CN107565121B - Preparation method of modified positive electrode material of lithium battery - Google Patents
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Abstract
The invention discloses a preparation method of a lithium battery modified anode material, which takes soluble nickel, cobalt and manganese salts as raw materials, adopts a coprecipitation reaction process, and prepares the lithium battery anode material by full-automatic control.
Description
The technical field is as follows:
the invention relates to a preparation method of a lithium ion battery anode material, in particular to a preparation method of a lithium ion battery modified anode material.
Background art:
as a novel green battery, the lithium ion battery is widely applied to various aspects such as wireless communication, transportation, aerospace and the like, and mainly comprises a positive electrode material such as a lithium-embedded transition metal oxide, a negative electrode material such as highly graphitized carbon, a diaphragm such as a polyolefin microporous membrane, an electrolyte material and the like. The lithium ion anode material is a crucial factor for restricting the performance of the lithium ion battery in all aspects. The performance of the lithium ion battery anode material, which is one of the key materials in the lithium ion battery, directly influences the performance of the whole lithium ion battery. Therefore, researchers mainly pay attention to the performance and characteristics of the positive and negative electrode materials of the lithium ion battery when solving the problems in the use of the lithium ion battery or improving the performance of the lithium ion battery. At present, lithium ion positive electrode materials on the market are more, and lithium cobaltate, lithium manganate and lithium iron phosphate are mainly used. The nickel cobalt lithium manganate serving as the ternary positive electrode material is unique in the positive electrode materials of various lithium batteries due to the excellent performance, high quality, low price and the like, and is widely applied.
Compared with L iCoO2 which is commercialized, the nickel-cobalt-manganese-lithium anode material is easier to synthesize and has relatively better cycle performance and thermal stability, compared with spinel L iMn O4, the nickel-cobalt-manganese-lithium anode material has a more stable structure in the charge and discharge processes, a JahnTeller effect cannot occur, Mn ions are stable, and the Mn ions cannot be dissolved in an electrolyte, and compared with L iFePO4, the nickel-cobalt-manganese-lithium anode material has large tap density and a high potential platform.
The Chinese patent publication No. CN103296270A discloses a lithium ion battery anode material nickel cobalt lithium manganate and a preparation method thereof, wherein nickel, cobalt and manganese in sulfate are mixed according to the molar ratio of 1:1 preparing a mixed aqueous solution, then reacting with sodium hydroxide and ammonia water in a reaction device, injecting nitrogen and water hydrazine, aging, filtering, washing with water, drying to obtain a nickel cobalt manganese hydroxide product, and mixing and sintering with lithium carbonate to obtain the spherical nickel cobalt lithium manganate.
However, the above method has the disadvantages of more added compounds, overlong reaction process steps and incapability of automatically controlling the reaction process. The labor intensity of manual operation is high, and the performance of the nickel cobalt lithium manganate positive battery prepared by reaction still has defects, which mainly show that certain defects exist in the aspects of discharge stability and cycle performance. The method for preparing the lithium nickel cobalt manganese oxide of the ternary positive electrode material has reliable quality, the lithium nickel cobalt manganese oxide of the ternary positive electrode material has excellent performance, namely a differential lithium nickel cobalt manganese oxide material, the whole preparation process is automatically controlled, and the prepared lithium nickel cobalt manganese oxide has stable product performance and excellent cycle performance.
On the other hand, the specific energy of the prepared lithium battery is not high by adopting the existing method for preparing the nickel cobalt lithium manganate, and meanwhile, the specific capacity and the conductivity-rate performance of the prepared lithium battery are also lower. The excellent performance of the lithium battery anode material can not be effectively exerted. The firing process is a chemical reaction process under an oxidizing atmosphere, and how to control the oxygen concentration, namely the oxygen atmosphere, in the firing process to ensure that the reaction can be fully performed is one of the key factors for preparing the high-quality modified lithium battery material.
Meanwhile, in the preparation process of the nickel cobalt lithium manganate type lithium battery anode material, due to the fact that particle size diameters of raw materials are different and have certain difference, reactants can not be in contact with each other more fully in the reaction process, particles of the materials are not mixed uniformly, certain performance difference is caused to products prepared after reaction, the battery performance of the lithium battery anode material is influenced, in the production and preparation process, the performance of the prepared nickel cobalt lithium manganate type lithium battery anode material is improved and enhanced well through multiple mechanical ball milling activation treatments, and the performance of the lithium battery anode material is greatly improved. So that the capacity and the cycle performance are more excellent.
The invention content is as follows:
the invention provides a preparation method of a modified positive electrode material of a lithium battery, which is characterized in that soluble nickel, cobalt and manganese sulfates are used as raw materials, a nickel-cobalt-manganese hydroxide precursor is prepared by adopting a coprecipitation reaction, the nickel-cobalt-manganese hydroxide precursor is mixed with a lithium salt, the product prepared in each step, such as the nickel-cobalt-manganese precursor, is subjected to mechanical activation ball milling treatment by optimizing a production process, and the prepared nickel-cobalt-manganese lithium manganate is modified, so that the modified positive electrode material product of the lithium battery with high quality and excellent capacity and cycle performance is prepared.
