淀剂优先与混合金属盐反应得到包裹强酸的沉淀颗粒，即得到包裹强酸的预造粒子，从而在后续以小粒径的预造粒子为晶种进行共沉淀反应过程中，作为晶种的预造粒子中强酸与晶种内形成的碳酸盐沉淀不断反应，从而得到空心结构颗粒。
本公开一实施例提供的步骤(3)中，伴随着搅拌，向上述得到预造粒子的反应釜中加入混合金属盐和沉淀剂，使得混合金属盐和沉淀剂在上述得到的预造粒子表面发生共沉淀反应，由于预造粒过程强酸的加入，使得得到的预造粒子中含有强酸，在以小粒径的预造粒子为晶种进行共沉淀反应过程中，作为晶种的预造粒子中强酸与晶种内形成的碳酸盐沉淀不断反应，从而得到含有空心结构颗粒的反应后液。
本公开一实施例提供的步骤(4)中，伴随着搅拌，步骤(3)得到的反应后料溢流至陈化釜与洗涤剂混合，得到一次洗涤后料。该过程采用的洗涤剂为本领域常规使用的洗涤剂，例如可以为氢氧化钠溶液，并且需要说明的是，本领域技术人员可以根据实际需要对搅拌转速和洗涤剂的加入量进行选择，只要能够实现去除反应后料中部分的钠和硫即可。
本公开一实施例提供的步骤(5)中，将步骤(4)得到的一次洗涤后料进行一次脱水，得到一次脱水后料，一次脱水可以采用离心机脱水，得到的一次脱水后料中含水率不高于10wt％。
本公开一实施例提供的步骤(6)中，将步骤(5)得到的一次脱水后料进行二次洗涤后脱水，以便得到二次脱水后料。采用纯水对一次脱水后料进行二次洗涤，以进一步去除一次脱水后料中的钠和硫等杂质，并且本领域技术人员可以根据实际需要对纯水用量和搅拌转速以及时间进行选择，只要能够实现洗涤至钠和硫含量合格即可，并且该脱水过程也采用离心机脱水，得到的二次脱水后料中含水率不高于10wt％。
在一实施例中，在步骤(1)中，所述可溶性镍盐和所述可溶性锰盐按照镍元素和锰元素摩尔比为(0.55～0.92)：(0.08～0.45)，例如0.55:0.45、0.6:0.4、 0.7:0.3、0.8:0.2、0.9:0.1或0.92:0.08等。
在一实施例中，在步骤(1)中，所述混合金属盐中，所述可溶性镍盐和所述可溶性锰盐的浓度分别独立地为1～2mol/L，例如1.0mol/L、1.1mol/L、1.2mol/L、1.3mol/L、1.4mol/L、1.5mol/L、1.6mol/L、1.7mol/L、1.8mol/L、1.9mol/L或2.0mol/L等。
在一实施例中，在步骤(1)中，所述可溶性镍盐为选自氯化镍和硫酸镍中的至少之一。
在一实施例中，在步骤(1)中，所述可溶性锰盐为选自氯化锰和硫酸锰中的至少之一。
在一实施例中，在步骤(2)中，基于1L所述反应釜，预先加入所述沉淀剂的含量2～10g，例如2g、3g、4g、5g、6g、7g、8g、9g或10g等。
本公开提供的一实施例中，如果预先加入的沉淀剂过高，所造的晶核会团聚，导致后续得到的前驱体球形度变差，而如果预先加入的沉淀剂含量过低，造成所得晶核的粒径过大，成核量也会变少，同时后期制备的前驱体的空心粒径也会变大，壁厚变薄，从而对装载该前驱体制备的正极材料的电池性能造成不好的影响。
在一实施例中，在步骤(2)中，所述搅拌的转速为200～500rpm，例如200rpm、250rpm、300rpm、350rpm、400rpm、450rpm或500rpm等。
在一实施例中，在步骤(2)中，将所述混合金属、所述沉淀剂和所述强酸按照摩尔比为1：(2.5～5)：(0.1～1)加入所述反应釜中，例如1:2.5:0.1、1:3:0.2、1:3.5:0.5、1:4:0.7或1:5:1等。
本公开提供的一实施例中，混合金属、所述沉淀剂和所述强酸按照摩尔比为1：(2.5～5)：(0.1～1)，如果三者摩尔比例太高，会造成前驱体球形度差，造成振实密度偏低，而如果三者摩尔比例过高，则在后期反应过程中得到空心结构前驱体的粒径会变大，壳层变薄，对装载该前驱体制备的正极材料的电池循环性能有这及其不好的影响。
在一实施例中，在步骤(2)中，所述强酸为盐酸、硫酸或硝酸.
