CN115353155B - Preparation method of phosphorus and lanthanum co-modified low-cobalt lithium-rich manganese-based lithium ion battery anode material - Google Patents

Preparation method of phosphorus and lanthanum co-modified low-cobalt lithium-rich manganese-based lithium ion battery anode material Download PDF

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CN115353155B
CN115353155B CN202211002809.9A CN202211002809A CN115353155B CN 115353155 B CN115353155 B CN 115353155B CN 202211002809 A CN202211002809 A CN 202211002809A CN 115353155 B CN115353155 B CN 115353155B
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lithium
atoms
cobalt
lanthanum
low
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CN115353155A (en
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朱晓波
佘钦
邓伊美
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Changsha University of Science and Technology
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Abstract

The invention discloses a preparation method of a phosphorus and lanthanum co-modified low-cobalt lithium-rich manganese-based lithium ion battery anode material, which comprises the steps of preparing xerogel by a sol-gel method through a lithium-containing compound, a manganese-containing compound, a nickel-containing compound and a cobalt-containing compound, and calcining the obtained xerogel through multi-step heating to obtain the low-cobalt lithium-rich manganese-based anode material; and then weighing the low-cobalt lithium-rich manganese-based anode material, the phosphorus-containing compound and the lanthanum-containing compound, dispersing the low-cobalt lithium-rich manganese-based anode material, the phosphorus-containing compound and the lanthanum-containing compound in a solvent, uniformly mixing, heating and stirring the obtained uniform solution until the uniform solution is dried, and calcining at a high temperature to obtain the low-cobalt lithium-rich manganese-based anode material jointly modified by phosphorus and lanthanum. The molar ratio of lithium atoms, manganese atoms, nickel atoms and cobalt atoms in the lithium-containing compound, the manganese-containing compound, the nickel-containing compound and the cobalt-containing compound is 40:20:0-4:0-4. The molar ratio of the phosphorus atoms in the low-cobalt lithium-rich manganese-based positive electrode material and the phosphorus atoms in the phosphorus-containing compound to the lanthanum atoms in the lanthanum-containing compound is 100:1-3:0.5-1.5, and the low-cobalt lithium-rich manganese-based positive electrode material and the lanthanum-containing compound are low in cost and high in specific capacity.

Description

Preparation method of phosphorus and lanthanum co-modified low-cobalt lithium-rich manganese-based lithium ion battery anode material
Technical Field
The invention belongs to the field of lithium ion battery development, and relates to a preparation method of a phosphorus and lanthanum co-modified low-cobalt lithium-rich manganese-based lithium ion battery anode material.
Background
The positive electrode material of the lithium-rich manganese-based lithium ion battery has a unique superlattice structure, is low in cost compared with the traditional positive electrode material, has specific capacity exceeding 250mAh/g, and has very high oxygen redox activity when cycled below 4.5VThe matching and combination of the specific energy of the lithium ion battery and the silicon-carbon anode material are very likely to promote the new energy electric automobile to reach the endurance mileage of 1000km in the future. From the industrial point of view, for the low cobalt lithium-rich manganese-based positive electrode material, the transition metal is selected from three types of Mn, ni and Co, and Mn has the following most obvious advantages: (1) Mn content in crust is tens times higher than other two (Ni, co), and raw materials price is only 7% and 1.4% of nickel and cobalt raw materials; (2) Manganese, because of its unique atomic/electronic structure, is derived from Li 2 MnO 3 And the like having oxygen anions to participate in the reaction; (3) Mn has lower atomic mass, so that the theoretical capacity of the positive electrode material can be improved; (4) Mn has low toxicity relative to Ni and Co, and has the characteristic of environmental friendliness.
However, although the reduction of the cobalt content can reduce the material cost, adverse effects can be generated on electron conductivity and element mixing, and the problems of low initial coulombic efficiency, poor rate capability and the like caused by oxygen loss and structural distortion in the lithium-rich material, and serious voltage attenuation in the circulation process are caused, so that the industrial application of the lithium-rich material is further hindered.
Disclosure of Invention
The embodiment of the invention aims to provide a preparation method of a phosphorus and lanthanum co-modified low-cobalt lithium-rich manganese-based lithium ion battery positive electrode material, which adopts non-metal element phosphorus and metal element lanthanum co-modification to solve the problems of low initial coulomb efficiency, poor multiplying power performance and serious voltage attenuation in the circulation process of the lithium-rich manganese-based lithium ion battery positive electrode material caused by surface oxygen loss and structural distortion.
