CN112174227B - Single crystal material precursor and composite oxide powder, and preparation method and application thereof - Google Patents
Single crystal material precursor and composite oxide powder, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of materials, and relates to single crystal material precursor and composite oxide powder, and preparation methods and applications thereof. The single crystal material precursor comprises an inner core and an outer shell layer coated on the surface of the inner core, wherein the inner core is made of divalent metal hydroxide, the outer shell layer is made of a mixture of divalent metal hydroxide and trivalent metal hydroxide, and the proportion of the trivalent metal hydroxide in the single crystal material precursor is less than 10%. Compared with a coprecipitation method, the method for preparing the single crystal material precursor by using the chemical corrosion crystallization method has the advantages that the DCR of the lithium ion battery can be reduced, water is used as a raw material to participate in the reaction, the water is continuously consumed, no redundant wastewater is generated, and the purpose of being environment-friendly can be achieved.
Description
Technical Field
The invention belongs to the field of materials, and relates to a single crystal material precursor, composite oxide powder, and preparation methods and applications thereof.
Background
Along with the application of the composite multi-element lithium ion battery in the electric automobile, the research direction of the composite multi-element lithium ion battery anode material is diversified: high-capacity, high-voltage, single crystal, polycrystal and the like, composite multi-component materials become research hotspots, particularly, since 2017, multi-component single crystal materials are mature day by day and are popularized in large areas in the field of vehicles, the single crystal materials become the mainstream direction of domestic markets at present, single crystal routes are opened for medium and high nickel materials, and the market demands are increased day by day.
With the rapid development of single crystal materials in the field of vehicles, the requirements on the single crystal battery materials are continuously increased, and especially higher requirements on Direct Current Resistance (DCR) and compaction density of the materials are provided. Indexes such as DCR, compaction density and the like have more defects in the direction of a single crystal material, so that the electrochemical performance of the material is influenced, and the volume specific capacity is insufficient. In order to improve the electrochemical performance of the material, research has been conducted to solve the structural defects of the material by improving the structure and morphology of the precursor. Meanwhile, a conventional coprecipitation control crystallization technology is adopted to prepare a precursor, specifically, a metal salt solution and a hydroxide are added into a stirring reactor in a parallel flow manner for coprecipitation, a large amount of sulfate is retained in a mother solution after coprecipitation crystallization, ammonia water is added into a precipitation system as a complexing agent, ammonia is finally retained in a reaction system in the form of ammonium salt, the mother solution part containing ammonia, ammonium salt and sulfate in a solid precursor is removed after solid-liquid separation, and a part of heavy metal and small solid particles can be dissolved in the mother solution.
Disclosure of Invention
The invention aims to overcome the defects that a lithium ion battery DCR (direct current resistance) corresponding to a precursor obtained by adopting the existing coprecipitation crystallization method is higher and can cause huge burden to the environment, and provides a single crystal material precursor and composite oxide powder which can reduce the DCR of the lithium ion battery and can not cause burden to the environment, and a preparation method and application thereof.
Under the condition that the pH value is 6-12, because of H in the solution+The concentration is usually low, and oxidation-reduction reaction cannot occur by taking the metal simple substance and/or the metal oxide as raw materials in a proton mass transfer mode, so that the traditional process cannot prepare a precursor by taking the metal simple substance and/or the metal oxide as raw materials. The inventors of the present invention have conducted extensive studies and found that a simple metal and/or a metal oxide is oxidizedThe agent, water, conductive metal salt and optional ammonia-containing solution are placed under the conditions that the conductivity is more than or equal to 200uS/cm, the oxidation-reduction potential ORP value is less than or equal to 100mv, and the concentration of a complexing agent is 3-50 g/L for reaction, so that the mass transfer rate of the solution can be accelerated, an interface film formed on the surface of a metal simple substance and/or a metal oxide can be broken down, the electronic conduction of a liquid-solid interface film is realized, the electrochemical corrosion is generated on the surface of a solid metal simple substance and/or the metal oxide, the oxidation-reduction reaction which cannot be realized by the traditional chemical reaction is solved, oxidant is continuously added in the middle and later stages of the reaction, the appearance of primary particles is controlled by adjusting the oxidation-reduction potential ORP value of a reaction system, the internal structure of the obtained precursor is more suitable for single crystal materials, the DCR value can be more effectively reduced after the precursor is sintered into the anode material of a lithium ion battery, meanwhile, the process adopts the metal simple substance and/or the metal oxide as the raw material, water is continuously consumed in the reaction process, no redundant wastewater is generated, and the process is environment-friendly. Based on this, the present invention has been completed.