The invention relates to a method for preparing a modified cathode material of a lithium battery, which takes soluble nickel, cobalt and manganese salts as raw materials, adopts a coprecipitation reaction process, and prepares the cathode material of the lithium battery by full automation control, and comprises the following process steps,
1) mechanical activation treatment of raw materials, namely mixing the raw materials of each component of soluble nickel, cobalt and manganese salt according to a stoichiometric ratio, placing the mixture into a ball milling device for mechanical activation ball milling treatment, controlling the mechanical activation ball milling treatment to be carried out under the condition of moisture atmosphere, and controlling the mass molar ratio of the nickel salt, the cobalt salt and the manganese salt of each component to be 0.5: 0.1-0.4: 0.4-0.1, and simultaneously controlling the sum of the mass mol ratio of each component to be 1 to obtain an activated mixed material;
2) coprecipitation reaction is carried out to prepare a crude nickel-cobalt-manganese precursor, the activated mixed material obtained in the step 1) is mixed with a solution of sodium hydroxide or potassium hydroxide and ammonium bicarbonate to prepare a mixed reaction solution, the mixed reaction solution is heated and reacts in a vacuum state until the pH value of the reaction solution is 9.5-10.3, and the reaction time is controlled to be 8-10 hours; heating, filtering and carrying out solid-liquid separation to obtain a solid, namely a crude precursor;
3) preparing a pretreatment precursor, fully washing the crude precursor with water until the washed water is neutral, controlling the pH of the washed water to be 7.5-8 to obtain a washing precursor, drying and drying the washing precursor for 4-6 hours, and then mechanically activating and ball-milling the washing precursor to obtain the pretreatment precursor;
4) preparing a lithium salt and pretreatment precursor fine particle mixture, fully stirring and mixing the pretreatment precursor and the lithium salt, and controlling the mass molar ratio of the lithium salt to the pretreatment precursor to be 1.15-1.2: 1, continuing mechanical activation ball milling treatment for 3-5 hours to obtain a mixture of lithium salt and pretreated precursor fine particles;
5) preparing a crude lithium battery anode material, placing a mixture of lithium salt and the pretreated precursor fine particles in a sintering device, pre-sintering for 4-8 hours under the oxygen-containing atmosphere or air atmosphere, cooling to room temperature along with a furnace, then carrying out crude crushing, then carrying out secondary sintering for 8-10 hours under the same atmosphere condition as the pre-sintering atmosphere, cooling and crushing to obtain single crystal or quasi-single crystal nickel cobalt lithium manganate serving as the crude lithium battery anode material;
6) and (3) preparing a modified lithium battery cathode material product, mixing the single crystal or single crystal-like nickel cobalt lithium manganate, the graphene nanosheets and the binder obtained in the step 5), homogenizing, vacuum drying, crushing, deironing, sieving and packaging to obtain the modified lithium battery cathode material product.
In the preparation method of the modified cathode material for the lithium battery, the soluble nickel, cobalt and manganese salts are nickel sulfate, cobalt sulfate and manganese sulfate, or nickel nitrate, cobalt nitrate and manganese nitrate, or nickel carbonate, cobalt carbonate and manganese carbonate; the concentration of each metal ion in the soluble nickel, cobalt and manganese salts is controlled to be 0.2-0.8 mol/L respectively.
Preferably, the heating in the step 2) is controlled to be microwave heating, the heating reaction temperature is 50-60 ℃, and the reaction is preferably controlled to be carried out under inert protective gas.
Preferably, the drying in step 3) is microwave drying or drying in a muffle furnace, and the drying temperature is controlled to be 150-300 ℃.
Preferably, in the preparation method of the modified cathode material for the lithium battery, in the step 5), the oxygen-containing atmosphere is oxygen, the gas flow rate of the oxygen-containing atmosphere or the air atmosphere is controlled to be 300-.
Further, 5) controlling the pre-sintering temperature to be 350-.
Preferably, the binder in step 6) is sodium alginate and/or polyacrylic acid or styrene butadiene rubber or sodium hydroxymethyl cellulose; the vacuum drying temperature of the step is controlled to be 100-160 ℃.
Preferably, the water is deionized water, and the average particle size of the prepared modified cathode material of the lithium battery is controlled to be 8-12 um.
The method comprises the following process steps: activating nickel cobalt manganese sulfate → preparing solution + alkali solution after activating nickel cobalt manganese sulfate → coprecipitation reaction → cleaning → detecting, drying → nickel cobalt manganese hydroxide precursor → mixing lithium salt and activating → pre-firing → crushing → secondary firing for preparing single crystal nickel cobalt lithium manganate → modifying graphene nano-sheet → sieving → mixing → deironing, and packaging to obtain the modified nickel cobalt lithium manganate product.
The lithium battery modified anode material prepared by the method is modified on the basis of the existing process for preparing the ternary nickel cobalt manganese oxide lithium battery anode material, and mechanical ball milling activation treatment is repeatedly used in the preparation process, so that the prepared lithium battery modified anode material has uniform particle size from an intermediate product to a finished product, the mixtures generate better bonding effect, lithium ions can be uniformly embedded into the precursor during sintering, and the prepared precursor has uniform particle distribution and uniform particle size. The electrochemical performance of the modified cathode material of the prepared lithium battery is better. The prepared monocrystal or monocrystal-like nickel cobalt lithium manganate is subjected to nano modification, namely the monocrystal or monocrystal-like nickel cobalt lithium manganate and the graphene nanosheet are mixed with the binder and then modified, or the monocrystal or monocrystal-like nickel cobalt lithium manganate and the carbon nanotube composite are modified and then modified with the graphene nanosheet, so that the lithium battery modified cathode material with more excellent performance is prepared. In the preparation process, mechanical ball-milling activation treatment is carried out on each component of soluble nickel, cobalt and manganese salts such as nickel sulfate, cobalt sulfate and manganese sulfate raw materials, and mechanical ball-milling activation treatment is also carried out on the prepared precursor, monocrystal nickel cobalt lithium manganate and the like, so that the prepared modified positive electrode material of the lithium battery has excellent performance, particularly the electrical cycle performance is greatly improved, and the specific capacity of the 10C multiplying power after thousands of cycles reaches more than 148 mAh/g.
