CN112744872A - Liquid-phase phosphorus element doping modification preparation method of high-nickel anode material - Google Patents
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Abstract
The invention discloses a liquid phase method phosphorus element doping modification preparation method of a high nickel anode material, which comprises the steps of firstly realizing liquid phase method doping of phosphorus element on a precursor material through hydroxide coprecipitation reaction, and then mixing the precursor material containing the phosphorus element with a lithium source and sintering at high temperature to prepare Li with a fast ion conductor3PO4A coated high nickel positive electrode material. The invention generates Li at the level of primary particles by the technical means of uniformly doping P element in the primary particles3PO4High nickel anode material with fast ion conductor characteristic. TheThe method stabilizes the structure of the material without sacrificing the capacity of the material, and improves the cycle stability and rate capability of the high nickel material.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials and electrochemistry, and relates to a method for preparing a high-nickel anode material by doping phosphorus element by a liquid phase method.
Background
The excessive development and use of non-renewable fossil energy bring serious threats to the global ecosystem, and the green sustainable development concept is gradually deepened into the mind. The lithium ion battery as an efficient energy storage device provides a great deal of convenience for human life. Lithium ion batteries play an important role from 3C electronics to rail vehicles. Since lithium cobaltate was applied to mobile phone products by Sony corporation as a first-generation commercial lithium ion battery in 1990, lithium ion batteries have attracted much attention in both the scientific and technical fields.
Presently, ternary LiNixCoyMn1-x-yO2The material has high specific capacity, excellent safety, good matching degree of working voltage and the current electrolyte system, and is relative to LiCoO2Has the characteristics of lower price and the like, and is taken as the preferred material of the current lithium ion power battery. The NCM333 and NCM523 materials, which are currently commercially available on a large scale, have problems of anxiety in journey and panic of resources due to their low energy density and high Co content. Development and use of high nickel materials (content)>0.7) materials have become the strategic target of the current lithium battery enterprise. However, materials with Ni content above 0.7 have not been well used, but the main reason for this is the relatively poor thermal stability of high nickel materials.
The modification of the high nickel material mainly adopts two technical means of doping and coating. The doping is mainly to introduce inactive elements which do not participate in electrochemical reaction, so as to enhance the structural stability of the high-nickel material in the charging and discharging processes, such as Al, Mg, Ti and other elements, and the inactive elements must replace the sites where the transition metals are located, thereby reducing the capacity and energy density of the material, and the doping at the high-temperature solid-phase reaction stage is difficult to ensure the distribution uniformity of the doped elements; the surface coating is mainly used for improving the interface characteristics of the high-nickel material, and the interface mainly comprises the storage performance in air (solid/gas interface) and the corrosion resistance of electrolyte (solid/liquid interface). The cladding material is typically selected to be structurally stable Al2O3、ZnO、AlF3However, the coating of the secondary particle surface is not effective in preventing the particle pulverization problem due to the anisotropic phase transition of the high nickel material in the 4.2V high voltage region. At the same time, the coating of electronically and ionically insulating materials is not effective as a promoterAnd (4) releasing the performance. It is reported that Li in amorphous phase3PO4As a fast ion conductor coated on the surface of the material, the material can obviously improve the cycling stability and the rate capability. However, the coating on the surface of the secondary particle of the polycrystalline material is difficult to maintain the structural stability among the primary particles, so the process of coating the surface of the secondary particle has a general problem of 'addressing symptoms and not addressing the root causes'.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a high-nickel anode material of a lithium ion battery, which generates Li at the level of primary particles by a technical means of uniformly doping P element in the primary particles3PO4The fast ion conductor is a high nickel anode material. The method stabilizes the structure of the material without sacrificing the capacity of the material, and improves the cycle stability and rate capability of the high nickel material.
The technical scheme of the invention is as follows:
a preparation method of a high-nickel anode material of a lithium ion battery is provided, wherein the chemical formula of the high-nickel anode material is (1-Y) LiNixCo1-xO2·YLi3PO4Wherein 0.7<x<1，0.1<Y<0.2, the preparation method comprises the following steps:
1) preparing P-doped Ni and Co hydroxide precursor materials by a liquid-phase coprecipitation method;
2) fully grinding and mixing the precursor material prepared in the step 1) with a lithium source, and sintering at a high temperature to obtain a target product.
In the method, the liquid phase doping of phosphorus element is realized on a precursor material through hydroxide coprecipitation reaction in step 1), and then the precursor material containing the phosphorus element and a lithium source are mixed and sintered at high temperature in step 2) to prepare the Li with the fast ion conductor3PO4A coated high nickel positive electrode material.