The technical scheme adopted by the embodiment of the invention is as follows: the preparation method of the low-cobalt lithium-rich manganese-based positive electrode material comprises the following steps:
step S1: preparing xerogel by a sol-gel method by adopting a lithium-containing compound, a manganese-containing compound, a nickel-containing compound and a cobalt-containing compound;
s2: and (3) carrying out multi-step heating and calcining on the obtained xerogel to obtain the low-cobalt lithium-rich manganese-based anode material.
Further, in step S1, the mass of the lithium-containing compound, the manganese-containing compound, the nickel-containing compound, and the cobalt-containing compound is determined by the molar mass of the lithium atom, the manganese atom, the nickel atom, and the cobalt atom, wherein the molar ratio of the lithium atom, the manganese atom, the nickel atom, and the cobalt atom is 40:20:0-4:0-4.
Further, in step S1:
the lithium-containing compound is at least one of lithium nitrate, lithium acetate and lithium sulfate;
the manganese-containing compound is at least one of manganese acetate, manganese sulfate and manganese nitrate;
the nickel-containing compound is specifically at least one of nickel acetate, nickel sulfate and nickel nitrate;
the cobalt-containing compound is specifically at least one of cobalt acetate, cobalt sulfate and cobalt nitrate.
Further, in the step S1, firstly, a lithium-containing compound, a manganese-containing compound, a nickel-containing compound and a cobalt-containing compound are dissolved in deionized water to obtain a uniform solution with the total concentration of 0.1-2 mol/L, acrylic acid is added, the ratio of the acrylic acid to the total amount of substances of lithium atoms, manganese atoms, nickel atoms and cobalt atoms is 1:0.5-2, and then the mixture is heated and stirred at the temperature of 100-200 ℃ and the stirring speed of 50-300 r/min until xerogel is formed;
in the step S2, the xerogel is heated for 2-5 hours at 200-300 ℃, then heated for 2-5 hours at 400-600 ℃, and finally heated for 8-12 hours at 800-1000 ℃.
The embodiment of the invention adopts another technical scheme that: the preparation method of the phosphorus and lanthanum co-modified low-cobalt lithium-rich manganese-based lithium ion battery anode material comprises the following steps:
step 1: weighing a certain proportion of low-cobalt lithium-rich manganese-based positive electrode material, a phosphorus-containing compound and a lanthanum-containing compound, dispersing in a solvent, and uniformly mixing;
step 2: heating and stirring the obtained uniform solution until the solution is dry;
step 3: and (3) performing high-temperature calcination treatment to obtain the phosphorus and lanthanum co-modified low-cobalt lithium-rich manganese-based anode material.
Further, in the step 1, the mass of the low-cobalt lithium-rich manganese-based positive electrode material, the phosphorus-containing compound and the lanthanum-containing compound is determined by the mass of the phosphorus atoms in the low-cobalt lithium-rich manganese-based positive electrode material and the lanthanum atoms in the phosphorus-containing compound and the lanthanum atoms in the lanthanum-containing compound, wherein the molar ratio of the low-cobalt lithium-rich manganese-based positive electrode material to the phosphorus atoms and the lanthanum atoms is 100:1-3:0.5-1.5.
Further, in step 1:
the dispersion solvent is deionized water or absolute ethyl alcohol;
the low cobalt lithium-rich manganese-based positive electrode material, the phosphorus-containing compound and the lanthanum-containing compound are dispersed in a solvent and uniformly mixed to obtain a uniform solution with the total concentration of 0.5-1 mol/L.
In step 1, the phosphorus-containing compound is at least one of ammonium phosphate and diammonium phosphate, and the lanthanum-containing compound is at least one of lanthanum nitrate and lanthanum acetate.
In the step 2, the heating temperature is 60-90 ℃, and the stirring speed is 50-300 rpm.
In the step 3, the calcination condition is that the calcination is carried out at 400-600 ℃ for 1-5 hours.