The crude lithium battery anode material prepared by the method, namely a nickel cobalt lithium manganate (the stoichiometric ratio of nickel, cobalt and manganese is 5:2: 3), product is detected by relevant departments, and various technical indexes are shown in the following table 1, wherein the storage and transportation conditions are shady, cool, dry, moisture-proof and damp-proof.
TABLE 1 (partial data detection value)
In the description, the following steps are carried out,
the crude lithium battery anode material prepared by the method can be used as a lithium ion battery anode material product, and has excellent safety performance, high-temperature performance and long cycle life. Firstly, performing mechanical ball milling activation on the material by using a mechanical ball milling method to ensure that the particle size of the material is uniform, thereby achieving the purpose of fully and uniformly mixing the materials; the compound of the mixture can generate proper binding action, thereby ensuring that lithium ions are uniformly inserted into a precursor during sintering; performing mechanical ball milling activation on the mixture, and further enabling precursor particles to be uniformly distributed and uniform in particle size; and then the crude lithium battery anode material of the cobalt nickel lithium manganate with excellent electrochemical performance is obtained through presintering and roasting.
Description of the drawings:
FIG. 1 is an XRD (X-ray diffraction) diagram of a product of a nickel cobalt lithium manganate material as a crude lithium battery anode material prepared by the method of the invention;
the specific implementation mode is as follows: the invention is described in further detail below with reference to specific embodiments, it being understood that the foregoing general description and the following detailed description of the invention are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. The stoichiometric ratio in this example is a mass-to-mole ratio. The method adopts full-process automatic control, automatic feeding and batching, automatic temperature control and the like.
The invention discloses a method for preparing modified anode material of lithium battery, which takes soluble nickel, cobalt and manganese salt as raw materials, wherein the soluble nickel, cobalt and manganese salt can be corresponding carbonic acid or sulfuric acid or acetic acid salt such as nickel carbonate, cobalt carbonate, manganese carbonate and the like, and adopts coprecipitation reaction process to prepare the modified anode material of lithium battery automatically in the whole process, comprising the following process steps,
1) mechanical activation treatment of raw materials, namely mixing the raw materials of soluble nickel, cobalt and manganese salts such as nickel sulfate, cobalt sulfate and manganese sulfate according to a stoichiometric ratio, putting the mixture into a ball mill for mechanical activation ball milling treatment, simultaneously controlling the concentration of each metal ion in the soluble nickel, cobalt and manganese salts to be 0.2-0.8 mol/L respectively, controlling the mechanical activation ball milling treatment to be carried out under the condition of moisture atmosphere, simultaneously controlling the mechanical ball milling to be about 300r/min, and for the moisture humid atmosphere condition, after the mechanical ball milling activation raw materials are added into the ball mill, spraying water mist on the materials in the inner cavity of the ball mill to enable the inner cavity of the ball mill to be ball milled under moisture humidity, and controlling the mass molar ratio of each component of nickel salt, cobalt salt and manganese salt to be 0.5: 0.1-0.4: 0.4-0.1, namely controlling the mass mole ratio of the metal ions in each salt to be nickel: cobalt: manganese = 0.5: 0.1-0.4: 0.4-0.1, and simultaneously controlling the sum of the mass mol ratio of each component to be 1, namely the sum of the mass mol ratio of nickel + cobalt + manganese to be 1, so as to obtain an activated mixed material;
2) co-precipitation reaction to prepare a crude nickel-cobalt-manganese precursor, mixing the activated mixed material obtained in the step 1) with a solution of sodium hydroxide or potassium hydroxide and ammonium bicarbonate to obtain a mixed reaction solution, heating, reacting in a vacuum state, or reacting in the presence of a protective gas, such as nitrogen or argon, until the pH value of the reaction solution is 9.5-10.3, and controlling the reaction time to be 8-10 hours; the heating is microwave heating, filtering and solid-liquid separation, and the solid is a crude precursor;
3) preparing a pretreatment precursor, fully washing the crude precursor with water until the washed water is neutral, namely controlling the pH of the washed water to be 7.5-8 to obtain a washing precursor, drying and drying the washing precursor for 4-6 hours, and then mechanically activating and ball-milling the washing precursor to obtain the pretreatment precursor;
4) preparing a lithium salt and pretreatment precursor fine particle mixture, fully stirring and mixing the pretreatment precursor and the lithium salt, controlling the stirring and mixing time to be 4-5 hours, controlling the stirring and mixing time according to the prior art, and controlling the mass molar ratio of the lithium salt to the pretreatment precursor to be 1.15-1.2: 1, the lithium salt is preferably lithium carbonate, lithium acetate or lithium sulfate, or lithium chloride or lithium hydroxide and the like, and the mechanical activation ball milling treatment is continued for 3 to 5 hours to obtain a mixture of the lithium salt and the pretreatment precursor fine particles;