Specifically, in the step 1), a compound containing Ni and Co elements is prepared into a solution with a certain concentration according to a stoichiometric ratio, and the solution is marked as a solution A; respectively preparing the hydroxide, the pyrophosphate and the complexing agent into solutions, or preparing two or three of the solutions into a mixed solution, then dropwise adding the mixed solution into the solution A, and reacting to obtain the P-doped precursor material.
The hydroxide is preferably one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide; the pyrophosphate is preferably one or more of sodium pyrophosphate, potassium pyrophosphate and pyrophosphoric acid; the complexing agent is preferably one or more of ammonia water, ethylenediamine, ammonium bicarbonate and ammonium pyrophosphate.
In some embodiments of the present invention, LiNi of formula (1-Y) is weighedxCo1-xO2·YLi3PO4Wherein 0.7<x<1，0.1<Y<Preparing a solution with a certain concentration by using a compound containing Ni and Co elements in a stoichiometric ratio shown in 0.2, and marking the solution as a solution A; weighing stoichiometric ratio of hydroxide (such as NaOH) and pyrophosphate (such as Na)4P2O7) Preparing a solution with a certain concentration as a precipitator, and adding ammonia water with a certain concentration as a complexing agent to prepare a mixed solution B. The hydroxide coprecipitation reaction is carried out in a reaction kettle, the solution A is added into the reaction kettle at a constant flow rate, other solutions (such as the mixed solution B) are dripped into the reaction kettle in a frequency conversion manner through a pH feedback self-regulation mechanism, and the pH of a reaction system is controlled to be stabilized at a certain value; reacting for a certain time to obtain green precipitate, washing with deionized water for several times, oven drying to obtain dry powder, and sieving.
The Ni and Co element-containing compound can be selected from NiSO4、NiCH3COOH、Ni(NO3)2、CoSO4、CoCH3COOH、Co(NO3)2The total concentration of the two or more of (1) to (5) mol/L solution is prepared.
Preparing a solution with the concentration of 2-10 mol/L by using the hydroxide as a precipitator; the concentration ratio of the hydroxide to the pyrophosphate is 1: 0.05-1: 1; the preparation concentration of the ammonia water as the complexing agent is 0.1-3 mol/L.
Preferably, during the reaction in the reaction kettle, the flow rate of the solution A is controlled to be 10-80 mL/h (more preferably 20-50 mL/h), the pH value of the reaction system is controlled to be 10-13, the reaction time is 30-50 h, the precipitate is filtered and washed for 4-8 times, and the precipitate is dried for 10-30 h in a forced air oven.
The above method is selected from the group consisting of M (OH)2Pyrophosphate with equivalent (M ═ Ni, Co) precipitation rate is taken as doping agent of P element, avoiding direct adoption of PO4 3-The non-uniformity of particle size is caused by the mismatch of precipitation rate caused by ions as P-element dopant. In the P-doped precursor material prepared in the step 1), phosphorus is uniformly distributed in particles, the overall particle size distribution is 8-9 μm, and the particle size distribution trend is (D90-D50)/D50-0.8.
And 2) fully grinding and mixing the precursor material and the Li source, and sintering at high temperature in an oxygen atmosphere.
In step 2), the lithium source may be selected from: li2CO3、LiOH、LiOH·H2O、Li2O、Li2O2One or more of lithium acetate, lithium oxalate and lithium nitrate. The lithium excess is preferably 1-10% in the sintering process.
In some embodiments of the invention, after uniformly mixing a precursor material and a Li source, heating to 200-600 ℃ at a heating rate of 2-10 ℃/min in an oxygen atmosphere, presintering at 200-600 ℃ for 2-6 h, then heating to 600-800 ℃ at a heating rate of 1-10 ℃/min, and sintering at 600-800 ℃ for 8-30 h to obtain the target cathode material.
The prepared cathode material has the overall particle size distribution of 8-10 mu m, and the particle size distribution trend of (D90-D50)/D50 is 0.8.