The embodiment of the invention has the beneficial effects that:
1. the low-cobalt lithium-rich manganese-based anode material with low raw material price cost and high specific capacity is prepared by regulating and controlling the chemical composition of the lithium-rich material, and is jointly modified by nonmetallic element phosphorus and metallic element lanthanum; the modification of phosphorus can introduce stronger P-O bond, stabilize lattice oxygen in the material, and enhance structural stability and safety; the metal element lanthanum is adopted for common modification, so that a stable phase matched with epitaxially grown grains can be formed on the surface of the lithium-rich material, effective charge transfer can be ensured when the lithium-rich material circulates under high voltage, dissolution of transition metal can be effectively inhibited, structural stability is enhanced, voltage and capacity attenuation in the circulating process are inhibited, the problem of voltage and capacity attenuation in the circulating process of the lithium-rich material can be well solved, specific discharge capacity is improved, and commercial application prospect of the lithium-rich material is increased;
2. the problems of low first coulomb efficiency and poor multiplying power performance of the lithium-rich material in the circulation process can be well solved, side reactions of the active material and electrolyte are avoided, the stability of a special layered structure of the two-phase mixed discharge of the lithium-rich material in the circulation process is stabilized, the transition from the layered structure of the lithium-rich material to a spinel phase is slowed down by inhibiting the release of lattice oxygen and the migration of transition metal cations, and the capacity and the circulation stability of the lithium-rich material are further improved while the first coulomb efficiency is improved;
3. in the process of preparing the battery anode material, the raw material cost is low, the operation is simple, the process time is short, and the obtained lithium ion battery material is suitable for large-scale industrialized development;
4. the phosphorus and lanthanum are introduced after the preparation of the low-cobalt lithium-rich manganese-based positive electrode material, compared with the simple synchronous introduction, the method can avoid the influence of modified ions on the formation and growth of crystal grains of the positive electrode material, and is beneficial to forming the positive electrode material with larger crystal grain size and better crystallinity.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction chart of examples 1 to 4 of the present invention.
Fig. 2 is a graph showing the comparison of cycle curves of lithium ion batteries assembled by the low-cobalt lithium-rich manganese-based positive electrode materials prepared in examples 1-4 at current densities of 25mAh/g and 250mAh/g (Capacity represents specific discharge Capacity).
FIG. 3 is a graph comparing the cycle curves of the lithium ion battery assembled by the low cobalt lithium-rich manganese-based positive electrode material prepared in the embodiment 3 and the low cobalt lithium-rich manganese-based positive electrode material prepared in the embodiment 5 and modified by the low cobalt lithium-rich manganese-based positive electrode material with the material amount of 1.5% of phosphorus and the material amount of 0.5% of lanthanum at the current densities of 25mAh/g and 250 mAh/g.
Fig. 4 is a graph comparing the cycle curves of the lithium ion battery assembled by the lanthanum co-modified low-cobalt lithium-rich manganese-based cathode material with the phosphorus content of 1.5% and the lanthanum content of 0.5% in the embodiment 5 and the lanthanum co-modified low-cobalt lithium-rich manganese-based cathode material with the phosphorus content of 1% and the lanthanum content of 0.5% in the embodiment 6 at the current densities of 25mAh/g and 250 mAh/g.
Fig. 5 is a graph comparing the cycle curves of the lithium ion battery assembled by the low cobalt lithium-rich manganese-based positive electrode material co-modified by lanthanum with the mass of 1.5% and the mass of 0.5% in example 5 and the low cobalt lithium-rich manganese-based positive electrode material co-modified by lanthanum with the mass of 1.5% and the mass of 0.75% in example 7 at the current densities of 25mAh/g and 250 mAh/g.
Fig. 6 is a graph comparing the cycle curves of the lithium ion battery assembled by the low cobalt lithium-rich manganese-based cathode material co-modified by lanthanum with the mass of 1.5% and the mass of 0.5% in example 5 and the low cobalt lithium-rich manganese-based cathode material co-modified by lanthanum with the mass of 2% and the mass of 1% in example 8 at the current densities of 25mAh/g and 250 mAh/g.
