CN114744188B - Lithium ion battery anode material with non-hollow porous structure and preparation method and application thereof - Google Patents
Lithium ion battery anode material with non-hollow porous structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a lithium ion battery anode material with a non-hollow porous structure, a preparation method and application thereof (1‑x‑y) Co x Mn y LiCO 3 The outer shell is composed of Ni (1‑x‑y) Co x Mn y CO 3 And the thickness ratio of the precursor to the core shell is 0.3-0.7:1, the precursor and the dopant are uniformly mixed, primary presintering is carried out, then the precursor and the lithium salt are uniformly mixed, secondary sintering is carried out, a product obtained after the secondary sintering is crushed, crushed and sieved to obtain a non-hollow porous structure anode material, and finally the surface of the anode material is coated with phosphate. The anode material prepared by the invention has the advantages of high particle strength, sufficient contact with electrolyte, short lithium ion diffusion path, low resistance, excellent rate performance and power.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery anode material with a non-hollow porous structure and a preparation method and application thereof.
Background
The power type battery positive electrode material which is commercialized in the market at present has some problems: (1) the rate performance of the positive electrode material is improved by increasing the reaction area and reducing the diffusion distance of lithium ions in the particles by a method of reducing the particle size of the positive electrode material, however, it causes problems in commercial use, such as reduction in production efficiency due to reduction in powder flowability and sieving performance; (2) most of the power type materials are secondary particles tightly stacked by primary particles, so that electrolyte cannot be fully infiltrated, a lithium ion diffusion path is increased, the resistance is high, and cracks and even pulverization occur in the particles due to stress formed by volume change of active substances in the repeated charging and discharging process, so that the capacity, the cycle performance and the rate performance of the anode material are seriously influenced; (3) the purpose of improving the rate performance is achieved by adding a large amount of cobalt element, so that the cost of the anode material is greatly improved; (4) the surface is coated with a phosphate fast ion conductor, so that the conductivity of the material is improved, the internal resistance is reduced, and the high-rate charge and discharge of the lithium ion battery are realized.
Research shows that the cathode material with the hollow porous structure has better rate performance due to the larger specific surface area and the shorter lithium ion diffusion path. A precursor with a loose and compact core shell is prepared by a kernel oxidation method and a two-step coprecipitation method (reaction parameters such as pH, complexing agent concentration, stirring speed and the like of two-step synthesis of the precursor are changed), the precursor is mixed with lithium salt to prepare a hollow porous anode material, such as patents CN202010091051.5, CN201911291031.6, CN202110433232.6 and the like, although the anode material has a large specific surface area and is enhanced in contact with electrolyte, the multiplying power and power performance of the anode material can be improved to a certain extent, the loose core of the precursor is easy to shrink towards a shell layer in the sintering process, a large cavity is formed in the anode material, so that the difference exists between an internal structure and an external structure, the material is easy to collapse, the tap density is low, the particle strength is not high, and particles of the anode material are easy to break when a pole piece is rolled, so that the structure of the anode material is damaged, and the electrical performance of the material is influenced. In addition, as in patent CN104253272A, after the phosphate is coated by a wet method, harmful anions are removed through a washing process, but the washing easily causes lithium loss on the surface of the material, affects the capacity exertion and rate capability, and causes reduction of production efficiency and increase of cost.
Disclosure of Invention
The invention mainly solves the technical problem of overcoming the defects of the hollow porous structure material and the phosphate coating in the background technology, and provides a lithium ion battery anode material with a non-hollow porous structure, and a preparation method and application thereof. The anode material has a large specific surface area, enhances the contact between the anode material and electrolyte, and reduces the anode resistance, and compared with a hollow structure material, the anode material can support the filling property of the anode material, so that the tap density and the particle strength of the anode material are improved, and other electrical properties are ensured while the multiplying power and the power performance of the anode material are improved. In addition, the coating agent used for coating the phosphate is environment-friendly and low in price, a stable coating substance is synthesized by wet coating, meanwhile, the generated by-product is harmless to the environment and does not need to be washed and removed, the coating substance is uniformly and tightly coated on the surface of the material, the ionic conductivity of the material is improved, the rate capability is further improved, the side reaction of the anode material and the electrolyte is inhibited, the capacity attenuation is slowed down, and the cycle performance is improved.
The invention provides a lithium ion battery anode material with a non-hollow porous structure, and the chemical general formula is B 3 (PO 4 ) 2 /Li a Ni x Co y Mn (1-x-y-b) A b O 2 Wherein a is more than or equal to 0.95 and less than or equal to 1.20, x is more than or equal to 0.3 and less than or equal to 0.65, y is more than or equal to 0 and less than or equal to 0.35, B is more than 0.001 and less than or equal to 0.003, x + y + B =1, A is at least one of Zr, W, Ta, Mo and Nb, and B is at least one of Co, Mn and Mg.
Preferably, the positive electrode material is a secondary particle formed by aggregating primary particles, and has an average particle diameter D50 of 2.8 to 7.0 μm and a tap density of 1.2 to 2.5g/cm 3 The specific surface area is 1.0-2.6 square meters per gram, the porosity is 10% -35%, the particle strength is 80-120MPa, the cross section of the positive electrode material is a non-hollow porous structure, and the surface of the positive electrode material is provided with a phosphate coating layer with the thickness of 20-50 nm.