The phosphorus-doped high-nickel anode material synthesized by the method avoids the problem of non-uniformity of component distribution caused by solid phase doping, and effectively ensures the consistency of products. In addition, the cathode material synthesized by the method shows excellent electrochemical cycling stability and rate capability. Besides, the proportion of the precursor components prepared by the method is not limited at all. In particular, compared with the prior art, the invention has the following beneficial effects:
the invention carries out P doping on the material in the process of synthesizing the precursor in a liquid phase. For doped P elementThe source of the element is mainly considered to be the nucleation rate determined by the solubility product in the precipitation process. For PO4 3-System, Ni under the product3(PO4)3Solubility product of (K)sp＝4.74×10-32) Ni (OH)2Solubility product of (K)sp＝5.48×10-16) 16 orders of magnitude smaller, and therefore preferentially nucleates during precipitation, resulting in non-uniformity in the distribution of the P element. And P we chose for2O7 4-The root is taken as a source of the P element, so that the problem of element distribution nonuniformity caused by overlarge difference of nucleation rates is well avoided. And as can be seen from the particle distribution of the material, using P2O7 4-The material synthesized by taking the root as the P source has uniform particle size distribution and does not have the appearance of micro powder particles. Not only this, Li is generated in the material after sintering with lithium3PO4The phase, which is uniformly present on the surface of the primary particles, can effectively protect the primary particles inside the material to maintain structural stability during long cycles. The capacity retention rate of 100 circles can reach 90 percent under the current density of 100mA g < -1 >; the retention rate of the circulation capacity of 300 circles under the current density of 200mA g < -1 > is over 86 percent; and can give a specific discharge capacity of 130mAh g-1 at a current density of 2 Ag-1. In addition, the doping technology is connected with the existing coprecipitation process, can be used for large-scale production through a coprecipitation reaction kettle, and has a high practical application value.
Drawings
FIG. 1 is an SEM image of a P-doped high-nickel precursor material prepared in example 1 of the present invention.
Fig. 2 shows the XRD pattern of the P-doped high nickel precursor material prepared in example 1 of the present invention.
FIG. 3 is a graph of the particle size distribution of the P-doped high nickel precursor material prepared in example 1 of the present invention.
FIG. 4 shows the first-turn charge-discharge curve of the positive electrode material synthesized in example 1 of the present invention in the voltage range of 3.0-4.3V at a current density of 20 mA/g.
FIG. 5 is a graph of cycling performance of the synthesized positive electrode material of example 1 of the present invention over 100 cycles at a voltage range of 3.0-4.3V at a current density of 100 mA/g.
FIG. 6 is a graph of cycle performance of the positive electrode material synthesized in example 1 of the present invention at a voltage range of 3.0-4.3V at a current density of 200mA/g for 300 cycles.
FIG. 7 shows the step rate performance of the cathode material synthesized in example 1 of the present invention.
Detailed Description
The invention is further illustrated but not limited thereto. All modifications and equivalents of the embodiments of the invention described above are intended to be included within the scope of the invention.
Example 1 Co-feeding of sodium pyrophosphate + NaOH + Ammonia as a Mixed solution
Step 1, weighing a proper amount of nickel source and cobalt source compounds according to a proportion of 9:1 and a total ion concentration of 1mol/L, and completely dissolving the nickel source and cobalt source compounds in 2L of deionized water to obtain a solution A; weighing NaOH and sodium pyrophosphate according to the total ion concentration of 2mol/L, and completely dissolving the NaOH and the sodium pyrophosphate in 2L of deionized water, wherein the NaOH and the Na are4P2O7The molar ratio of the mixed solution is 1:0.05, a certain amount of ammonia water is added into the mixed solution as a complexing agent, the concentration of the ammonia water is controlled to be 2mol/L, and the mixed solution is marked as solution B. The solution A is injected into the reaction kettle at a constant rate of 30mL/h, and the solution B is injected into the reaction kettle through a pH self-feedback adjusting system in a variable frequency mode; the reaction temperature is controlled at 55 ℃; the pH value of the reaction is 11.5, and the target P-doped precursor is synthesized by stirring at the rotating speed of 700 revolutions per minute. Taking a precursor material synthesized by a liquid phase method, carrying out suction filtration and washing for 5 times, drying in a forced air drying oven at 100 ℃ for 20h, taking out, and sieving with a 400-mesh sieve to obtain a dried target precursor.
And 2, respectively weighing lithium hydroxide and the precursor obtained in the step 1 according to the molar ratio of 1.05:1 (excess lithium), and mixing and sintering. Presintering at 500 deg.C for 1h at a sintering temperature of 10 deg.C/min, heating to 800 deg.C at a heating rate of 10 deg.C/min, and sintering for 12 h. And finally obtaining the target cathode material.
And 3, mixing the target product with carbon black and PVDF in a mass ratio of 8:1:1, grinding the mixture uniformly by using N-methyl pyrrolidone as a solvent, then coating the mixture on an aluminum foil, and placing the aluminum foil in a forced air drying oven to dry for 12 hours at 100 ℃. After taking out, the electrode wafer is cut after rolling on a rolling machine for several times. The lithium ion battery is used as a positive plate, a lithium plate is used as a negative plate, glass microfiber filter paper GF/D produced by whatman company and electrolyte is high-pressure electrolyte of a lithium ion battery produced by Beijing chemical reagent research institute, a button battery is assembled in a glove box and tested on a Xinwei battery testing system at the room temperature of 25 ℃.