Fig. 7 is a graph comparing the cycle curves of the lithium ion battery assembled by the lanthanum co-modified low-cobalt lithium-rich manganese-based cathode material with the phosphorus content of 1.5% and the lanthanum content of 0.5% in the embodiment 5 and the lanthanum co-modified low-cobalt lithium-rich manganese-based cathode material with the phosphorus content of 3% and the lanthanum content of 1.5% in the embodiment 9 at the current densities of 25mAh/g and 250 mAh/g.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparation of the chemical formula Li 1.25 Mn 0.625 Co 0.125 O 2 The nickel-free low-cobalt lithium-rich manganese-based positive electrode material comprises the following steps:
step S1: weighing 6.695g of lithium acetate dihydrate, 7.659g of manganese acetate tetrahydrate and 1.557g of cobalt acetate tetrahydrate, dissolving in 1000mL deionized water to obtain a uniform solution with the total concentration of 0.1mol/L, wherein the molar ratio of lithium atoms to manganese atoms to cobalt atoms is 10:5:1, adding 14.2 g acrylic acid as a complexing agent, the ratio of the acrylic acid to the total substances of lithium atoms to manganese atoms to cobalt atoms is 1:0.5, and heating and stirring at the temperature of 100 ℃ and the stirring speed of 300 revolutions per minute until xerogel is formed;
step S2: heating and calcining the obtained xerogel to obtain the nickel-free low-cobalt lithium-rich manganese-based positive electrode material Li 1.25 Mn 0.625 Co 0.125 O 2 And designated as LMNO1, the heating condition is that the heating is carried out for 5 hours at 200 ℃, the calcining condition is that the calcining is carried out for 5 hours at 400 ℃ and the calcining is carried out for 12 hours at 800 ℃.
Example 2
Preparation of the chemical formula Li 1.25 Mn 0.625 Ni 0.125 O 2 The cobalt-free low-nickel lithium-rich manganese-based positive electrode material comprises the following steps:
step S1: 9.048g of lithium nitrate, 15.688g of manganese nitrate tetrahydrate and 3.634g of nickel nitrate hexahydrate are weighed and dissolved in 100mL of deionized water to obtain a uniform solution with the total concentration of 2mol/L, wherein the molar ratio of lithium atoms to manganese atoms to nickel atoms is about 10:5:1; adding 7.2g of acrylic acid as a complexing agent, wherein the mass ratio of the acrylic acid to the total substances of lithium atoms, manganese atoms and cobalt atoms is 1:2, and heating and stirring at 200 ℃ at a stirring speed of 50 revolutions per minute until xerogel is formed;
step S2: the obtained xerogel is heated and calcined to obtain the low-cobalt lithium-rich manganese-based positive electrode material Li 1.25 Mn 0.625 Ni 0.125 O 2 Designated as LMNO2, the xerogel is heated at 300 ℃ for 2 hours, the calcination conditions are 600 ℃ for 2 hours and 1000 ℃ for 8 hours.
Example 3
Preparation of the chemical formula Li 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 The low cobalt lithium-rich manganese-based positive electrode material is prepared by the following steps ofThe method comprises the following steps:
step S1: 20.085g of lithium acetate dihydrate, 23.532g of manganese nitrate tetrahydrate, 2.332g of nickel acetate tetrahydrate and 2.728g of cobalt sulfate heptahydrate are weighed and dissolved in 600mL of deionized water to obtain a uniform solution with the total concentration of 0.5mol/L, and the molar ratio of lithium atoms to manganese atoms to nickel atoms to cobalt atoms is 20:10:1:1; 21.618g of acrylic acid is added as a complexing agent, the weight ratio of the acrylic acid to the total substances of lithium atoms, manganese atoms and cobalt atoms is 1:1, and the mixture is heated and stirred at the temperature of 150 ℃ and the stirring speed of 200 r/min until xerogel is formed;
step S2: the obtained xerogel is heated and calcined to obtain the low-cobalt lithium-rich manganese-based positive electrode material Li 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 Designated as LMNO3, the heating condition is that the heating is carried out at 260 ℃ for 3 hours, the calcining condition is that the calcining is carried out at 500 ℃ for 3 hours and the calcining is carried out at 900 ℃ for 9 hours.