在一实施例中，在步骤(2)中，所述强酸的浓度为0.1～1mol/L，例如0.1mol/L、0.2mol/L、0.3mol/L、0.4mol/L、0.5mol/L、0.6mol/L、0.7mol/L、0.8mol/L、0.9mol/L或1mol/L等。
本公开提供的一实施例中，强酸浓度为0.1～1mol/L，如果强酸浓度过高，则会造成前驱体壳层破坏，而如果强酸浓度过低，则在后期反应过程中对内部空心刻蚀不完全，达不到完全空心的结构。
在一实施例中，在步骤(2)中，所述沉淀剂为选自碳酸钠、碳酸铵、碳酸氢铵或氨水中的至少之一。
在一实施例中，所述碳酸钠的浓度为1～2mol/L，例如1.0mol/L、1.1mol/L、1.2mol/L、1.3mol/L、1.4mol/L、1.5mol/L、1.6mol/L、1.7mol/L、1.8mol/L、1.9mol/L或2.0mol/L等。
在一实施例中，所述碳酸铵的浓度为2～6mol/L，例如2.0mol/L、2.5mol/L、3.0mol/L、3.5mol/L、4.0mol/L、4.5mol/L、5.0mol/L、5.5mol/L或6.0mol/L等。
在一实施例中，所述碳酸氢铵的浓度为1～7mol/L，例如1mol/L、2mol/L、3mol/L、4mol/L、5mol/L、6mol/L或7mol/L等。
在一实施例中，所述氨水的浓度为0.2～1.5mol/L，例如0.2mol/L、0.3mol/L、0.4mol/L、0.5mol/L、0.6mol/L、0.7mol/L、0.8mol/L、0.9mol/L、1.0mol/L、1.1mol/L、1.2mol/L、1.3mol/L、1.4mol/L或1.5mol/L等。
在一实施例中，在步骤(2)中，所述共沉淀反应的温度为30～80℃，例如30℃、35℃、40℃、45℃、50℃、55℃、60℃、65℃、70℃、75℃或80等；时间为0.1～5h，例如0.1h、1h、1.5h、2h、2.5h、3h、3.5h、4h、4.5h或5h等。
在一实施例中，在步骤(2)中，所述预造粒子粒径为0.5～3μm，例如0.5μm、1μm、1.5μm、2μm、2.5μm或3μm等。
本公开一实施例中预造粒子粒径为0.5～3μm，如果所得预造粒子粒径过低，导致在后期反应过程沉淀生长过慢，反应时间加长，最终得到前驱体空心的范围会降低，而如果所得预造粒子粒径过高，后期制备前驱体时空心范围扩大，所得前驱体壳层厚度会变小。
在一实施例中，在步骤(3)中，所述预造粒子、所述混合金属盐与所述沉淀剂的摩尔比为(2～3)：(1.01～1.5)：(2.02～3.02)，例如2:1.01:2.02、2.3:1.1:2.1、2.5:1.3:2.5、2.7:1.3:2.7或3:1.5:3.02等。
在一实施例中，在步骤(3)中，所述搅拌转速为700～1000rpm，例如700rpm、750rpm、800rpm、850rpm、900rpm、950rpm或1000rpm等；温度为50～70℃，例如50℃、55℃、60℃、65℃或70等；时间为5～60h，例如5h、10h、15h、20h、 25h、30h、35h、40h、45h、50h、55h、60h、65h或70h等；所述反应后液的pH为8～9.5，例如8.0、8.1、8.2、8.3、8.4、8.5、8.6、8.7、8.8、8.9、9.0、9.1、9.2、9.3、9.4或9.5等；所述反应后液的固含量为10～30wt％，例如10wt％、12wt％、14wt％、16wt％、18wt％、20wt％、22wt％、24wt％、26wt％、28wt％或30wt％等。
本公开一实施例中，pH为8～9.5，如果反应后液pH过高时，则沉淀物并不能团聚成球体，而为松散的小颗粒聚集体，而如果反应后液pH过低时，沉淀物团聚严重，生成的前驱体形貌各异。
本公开在一实施例中提供一种制备正极材料的方法，包括：
(a)将前驱体材料进行预烧，以便得到预烧后料；
(b)将所述预烧后料与锂盐混合进行一次烧结，以便得到一次烧结料；
(c)将所述一次烧结料破碎后进行二次烧结，以便得到正极材料，