Wherein, the mixing ratio of the nickel source and the cobalt source compound in the step 1 is 9:1, the SEM electron microscope picture and XRD picture of the prepared P-doped high-nickel precursor material are respectively shown in figure 1 and figure 2, which shows that the sphericity of the particles is good, and no small-particle powder particles appear, thus the synthesis method can effectively avoid the independent precipitation of nickel phosphate and is beneficial to improving the tap density of the material. The particle distribution state of the material is shown in fig. 3, the particle size distribution of the material is uniform, and no micro powder particles appear.
The cathode material synthesized by the method shows excellent electrochemical cycling stability and rate capability. In the test of the half cell, the capacity retention rate of 100 circles under the current density of 100mA g < -1 > can reach 90 percent (see figure 5); the retention rate of the cycling capacity of 300 circles at the current density of 200mA/g is more than 86% (see figure 6); and can give a specific discharge capacity of 130mAh/g at a current density of 2A/g (see FIG. 7).
EXAMPLE 2 separate feeding of sodium pyrophosphate and NaOH + Ammonia water mixed lye
In contrast to step 1 of example 1, the phosphorus source was fed separately from the NaOH solution and the rest of the procedure was the same.
The method comprises the following specific steps: weighing a proper amount of nickel source and cobalt source compounds according to the proportion of 9:1, 8:2, 7:3 or 6:4 and the total ion concentration of 1mol/L, and completely dissolving the nickel source and cobalt source compounds in 2L of deionized water to obtain solution A; weighing NaOH with the total ion concentration of 2mol/L, completely dissolving the NaOH in 2L of deionized water, and adding ammonia water with the concentration of 2mol/L into the sodium hydroxide solution to form a mixed solution, namely solution B. Weighing Na with the stoichiometric ratio of 1:0.05 to sodium hydroxide4P2O7Dissolve in 100mL deionized water and record as solution C. The solution A is injected into the reaction kettle at a constant rate of 30mL/h, the solution B is injected into the reaction kettle through a pH self-feedback adjusting system in a variable frequency mode, and the solution C is added into the reaction kettle at a constant rate of 3.3 mL/h. The reaction temperature is controlled at 55 ℃; the pH value of the reaction is 11.5, the reaction is stirred at the rotating speed of 700 r/min, and the target P-doped precursor is synthesized after the reaction is carried out for 30 hours. Taking a precursor material synthesized by a liquid phase method, carrying out suction filtration and washing for 5 times, drying in a forced air drying oven at 100 ℃ for 20h, taking out, and sieving with a 400-mesh sieve to obtain a dried target precursor.
Steps 2 and 3 were the same as in example 1, and the particles of the prepared positive electrode material were large, and the value of D50 was 9 to 10 μm. The performance is slightly inferior to that of the material synthesized in step 1. The cathode material synthesized by the method. In the test of the half cell, the capacity retention rate of 100 circles can reach 85% under the current density of 100 mA/g; the retention rate of the circulation capacity of 300 circles under the current density of 200mA/g is more than 80 percent; and can give a specific discharge capacity of 115mAh/g at a current density of 2A/g.
Example 3 sodium pyrophosphate + Ammonia water complexing agent mixture solution and NaOH lye were fed separately
The difference from example 2 is: adding ammonia water with medium concentration to the solution C as a complexing agent, and dripping the solution C into the reaction kettle at a constant speed of 3.3 mL/h.
The particles of the anode material prepared from the prepared anode material are small, the D50 value is 5-6 μm, but the powder with small particles still does not exist. The initial capacity of the material is high, the capacity of the first circle can reach 212mAh/g, but the circulation retention rate of 100 circles is only 75% under the current density of 50mA/g with poor capacity retention rate.
Example 4 feeding a mixed solution of sodium pyrophosphate and sodium hydroxide and an aqueous ammonia complexing agent separately
The difference from example 3 is: the solution B is a mixed solution of sodium pyrophosphate and sodium hydroxide, wherein ammonia water serving as a complexing agent is not added; only the complexing agent with the ammonia water concentration of 2mol/L exists in the solution C.
The particles of the anode material prepared from the prepared anode material are small, the D50 value is 4-5 mu m, and no powder with small particles exists. The initial capacity of the material is high, the capacity of the first circle can reach 215mAh/g, but the circulation retention rate of 100 circles is only 70% under the current density of 50mA/g with poor capacity retention rate.