5) preparing a crude lithium battery anode material, placing a mixture of lithium salt and the pretreated precursor fine particles in a sintering device, pre-sintering for 4-8 hours under the condition of oxygen-containing atmosphere or air atmosphere, cooling to room temperature along with a furnace, then carrying out crude crushing, then carrying out secondary sintering for 8-10 hours under the same atmosphere condition as the pre-sintering atmosphere, cooling and crushing to obtain single crystal or quasi-single crystal nickel cobalt lithium manganate; controlling the oxygen-containing atmosphere or air atmosphere in the sintering device during pre-sintering and secondary sintering, wherein the gas flow rate of the oxygen-containing atmosphere or air atmosphere is controlled to be 300-5000ml/min, and the heating rates during pre-sintering and secondary sintering are controlled to be 5-10 ℃/min; meanwhile, the temperature rise rate during the pre-sintering can be controlled to be 2-5 ℃/min, and the temperature rise rate during the secondary sintering is controlled to be 5-10 ℃/min; the single crystal or quasi-single crystal nickel cobalt lithium manganate of the anode material of the crude lithium battery can be prepared with more stable and excellent performance by differentially controlling the temperature rise rate during sintering. Meanwhile, the oxygen can be fully mixed and contacted with the mixed materials in the sintering device, so that the sintering reaction is full; controlling the pre-sintering temperature to 350-550 ℃, and controlling the secondary sintering temperature to 1050-1200 ℃ to obtain the prepared nickel cobalt lithium manganate; thus obtaining the crude lithium battery anode material;
6) preparing a modified positive electrode material product of a lithium battery, namely mixing the monocrystal or monocrystal-like nickel cobalt lithium manganate and the graphene nanosheet of the positive electrode material of the crude lithium battery obtained in the step 5) and a binder, wherein the binder is sodium alginate and/or polyacrylic acid or styrene butadiene rubber or sodium hydroxymethyl cellulose; homogenizing, vacuum drying at the temperature of 100-.
The lithium battery modified positive electrode material product prepared in the step 6) can be prepared by a method comprising the following steps of taking the monocrystal or monocrystal-like nickel cobalt lithium manganate and the carbon nano-tube composite material of the crude lithium battery positive electrode material prepared in the step 5) as raw materials, firstly mixing the monocrystal or monocrystal-like nickel cobalt lithium manganate and the carbon nano-tube composite material in proportion, carrying out mechanical ball-milling activation treatment, then using a binder and a graphene nanosheet for bonding and mixing, and controlling the mass ratio of the monocrystal or monocrystal-like nickel cobalt lithium manganate to the carbon nano-tube composite material to be 110-: and 1, controlling the mechanical ball-milling activation treatment time to be 8-12 hours, preparing monocrystal or monocrystal-like nickel cobalt lithium manganate and carbon nano tube composite material particles, and mixing the monocrystal or monocrystal-like nickel cobalt lithium manganate and carbon nano tube composite material particles, graphene nanosheets and a binder to prepare the lithium battery modified cathode material product according to the method in the step 6). The adding amount of the binder is controlled to be 60-100 times of the amount of the single crystal or quasi-single crystal nickel cobalt lithium manganate and carbon nano tube composite particles. Namely, the mass ratio of the binder to the single crystal or quasi-single crystal nickel cobalt lithium manganate and carbon nano tube composite material particles is 1: 60-100.
Example 1 the parts not described in this example are the same as those described in the above embodiment, and the following description is given.
In this embodiment 1, the method for preparing a modified cathode material for a lithium battery according to the present invention uses soluble nickel, cobalt, and manganese salts as raw materials, where the soluble nickel, cobalt, and manganese salts may be corresponding carbonate or sulfate or acetate salts such as nickel carbonate, cobalt carbonate, and manganese carbonate, and so on. In this example, nickel sulfate, cobalt sulfate, and manganese sulfate were used as raw materials.
The stoichiometric ratio of nickel, cobalt and manganese of the material of this example was 5:2:3, which means L i, Ni, Co, Mn = 1: 0.5: 0.2: 0.3, and the chemical formula was L iNi0.5Co0.2Mn0.3O2The process is carried out by controlling the mass mol sum of nickel, cobalt and manganese as 1, that is, the mass mol ratio sum of nickel + cobalt + manganese as 1,
1) performing mechanical activation treatment on raw materials, namely mixing the raw materials of soluble nickel, cobalt and manganese salts, namely nickel sulfate, cobalt sulfate and manganese sulfate according to a stoichiometric ratio, placing the mixture in a ball milling device for mechanical activation ball milling treatment, and controlling the mechanical activation ball milling treatment to be performed under the moisture-wet atmosphere condition, namely spraying water mist on an inner cavity of the mechanical ball milling device containing the raw materials to perform ball milling mechanical activation on the nickel sulfate, cobalt sulfate and manganese sulfate under the moisture-wet atmosphere condition, wherein the used water is deionized water; controlling the concentration of each metal ion in the soluble nickel, cobalt and manganese salts to be 0.2-0.8 mol/l respectively, wherein in the mechanical ball milling activation in the embodiment, the ball-to-material ratio in the mechanical ball milling activation is controlled to be 10: 1, controlling the rotation speed of mechanical ball milling to be about 300r/min, and obtaining an activated mixed material by the same method;
2) co-precipitation reaction to prepare a crude nickel-cobalt-manganese precursor, mixing the activated mixed material obtained in the step 1) with a solution of sodium hydroxide and ammonium bicarbonate to prepare a mixed reaction solution, heating, controlling the heating reaction temperature to be 50-60 ℃, reacting in a vacuum state until the pH value of the reaction solution is 9.5-10.3, and controlling the reaction time to be 8-10 hours; the heating is microwave heating, filtering and solid-liquid separation, and the solid is a crude precursor; the mixture ratio of the activated mixed material, sodium hydroxide or potassium hydroxide and solution of ammonium bicarbonate or ammonia water is controlled according to the mixture ratio of the prior art;