Example 4
Preparation of the chemical formula Li 1.25 Mn 0.625 Ni 0.09375 Co 0.03125 O 2 The low-cobalt lithium-rich manganese-based positive electrode material comprises the following steps:
step S1: weighing 6.871 g lithium sulfate dihydrate, 13.941g manganese sulfate tetrahydrate, 2.464g nickel sulfate hexahydrate and 0.8784g cobalt sulfate heptahydrate, dissolving in 200mL deionized water to obtain a uniform solution with the total concentration of 1mol/L, wherein the molar ratio of lithium atoms to manganese atoms to nickel atoms to cobalt atoms is 40:20:3:1; adding 19.216 g acrylic acid as a complexing agent, wherein the ratio of the acrylic acid to the total metal ion substances is 1:0.75, and heating and stirring at 125 ℃ at a stirring speed of 100 revolutions per minute until xerogel is formed;
step S2: the obtained xerogel is heated and calcined to obtain the low-cobalt lithium-rich manganese-based positive electrode material Li 1.25 Mn 0.625 Ni 0.09375 Co 0.03125 O 2 Designated as LMNO4, the heating condition is that the heating is carried out at 250 ℃ for 2.5 hours, the calcining condition is that the calcining is carried out at 450 ℃ for 2.5 hours and at 850 ℃ for 8.5 hours.
Example 5
Preparation of the chemical formula Li 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 Phosphorus and lanthanum modified low cobalt lithium-rich manganese-based positive electrode material:
step S1: 60.255g of lithium acetate dihydrate, 68.931g of manganese acetate tetrahydrate, 6.998g of nickel acetate tetrahydrate and 7.00g of cobalt acetate tetrahydrate are weighed and dissolved in 1000mL of deionized water to obtain a uniform solution with the total concentration of 0.9mol/L, and the molar ratio of lithium atoms to manganese atoms to nickel atoms to cobalt atoms is 20:10:1:1; 54.045g of acrylic acid is added as a complexing agent, the ratio of the acrylic acid to the sum of the amounts of substances of lithium atoms, manganese atoms, nickel atoms and cobalt atoms is 1:1.2, and the mixture is heated and stirred at 160 ℃ and a stirring speed of 125 revolutions per minute until xerogel is formed;
step S2: the obtained xerogel is heated and calcined to obtain the low-cobalt lithium-rich manganese-based positive electrode material Li 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 Heating at 250 ℃ for 3 hours, calcining at 500 ℃ for 3 hours and 900 ℃ for 10 hours to obtain the low-cobalt lithium-rich manganese-based positive electrode material Li 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 ；
And the phosphorus with the mass of 1.5% and the lanthanum with the mass of 0.5% are used for common modification to prepare the low-cobalt lithium-rich manganese-based lithium ion battery anode material with the common modification of the phosphorus and the lanthanum, and the method specifically comprises the following steps of:
step 1: 1.25g of low-cobalt lithium-rich manganese-based positive electrode material Li is weighed 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 29.9mg of diammonium hydrogen phosphate and 32.7mg of lanthanum nitrate hexahydrate are dispersed in 30.93mL of absolute ethyl alcohol and uniformly mixed to obtain a uniform solution with the concentration of 0.5mol/L, and the molar ratio of the low-cobalt lithium-rich manganese-based positive electrode material to phosphorus atoms and lanthanum atoms is 100:1.5:0.5;
step 2: heating and stirring at 65deg.C and stirring speed of 300 r/min until it is dried;
step 3: calcining at 400 ℃ for 5 hours to obtain the low-cobalt lithium-rich manganese-based positive electrode material modified by phosphorus and lanthanum together, and the material is named as LMNO5.