Specifically, the invention provides a single crystal material precursor, wherein the single crystal material precursor comprises an inner core and an outer shell layer coated on the surface of the inner core, the inner core is a divalent metal hydroxide, the outer shell layer is a mixture of the divalent metal hydroxide and a trivalent metal hydroxide, the proportion of the trivalent metal hydroxide in the single crystal material precursor is less than 10%, and the single crystal material precursor can be converted into a single crystalline metal oxide after being subjected to oxidizing roasting. The proportion of the trivalent metal hydroxide is 10% or less, and may be, for example, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or the like.
In a preferred embodiment, the particle diameter D50 of the single crystal material precursor is 3 to 12 μm, and may be, for example, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, or the like.
In a preferred embodiment, the particle diameter D50 of the inner core is 1/5-1/2 of the whole particle diameter D50 of the single crystal material precursor, for example, 1/5, 1/4, 1/3, 1/2 and the like.
In a preferred embodiment, the metal element in the single-crystal material precursor is selected from at least one of nickel, cobalt, manganese, aluminum, zirconium, tungsten, magnesium, strontium, and yttrium, and particularly preferably a nickel-cobalt-manganese combination or a combination of nickel-cobalt-manganese and at least one of aluminum, zirconium, tungsten, magnesium, strontium, and yttrium.
The invention provides a preparation method of a single crystal material precursor, which comprises the following steps:
s1, carrying out chemical corrosion crystallization reaction on a metal simple substance and/or a metal oxide, an oxidant I, water, a conductive metal salt and an optional ammonia-containing solution under the conditions that the conductivity is more than or equal to 200uS/cm, the oxidation-reduction potential ORP value is less than or equal to 100mv, and the concentration of a complexing agent is 3-50 g/L to generate metal hydroxide particles, adding an oxidant II to carry out oxidation reaction when the particle diameter D50 of the particles is as long as 1/5-1/2 of the target particle diameter D50 of the precursor of the single crystal material, wherein the oxidation-reduction potential ORP value of the oxidation reaction is not lower than the oxidation-reduction potential ORP value of the chemical corrosion crystallization reaction, and obtaining precipitation slurry;
s2, carrying out magnetic separation on the precipitation slurry to obtain magnetic particles and slurry, carrying out solid-liquid separation on the slurry to obtain solid particles and filtrate, and washing and drying the solid particles to obtain the single crystal material precursor.
In a preferred embodiment, the metal element in the elemental metal and/or metal oxide is selected from at least one of nickel, cobalt, manganese, aluminum, zirconium, tungsten, magnesium, strontium, and yttrium, and particularly preferably a nickel cobalt manganese combination or a combination of nickel cobalt manganese and at least one of aluminum, zirconium, tungsten, magnesium, strontium, and yttrium.
In a preferred embodiment, the ammoniated solution is selected from at least one of ammonia, ammonium sulphate, ammonium chloride, ethylenediaminetetraacetic acid and ammonium nitrate.
In the present invention, the term "complexing agent" refers to a substance capable of complexing metal ions formed during a chemical etching crystallization reaction and reducing a supersaturation coefficient of a system, wherein ammonia gas generated after nitric acid (oxidizing agent) participates in the chemical etching crystallization reaction and an ammonia-containing solution can be both used as the complexing agent, that is, the concentration of the complexing agent refers to the total concentration of the ammonia gas generated by the oxidizing agent and the ammonia-containing solution. When the oxidant I is nitric acid, ammonia gas is generated in a reaction product, and at the moment, an ammonia-containing solution serving as a complexing agent does not need to be added additionally or only a small amount of ammonia-containing solution is added; when the oxidant is oxygen, air, sodium chlorate, potassium permanganate, hydrogen peroxide and the like, ammonia-containing solution is required to be added as a complexing agent. The concentration of the complexing agent in the chemical etching crystallization reaction process is 3-50 g/L, for example, 3g/L, 4g/L, 5g/L, 6g/L, 7g/L, 8g/L, 9g/L, 10g/L, 15g/L, 20g/L, 25g/L, 30g/L, 35g/L, 40g/L, 45g/L, 50g/L and the like.