其中，在步骤(a)中，所述前驱体材料为一实施例所述的二元前驱体或采用一实施例所述的方法得到的二元前驱体。
本公开一实施例提供的制备正极材料的方法通过将上述具有球形结构且粒度分布均匀、电化学性能优异的空心结构的碳酸盐二元前驱体进行预烧后再进行一次烧结和二次烧结，其中，预烧使得碳酸盐二元前驱体分解，一次烧结过程保证碳酸盐二元前驱体分解完全，得到氧化物，再经二次烧结使得锂离子迁移进入前驱体内部，从而制备得到具有高比容量以及优异的循环性能和电化学放电性能的正极材料。需要说明的是，上述针对空心结构碳酸盐二元前驱体及其制备方法所描述的特征和优点同样适用于该制备正极材料的方法，此处不再赘述。
在一实施例中，在步骤(a)中，所述预烧的温度为400～500℃，例如400℃、410℃、420℃、430℃、440℃、450℃、460℃、470℃、480℃、490℃或500℃等；时间为2～6h，例如2h、2.5h、3.0h、3.5h、4.0h、4.5h、5.0h、5.5h或6.0h等。
在一实施例中，在步骤(b)中，所述预烧后料与所述锂盐的摩尔比为1：(1.02～1.08)，例如1:1.02、1:1.03、1:1.04、1:1.05、1:1.06、1:1.07或1:1.08等。
在一实施例中，在步骤(b)中，所述一次烧结的温度为700～850℃，时间为8～20h，例如8h、9h、10h、11h、12h、13h、14h、15h、16h、17h、18h、19h或20h等。
在一实施例中，在步骤(c)中，所述二次烧结的温度为580～650℃，例如580℃、590℃、600℃、610℃、620℃、630℃、640℃或650℃等；时间为8～12h，例如8.0h、8.5h、9.0h、9.5h、10.0h、10.5h、11.0h、11.5h或12.0h等。
本公开在一实施例中提供一种正极材料，所述正极材料采用一实施例所述的方法制备得到。
本公开一实施例提供的正极材料具有较高比容量以及优异的循环性能和电化学放电性能。
本公开一实施例中提供一种锂电池，所述锂电池具有一实施例所述的正极材料。
本公开一实施例提供的锂电池具有高比能量和长循环寿命。
本公开在一实施例中提供一种汽车，所述汽车具有一实施例所述的锂电池。
本公开一实施例提供的汽车装载有上述具有高比能量和长循环寿命锂电池，具有优异的续航能力。
附图说明
附图用来提供对本公开技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本公开的技术方案，并不构成对本公开技术方案的限制。
图1是本公开一个实施例制备空心结构碳酸盐二元前驱体的方法流程示意图；
图2是本公开一个实施例制备正极材料的方法流程示意图；
图3是本公开一个实施例制备得到的空心结构碳酸盐二元前驱体的扫描电镜图；
图4是本公开一个实施例制备得到的空心结构碳酸盐二元前驱体剖面扫描电镜图。
具体实施例
下面结合附图并通过具体实施方式来进一步说明本公开的技术方案。
在一个实施例中，本公开提供了一种空心结构碳酸盐二元前驱体，化学式为Ni xMn (1-x)CO 3，其中，x为0.55～0.92。该空心结构碳酸盐二元前驱体具有粒 度可控且粒度分布均匀、球形度高、电化学性能和能量密度优异的优势，其在有氨体系和无氨体系均可稳定生产，特别是在无氨体系下，没有含氨废水产生，对环境友好，同时该空心结构碳酸盐二元前驱体不含金属钴，较现有的三元镍钴锰前驱体不仅降低了原料成本，而且不会产生环境污染，另外采用该前驱体制备得到的正极材料具有较高的比容量以及优异的循环性能和电化学放电性能。如果前驱体中镍含量过高，则得到的正极材料中锂镍混排严重，导致其装载该锂电池的循环性能变差，而如果前驱体中镍含量过低，则采用该前驱体制备的正极材料的锂电池容量会变低。上述前驱体层厚度为2～3μm，如果前驱体层厚过高，则在装载该前驱体制备的正极材料的锂电池中电解液渗透会变差，锂离子传输距离变长，导致电池性能变差，而如果前驱体层厚过低，则在装载该前驱体制备的正极材料的锂电池中锂离子传输过程中，壳层会遭到破坏，电池的循环性能会极大下降。该前驱体粒径为8～15μm。