The invention also provides a preparation method of the lithium ion battery anode material with the non-hollow porous structure, which comprises the following steps:
(1) precursor kernel growth phase S1: respectively adding a metal salt solution, a lithium salt solution, a sodium carbonate precipitator solution and a complexing agent solution mixed by nickel, cobalt and manganese into a reaction kettle using pure water as a base solution for reaction, continuously adding the solutions in the reaction process, controlling the temperature at 40-60 ℃, controlling the stirring speed at 200-800r/min, controlling the pH at 11.8-12.3, controlling the ammonia concentration of the complexing agent at 5-15g/L, controlling the reaction time at 8-15h, continuously introducing nitrogen into the reaction kettle, controlling the pH at 11.8-12.3 by finely adjusting the flow of the precipitator solution and ammonia water, stopping adding the lithium salt when the grain diameter D50 of an inner core is 1.05-1.40 mu m, and ending the growth stage of the precursor inner core;
(2) precursor shell growth phase S2: stopping adding the lithium salt solution, continuously adding the metal salt solution, the sodium carbonate precipitator solution and the complexing agent solution, reducing the stirring speed by 50-150r/min, reducing the pH value by 0.3-0.8 by finely adjusting the flow rates of the precipitator solution and the ammonia water, controlling the ammonia concentration of the supernatant in the reaction stage to be 3-8g/L and lower than the ammonia concentration of S1, controlling the reaction time in the stage to be 20-45h, continuously introducing nitrogen into the reaction kettle, stopping the reaction when the whole precursor D50 including the inner core and the shell part grows to 2.5-6.0 mu m, and ending the precursor shell growth stage;
(3) carrying out solid-liquid separation, aging, washing and drying on the precipitate obtained in the step (2) to obtain a carbonate precursor with a core-shell structure;
(4) uniformly mixing the carbonate precursor obtained in the step (3) with a doping agent, and performing primary presinteringKeeping the temperature at 300-700 ℃ for 2-8h, the heating rate is 3 ℃/min, the sintering atmosphere is air, and obtaining porous structure oxide precursor Ni with uniformly distributed doping agent after cooling (1-x-y) Co x Mn y LiA b O；
(5) Uniformly mixing the oxide precursor obtained in the step (4) with lithium salt, performing secondary sintering by adopting a one-stage temperature-controlled sintering mode, performing heat preservation for 8-14h at the temperature of 700 ℃ and 1000 ℃, wherein the heating rate is 3 ℃/min, the sintering atmosphere is air, oxygen or a mixed gas of air and oxygen, and crushing, crushing and sieving the mixture after cooling to obtain a non-hollow porous structure anode material;
(6) and (3) dispersing the positive electrode material obtained in the step (5) in a mixed solution formed by deionized water and phosphate, stirring for 1h, directly performing rotary evaporation and drying, then performing tertiary sintering, keeping the temperature at 400-600 ℃ for 4-8h, wherein the heating rate is 3 ℃/min, the sintering atmosphere is air, oxygen or a mixed gas of air and oxygen, and sieving after cooling to obtain the positive electrode material with the surface coated with phosphate and a non-hollow porous structure.
Preferably, in the step (1), the metal salt solution is one or more of a sulfate solution and an acetate solution, the total metal ion concentration in the metal salt solution is 0.05-2.8mol/L, the lithium salt solution is a lithium hydroxide solution, the lithium ion concentration is 1-2mol/L, the complexing agent solution is an ammonia water solution, the ammonium ion concentration is 3-6mol/L, and the carbonate ion concentration in the sodium carbonate solution is 1-5 mol/L.
Preferably, the carbonate precursor in step (3) is a secondary particle formed by aggregation of primary particles, wherein the primary particle has a length of 150-1200nm and a width of 80-400nm, the average particle diameter D50 of the secondary particle is 2.5-6.0um, the carbonate precursor has a core-shell structure, and the ratio of the thickness of the core-shell is 0.3-0.7: 1.
Preferably, in the step (4), the dopant is a compound containing a, and a accounts for 0.1-0.3% of the positive electrode material by mass.
Preferably, the lithium salt in step (5) comprises one or more of lithium carbonate, lithium hydroxide, lithium oxalate and lithium acetate, wherein the molar ratio of Li to the total metals Ni + Co + Mn is 0.95-1.2: 1.
Preferably, the phosphate in step (6) is Co 3 (PO4) 2 、Mn 3 (PO4) 2 、Mg 3 (PO4) 2 The phosphate is formed by a soluble acetate salt of the corresponding metal with (NH) 4 ) 2 The anode material is synthesized from HPO4, and the mass percent of Co, Mn or Mg in the anode material is 0.05-0.2%.
The invention also provides application of the lithium ion battery anode material with the non-hollow porous structure in a lithium ion battery.
The invention has the following beneficial effects:
(1) lithium salt is introduced at the early stage of synthesis of the precursor, lithium ions exist in the core, the core which is connected in a staggered manner and loose and porous can be formed, and the phenomenon that the core layer shrinks towards the shell layer to cause the material to form hollow during secondary sintering is effectively avoided; compared with a hollow structure, the tap density and the particle strength of the material are improved, and meanwhile, the material has a large specific surface area, is fully contacted with an electrolyte, is short in lithium ion diffusion path, and has low resistance, excellent rate performance and power performance.