In a preferred embodiment, the oxidizing agent i is selected from at least one of nitric acid, oxygen, air, sodium chlorate, potassium permanganate, and hydrogen peroxide; the oxidant II is at least one selected from oxygen, air and hydrogen peroxide. When the oxidant I is nitric acid, ammonia gas can be generated by chemical corrosion precipitation reaction and can be used as a complexing agent, and at the moment, no extra ammonia-containing solution or only a small amount of ammonia-containing solution is needed to be added in the chemical corrosion crystallization reaction process so as to meet the concentration requirement. If other oxidants are adopted as the oxidant I, a complexing agent is additionally added for control.
In the invention, the reaction of converting the elementary metal and/or the metal oxide into the divalent metal hydroxide by electrochemical corrosion runs through the whole chemical corrosion crystallization reaction and the oxidation reaction, and the specific reaction process is as follows: me → Men++ne，MexOy→Men++ (n-2x/y) e. The chemical corrosion crystallization reaction generates divalent metal hydroxide particles, then oxidizing by adding an oxidizing agent II, at least part of metal ions on the outer surface of the divalent metal hydroxide particles are oxidized into trivalent ions, meanwhile, metal monomer and/or metal oxide surface is continuously subjected to electrochemical corrosion to form new divalent metal hydroxide, the new divalent metal hydroxide is continuously deposited on the surface of the original particles, part of metal ions are oxidized into trivalent ions in the electrochemical corrosion and deposition processes, and thus, the mono-metal hydroxide comprising an inner core (divalent metal hydroxide) and an outer shell layer (mixture of the divalent metal hydroxide and the trivalent metal hydroxide) coated on the surface of the inner core is obtainedA crystal material precursor. The oxidant I and the water are used as raw materials to participate in electrochemical corrosion reaction of the simple metal and/or the metal oxide, and the use amount of the oxidant I and the water is only required to convert the simple metal and/or the metal oxide into corresponding divalent metal hydroxide. The oxidizing agent II is used as a raw material to participate in the oxidation reaction of the divalent metal hydroxide in an amount sufficient to ensure that the proportion of the trivalent metal hydroxide is 10% or less. In the chemical corrosion crystallization reaction process, water is used as a raw material to participate in the reaction, water is continuously consumed in the crystallization process, and no redundant wastewater is generated, so that the purpose of environmental friendliness is achieved in the crystallization process.
In the invention, the conductivity needs to be controlled to be more than 200uS/cm in the chemical corrosion crystallization reaction process, and is preferably controlled to be 200-50000 uS/cm. The conductivity may be, for example, 200uS/cm, 300uS/cm, 400uS/cm, 500uS/cm, 600uS/cm, 700uS/cm, 800uS/cm, 900uS/cm, 1000uS/cm, 1100uS/cm, 1200uS/cm, 1300uS/cm, 1400uS/cm, 1500uS/cm, 1600uS/cm, 1700uS/cm, 1800uS/cm, 1900uS/cm, 2000uS/cm, 3000uS/cm, 4000uS/cm, 5000uS/cm, 10000uS/cm, 15000uS/cm, 20000uS/cm, 25000uS/cm, 30000uS/cm, 35000uS/cm, 45000uS/cm, 50000uS/cm or the like. When the conductivity of the chemical corrosion crystallization reaction is controlled to be in the above range, the mass transfer rate is accelerated, and H+The interface film formed on the surface of the metal simple substance and/or the metal oxide can be broken down, so that the oxidation-reduction reaction is smoothly carried out, and the metal simple substance and/or the metal oxide is converted into corresponding metal hydroxide. In addition, the conductivity can be controlled by the amount of the conductive metal salt. Specific examples of the conductive metal salt include, but are not limited to: at least one of sulfate, chloride and nitrate of sodium and/or lithium, specifically at least one selected from sodium sulfate, sodium chloride, sodium nitrate, lithium sulfate, lithium chloride and lithium nitrate.