在一个实施例中，本公开提供了一种制备上述空心结构碳酸盐二元前驱体的方法。如图1所示，所述方法具体包括如下步骤：
S100：将可溶性镍盐和可溶性锰盐混合，得到混合金属盐。可溶性镍盐为选自氯化镍和硫酸镍中的至少之一；可溶性锰盐为选自氯化锰和硫酸锰中的至少之一。混合金属盐中，可溶性镍盐和可溶性锰盐的浓度分别独立地为1～2mol/L，可溶性镍盐和可溶性锰盐按照镍元素和锰元素摩尔比为(0.55～0.92)：(0.08～0.45)；
S200：在反应釜中预先加入沉淀剂，然后伴随着搅拌，将混合金属盐的一部分、沉淀剂和强酸同时加入反应釜中进行共沉淀反应，得到预造粒子。基于1L反应釜，预先加入沉淀剂的含量2～10g。沉淀剂为选自碳酸钠、碳酸铵、碳酸氢铵或氨水中的至少之一，碳酸钠的浓度为1～2mol/L，碳酸铵的浓度为2～6mol/L，碳酸氢铵的浓度为1～7mol/L，氨水的浓度为0.2～1.5mol/L。强酸为盐酸、硫酸或硝酸，强酸的浓度为0.1～1mol/L，搅拌过程的转速为200～500rpm，混合金属、沉淀剂和强酸按照摩尔比为1：(2.5～5)：(0.1～1)加入反应釜中。共沉淀反应温度为30～80℃，时间为0.1～5h。得到的预造粒子粒径为0.5～3μm；
S300：伴随着搅拌，向步骤S200得到预造粒子的反应釜中加入混合金属盐和沉淀剂，使得混合金属盐和沉淀剂在上述得到的预造粒子表面发生共沉淀反 应，预造粒子、混合金属盐与沉淀剂的摩尔比(2～3)：(1.01～1.5)：(2.02～3.02)，控制该过程的搅拌转速为700～1000rpm，温度为50～70℃，时间为5～60h，控制反应后液的pH为8～9.5，共沉淀反应时间为10～20h，得到的反应后液中固含量为10～30wt％，例如10wt％、11wt％……29wt％、30wt％。进一步的，沉淀剂和混合金属盐与步骤S200相同；
S400：伴随着搅拌，步骤S300得到的反应后料溢流至陈化釜与洗涤剂混合，得到一次洗涤后料，搅拌时间为0.1～5h；
S500：将步骤S400得到的一次洗涤后料进行一次脱水，得到一次脱水后料，一次脱水采用离心机脱水，得到的一次脱水后料中含水率不高于10wt％；
S600：采用纯水对步骤S500得到的一次脱水后料进行二次洗涤后脱水，得到二次脱水后料，去除一次脱水后料中的钠和硫等杂质，脱水过程采用离心机脱水，得到的二次脱水后料中含水率不高于10wt％。
S700：将二次脱水后料干燥后筛分除铁，得到空心结构碳酸盐二元前驱体。
在一个实施例中，本公开提供了一种制备正极材料，如图2所示，所述方法包括如下步骤：
Sa：将上述实施例制备得到的碳酸盐二元前驱体在400～500℃下预烧2～6h，使得空心结构碳酸盐前驱体分解，得到氧化物前驱体预烧料。
Sb：将Sa得到的预烧料与锂盐混合进行一次烧结，使得碳酸盐前驱体充分分解，即得到一次烧结料，锂盐为选自氢氧化锂和碳酸锂中的至少之一，前驱体材料与锂盐的摩尔比为1：(1.02～1.08)，一次烧结的温度为700～850℃，时间为8～20h。
Sc：将Sb得到的一次烧结料破碎后进行二次烧结，使得锂盐迁移进入前驱体内部，得到正极材料。二次烧结的580～650℃℃，时间为8～12h。
在一个实施例中，本公开提供了一种采用上述实施例提供的制备方法制备得到的正极材料。
在一个实施例中，本公开提供了一种锂电池，具有上述实施例提供的正极材料。
在一个实施例中，本公开提供了一种汽车，具有上述实施例提供的锂电池。
实施例1
制备空心结构碳酸盐二元前驱体的方法如下：
(1)将硫酸镍、硫酸锰按照镍锰元素摩尔比为0.88:0.16进行混合，得到混合金属盐，并且混合金属盐中硫酸镍和硫酸锰的浓度均为1mol/L；
(2)在5L反应釜中预先加入10g沉淀剂(沉淀剂包括浓度为1.2mol/L的碳酸钠和浓度为0.4mol/L的氨水)，然后伴随着搅拌(搅拌转速为300rpm)，将混合金属盐、沉淀剂和盐酸(浓度为0.1mol/L)按照摩尔比为1:2.5:0.1同时加入反应釜中进行共沉淀反应，其中控制温度为40℃，搅拌时间为0.1h，得到粒径为1.5～2.5μm的预造粒子；