(2) The stability of the carbonate precursor is higher than that of the hydroxide precursor, and the carbonate precursor can form a porous structure in the primary presintering process, so that the doping uniformity and the permeation rate of the electrolyte are improved, the lithium ion transmission distance is effectively shortened, the anode resistance is reduced, and the rate performance and the power performance are improved. The high-valence element A can be doped to play a role in stabilizing the structure of the material, so that the cycling stability and the thermal stability of the material are improved, and particularly the structural stability of the material during high-rate charge and discharge is improved.
(3) The phosphate coating layer on the surface of the anode material is formed by wet coating, can be uniformly coated on the surface of the anode material, is environment-friendly and low in price, byproducts generated while the phosphate coating layer is generated in a compounding mode are harmless to the environment and do not need to be washed and removed, the phosphate coating layer has high ionic conductivity, the conductivity of the material is improved, the internal resistance of a battery is reduced, the power performance of the anode material is improved, the side reaction of the anode material and electrolyte is inhibited, the capacity attenuation is slowed down, and the cycle performance is improved.
Drawings
Fig. 1 is a cross section of a positive electrode material prepared in example 1;
fig. 2 is a cross section of the positive electrode material prepared in comparative example 1;
fig. 3 is a graph comparing the different rate discharge capacity retention rates of pouch cells of the positive electrode materials prepared in examples 1 and 2 and comparative examples 1, 2, 3 and 4;
fig. 4 is a graph comparing the DCR discharge under different conditions for pouch cells of the positive electrode materials prepared in examples 1 and 2 and comparative examples 1, 2, 3 and 4.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Coated Co 3 (PO 4 ) 2 The lithium ion battery anode material Co with a non-hollow porous structure 3 (PO 4 ) 2 /Li 1.1 Ni 0.499 Co 0.2 Mn 0.3 Zr 0.001 O 2 The preparation method of (1), wherein the thickness ratio of the precursor core shell is 0.4:1, comprises the following steps:
synthesizing Ni-Co-Mn carbonate precursor Ni with core-shell structure by adopting coprecipitation method 0.5 Co 0.2 Mn 0.3 LiCO 3 : preparing a mixed metal salt solution with the total metal ion concentration of 2mol/L by using sulfates containing Ni, Co and Mn, wherein the molar ratio of Ni to Co to Mn is 5:2:3, preparing an ammonia water solution with the ammonium ion concentration of 5mol/L, preparing a lithium hydroxide solution with the lithium ion concentration of 1.2mol/L, preparing a sodium carbonate solution with the carbonate ion concentration of 3mol/L, and then respectively adding the sodium carbonate solution into a reaction kettle using pure water as a base solution for reaction; continuously adding the solution in the reaction process, controlling the temperature at 50 ℃, the stirring speed at 600r/min and the pH at 12.1, continuously introducing nitrogen into the reaction kettle, stopping adding the lithium salt solution when the particle size D50 of the precursor core is 1.2 mu m after the reaction is carried out for 11 hours, continuously adding the mixed metal salt solution, the sodium carbonate precipitator solution and the complexing agent solution, and regulating the stirring speed until the stirring speed is reduced to the lower value530r/min, controlling the pH value to be 11.70 by finely adjusting the flow rates of the precipitant solution and ammonia water, reacting for 36h, then, allowing the whole precursor D50 including the inner core and the shell part to grow to 4.2 mu m, stopping the reaction, separating, aging, washing and drying the obtained solid-liquid mixture to obtain a carbonate precursor with the thickness ratio of the core shell to the shell being 0.4: 1;
carbonate precursor Ni with core-shell structure 0.5 Co 0.2 Mn 0.3 LiCO 3 And ZrO 2 Uniformly mixing, performing primary presintering, keeping the temperature at 500 ℃ for 5 hours, taking air as sintering atmosphere, and cooling to obtain a nickel-cobalt-manganese oxide precursor Ni with a porous structure 0.5 Co 0.2 Mn 0.3 LiZrO。
Ni as precursor of Ni-Co-Mn oxide with porous structure 0.5 Co 0.2 Mn 0.3 Uniformly mixing LiZrO and lithium carbonate, wherein the molar ratio of Li to total metals (Ni + Co + Mn) is 1.1:1, performing secondary sintering by adopting a one-stage temperature-controlled sintering mode, keeping the temperature at 890 ℃ for 12 hours, wherein the sintering atmosphere is air, reducing the temperature, crushing and sieving to obtain the non-hollow porous structure lithium nickel cobalt manganese oxide Li 1.1 Ni 0.499 Co 0.2 Mn 0.3 Zr 0.001 O 2 。