The oxidation-reduction potential ORP value of the oxidation reaction needs to be not lower than the oxidation-reduction potential ORP value of the chemical etching crystallization reaction. Specifically, the chemical corrosion crystallization reaction is carried out under the condition that the oxidation-reduction potential ORP value is less than or equal to 100mv, and preferably between-2000 mv and 100 mv. The oxidation-reduction potential ORP value of the chemical etching crystallization reaction may be, for example, -2000mv, -1900mv, -1800mv, -1700mv, -1600mv, -1500mv, -1400mv, -1300mv, -1200mv, -1100mv, -1000mv, -900mv, -800mv, -700mv, -600mv, -500mv, -400mv, -300mv, -200mv, -100mv, 0mv, 100mv, etc. In a preferred embodiment, the oxidation reaction has an oxidation-reduction potential ORP value 100 to 500mv higher than that of the chemical etching crystallization reaction. Specifically, the oxidation reaction can be carried out under the condition that the oxidation-reduction potential ORP value is-800-100 mv, preferably-500-100 mv. The oxidation reaction oxidation reduction potential ORP value can be, for example, -800mv, -700mv, -600mv, -500mv, -400mv, -300mv, -200mv, -100mv, 0mv, 100mv, etc. When the oxidation-reduction potential ORP value of the chemical corrosion crystallization reaction and the oxidation reaction is controlled within the above range, not only can the electrochemical corrosion of the liquid-solid interface film be realized, the oxidation of the metal simple substance and/or the metal oxide is promoted and the metal oxide is crystallized to form the divalent metal hydroxide core, but also the ORP value can be controlled by adjusting the adding amount of the oxidant, so that the metal on the surface of the divalent metal hydroxide core is continuously oxidized into trivalent metal, and new metal hydroxide is continuously deposited on the surface of the core. The extent of oxidation of the divalent metal hydroxide to the trivalent metal hydroxide is controlled primarily by the ORP value. In addition, because the colors of the metal ions in different valence states are generally different, for example, divalent nickel is green, trivalent nickel is yellow green, divalent cobalt is pink, and trivalent cobalt is light pink, the degree of oxidation of divalent metal hydroxide into trivalent metal hydroxide can be finely controlled by a color spectrometer, and the degree of oxidation can be known by comparing the product color with a standard color card. The oxidation-reduction potential ORP value can be controlled by the combination of the conductivity and the ammonia and/or ammonium concentration in the reaction system. In the present invention, the oxidation-reduction potential ORP value is measured by a Mettler-Torledo S220 multiparameter tester.
The chemical corrosion crystallization reaction and the oxidation reaction are continuous reactions or batch reactions. In a preferred embodiment, the chemical etching crystallization reaction conditions include an oxidation reduction potential ORP value of 100mv or less and a reaction temperature of 100mv or lessThe stirring input power is 1-7 kw/m at 20-90 DEG C2H, the concentration of metal ions in the reaction system is 1-30 g/L, the concentration of a complexing agent is 3-50 g/L, the pH value is 6-12, and the reaction time is 30-150 h. In a preferred embodiment, the oxidation reaction conditions include an oxidation-reduction potential ORP value of-800-100 mv, a reaction temperature of 20-90 ℃, and a stirring input power of 1-7 kw/m2H, the pH value is 6-12, and the reaction time is 30-150 h.
In a preferred embodiment, the magnetic separation is intermittent magnetic separation or continuous magnetic separation, and the magnetic separation intensity is 100-5000 Gas.
In a preferred embodiment, the method for preparing the precursor of the single crystal material further comprises returning the magnetic particles, the filtrate and the washing water to the chemical corrosion crystallization reaction system to replenish water consumed in the crystallization process.
The invention also provides a preparation method of the composite oxide powder, which comprises the steps of mixing the single crystal material precursor with a lithium source and then roasting.
In a preferred embodiment, the single crystal material precursor and the lithium source have a molar ratio of Li/Me of (0.9-1.3): 1.
In a preferred embodiment, the roasting condition comprises that the temperature is 600-1100 ℃ and the time is 5-40 h, and the roasting atmosphere is air atmosphere or oxygen atmosphere.
In a preferred embodiment, the lithium source is selected from at least one of lithium hydroxide, lithium acetate, lithium nitrate, lithium sulfate, and lithium bicarbonate.