(3)以上述预造粒为底液，控制转速为800～1000rpm，温度为55℃，向反应釜中加入混合金属盐和沉淀剂，混合金属盐和沉淀剂同于步骤(2)，预造粒子、混合金属盐与沉淀剂的摩尔比为2：1.01：2.02，控制体系pH为8.5，反应50h，得到固含量为10.5wt％的反应后液；
(4)将上述得到的反应后料与氢氧化钠溶液混合搅拌1h，得到一次洗涤后料；
(5)采用离心机对对上述得到的反应后料进行离心脱水，得到含水率不高于10wt％的一次脱水后料；
(6)采用纯水对上述得到的一次脱水后料进行洗涤和脱水，得到二次脱水后料，得到的二次脱水后料中含水率不高于10wt％；
(7)将上述得到的二次脱水后料干燥后筛分除铁，得到粒径10μm、层厚5-7μm的空心结构碳酸盐二元前驱体，该前驱体化学式为Ni 0.88Mn 0.12CO 3。
制备正极材料的方法如下：
Sa：将上述步骤(7)得到的空心结构碳酸盐二元前驱体在500℃下预烧4h，得到预烧料；
Sb：将上述得到的预烧料与氢氧化锂按照摩尔比为1:1.02混合在空气气氛下于850℃进行一次烧结18h，得到一次烧结料；
Sc：将上述得到的一次烧结料破碎后在600℃进行二次烧结12h，得到正极材料。
图3是本公开一实施例制备得到的空心结构碳酸盐二元前驱体材料的扫描电镜图，由图3可以看出，该方法得到的前驱体材料具有球形结构、粒度分布均匀，并且使用激光粒度仪检测前驱体粒径分布进一步发现其粒度分布均匀。图4是本公开一实施例制备得到的空心结构碳酸盐二元前驱体剖面扫描电镜图，由图4可以看出，该方法得到的前驱体材料具有空心结构，同时检测得到的前驱体钠含量小于300ppm，硫含量小于1000ppm，同时将得到的正极材料进行扣电组装，采用EC/DMC(乙烯碳酸酯/碳酸二甲酯)电解液，六氟磷酸锂含量1.0mol/L，并检测电化学性能，得到产品0.1C克容量在209～215mAh/g，首效92.5％，并且50周循环容量保持率98.5％。
实施例2
制备空心结构碳酸盐二元前驱体的方法如下：
(1)将硫酸镍、硫酸锰按照镍锰元素摩尔比为0.92:0.08进行混合，得到混合金属盐，并且混合金属盐中硫酸镍和硫酸锰的浓度均为1.2mol/L；
(2)在5L反应釜中预先加入20g沉淀剂(沉淀剂包括浓度为1.5mol/L的碳酸钠和浓度为5mol/L的碳酸铵)，然后伴随着搅拌(搅拌转速为400rpm)，将混合金属盐、沉淀剂和硫酸(浓度为0.3mol/L)按照摩尔比为1:3:0.5同时加入反应釜中进行共沉淀反应，其中控制温度为50℃，搅拌时间为0.3h，得到粒径为2.3-4μm的预造粒子；
(3)以上述预造粒为底液，控制转速为800～1000rpm，温度为60℃，向反应釜中加入混合金属盐和沉淀剂，混合金属盐和沉淀剂同于步骤(2)，预造粒子、混合金属盐与沉淀剂的摩尔比为2.2：1.2：2.4，控制体系pH为9，反应30h，得到固含量为20.5wt％的反应后液；
(4)将上述得到的反应后料与氢氧化钠溶液混合搅拌1h，得到一次洗涤后料；
(5)采用离心机对对上述得到的反应后料进行离心脱水，得到含水率不高于10wt％的一次脱水后料；
(6)采用纯水对上述得到的一次脱水后料进行洗涤和脱水，得到二次脱水后料，得到的二次脱水后料中含水率不高于10wt％；
(7)将上述得到的二次脱水后料干燥后筛分除铁，得到粒径10μm、层厚6.0-7.7μm的空心结构碳酸盐二元前驱体，该前驱体化学式为Ni 0.92Mn 0.08CO 3。
制备正极材料的方法如下：
Sa：将上述步骤(7)得到的空心结构碳酸盐二元前驱体在450℃下预烧4h，得到预烧料；
Sb：将上述得到的预烧料与氢氧化锂按照摩尔比为1:1.05混合在空气气氛下于780℃进行一次烧结20h，得到一次烧结料；
Sc：将上述得到的一次烧结料破碎后在590℃进行二次烧结10h，得到正极材料。
本公开一实施例制备得到的前驱体材料具有球形结构、粒度分布均匀，并且使用激光粒度仪检测前驱体粒径分布进一步发现其粒度分布均匀，检测得到的前驱体钠含量小于300ppm，硫含量小于1000ppm，同时将得到的正极材料进行扣电组装(采用EC/DMC电解液，六氟磷酸锂含量1.0mol/L)并检测电化学性能，得到产品0.1C克容量在205～210mAh/g，首效88.5％，并且50周循环容量保持率94.6％。