Dissolve 0.85g (CH) in 100mL of deionized water 3 COO) 2 Co·4H 2 O and 0.30g (NH) 4 ) 2 HPO 4 Wherein Co accounts for 0.1 percent of the mass of the anode material, the molar ratio of P to Co is 2:3, and the two solutions are mixed and stirred uniformly to obtain a coating substance Co 3 (PO 4 ) 2 Then 200g of lithium nickel cobalt manganese oxide Li with a non-hollow porous structure 1.1 Ni 0.499 Co 0.2 Mn 0.3 Zr 0.001 O 2 Adding the mixed solution, uniformly stirring the nickel cobalt lithium manganate and deionized water used by the mixed solution according to the weight ratio of 1:1 for 1h, directly pouring the mixture into a rotary steaming bottle, drying the mixture in a water bath at 100 ℃ for 3h, carrying out three-stage sintering on the dried material by adopting a one-stage temperature-controlled sintering mode, keeping the temperature at 500 ℃ for 5h, taking the sintering atmosphere as air, cooling and sieving to obtain the Co-coated lithium manganese oxide 3 (PO 4 ) 2 Non-hollow porous structure positive electrode material Co 3 (PO 4 ) 2 /Li 1.1 Ni 0.499 Co 0.2 Mn 0.3 Zr 0.001 O 2 。
Example 2
Co-coated steel sheet 3 (PO 4 ) 2 Non-hollow porous structure anode material Co 3 (PO 4 ) 2 /Li 1.1 Ni 0.499 Co 0.2 Mn 0.3 Zr 0.001 O 2 The preparation method of (1), wherein the thickness ratio of the precursor core shell is 0.7:1, comprises the following steps:
co-precipitation method is adopted to synthesize Ni-Co-Mn carbonate precursor Ni with core-shell structure 0.5 Co 0.2 Mn 0.3 LiCO 3 : preparing a mixed metal salt solution with the total metal ion concentration of 2mol/L by using sulfates containing Ni, Co and Mn, wherein the molar ratio of Ni to Co to Mn is 5:2:3, preparing an ammonia water solution with the ammonium ion concentration of 5mol/L, preparing a lithium hydroxide solution with the lithium ion concentration of 1.2mol/L, preparing a sodium carbonate solution with the carbonate ion concentration of 3mol/L, and then respectively adding the sodium carbonate solution into a reaction kettle using pure water as a base solution for reaction; in the reaction process, the solution is continuously added, the temperature is controlled at 50 ℃, the stirring speed is controlled at 600r/min, the pH is controlled at 12.1, nitrogen is continuously introduced into the reaction kettle, after the reaction is carried out for 11 hours, when the particle size D50 of the precursor core is 1.2 mu m, the lithium salt solution is stopped being added, the mixed metal salt solution, the sodium carbonate precipitator solution and the complexing agent solution are continuously added, the stirring speed is regulated to 530r/min, the pH is controlled at 11.70 by finely adjusting the flow of the precipitator solution and ammonia water, after the reaction is carried out for 31 hours, the whole precursor D50 including the core and the shell part is 2.9 mu m long, the reaction is stopped, and the obtained solid-liquid mixture is separated, aged, washed and dried to obtain a carbonate precursor with the thickness ratio of 0.7: 1;
carbonate precursor Ni with core-shell structure 0.5 Co 0.2 Mn 0.3 LiCO 3 And ZrO 2 Uniformly mixing, performing primary presintering, keeping the temperature at 500 ℃ for 5 hours, taking air as sintering atmosphere, and cooling to obtain a nickel-cobalt-manganese oxide precursor Ni with a porous structure 0.5 Co 0.2 Mn 0.3 LiZrO。
Ni as precursor of Ni-Co-Mn oxide with porous structure 0.5 Co 0.2 Mn 0.3 Uniformly mixing LiZrO and lithium carbonate, wherein the molar ratio of Li to total metals (Ni + Co + Mn) is 1.1:1, performing secondary sintering by adopting a one-stage temperature-controlled sintering mode, keeping the temperature at 890 ℃ for 12 hours, wherein the sintering atmosphere is air, reducing the temperature, crushing and sieving to obtain the non-hollow porous structure lithium nickel cobalt manganese oxide Li 1.1 Ni 0.499 Co 0.2 Mn 0.3 Zr 0.001 O 2 。
0.85g (CH) was dissolved in 100mL of deionized water of the same volume 3 COO) 2 Co· 4H 2 O and 0.30g (NH) 4 ) 2 HPO 4 Wherein Co accounts for 0.1 percent of the mass of the anode material, the molar ratio of P to Co is 2:3, and the two solutions are mixed and stirred uniformly to obtain a coating substance Co 3 (PO 4 ) 2 Then 200g of lithium nickel cobalt manganese oxide Li with a non-hollow porous structure 1.1 Ni 0.499 Co 0.2 Mn 0.3 Zr 0.001 O 2 Adding the mixed solution, uniformly stirring the nickel cobalt lithium manganate and deionized water used by the mixed solution according to the weight ratio of 1:1 for 1h, directly pouring the mixture into a rotary steaming bottle, drying the mixture in a water bath at 100 ℃ for 3h, carrying out three-stage sintering on the dried material by adopting a one-stage temperature-controlled sintering mode, keeping the temperature at 500 ℃ for 5h, taking the sintering atmosphere as air, cooling and sieving to obtain the Co-coated lithium manganese oxide 3 (PO 4 ) 2 Is not a hollow porous structure, and is a positive electrode material Co 3 (PO 4 ) 2 /Li 1.1 Ni 0.499 Co 0.2 Mn 0.3 Zr 0.001 O 2 。
Example 3
0.85g (CH) of example 1 3 COO) 2 Co·4H 2 O and 0.30g (NH) 4 ) 2 HPO 4 The conversion was 0.89g (CH) 3 COO) 2 Mn·4H 2 O and 0.32g (NH) 4 ) 2 HPO 4 Otherwise, the same procedure as in example 1 was repeated to obtain coated Mn 3 (PO 4 ) 2 Positive electrode material Mn of non-hollow porous structure 3 (PO 4 ) 2 /Li 1.1 Ni 0.499 Co 0.2 Mn 0.3 Zr 0.001 O 2 。
Example 4
0.85g (CH) of example 1 3 COO) 2 Co·4H 2 O and 0.30g (NH) 4 ) 2 HPO 4 Conversion to 1.77g (CH) 3 COO) 2 Mg·4H 2 O and 0.72g (NH) 4 ) 2 HPO 4 Otherwise, the same as example 1 was carried out to obtain Mg-coated 3 (PO 4 ) 2 Non-hollow porous structure positive electrode material Mg 3 (PO 4 ) 2 /Li 1.1 Ni 0.499 Co 0.2 Mn 0.3 Zr 0.001 O 2 。
Comparative example 1
A cathode material having a hollow porous structure was obtained in the same manner as in example 1 except that a lithium hydroxide solution was not added in the precursor core layer preparation step as compared with example 1.