The invention also provides the composite oxide powder prepared by the method.
In addition, the invention also provides the application of the composite oxide powder as the anode material of the single crystal type lithium ion battery.
Compared with a coprecipitation method, the method for preparing the single crystal material precursor by using the chemical corrosion crystallization method has the advantages that the DCR of the lithium ion battery can be reduced, water is used as a raw material to participate in the reaction, the water is continuously consumed, no redundant wastewater is generated, and the method is environment-friendly.
Drawings
FIG. 1 is an SEM photograph of a precursor of a single-crystal material obtained in example 1;
FIG. 2 is an SEM photograph of the composite oxide powder obtained in example 1.
Detailed Description
The present invention will be described in detail below by way of examples.
Example 1
S1, adding a metal mixture (Ni, Co, Mn and Al are mixed according to a molar ratio of 1:1:1: 0.01), nitric acid and high-purity water into a reactor in which a sodium chloride aqueous solution with a concentration of 50g/L is added in advance and simultaneously according to a molar ratio of 10:1:1, adding 2g/L ammonium sulfate, controlling an oxidation-reduction potential ORP value to be-1000 mv, controlling the electric conductivity to be 20000uS/cm, controlling the concentration of a complexing agent to be 15g/L and controlling the stirring input power to be 3.5kw/m under the normal pressure condition3H, controlling the concentration of metal ions at a value of 30g/L, pH to be 8.5, controlling the reaction temperature at 60 ℃ to perform chemical corrosion crystallization reaction for 40h, controlling the particle size d50 to be 1 mu m, introducing oxidant air at a speed of 10L/h, controlling the oxidation-reduction potential to be-800 mv, monitoring the color of the material by using a chromatograph, continuously staying the material in the reactor for 120h, continuously consuming water in the crystallization process without generating redundant wastewater, performing magnetic separation at a magnetic separation strength of 1000Gas after full reaction to obtain magnetic particles and slurry, performing solid-liquid separation on the slurry to obtain solid particles and filtrate, washing and drying the solid particles to obtain a single crystal material precursor, returning the magnetic particles, the filtrate and the washing water to the reaction kettle to continue the reaction, and supplementing water consumed in the crystallization process. The SEM image of the precursor of the single crystal material is shown in figure 1, and as can be seen from figure 1, the particles of the precursor of the single crystal material are uniformly distributed, the appearance is similar to a sphere, and the surface is loose and porous. XRD detection results show that the single crystal material precursor is metal hydroxide particles and comprises an inner core and an outer shell layer coated on the surface of the inner core, the inner core is composed of divalent metal hydroxide, the outer shell layer is composed of a mixture of divalent metal hydroxide and trivalent metal hydroxide, and the trivalent metal hydroxide in the single crystal material precursor accounts for The ratio is 5-6%. The laser particle size detection result shows that the particle size D50 of the single crystal material precursor is 4.3 mu m.
The precursor and the lithium source are uniformly mixed according to the Li/Me molar ratio of 1.08:1, and then sintered at 940 ℃ for 12 hours to finally obtain the composite oxide powder with Li/Me of 1.08. The SEM image of the composite oxide powder is shown in fig. 2, and it can be seen from fig. 2 that the composite oxide powder is a single crystal product.
The composite oxide powder is used as a positive electrode material, and the positive electrode material, conductive carbon black and polyvinylidene fluoride (PVDF) are dissolved in an NMP solvent according to the mass ratio of 75:15:10 under a vacuum condition to prepare positive electrode slurry with the solid content of 70 weight percent. And coating the positive electrode slurry on a current collector aluminum foil, drying at 120 ℃ in vacuum for 12h, and punching to obtain a positive electrode wafer with the diameter of 19 mm. Graphite, CMC and SBR are dissolved in deionized water according to the mass ratio of 90:5:5 under the vacuum condition to prepare negative pole slurry with the solid content of 40 weight percent. And coating the negative electrode slurry on a current collector copper foil, drying at 100 ℃ in vacuum for 12h, and punching to obtain a negative electrode wafer with the diameter of 19 mm. The battery is assembled in a glove box filled with argon for operation, the assembly sequence is positive electrode shell-positive electrode sheet-diaphragm-negative electrode sheet-stainless steel sheet-spring sheet-negative electrode shell, the electrolyte is 1mol/L LiPF6/EC: DMC (volume ratio of 1:1) added with 10% (volume fraction) fluoroethylene carbonate (FEC), and the diaphragm is a polypropylene microporous membrane, thus obtaining the lithium ion battery. The 10% SOC DCR value of the lithium ion battery was 15m Ω. The lithium ion battery is charged and discharged at 4.45V, the first discharge capacity is 185mAh/g, and the first charge and discharge efficiency is 94.8%.