实施例3
制备空心结构碳酸盐二元前驱体的方法如下：
(1)将氯化镍、氯化锰按照镍锰元素摩尔比为0.83:0.17进行混合，得到混合金属盐，并且混合金属盐中氯化镍和氯化锰的浓度均为1.5mol/L；
(2)在5L反应釜中预先加入30g浓度为2mol/L的碳酸钠溶液，然后伴随着搅拌(搅拌转速为500rpm)，将混合金属盐、碳酸钠溶液和硝酸(浓度为0.5mol/L)按照摩尔比为1:3.5:0.6同时加入反应釜中进行共沉淀反应，其中控制温度为60℃，搅拌时间为2h，得到粒径为3-5μm的预造粒子；
(3)以上述预造粒为底液，控制转速为700～1000rpm，温度为65℃，向反应釜中加入混合金属盐和碳酸钠溶液，其中，预造粒子、混合金属盐与碳酸钠 溶液的摩尔比为2.5：4.5：3，控制体系pH为9.5，反应55h，得到固含量为15.5wt％的反应后液；
(4)将上述得到的反应后料与氢氧化钠溶液混合搅拌1h，得到一次洗涤后料；
(5)采用离心机对对上述得到的反应后料进行离心脱水，得到含水率不高于10wt％的一次脱水后料；
(6)采用纯水对上述得到的一次脱水后料进行洗涤和脱水，得到二次脱水后料，得到的二次脱水后料中含水率不高于10wt％；
(7)将上述得到的二次脱水后料干燥后筛分除铁，得到粒径8μm、层厚3-5μm的空心结构碳酸盐二元前驱体，该前驱体化学式为Ni 0.83Mn 0.17CO 3。
制备正极材料的方法如下：
Sa：将上述步骤(7)得到的空心结构碳酸盐二元前驱体在400℃下预烧4h，得到预烧料；
Sb：将上述得到的预烧料与碳酸锂按照摩尔比为1:1.03混合在空气气氛下于740℃进行一次烧结20h，得到一次烧结料；
Sc：将上述得到的一次烧结料破碎后在580℃进行二次烧结10h，得到正极材料。
本公开一实施例制备得到的前驱体材料具有球形结构、粒度分布均匀，并且使用激光粒度仪检测前驱体粒径分布进一步发现其粒度分布均匀，检测得到的前驱体钠含量小于300ppm，硫含量小于1000ppm，同时将得到的正极材料进行扣电组装(采用EC/DMC电解液，六氟磷酸锂含量1.0mol/L)并检测电化学性能，得到产品0.1C克容量在208～213mAh/g/g，首效88.6％，并且50周循环容量保持率95.2％。
实施例4
制备空心结构碳酸盐二元前驱体的方法如下：
(1)将氯化镍、氯化锰按照镍锰元素摩尔比为0.55:0.45进行混合，得到混合金属盐，并且混合金属盐中氯化镍和氯化锰的浓度均为1mol/L；
(2)在5L反应釜中预先加入10g浓度为2mol/L的碳酸铵溶液，然后伴随着搅拌(搅拌转速为200rpm)，将混合金属盐、碳酸钠溶液和硝酸(浓度为0.1mol/L)按照摩尔比为1:2.5:0.1同时加入反应釜中进行共沉淀反应，其中控制温度为30℃，搅拌时间为5h，得到粒径为0.5～0.8μm的预造粒子；
(3)以上述预造粒为底液，控制转速为700～800rpm，温度为70℃，向反应釜中加入混合金属盐和碳酸钠溶液，其中，预造粒子、混合金属盐与碳酸钠溶液的摩尔比为2：1.01：2.02，控制体系pH为8，反应5h，得到固含量为10wt％的反应后液；
(4)将上述得到的反应后料与氢氧化钠溶液混合搅拌0.1h，得到一次洗涤后料；
(5)采用离心机对对上述得到的反应后料进行离心脱水，得到含水率不高于10wt％的一次脱水后料；
(6)采用纯水对上述得到的一次脱水后料进行洗涤和脱水，得到二次脱水后料，得到的二次脱水后料中含水率不高于10wt％；
(7)将上述得到的二次脱水后料干燥后筛分除铁，得到粒径8μm、层厚2～2.5μm的空心结构碳酸盐二元前驱体，该前驱体化学式为Ni 0.55Mn 0.45CO 3。
制备正极材料的方法如下：
Sa：将上述步骤(7)得到的空心结构碳酸盐二元前驱体在400℃下预烧4h，得到预烧料；
Sb：将上述得到的预烧料与碳酸锂按照摩尔比为1:1.03混合在空气气氛下于740℃进行一次烧结20h，得到一次烧结料；