3) preparing a pretreatment precursor, fully washing the crude precursor with water until the washed water is neutral, using deionized water as the used water, namely controlling the pH of the washed water to be 7.5-8, washing the crude precursor with water to obtain a washed precursor, drying and drying the washed precursor for 4-6 hours, drying by adopting a muffle furnace device, controlling the drying temperature to be 150-300 ℃, and then performing mechanical activation ball milling treatment, wherein the ball-to-material ratio during the mechanical ball milling activation is 10: 1, controlling the rotation speed of mechanical ball milling to be about 300r/min to be a pretreatment precursor;
4) preparing a crude lithium battery positive electrode material, fully stirring and mixing a pretreatment precursor and a lithium salt, wherein the lithium salt is any one of lithium carbonate, lithium sulfate, lithium acetate and lithium hydroxide, in the embodiment, preferably, lithium sulfate is used, and the mass molar ratio of the lithium salt to the pretreatment precursor is controlled to be 1.15-1.2: 1, continuing mechanical activation ball milling treatment for 3-5 hours to obtain a mixture of lithium salt and pretreated precursor fine particles;
5) preparing a crude lithium battery anode material, wherein a secondary sintering process is adopted, firstly, a mixture of lithium salt and pretreated precursor fine particles is placed in a sintering device, pre-sintering is carried out for 4-8 hours under the condition of oxygen-containing atmosphere or air atmosphere, furnace cooling is carried out to room temperature, coarse crushing is carried out, then, secondary sintering is carried out for 8-11 hours under the condition of the same atmosphere as the pre-sintering atmosphere, cooling and crushing are carried out, and the crude lithium battery anode material is a single crystal or monocrystal-like nickel cobalt lithium manganate; controlling the oxygen-containing atmosphere in the sintering device during pre-sintering and secondary sintering to be 5000ml/min with the gas flow rate of 300-; the atmosphere of air atmosphere is an air gas having an oxygen content higher than that of air. Controlling the heating rate of 2-5 ℃/min during pre-sintering and the heating rate of 5-10 ℃/min during secondary sintering; thus, the oxygen can be fully mixed and contacted with the mixed material in the sintering device, so that the sintering reaction is full; meanwhile, the temperature during pre-sintering is controlled to 350-; the prepared nickel cobalt lithium manganate is of a single crystal or quasi-single crystal structure, and the average grain diameter of the crushed single crystal or quasi-single crystal nickel cobalt lithium manganate is generally controlled to be less than 100 um;
6) preparing a modified positive electrode material product of a lithium battery, and mixing the monocrystal or monocrystal-like nickel cobalt lithium manganate prepared in the step 5) as the positive electrode material of the crude lithium battery, a graphene nanosheet and a binder, wherein the binder is sodium alginate and/or polyacrylic acid or styrene butadiene rubber or sodium hydroxymethyl cellulose; in the embodiment, the preferred binder is sodium alginate, the homogenization and the vacuum drying are carried out at the temperature of 100 ℃ and 160 ℃, the crushing and the iron removal can be carried out according to the prior art, and the obtained product is packaged into a modified lithium battery cathode material product. The average particle size of the prepared modified positive electrode material of the lithium battery is 8-12 um. The mass ratio of the graphene nanosheet to the monocrystal or monocrystal-like nickel cobalt lithium manganate serving as the anode material of the crude lithium battery is controlled to be determined according to the proportion of the prior art, and the graphene nanosheet can be prepared from the following raw materials in percentage by mass: crude lithium battery positive electrode material = 1: 110-120 ingredient mixing; the use of the binder can also be carried out in the above-mentioned proportions.
The oxygen-containing atmosphere means that the oxygen-containing gas can be sufficiently contacted with the mixture in the sintering device by the corresponding oxygen supply device under the condition that the gas flow rate in the mixture in the sintering device is controlled, namely, the outlet end of the oxygen-containing gas can extend into the mixture of the required sintering mixture, so that the oxygen-containing gas and the mixture can be maximally contacted and combusted. And fully contacting and reacting the lithium salt and the pretreatment precursor to prepare the high-quality crude nickel cobalt lithium manganate. The nickel cobalt manganese oxide material with high nickel content and excellent chemical property is prepared by the full reaction of the nickel cobalt manganese hydroxide precursor and lithium carbonate or lithium hydroxide.
The specification of the required raw materials is as follows, nickel sulfate, cobalt sulfate, manganese sulfate and lithium carbonate are all battery grade; liquid caustic soda, sodium hydroxide and potassium are industrial grade and prepared into the liquid caustic soda with the mass concentration of about 30 percent; ammonium bicarbonate or ammonia water, industrial grade, with a mass concentration of about 20%.
The raw materials of nickel sulfate, cobalt sulfate and manganese sulfate for reaction, which are purchased from the market and have the mass, are sent to a raw material warehouse for storage, are respectively conveyed to a nickel sulfate, cobalt sulfate and manganese sulfate bin reaction device of a raw material workshop according to the required amount, are weighed in an electronic decrement way, and are sent to an intermediate storage tank. The ammonium bicarbonate or the ammonia water is purchased from the market and sent into an ammonia water tank or other places for storage. According to the required quantity, the ammonium bicarbonate and the ammonia water are prepared into the ammonia water with the specified concentration, the ammonium bicarbonate is prepared into the aqueous solution with the specified concentration, and the aqueous solution is sent into an intermediate storage tank for standby.