Example 2
S1, adding a metal mixture (five metals of Ni, Co, Mn, Al and Zr are mixed according to a molar ratio of 7:1:3:0.006: 0.003), nitric acid and high-purity water into a reactor in which a sodium chloride aqueous solution with the concentration of 40g/L is added in advance in parallel according to a molar ratio of 10:1:2, adding 30g/L ammonium sulfate simultaneously, controlling the oxidation-reduction potential ORP value to be-700 mv, the conductivity to be 10000uS/cm, the concentration of a complexing agent to be 50g/L and the stirring input power to be 3.0kw/m under the normal pressure condition3H, controlling the metal ion concentration at 35g/L, pH value at 9.0 and the reaction temperature at 60 DEG CThe method comprises the following steps of carrying out chemical corrosion crystallization reaction for 24 hours under the condition of (1.5) micron particle size d50, introducing oxidant air at the rate of 30L/h, controlling the oxidation-reduction potential ORP value to be-400 mv, monitoring the color of the material by using a chromatograph, continuously keeping the material in a reactor for 80 hours, continuously consuming water in the crystallization process, not generating redundant wastewater, carrying out magnetic separation under the magnetic separation strength of 3000Gas after full reaction to obtain magnetic particles and slurry, carrying out solid-liquid separation on the slurry to obtain solid particles and filtrate, washing and drying the solid particles to obtain a single crystal material precursor, returning the magnetic particles, the filtrate and washing water to the reaction kettle for continuous reaction, and supplementing water consumed in the crystallization process. SEM detection results show that the precursor particles of the single crystal material are uniformly distributed, the appearance is similar to a sphere, and the surface is loose and porous. XRD detection results show that the single crystal material precursor is metal hydroxide particles and comprises an inner core and an outer shell layer coated on the surface of the inner core, the inner core is composed of divalent metal hydroxide, the outer shell layer is composed of a mixture of the divalent metal hydroxide and trivalent metal hydroxide, and the proportion of the trivalent metal hydroxide in the single crystal material precursor is 4-5%. The laser particle size detection result shows that the particle size D50 of the single crystal material precursor is 3.8 μm.
The precursor and the lithium source are uniformly mixed at a Li/Me molar ratio of 1.05:1, and then sintered at 900 ℃ for 24 hours to finally obtain the composite oxide powder with Li/Me of 1.05. SEM results of the composite oxide powder show that the composite oxide powder is a single crystal product.
The lithium ion battery was prepared by the method of example 1 using the composite oxide powder as a positive electrode material. The DCR value of the lithium ion battery at 10% SOC is 20m Ω. The lithium ion battery is charged and discharged at 4.45V, the first discharge capacity is 212mAh/g, and the first charge and discharge efficiency is 94.3%.