Sc：将上述得到的一次烧结料破碎后在580℃进行二次烧结10h，得到正极材料。
本公开一实施例制备得到的前驱体材料具有球形结构、粒度分布均匀，并且使用激光粒度仪检测前驱体粒径分布进一步发现其粒度分布均匀，检测得到的前驱体钠含量小于300ppm，硫含量小于1000ppm，同时将得到的正极材料进行扣电组装(采用EC/DMC电解液，六氟磷酸锂含量1.0mol/L)并检测电化学 性能，得到产品0.1C克容量在160～165mAh/g，首效92％，并且50周循环容量保持率98％。
实施例5
制备空心结构碳酸盐二元前驱体的方法如下：
(1)将氯化镍、氯化锰按照镍锰元素摩尔比为0.92:0.08进行混合，得到混合金属盐，并且混合金属盐中氯化镍和氯化锰的浓度均为2mol/L；
(2)在5L反应釜中预先加入50g浓度为7mol/L的碳酸氢铵溶液，然后伴随着搅拌(搅拌转速为500rpm)，将混合金属盐、碳酸钠溶液和硫酸(浓度为1mol/L)按照摩尔比为1:5:1同时加入反应釜中进行共沉淀反应，其中控制温度为80℃，搅拌时间为0.1h，得到粒径为2.5～3μm的预造粒子；
(3)以上述预造粒为底液，控制转速为900～1000rpm，温度为50℃，向反应釜中加入混合金属盐和碳酸钠溶液，其中，预造粒子、混合金属盐与碳酸钠溶液的摩尔比为3：1.5：3.02，控制体系pH为9.5，反应60h，得到固含量为30wt％的反应后液；
(4)将上述得到的反应后料与氢氧化钠溶液混合搅拌1h，得到一次洗涤后料；
(5)采用离心机对对上述得到的反应后料进行离心脱水，得到含水率不高于10wt％的一次脱水后料；
(6)采用纯水对上述得到的一次脱水后料进行洗涤和脱水，得到二次脱水后料，得到的二次脱水后料中含水率不高于10wt％；
(7)将上述得到的二次脱水后料干燥后筛分除铁，得到粒径15μm、层厚2.5～3μm的空心结构碳酸盐二元前驱体，该前驱体化学式为Ni 0.92Mn 0.08CO 3。
制备正极材料的方法如下：
Sa：将上述步骤(7)得到的空心结构碳酸盐二元前驱体在500℃下预烧2h，得到预烧料；
Sb：将上述得到的预烧料与碳酸锂按照摩尔比为1:1.08混合在空气气氛下于850℃进行一次烧结8h，得到一次烧结料；
Sc：将上述得到的一次烧结料破碎后在650℃进行二次烧结8h，得到正极材料。
本公开一实施例制备得到的前驱体材料具有球形结构、粒度分布均匀，并且使用激光粒度仪检测前驱体粒径分布进一步发现其粒度分布均匀，检测得到的前驱体钠含量小于300ppm，硫含量小于1000ppm，同时将得到的正极材料进行扣电组装(采用EC/DMC电解液，六氟磷酸锂含量1.0mol/L)并检测电化学性能，得到产品0.1C克容量在210～215mAh/g，首效90.6％，并且50周循环容量保持率94.2％。

Claims (30)

  1. 一种空心结构碳酸盐二元前驱体，所述前驱体化学式为Ni xMn (1-x)CO 3，x为0.55～0.92。
  2. 根据权利要求1所述的前驱体，其中，所述前驱体层厚为2～3μm。
  3. 根据权利要求1或2所述的前驱体，其中，所述前驱体粒径为8～15μm。
  4. 一种制备权利要求1-3任一项所述前驱体的方法，包括：
    (1)将可溶性镍盐和可溶性锰盐进行混合，以便得到混合金属盐；
    (2)在反应釜中预先加入沉淀剂，然后伴随着搅拌，将所述混合金属盐的一部分、所述沉淀剂和强酸加入反应釜中进行共沉淀反应，以便得到预造粒子；
    (3)伴随着搅拌，向所述反应釜中加入所述混合金属盐的另一部分和所述沉淀剂，使得所述混合金属盐和所述沉淀剂在所述预造粒子表面发生共沉淀反应，以便得到反应后液；
    (4)伴随着搅拌，将所述反应后料与洗涤剂混合，以便得到一次洗涤后料；
    (5)将所述一次洗涤后料进行一次脱水，以便得到一次脱水后料；
    (6)伴随着搅拌，将所述一次脱水后料进行二次洗涤后脱水，以便得到二次脱水后料；
    (7)将所述二次脱水后料干燥后筛分除铁，以便得到空心结构碳酸盐二元前驱体。