Comparative example 2
Co-coated steel sheet 3 (PO 4 ) 2 Non-hollow porous structure anode material Co 3 (PO 4 ) 2 /Li 1.1 Ni 0.499 Co 0.2 Mn 0.3 Zr 0.001 O 2 The preparation method of (1), wherein the thickness ratio of the precursor core shell is 0.2:1, comprises the following steps:
synthesizing Ni-Co-Mn carbonate precursor Ni with core-shell structure by adopting coprecipitation method 0.5 Co 0.2 Mn 0.3 LiCO 3 : preparing a mixed metal salt solution with the total metal ion concentration of 2mol/L by using sulfates containing Ni, Co and Mn, wherein the molar ratio of Ni to Co to Mn is 5:2:3, preparing an ammonia water solution with the ammonium ion concentration of 5mol/L, preparing a lithium hydroxide solution with the lithium ion concentration of 1.2mol/L, preparing a sodium carbonate solution with the carbonate ion concentration of 3mol/L, and then respectively adding the sodium carbonate solution into a reaction kettle using pure water as a base solution for reaction; continuously adding the solution in the reaction process, controlling the temperature at 50 ℃, the stirring speed at 600r/min and the pH at 12.1, continuously introducing nitrogen into the reaction kettle, stopping adding the lithium salt solution when the particle size D50 of the precursor core is 1.2 mu m after the reaction is carried out for 11 hours, and simultaneously stopping adding the lithium salt solutionContinuously adding mixed metal salt solution, sodium carbonate precipitator solution and complexing agent solution, regulating the stirring speed to 530r/min, controlling the pH value to be 11.70 by finely adjusting the flow rates of the precipitator solution and ammonia water, reacting for 49 hours until the length of the whole precursor D50 including the inner core and the shell part is 7.2 mu m, stopping the reaction, separating, aging, washing and drying the obtained solid-liquid mixture to obtain a carbonate precursor with the core-shell thickness ratio of 0.2: 1;
carbonate precursor Ni with core-shell structure 0.5 Co 0.2 Mn 0.3 LiCO 3 And ZrO 2 Uniformly mixing, performing primary presintering, keeping the temperature at 500 ℃ for 5 hours, taking air as sintering atmosphere, and cooling to obtain a nickel-cobalt-manganese oxide precursor Ni with a porous structure 0.5 Co 0.2 Mn 0.3 LiZrO。
Ni as precursor of Ni-Co-Mn oxide with porous structure 0.5 Co 0.2 Mn 0.3 Uniformly mixing LiZrO and lithium carbonate, wherein the molar ratio of Li to total metals (Ni + Co + Mn) is 1.1:1, performing secondary sintering by adopting a one-stage temperature-controlled sintering mode, keeping the temperature at 890 ℃ for 12 hours, wherein the sintering atmosphere is air, reducing the temperature, crushing and sieving to obtain the non-hollow porous structure lithium nickel cobalt manganese oxide Li 1.1 Ni 0.499 Co 0.2 Mn 0.3 Zr 0.001 O 2 。
Dissolve 0.85g (CH) in 100mL of deionized water 3 COO) 2 Co·4H 2 O and 0.30g (NH) 4 ) 2 HPO 4 Wherein Co accounts for 0.1 percent of the mass of the anode material, the molar ratio of P to Co is 2:3, and the two solutions are mixed and stirred uniformly to obtain a coating substance Co 3 (PO 4 ) 2 Then 200g of lithium nickel cobalt manganese oxide Li with a non-hollow porous structure 1.1 Ni 0.499 Co 0.2 Mn 0.3 Zr 0.001 O 2 Adding the mixed solution, uniformly stirring the nickel cobalt lithium manganate and deionized water used by the mixed solution according to the weight ratio of 1:1 for 1h, directly pouring the mixture into a rotary steaming bottle, drying the mixture in a water bath at 100 ℃ for 3h, carrying out three-stage sintering on the dried material by adopting a one-stage temperature-controlled sintering mode, keeping the temperature at 500 ℃ for 5h, taking the sintering atmosphere as air, cooling and sieving to obtain the lithium nickel cobalt manganese oxide lithium saltTo cladding of Co 3 (PO 4 ) 2 Is not a hollow porous structure, and is a positive electrode material Co 3 (PO 4 ) 2 /Li 1.1 Ni 0.499 Co 0.2 Mn 0.3 Zr 0.001 O 2 。
Comparative example 3
Coated Co 3 (PO 4 ) 2 Non-hollow porous structure anode material Co 3 (PO 4 ) 2 /Li 1.1 Ni 0.499 Co 0.2 Mn 0.3 Zr 0.001 O 2 The preparation method of (1), wherein the thickness ratio of the precursor core shell is 1:1, comprises the following steps:
synthesizing Ni-Co-Mn carbonate precursor Ni with core-shell structure by adopting coprecipitation method 0.5 Co 0.2 Mn 0.3 LiCO 3 : preparing a mixed metal salt solution with the total metal ion concentration of 2mol/L by using sulfates containing Ni, Co and Mn, wherein the molar ratio of Ni to Co to Mn is 5:2:3, preparing an ammonia water solution with the ammonium ion concentration of 5mol/L, preparing a lithium hydroxide solution with the lithium ion concentration of 1.2mol/L, preparing a sodium carbonate solution with the carbonate ion concentration of 3mol/L, and then respectively adding the sodium carbonate solution into a reaction kettle using pure water as a base solution for reaction; in the reaction process, the solution is continuously added, the temperature is controlled at 50 ℃, the stirring speed is controlled at 600r/min, the pH is controlled at 12.1, nitrogen is continuously introduced into the reaction kettle, after the reaction is carried out for 11 hours, when the particle size D50 of the precursor core is 1.2 mu m, the lithium salt solution is stopped being added, the mixed metal salt solution, the sodium carbonate precipitator solution and the complexing agent solution are continuously added, the stirring speed is regulated to 530r/min, the pH is controlled at 11.70 by finely adjusting the flow of the precipitator solution and ammonia water, after the reaction is carried out for 20 hours, the whole precursor D50 including the core and the shell part is 2.4 mu m long, the reaction is stopped, and the obtained solid-liquid mixture is separated, aged, washed and dried to obtain a carbonate precursor with the thickness ratio of 1: 1;
carbonate precursor Ni with core-shell structure 0.5 Co 0.2 Mn 0.3 LiCO 3 And ZrO 2 Uniformly mixing, presintering at 500 deg.C for 5 hr in air, and coolingObtaining the precursor Ni of the nickel-cobalt-manganese oxide with porous structure 0.5 Co 0.2 Mn 0.3 LiZrO。
Ni as precursor of Ni-Co-Mn oxide with porous structure 0.5 Co 0.2 Mn 0.3 Uniformly mixing LiZrO and lithium carbonate, wherein the molar ratio of Li to total metals (Ni + Co + Mn) is 1.1:1, performing secondary sintering by adopting a one-stage temperature-controlled sintering mode, keeping the temperature at 890 ℃ for 12 hours, wherein the sintering atmosphere is air, reducing the temperature, crushing and sieving to obtain the non-hollow porous structure lithium nickel cobalt manganese oxide Li 1.1 Ni 0.499 Co 0.2 Mn 0.3 Zr 0.001 O 2 。
0.85g (CH) was dissolved in 100mL of deionized water of the same volume 3 COO) 2 Co·4H 2 O and 0.30g (NH) 4 ) 2 HPO 4 Wherein Co accounts for 0.1 percent of the mass of the anode material, the molar ratio of P to Co is 2:3, and the two solutions are mixed and stirred uniformly to obtain a coating substance Co 3 (PO 4 ) 2 Then 200g of lithium nickel cobalt manganese oxide Li with a non-hollow porous structure 1.1 Ni 0.499 Co 0.2 Mn 0.3 Zr 0.001 O 2 Adding the mixed solution, uniformly stirring the nickel cobalt lithium manganate and deionized water used by the mixed solution according to the weight ratio of 1:1 for 1h, directly pouring the mixture into a rotary evaporation bottle, drying the mixture in water bath at 100 ℃ for 3h, carrying out three-stage sintering on the dried material by adopting a one-stage temperature-controlled sintering mode, keeping the temperature at 500 ℃ for 5h in the sintering atmosphere of air, cooling and sieving to obtain the Co-coated lithium manganate 3 (PO 4 ) 2 Is not a hollow porous structure, and is a positive electrode material Co 3 (PO 4 ) 2 /Li 1.1 Ni 0.499 Co 0.2 Mn 0.3 Zr 0.001 O 2 。
Comparative example 4
In the same manner as in example 1 except that the phosphate coating step was not performed, as compared with example 1, a positive electrode material Li having a non-hollow porous structure and not coated was obtained 1.1 Ni 0.499 Co 0.2 Mn 0.3 Zr 0.001 O 2 。
Physical and chemical indexes and electrical property evaluation of the cathode materials in examples and comparative examples
The obtained positive electrode material was evaluated for profile morphology and porosity, specific surface area, particle strength, cycle performance, rate performance, and power performance in the following manner
(1) Profile morphology and porosity
The positive electrode material was embedded in a resin, the positive electrode material embedded in the resin was cut by argon sputtering using a cross-section polisher to expose the cross section of the particles, and then the exposed cross section was observed using a scanning electron microscope, and the porosity was calculated by an image analysis software.
(2) Specific surface area
BET was measured using a specific surface area tester of a flow-mode nitrogen adsorption method.