Example 3
S1, adding a metal mixture (five metals of Ni, Co, Mn and Mg are mixed according to a molar ratio of 6:2:2: 0.002), nitric acid and high-purity water into a reactor in which a sodium sulfate aqueous solution with a concentration of 90g/L is added in parallel according to a molar ratio of 10:1:1.5, adding 10g/L of ammonium sulfate simultaneously, and oxidizing under normal pressureThe reduction potential ORP value is controlled at-500 mv, the conductivity is controlled at 1000uS/cm, the concentration of the complexing agent is controlled at 30g/L, and the stirring input power is controlled at 3.0kw/m3H, controlling the concentration of metal ions at 35g/L, pH value to 9.0, controlling the reaction temperature at 60 ℃ to perform chemical corrosion crystallization reaction for 48h, controlling the particle diameter d50 to 2 mu m, introducing oxidant air at the speed of 30L/h, controlling the oxidation-reduction potential ORP value to 0mv, monitoring the color of the material by using a chromatograph, continuously staying the material in the reactor for 76h, continuously consuming water in the crystallization process without generating redundant wastewater, performing magnetic separation at the magnetic separation strength of 5000Gas after full reaction to obtain magnetic particles and slurry, performing solid-liquid separation on the slurry to obtain solid particles and filtrate, washing and drying the solid particles to obtain a single crystal material precursor, returning the magnetic particles, the filtrate and the washing water to the reaction kettle to continue reaction, and supplementing the water consumed in the crystallization process. SEM detection results show that the precursor particles of the single crystal material are uniformly distributed, the appearance is similar to a sphere, and the surface is loose and porous. XRD detection results show that the single crystal material precursor is metal hydroxide particles and comprises an inner core and an outer shell layer coated on the surface of the inner core, the inner core is composed of divalent metal hydroxide, the outer shell layer is composed of a mixture of the divalent metal hydroxide and trivalent metal hydroxide, and the proportion of the trivalent metal hydroxide in the single crystal material precursor is 8-9%. The laser particle size detection result shows that the particle size D50 of the single crystal material precursor is 5.2 μm.
The precursor and the lithium source are uniformly mixed at a Li/Me molar ratio of 1.05:1, and then sintered at 900 ℃ for 24 hours to finally obtain the composite oxide powder with Li/Me of 1.05. SEM results of the composite oxide powder show that the composite oxide powder is a single crystal product.
The lithium ion battery was prepared by the method of example 1 using the composite oxide powder as a positive electrode material. The DCR value of the lithium ion battery at 10% SOC is 20m Ω. The lithium ion battery is charged and discharged at 4.45V, the first discharge capacity is 205mAh/g, and the first charge and discharge efficiency is 94.7%.
Comparative example 1
Preparing a single crystal material precursor and composite oxide powder according to the method of example 1, except that air is not introduced for continuous oxidation after the particle diameter d50 is as long as 1 μm, and magnetic separation and subsequent steps are carried out after the reaction is continued for 120h under the original condition, and the rest conditions are the same as those in example 1, so as to obtain the reference single crystal material precursor.
SEM detection results show that the precursor particles of the reference single crystal material are uniformly distributed, the appearance is similar to a sphere, and the surface is loose and porous. XRD detection results show that the reference single crystal material precursor is metal hydroxide particles, and all metals in the metal hydroxide particles are divalent. The laser particle size detection result shows that the particle size D50 of the reference monocrystalline material precursor is 4.8 μm.
The Li/Me molar ratio of the precursor to the lithium source is 1.05:1, the mixture is uniformly mixed and then sintered at 900 ℃ for 24 hours, and finally the reference composite oxide powder with Li/Me of 1.05 is obtained. SEM results of the reference composite oxide powder show that the composite oxide powder is a single crystal product.
The lithium ion battery was prepared by the method of example 1 using the reference composite oxide powder as a positive electrode material. The 10% SOC DCR value of the lithium ion battery is 80m omega. The lithium ion battery is charged and discharged at 4.45V, the first discharge capacity is 165mAh/g, and the first charge and discharge efficiency is 90.8%.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (14)
1. A method for preparing a precursor of a single crystal material, comprising:
s1, carrying out chemical corrosion crystallization reaction on a metal simple substance and/or a metal oxide, an oxidant I, water, a conductive metal salt and an optional ammonia-containing solution under the conditions that the conductivity is more than or equal to 200uS/cm, the oxidation-reduction potential ORP value is less than or equal to 100mv, and the concentration of a complexing agent is 3-50 g/L to generate metal hydroxide particles, adding an oxidant II to carry out oxidation reaction when the particle diameter D50 of the particles is as long as 1/5-1/2 of the target particle diameter D50 of the precursor of the single crystal material, wherein the oxidation-reduction potential ORP value of the oxidation reaction is not less than the oxidation-reduction potential ORP value of the chemical corrosion crystallization reaction, and obtaining precipitation slurry;
S2, carrying out magnetic separation on the precipitation slurry to obtain magnetic particles and slurry, carrying out solid-liquid separation on the slurry to obtain solid particles and filtrate, and washing and drying the solid particles to obtain a single crystal material precursor;
the metal element in the metal simple substance and/or the metal oxide is selected from at least one of nickel, cobalt, manganese, aluminum, zirconium, tungsten, magnesium, strontium, titanium and yttrium;
the oxidant I is at least one selected from nitric acid, oxygen, air, sodium chlorate, potassium permanganate and hydrogen peroxide;
the oxidant II is at least one selected from oxygen, air and hydrogen peroxide;
the single crystal material precursor comprises an inner core and an outer shell layer coated on the surface of the inner core, wherein the inner core is a divalent metal hydroxide, the outer shell layer is a mixture of the divalent metal hydroxide and a trivalent metal hydroxide, the proportion of the trivalent metal hydroxide in the single crystal material precursor is less than 10%, and the single crystal material precursor can be converted into a single crystalline metal oxide after being oxidized and roasted.