  5. 根据权利要求4所述的方法，其中，在步骤(1)中，所述可溶性镍盐和所述可溶性锰盐按照镍元素和锰元素摩尔比为(0.55～0.92)：(0.08～0.45)。
  6. 根据权利要求4或5所述的方法，其中，在步骤(1)中，所述混合金属盐中，所述可溶性镍盐和所述可溶性锰盐的浓度分别独立地为1～2mol/L。
  7. 根据权利要求4-6任一项所述的方法，其中，在步骤(1)中，所述可溶性镍盐为选自氯化镍和硫酸镍中的至少之一。
  8. 根据权利要求4-7任一项所述的方法，其中，在步骤(1)中，所述可溶性锰盐为选自氯化锰和硫酸锰中的至少之一。
  9. 根据权利要求4-8任一项所述的方法，其中，在步骤(2)中，基于1L所述反应釜，预先加入所述沉淀剂的含量2～10g。
  10. 根据权利要求4-9任一项所述的方法，其中，在步骤(2)中，所述搅拌的转速为200～500rpm。
  11. 根据权利要求4-10任一项所述的方法，其中，在步骤(2)中，将所述 混合金属、所述沉淀剂和所述强酸按照摩尔比为1：(2.5～5)：(0.1～1)加入所述反应釜中。
  12. 根据权利要求4-11任一项所述的方法，其中，在步骤(2)中，所述强酸为盐酸、硫酸或硝酸。
  13. 根据权利要求4-12任一项所述的方法，其中，在步骤(2)中，所述强酸的浓度为0.1～1mol/L。
  14. 根据权利要求4-13任一项所述的方法，其中，在步骤(2)中，所述沉淀剂为选自碳酸钠、碳酸铵、碳酸氢铵或氨水中的至少之一。
  15. 根据权利要求14所述的方法，其中，所述碳酸钠的浓度为1～2mol/L。
  16. 根据权利要求14或15所述的方法，其中，所述碳酸铵的浓度为2～6mol/L。
  17. 根据权利要求14-16任一项所述的方法，其中，所述碳酸氢铵的浓度为1～7mol/L。
  18. 根据权利要求14-17任一项所述的方法，其中，所述氨水的浓度为0.2～1.5mol/L。
  19. 根据权利要求4-18任一项所述的方法，其中，在步骤(2)中，所述共沉淀反应的温度为30～80℃，时间为0.1～5h。
  20. 根据权利要求4-19任一项所述的方法，其中，在步骤(2)中，所述预造粒子粒径为0.5～3μm。
  21. 根据权利要求4-20任一项所述的方法，其中，在步骤(3)中，所述预造粒子、所述混合金属盐与所述沉淀剂的摩尔比为(2～3)：(1.01～1.5)：(2.02～3.02)。
  22. 根据权利要求4-21任一项所述的方法，其中，在步骤(3)中，所述搅拌转速为700～1000rpm，温度为50～70℃，时间为5～60h，所述反应后液的pH为8～9.5，所述反应后液的固含量为10～30wt％。
  23. 一种制备正极材料的方法，包括：
    (a)将前驱体材料进行预烧，以便得到预烧后料；
    (b)将所述预烧后料与锂盐混合进行一次烧结，以便得到一次烧结料；
    (c)将所述一次烧结料破碎后进行二次烧结，以便得到正极材料，
    其中，在步骤(a)中，所述前驱体材料为权利要求1-3中任一项所述的二 元前驱体或采用权利要求4-22中任一项所述的方法得到的二元前驱体。
  24. 根据权利要求23所述的方法，其中，在步骤(a)中，所述预烧的温度为400～500℃，时间为2～6h。
  25. 根据权利要求23或24所述的方法，其中，在步骤(b)中，所述预烧后料与所述锂盐的摩尔比为1：(1.02～1.08)。
  26. 根据权利要求23-25任一项所述的方法，其中，在步骤(b)中，所述一次烧结的温度为700～850℃，时间为8～20h。
  27. 根据权利要求23-26任一项所述的方法，其中，在步骤(c)中，所述二次烧结的温度为580～650℃，时间为8～12h。
  28. 一种正极材料，所述正极材料采用权利要求23-27任一项所述的方法制备得到。
  29. 一种锂电池，所述锂电池具有权利要求28所述的正极材料。
  30. 一种汽车，所述汽车具有权利要求29所述的锂电池。
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