The reactants flow into each reaction device according to the set measurement by the computer control system, and the nickel, cobalt, manganese and ammonium bicarbonate or ammonia water are quantitatively fed into each reaction kettle of the coprecipitation reaction by the computer DCS control system according to the process requirements. The concentration of the sodium hydroxide solution is generally controlled to be 7.2-7.5 mol/l; the concentration of the added ammonia water is about 10 Wt%.
The continuous detection pH meter is arranged in each reaction kettle, the computer compares the detected pH value with a set pH value, and the artificial intelligent control algorithm is adopted to automatically adjust the given amount of the alkali liquor such as sodium hydroxide solution through the mass flow controller, so that the reaction is always carried out within the set pH value range, and the synthesis quality of the precursor is ensured. And (3) cleaning the coprecipitation reaction slurry from the coprecipitation reaction kettle to remove impurity ions, washing with clear water during cleaning, and controlling the pH of the material to be lower than 8.0. And (4) sending the washed slurry into a dryer device for drying, and drying to ensure that crystal water in the precursor is not decomposed. And (3) feeding the washing waste liquid into a sewage treatment station, removing ammonia nitrogen ions by an ammonia distillation method, feeding into a sewage treatment plant, treating to reach the standard, and discharging.
Crushing the lithium nickel cobalt manganese oxide by a crusher, then crushing the lithium nickel cobalt manganese oxide by a crusher, sieving the crushed lithium nickel cobalt manganese oxide by a vibrating screen to obtain the lithium nickel cobalt manganese oxide with the granularity requirement, and mixing, sieving and removing iron from the materials.
In the firing process, the method provided by the invention enables materials to react, the pretreated precursor fine particle mixture and L i2CO3 can fully react, and the + 3-valent nickel ions in the material can stably exist, so that residual lithium on the surface of the material is effectively controlled, and the final product can exert excellent electrochemical performance.
Example 2
In this embodiment 1, soluble nickel, cobalt, and manganese salts are used as raw materials, and the raw materials of the soluble nickel, cobalt, and manganese salts may be corresponding carbonic acid salts, sulfuric acid salts, or acetic acid salts, such as nickel carbonate, cobalt carbonate, and manganese carbonate salts, and so on.
The stoichiometric ratio of nickel, cobalt and manganese in the material of the embodiment is 5: 3: 2, and the chemical formula is L iNi0.5Co0.3Mn0.2O2L i, wherein the ratio of Ni to Co to Mn is = 1: 0.5: 0.3: 0.2, the sum of the mass mol of metal nickel, cobalt and manganese is controlled to be 1, namely the sum of the mass mol ratio of nickel + cobalt + manganese is 1, namely the mass mol ratio of lithium nitrate, nickel nitrate, cobalt nitrate and manganese nitrate is controlled to be 1: 0.5: 0.3: 0.2, the temperature rise rates of presintering and secondary sintering are controlled to be 5-10 ℃/min, and 6) the lithium battery modified positive electrode material product is prepared by the following method, wherein the mass ratio of the single crystal or the single crystal-like nickel cobalt lithium manganate and the carbon nano composite material of the crude lithium battery positive electrode material prepared in the step 5) is controlled to be 110: 1, the mechanical ball milling activation treatment time is controlled to be 8-12 hours, the single crystal or the single crystal-like nickel cobalt lithium manganate and the carbon nano composite material are then bonded by using a binder and graphene nano sheet, the mass ratio of the single crystal or the single crystal-like nickel cobalt lithium battery or the single crystal-like nickel cobalt nano composite material and the carbon nano tube composite material is controlled to be 110: 1, and the specific method for preparing the single crystal lithium battery modified lithium battery positive electrode material by using the single crystal-like lithium nickel cobalt nano composite material and the step 6) and the single crystal lithium battery composite material.
According to the modified cathode material of the lithium battery prepared by the method, the carbon nano tube and the graphene nano sheet coated on the surface, which are internally and alternately formed into the conductive network, can greatly improve the conductivity of the cathode material, improve the power density and the charging and discharging speed of the battery, and effectively improve the capacitance of the lithium battery, the specific discharge capacity is up to 169.0 mAh.g < -1 >, and the specific capacity retention rate is more than 91% after 1000 cycles of 10C multiplying power, which is shown in Table 2;
example 3
In this embodiment 1, soluble nickel, cobalt, and manganese salts are used as raw materials, and the raw materials of the soluble nickel, cobalt, and manganese salts may be corresponding carbonic acid salts, sulfuric acid salts, or acetic acid salts, such as nickel carbonate, cobalt carbonate, and manganese carbonate salts, and so on.
The stoichiometric ratio of nickel, cobalt and manganese in the material of the embodiment is 5: 1:4, and the chemical formula is L iNi0.5Co0.1Mn0.4O2The specific process steps of the method are as in example 1, wherein the sum of the mass moles of the metal nickel, cobalt and manganese is controlled to be 1, namely the sum of the mass mole ratio of nickel + cobalt + manganese is 1, namely the mass mole ratio of lithium nitrate, nickel nitrate, cobalt nitrate and manganese nitrate is controlled to be 1: 0.5: 0.1: 0.4, namely L i: Ni: Co: Mn = 1: 0.5: 0.1: 0.4.