(3) Strength of particles
The particle strength at the time of breakage was calculated by applying a load to 1 particle with an indenter using a micro-strength evaluation tester, and the average value of 10 particles tested per sample was the particle strength.
(4) Rate capability
The obtained positive electrode material is made into 604062 type soft package batteries, the soft package batteries are conventionally formed after being prepared, the formed batteries are subjected to different-rate discharge tests at the normal temperature of 23 ℃, the charge rates are unified to be 1C, the discharge rates are respectively 1C, 3C, 5C, 7C and 10C, and the discharge capacity retention rates at different rates are calculated.
(5) Power performance
The obtained positive electrode material is made into an 604062 type soft package battery, the soft package battery is conventionally formed after being prepared, and the formed battery is subjected to discharge DCR test at the normal temperature of 23 ℃ and the low temperature of-20 ℃ respectively: discharging the 1C to 50% SOC after the 1C is fully charged at the normal temperature of 23 ℃, standing for 1h, then discharging the 1C to 10% SOC, and then performing 10C pulse for 10 s; then discharging to 50% SOC at the normal temperature of 23 ℃ after the 1C is fully charged, and then standing for 2h at the low temperature of-20 ℃ for 4C pulse 10 s; and calculating DCR under different conditions, wherein the calculation formula is DCR = (standing end voltage-voltage after pulse discharge)/pulse current.
TABLE 1 important physicochemical indices
TABLE 2 discharge capacity and retention at different rates
TABLE 3 discharging DCR
Evaluation of
As can be seen from fig. 1 and 2, the cross-sectional morphology of the cathode material prepared in example 1 is a non-hollow porous structure, and the porosity is 21%; the cross-sectional morphology of the cathode material prepared in comparative example 1 was a hollow porous structure, and the porosity was 36%.
As can be seen from table 1, the hollow porous structure cathode material prepared in comparative example 1 has significantly lower tap density and particle strength than the non-hollow porous structure cathode material prepared in example 1.
As can be seen from table 2 and fig. 3, the discharge capacity and capacity retention rate of the non-hollow cathode material prepared in comparative example 2 are significantly lower than those of the non-hollow cathode materials prepared in examples 1 and 2, which indicates that the rate performance is reduced due to the excessively small core-shell ratio of the precursor. As can be seen from table 1, the non-hollow cathode material prepared in comparative example 3 has significantly poorer particle strength than the non-hollow cathode materials prepared in examples 1 and 2, and is not favorable for cycle performance. Therefore, the core-shell ratio of the precursor needs to be controlled in a certain range, the preferred range is 0.3-0.7:1, the core-shell ratio is too small, the porosity of the anode material is low, the infiltration of electrolyte is not facilitated, the diffusion distance of lithium ions is increased, the resistance is increased, the rate performance is poor, the core-shell ratio is too high, the porosity of the anode material is too large, the particle strength of the material is reduced, the material is easy to break during the rolling of the battery, and the cycle performance of the material is not facilitated.
As can be seen from table 3 and fig. 4, compared with the non-hollow cathode materials prepared in examples 1 and 2, the non-hollow cathode material prepared in comparative example 2 has a larger discharge DCR, which indicates that the core-shell ratio of the precursor is too low, which results in a decrease in power performance, and therefore the core-shell ratio of the precursor cannot be too small, because the core-shell ratio is too small, the porosity of the cathode material is low, which is not favorable for the infiltration of the electrolyte, the diffusion distance of lithium ions is increased, the resistance is increased, and the power performance is poor.
As can be seen from table 2 and fig. 3, compared with the phosphate-coated non-hollow cathode material prepared in example 1, the non-hollow cathode material prepared in comparative example 4 has significantly lower discharge capacity and capacity retention rate at different rates, and particularly, at higher rates of 7C and 10C, the cathode material prepared in example 1 has significantly better rate performance because the coated phosphate is a fast ion conductor, which reduces the resistance of the cathode material and facilitates the exertion of the capacity and rate performance.
As can be seen from table 3 and fig. 4, the non-hollow cathode material without the phosphate coating prepared in comparative example 4 has a significantly larger DCR, i.e., poor power performance, at different SOCs and temperatures than the non-hollow cathode material coated with the phosphate prepared in example 1.
It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features related to the embodiments of the present invention described above may be combined with each other as long as they do not conflict with each other. In addition, the above embodiments are only some embodiments of the present invention, not all embodiments, and all other embodiments obtained by those skilled in the art based on the embodiments of the present invention without any creative work belong to the protection scope of the present invention.