Claims (10)
1. A preparation method of a high-nickel anode material of a lithium ion battery is provided, wherein the chemical formula of the high-nickel anode material is (1-Y) LiNixCo1-xO2·YLi3PO4Wherein 0.7<x<1，0.1<Y<0.2, the preparation method comprises the following steps:
1) preparing P-doped Ni and Co hydroxide precursor materials by a liquid-phase coprecipitation method;
2) fully grinding and mixing the precursor material prepared in the step 1) with a lithium source, and sintering at a high temperature to obtain a target product.
2. The preparation method according to claim 1, wherein in step 1), a compound containing Ni and Co elements is prepared into a solution with a certain concentration according to a stoichiometric ratio, and the solution is marked as solution A; respectively preparing the hydroxide, the pyrophosphate and the complexing agent into solutions, or preparing two or three of the solutions into a mixed solution, then dropwise adding the mixed solution into the solution A, and reacting to obtain the P-doped precursor material.
3. The preparation method according to claim 2, wherein the hydroxide is selected from one or more of sodium hydroxide, potassium hydroxide, and lithium hydroxide; the pyrophosphate is selected from one or more of sodium pyrophosphate, potassium pyrophosphate and pyrophosphoric acid; the complexing agent is selected from one or more of ammonia water, ethylenediamine, ammonium bicarbonate and ammonium pyrophosphate.
4. The method according to claim 2, wherein the Ni or Co element-containing compound in step 1) is selected from NiSO4、NiCH3COOH、Ni(NO3)2、CoSO4、CoCH3COOH、Co(NO3)2Is formulated to a total concentration of 1 to5mol/L of solution; preparing a solution with the concentration of 2-10 mol/L by using the hydroxide; the concentration ratio of the hydroxide to the pyrophosphate is 1: 0.05-1: 1; ammonia water is used as a complexing agent, and the preparation concentration is 0.1-3 mol/L.
5. The preparation method of claim 2, wherein the step 1) is carried out in a reaction kettle, the solution A is added into the reaction kettle at a constant flow rate, other solutions are dropwise added into the reaction kettle in a frequency conversion manner through a pH feedback self-regulation mechanism, the pH of the reaction system is controlled to be stable at 10-13, and the reaction time is 30-50 h.
6. The preparation method according to claim 1, wherein in the P-doped Ni, Co hydroxide precursor material prepared in step 1), phosphorus is uniformly distributed in the particles, the overall particle size distribution is 8-9 μm, and the particle size distribution trend is (D90-D50)/D50 is 0.8.
7. The method of claim 1, wherein the lithium source in step 2) is selected from Li2CO3、LiOH、LiOH·H2O、Li2O、Li2O2One or more of lithium acetate, lithium oxalate and lithium nitrate.
8. The method of claim 1, wherein the precursor material of step 2) is mixed with the lithium source by sufficient grinding, and high-temperature sintering is performed in an oxygen atmosphere.
9. The preparation method according to claim 8, wherein the precursor material and the lithium source are uniformly mixed in the step 2), and then the mixture is heated to 200-600 ℃ at a heating rate of 2-10 ℃/min in an oxygen atmosphere, presintered at 200-600 ℃ for 2-6 h, heated to 600-800 ℃ at a heating rate of 1-10 ℃/min, and sintered at 600-800 ℃ for 8-30 h to obtain the target anode material.
10. The preparation according to any one of claims 1 to 9The chemical formula of the high-nickel anode material of the lithium ion battery prepared by the method is (1-Y) LiNixCo1-xO2·YLi3PO4Wherein 0.7<x<1，0.1<Y<0.2; the overall particle size distribution is 8 to 10 μm, and the particle size distribution tendency is (D90-D50)/D50 is 0.8.
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| CN113422026A (en) * | 2021-06-25 | 2021-09-21 | 洛阳月星新能源科技有限公司 | Negative electrode material capable of being charged at low temperature and preparation method thereof |
| CN113562782A (en) * | 2021-07-30 | 2021-10-29 | 浙江帕瓦新能源股份有限公司 | Tungsten and lanthanum double-doped co-coated ternary positive electrode precursor and preparation method thereof |
| CN114883555A (en) * | 2022-06-09 | 2022-08-09 | 贵州高点科技有限公司 | Multiphase manganese material and preparation method thereof, positive plate and secondary battery |
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| CN114883555A (en) * | 2022-06-09 | 2022-08-09 | 贵州高点科技有限公司 | Multiphase manganese material and preparation method thereof, positive plate and secondary battery |
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