Example 4
In this embodiment 1, soluble nickel, cobalt, and manganese salts are used as raw materials, and the raw materials of the soluble nickel, cobalt, and manganese salts may be corresponding carbonic acid salts, sulfuric acid salts, or acetic acid salts, such as nickel carbonate, cobalt carbonate, and manganese carbonate salts, and so on.
The stoichiometric ratio of nickel, cobalt and manganese in the material of the embodiment is 5: 4: 1, and the chemical formula is L iNi0.5Co0.4Mn0.1O2The specific process steps are shown in example 1, wherein L i is Ni, Co, Mn = 1: 0.5: 0.4: 0.1, the sum of the mass moles of the metal nickel, cobalt and manganese is controlled to be 1, namely the sum of the mass mole ratios of nickel + cobalt + manganese is controlled to be 1, namely the mass mole ratio of the lithium nitrate, the nickel nitrate, the cobalt nitrate and the manganese nitrate is controlled to be 1: 0.5: 0.4: 0.1.
The embodiment shows that the preparation method of the modified lithium battery positive electrode material provided by the invention has the advantages that the precursor is prepared by a coprecipitation method, and the concentration of nickel, cobalt and manganese in a reaction system is controlled in the coprecipitation process, so that the concentration of three elements in the finally obtained precursor is in full-gradient distribution without obvious boundary, on one hand, the occurrence of core-shell separation or cracking during the subsequent sintering preparation of the positive electrode material can be effectively avoided, and on the other hand, the lithium ions can not be extracted and uniformly inserted; meanwhile, the concentration of nickel in the obtained precursor is reduced from inside to outside, and the concentration of cobalt and manganese is increased, so that the lithium battery anode material provided by the invention has the advantages of high capacity, high thermal stability, high cycle performance, high electrochemical performance and low cost.
The performance test of the modified cathode material of the lithium battery prepared by the preparation method of the modified cathode material of the lithium battery of the invention comprises the following steps: 1. XRD test A crude lithium battery cathode material nickel cobalt lithium manganate material prepared by sintering the coprecipitation precursor prepared in example 1 is tested by XRD, and the test result is shown as an XRD diagram in figure 1. 2. The charging and discharging tests show that the obtained modified cathode material of the lithium battery is assembled into a 2025 button battery, the discharging capacity and the cycle performance of the button battery are tested within the voltage range of 2.5-4.2V, the results are shown in Table 2, the discharging specific capacity of the product obtained in the embodiment is up to 169.0 mAh.g < -1 >, the specific capacity retention rate is more than 91% after 1000 cycles of 10C multiplying power, and the combined action of the carbon nano tube and the graphene is favorable for improving the performance of the cathode material of the lithium battery.
Mixing the modified positive electrode materials 1-40 of the lithium batteries prepared in the embodiments 1-4 with a conductive agent acetylene black and a related preparation according to a mass ratio, dispersing the materials into slurry by adopting NMP as a solvent, then drying the slurry in vacuum at 20 ℃ for 24h, grinding and sieving the powder, pressing the powder on a wafer nickel screen under the pressure of 2MPa to be used as a positive electrode, assembling the electrolyte into batteries of corresponding models, such as CR2016 type button batteries, after being configured according to the prior technical scheme, and performing constant current charging and discharging on the batteries by using a current of 1mA/cm2 (0.5C) on a battery performance detection device (such as a model BK-6016 AR/2), wherein the high-temperature test is performed at 55 ℃, the test device is a GiantForce Instrument Enterprise Co., L TD., corresponding models, the test conditions are that a soft package battery is used, the voltage is 2.75-4.20V, the volume-divided environmental temperature is 25 ℃, the test results are shown in a test table 2, and the test results are shown in a table 2
From the test results in table 2 above, it can be seen that the modified positive electrode material for lithium battery provided by the present invention has the advantages of high capacity, high thermal stability, high cycle performance, high electrochemical performance and low cost, and is significantly better than the sample of the comparative example. The comparative example is a lithium battery positive electrode material product obtained by the existing preparation technical method.