Claims (7)
1. The lithium ion battery anode material with a non-hollow porous structure is characterized in that the chemical general formula is B 3 (PO 4 ) 2 /Li a Ni x Co y Mn (1-x-y-b) A b O 2 Wherein a is more than or equal to 0.95 and less than or equal to 1.20, x is more than or equal to 0.3 and less than or equal to 0.65, y is more than 0 and less than or equal to 0.35, B is more than 0.001 and less than or equal to 0.003, A is at least one of Zr, W, Ta, Mo and Nb, and B is at least one of Co, Mn and Mg; the preparation method of the lithium ion battery anode material with the non-hollow porous structure comprises the following steps:
(1) precursor kernel growth phase S1: respectively adding a metal salt solution mixed with nickel, cobalt and manganese, a lithium hydroxide solution, a sodium carbonate precipitator solution and a complexing agent solution into a reaction kettle using pure water as a base solution for reaction, continuously adding the solutions in the reaction process, controlling the temperature to be 40-60 ℃, controlling the stirring speed to be 800r/min, controlling the pH to be 11.8-12.3, controlling the ammonia concentration of the complexing agent to be 5-15g/L, controlling the reaction time to be 8-15h, continuously introducing nitrogen into the reaction kettle, controlling the pH to be 11.8-12.3 by finely adjusting the flow of the precipitator solution and the ammonia water, stopping adding the lithium hydroxide solution when the grain diameter D50 of a core is 1.05-1.40 mu m, and ending the growth stage of a precursor core;
(2) precursor shell growth stage S2: stopping adding the lithium hydroxide solution, continuously adding the metal salt solution, the sodium carbonate precipitator solution and the complexing agent solution, reducing the stirring speed by 50-150r/min, reducing the pH value by 0.3-0.8 by finely adjusting the flow rates of the precipitator solution and the ammonia water, controlling the ammonia concentration of the supernatant in the reaction stage to be 3-8g/L and lower than the ammonia concentration of S1, controlling the reaction time in the reaction stage to be 20-45h, continuously introducing nitrogen into the reaction kettle, stopping the reaction when the whole precursor D50 including the inner core and the shell part grows to be 2.5-6.0 mu m, and ending the growth stage of the precursor shell;
(3) carrying out solid-liquid separation, aging, washing and drying on the precipitate obtained in the step (2) to obtain a carbonate precursor with a core-shell structure;
(4) uniformly mixing the carbonate precursor obtained in the step (3) with a dopant, wherein the dopant is a compound containing A, then performing primary presintering, keeping the temperature at 300-700 ℃ for 2-8h, the heating rate is 3 ℃/min, the sintering atmosphere is air, and cooling to obtain an oxide precursor with a porous structure, in which A is uniformly distributed, in the dopant;
(5) uniformly mixing the oxide precursor obtained in the step (4) with one or more of lithium carbonate, lithium hydroxide, lithium oxalate and lithium acetate, performing secondary sintering by adopting a one-stage temperature-controlled sintering mode, keeping the temperature at 1000 ℃ for 8-14h at 700 ℃ at the heating rate of 3 ℃/min, and obtaining a non-hollow porous-structure anode material by cooling, crushing and sieving, wherein the sintering atmosphere is air, oxygen or a mixed gas of air and oxygen;
(6) dispersing the positive electrode material obtained in the step (5) in a mixed solution formed by deionized water and phosphate, stirring for 1h, directly performing rotary evaporation and drying, then performing tertiary sintering, keeping the temperature at 400-600 ℃ for 4-8h, wherein the heating rate is 3 ℃/min, the sintering atmosphere is air, oxygen or a mixed gas of air and oxygen, and sieving after cooling to obtain the positive electrode material with the surface coated with phosphate and a non-hollow porous structure;
the carbonate precursor in the step (3) is secondary particles formed by gathering primary particles, wherein the length of the primary particles is 150-1200nm, the width of the primary particles is 80-400nm, the average particle size D50 of the secondary particles is 2.5-6.0um, the carbonate precursor has a core-shell structure, and the thickness ratio of the core shell to the shell is 0.3-0.7: 1.
2. The lithium ion battery positive electrode material with the non-hollow porous structure as claimed in claim 1, wherein the positive electrode material is a secondary particle formed by aggregation of primary particles, the positive electrode material has an average particle diameter D50 of 2.8-7.0 μm and a tap density of 1.2-2.5g/cm 3 The specific surface area is 1.0-2.6 square meters per gram, the porosity is 10% -35%, the particle strength is 80-120MPa, the cross section of the anode material is a non-hollow porous structure, and the surface of the anode material is provided with a phosphate coating layer with the thickness of 20-50 nm.
3. The lithium ion battery cathode material with a non-hollow porous structure as claimed in claim 1, wherein in step (1), the metal salt solution is one or more of a sulfate solution and an acetate solution, the total metal ion concentration in the metal salt solution is 0.05 mol/L to 2.8mol/L, the lithium ion concentration in the lithium hydroxide solution is 1 mol/L to 2mol/L, the complexing agent solution is an ammonia water solution, the ammonium ion concentration is 3mol/L to 6mol/L, and the carbonate ion concentration in the sodium carbonate solution is 1 mol/L to 5 mol/L.
4. The lithium ion battery cathode material with a non-hollow porous structure according to claim 1, wherein A accounts for 0.1-0.3 mol% of the cathode material.
5. The lithium ion battery positive electrode material with the non-hollow porous structure as claimed in claim 1, wherein the molar ratio of Li to the total metals Ni + Co + Mn is 0.95-1.2: 1.
6. The lithium ion battery cathode material with a non-hollow porous structure of claim 1, wherein the phosphate in step (6) is Co 3 (PO 4 ) 2 、Mn 3 (PO 4 ) 2 、Mg 3 (PO 4 ) 2 The phosphate is formed by a soluble acetate salt of the corresponding metal with (NH) 4 ) 2 HPO 4 And the mass percentage of Co, Mn or Mg in the anode material is 0.05-0.2%.
7. Use of the lithium ion battery positive electrode material with a non-hollow porous structure according to any one of claims 1 to 6 in a lithium ion battery.
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