2. The method for producing a single crystal material precursor according to claim 1, wherein the conductive metal salt is selected from at least one of a sulfate, a chloride, and a nitrate of sodium and/or lithium;
The ammoniated solution is at least one selected from ammonia water, ammonium sulfate, ammonium chloride, ethylenediamine tetraacetic acid and ammonium nitrate.
3. The method of producing a single crystal material precursor according to claim 1, wherein the chemical etching crystallization reaction and the oxidation reaction are a continuous reaction or a batch reaction.
4. The method for producing a precursor for a single crystal material according to claim 1, wherein an oxidation-reduction potential ORP value of the oxidation reaction is 100 to 500mv higher than an oxidation-reduction potential ORP value of the chemical etching crystallization reaction.
5. The method for preparing a precursor of a single crystal material according to claim 1, wherein the conditions for the chemical etching crystallization reaction include an oxidation-reduction potential ORP value of 100mv or less, a reaction temperature of 20 to 90 ℃, and a stirring input power of 1 to 7kw/m2H, the concentration of metal ions in the reaction system is 1-30 g/L, the concentration of a complexing agent is 3-50 g/L, the pH value is 6-12, and the reaction time is 30-150 h.
6. The method for preparing a precursor of a single crystal material according to claim 1, wherein the oxidation reaction conditions include an oxidation-reduction potential ORP value of-800 to 100mv, a reaction temperature of 20 to 90 ℃, and a stirring input power of 1 to 7kw/m 2H, the pH value is 6-12, and the reaction time is 30-150 h.
7. The method for preparing the precursor of the single crystal material according to claim 1, wherein the magnetic separation is continuous magnetic separation or intermittent magnetic separation, and the magnetic separation strength is 100-5000 Gas.
8. A single crystal material precursor prepared by the method of any one of claims 1 to 7, wherein the single crystal material precursor comprises an inner core and an outer shell layer coated on the surface of the inner core, the inner core is composed of divalent metal hydroxide, the outer shell layer is composed of a mixture of divalent metal hydroxide and trivalent metal hydroxide, the proportion of the trivalent metal hydroxide in the single crystal material precursor is less than 10%, and the single crystal material precursor can be converted into a single crystalline state metal oxide after being subjected to oxidizing roasting.
9. The single crystal material precursor according to claim 8, wherein the particle diameter D50 of the single crystal material precursor is 3 to 12 μm; the particle size D50 of the inner core is 1/5-1/2 of the whole particle size D50 of the single crystal material precursor.
10. The single-crystal material precursor according to claim 8 or 9, wherein the metal element in the single-crystal material precursor is at least one selected from the group consisting of nickel, cobalt, manganese, aluminum, zirconium, tungsten, magnesium, strontium, titanium, and yttrium.
11. A method for producing a composite oxide powder, comprising mixing the single-crystal material precursor according to any one of claims 8 to 10 with a lithium source and then firing the mixture.
12. The method for preparing the composite oxide powder according to claim 11, wherein the Li/Me molar ratio of the single-crystal material precursor to the lithium source is (0.9-1.3): 1; the roasting condition comprises that the temperature is 600-1100 ℃, the time is 5-40 h, and the roasting atmosphere is air atmosphere or oxygen atmosphere; the lithium source is selected from at least one of lithium hydroxide, lithium acetate, lithium nitrate, lithium sulfate and lithium bicarbonate.
13. Composite oxide powder obtainable by the process according to claim 11 or 12.
14. Use of the composite oxide powder of claim 13 as a positive electrode material for single crystal lithium ion batteries.
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