The performance of the modified lithium battery anode material is obtained by adopting another test mode: under the charging and discharging conditions of 40 ℃, 2-4.8V voltage and 60mA/g current, the cycle performance is excellent, the attenuation rate of the first 30 cycles is only 0.16%, the charging is carried out subsequently, and almost no attenuation is generated after 30 cycles. After thousands of cycles, the specific capacity still reaches over 145 mAh/g.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. A method for preparing modified anode material of lithium battery, which takes soluble nickel, cobalt and manganese salt as raw materials, adopts coprecipitation reaction process, and prepares anode material of lithium battery by automatic control in the whole process, and is characterized by comprising the following process steps,
1) mechanical activation treatment of raw materials, namely mixing the raw materials of each component of soluble nickel, cobalt and manganese salt according to a stoichiometric ratio, placing the mixture into a ball milling device for mechanical activation ball milling treatment, controlling the mechanical activation ball milling treatment to be carried out under the condition of moisture atmosphere, and controlling the mass molar ratio of the nickel salt, the cobalt salt and the manganese salt of each component to be 0.5: 0.1-0.4: 0.4-0.1, and simultaneously controlling the sum of the mass mol ratio of each component to be 1 to obtain an activated mixed material;
2) coprecipitation reaction is carried out to prepare a nickel-cobalt-manganese crude precursor, the activated mixed material obtained in the step 1) is mixed with a solution of sodium hydroxide or potassium hydroxide and ammonium bicarbonate to prepare a mixed reaction solution, the mixed reaction solution is heated and reacts in a vacuum state until the pH value of the reaction solution is 9.5-10.3, and the reaction time is controlled to be 8-10 hours; filtering, and carrying out solid-liquid separation to obtain a solid, namely a crude precursor;
3) preparing a pretreatment precursor, fully washing the crude precursor with water until the pH value of the washed water is 7.5-8, drying and drying the washed precursor for 4-6 hours, and then mechanically activating and ball-milling to obtain the pretreatment precursor;
4) preparing a mixture of lithium salt and the pre-treated precursor fine particles,
fully stirring and mixing the pretreatment precursor and the lithium salt, and controlling the mass molar ratio of the lithium salt to the pretreatment precursor to be 1.15-1.2: 1, continuing mechanical activation ball milling treatment for 3-5 hours to obtain a mixture of lithium salt and pretreated precursor fine particles;
5) preparing a crude lithium battery anode material, placing a mixture of lithium salt and pretreated precursor fine particles in a sintering device, presintering for 4-8 hours under the atmosphere condition of air atmosphere, cooling to room temperature along with a furnace, coarsely crushing, then sintering for 8-10 hours for the second time under the same atmosphere condition with the presintering atmosphere, cooling and crushing to obtain single crystal or quasi-single crystal nickel cobalt lithium manganate which is the crude lithium battery anode material;
6) preparing a modified positive electrode material product of the lithium battery, mixing the single crystal or the single crystal-like nickel cobalt lithium manganate, the graphene nanosheets and the binder obtained in the step 5), homogenizing, vacuum drying, crushing, removing iron, and packaging to obtain the modified positive electrode material product of the lithium battery;
the soluble nickel, cobalt and manganese salts are nickel sulfate, cobalt sulfate and manganese sulfate, or nickel nitrate, cobalt nitrate and manganese nitrate, or nickel carbonate, cobalt carbonate and manganese carbonate; controlling the concentration of each metal ion in soluble nickel, cobalt and manganese salts to be 0.2-0.8 mol/L respectively; the concentration of three elements in the finally obtained precursor is distributed in a full gradient manner, and no obvious boundary exists; the concentration of nickel in the obtained precursor is reduced, and the concentration of cobalt and manganese is increased from inside to outside;
and controlling the heating in the step 2) to be microwave heating, wherein the heating reaction temperature is 50-60 ℃, and the reaction is controlled to be carried out under inert protective gas.
2. The method as claimed in claim 1, wherein the step 3) is drying by microwave or muffle furnace at 150-300 ℃.
3. The method as claimed in claim 1, wherein the step 5) comprises controlling the gas flow rate of the air atmosphere to 300-5000ml/min and the sintering temperature rise rate to 5-10 ℃/min.
4. The method as claimed in claim 1, wherein the pre-sintering temperature is controlled to be 350-.
5. The method for preparing the modified cathode material of the lithium battery as claimed in claim 1, wherein the binder in step 6) is sodium alginate and/or polyacrylic acid or styrene butadiene rubber or sodium hydroxymethyl cellulose; the vacuum drying temperature of the step is controlled to be 100-160 ℃.
6. The method as claimed in claim 1, wherein the water is deionized water, and the average particle size of the modified positive electrode material is controlled to be 8-12 um.
7. The method for preparing the modified cathode material of the lithium battery as claimed in claim 1, wherein the mass ratio of the ball material during the mechanical activation ball milling treatment is controlled to be 10: 1.
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| CN108598435A (en) * | 2018-05-03 | 2018-09-28 | 东莞理工学院 | A kind of anode material of lithium battery and preparation method thereof |
| CN109962234B (en) * | 2019-03-29 | 2021-08-20 | 蜂巢能源科技有限公司 | Concentration gradient single crystal anode material and preparation method thereof |
| CN110767899B (en) * | 2019-10-24 | 2021-06-29 | 厦门厦钨新能源材料股份有限公司 | Preparation method of composite anode material of lithium ion battery |
| CN112713261B (en) * | 2019-10-24 | 2023-04-07 | 中国石油化工股份有限公司 | Preparation method of ternary cathode material and lithium ion battery containing ternary cathode material |
| CN111740153B (en) * | 2020-08-26 | 2021-01-26 | 清陶（昆山）能源发展有限公司 | All-solid-state lithium ion battery |
| CN114142022A (en) * | 2021-06-10 | 2022-03-04 | 宁夏汉尧石墨烯储能材料科技有限公司 | Micron-sized carbon-coated optimized mono-like anode material and application thereof |
| CN114156462A (en) * | 2021-06-15 | 2022-03-08 | 宁夏汉尧石墨烯储能材料科技有限公司 | Lithium ion battery electrode with nano-scale coating for improving performance of monocrystal-like anode material |
| CN114142023A (en) * | 2021-06-22 | 2022-03-04 | 宁夏汉尧石墨烯储能材料科技有限公司 | Coated mono-like anode material and application of coated mono-like anode material to lithium ion battery |
| CN114141996A (en) * | 2021-06-23 | 2022-03-04 | 宁夏汉尧石墨烯储能材料科技有限公司 | Preparation method of coating mode enhanced single crystal-like cathode material |
| CN114739762B (en) * | 2022-03-16 | 2022-12-02 | 国标（北京）检验认证有限公司 | Preparation method of nickel cobalt lithium manganate standard sample |
| CN115041459A (en) * | 2022-06-15 | 2022-09-13 | 江西理工大学 | Method for cleaning residual alkali on surface of anode material of lithium ion battery |
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