Example 6
Preparation of the chemical formula Li 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 Phosphorus and lanthanum modified low cobalt lithium-rich manganese-based positive electrode material:
step S1: weighing 20.613 g lithium sulfate dihydrate, 41.823 g manganese sulfate tetrahydrate, 4.929g nickel sulfate hexahydrate and 5.271 g cobalt sulfate heptahydrate, and dissolving in 400mL deionized water to obtain a uniform solution with the total concentration of 1.5mol/L, wherein the molar ratio of lithium atoms to manganese atoms to nickel atoms to cobalt atoms is 20:10:1:1; 28.824g of acrylic acid is added as a complexing agent, the ratio of the acrylic acid to the sum of the amounts of substances of lithium atoms, manganese atoms, nickel atoms and cobalt atoms is 1:1.5, and the mixture is heated and stirred at 170 ℃ and a stirring speed of 220 revolutions per minute until xerogel is formed;
step S2: the obtained xerogel is heated and calcined to obtain the low-cobalt lithium-rich manganese-based positive electrode material Li 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 Heating at 280 ℃ for 3 hours, calcining at 540 ℃ for 3 hours and at 940 ℃ for 9 hours to obtain the low-cobalt lithium-rich manganese-based positive electrode material Li 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 ；
And the phosphorus and lanthanum with the mass fraction of 1% and 0.5% are used for common modification to prepare the low-cobalt lithium-rich manganese-based lithium ion battery anode material which is jointly modified by the phosphorus and the lanthanum, and the method specifically comprises the following steps of:
step 1: weighing 8g low-cobalt lithium-rich manganese-based positive electrode material Li 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 Uniformly mixing 145 mg ammonium phosphate and 153 mg lanthanum acetate in 98.59mL deionized water to obtain a uniform solution with the concentration of 1mol/L, wherein the mass ratio of the low-cobalt lithium-rich manganese-based positive electrode material to the phosphorus atom and the lanthanum atom is 100:1:0.5;
step 2: heating and stirring at 90 ℃ at a stirring speed of 50 revolutions per minute until the mixture is dried;
step 3: calcining at 600 ℃ for 1 hour to obtain the low-cobalt lithium-rich manganese-based positive electrode material modified by phosphorus and lanthanum together, which is named as LMNO6.
Example 7
Preparation of the chemical formula Li 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 Phosphorus and lanthanum modified low cobalt lithium-rich manganese-based positive electrode material:
step S1: 50.212g of lithium acetate dihydrate, 57.442g of manganese acetate tetrahydrate, 6.817 g nickel nitrate hexahydrate and 6.589 g cobalt sulfate heptahydrate are weighed and dissolved in 625mL of deionized water to obtain a uniform solution with the total concentration of 1.2mol/L, and the molar ratio of lithium atoms to manganese atoms to nickel atoms to cobalt atoms is 20:10:1:1; 33.778g of acrylic acid is added as a complexing agent, the ratio of the acrylic acid to the sum of the amounts of substances of lithium atoms, manganese atoms, nickel atoms and cobalt atoms is 1:1.6, and the mixture is heated and stirred at 180 ℃ and a stirring speed of 210 revolutions per minute until xerogel is formed;
step S2: the obtained xerogel is heated and calcined to obtain the low-cobalt lithium-rich manganese-based positive electrode material Li 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 Heating at 290 ℃ for 2.5 hours, and calcining at 560 ℃ for 2.5 hours and 960 ℃ for 8.5 hours to obtain the low-cobalt lithium-rich manganese-based positive electrode material Li 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 ；
And the phosphorus with the mass of 1.5% and the lanthanum with the mass of 0.75% are used for common modification to prepare the low-cobalt lithium-rich manganese-based lithium ion battery anode material with the common modification of the phosphorus and the lanthanum, and the method specifically comprises the following steps of:
step 1: 15g of low-cobalt lithium-rich manganese-based positive electrode material Li is weighed 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 359mg of diammonium hydrogen phosphate and 430 mg lanthanum acetate are dispersed in 310.36mL of absolute ethyl alcohol and uniformly mixed to obtain a uniform solution with the concentration of 0.6mol/L, and the molar ratio of the low-cobalt lithium-rich manganese-based positive electrode material to phosphorus atoms and lanthanum atoms is 100:1.5:0.75;
step 2: heating and stirring at 75deg.C at stirring speed of 200 r/min until it is dried;
step 3: calcining for 3 hours at 500 ℃ to obtain the low-cobalt lithium-rich manganese-based positive electrode material jointly modified by phosphorus and lanthanum, and the material is named as LMNO7.
Example 8
Preparation of the chemical formula Li 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 Phosphorus and lanthanum modified low cobalt lithium-rich manganese-based positive electrode material:
step S1: weighing 36.2 g lithium nitrate, 55.765 g manganese sulfate tetrahydrate, 6.572 g nickel sulfate hexahydrate and 7.027 g cobalt sulfate heptahydrate, dissolving in 500mL of deionized water to obtain a uniform solution with the total concentration of 1.6mol/L, wherein the molar ratio of lithium atoms to manganese atoms to nickel atoms to cobalt atoms is 20:10:1:1; adding 72.06 g acrylic acid as a complexing agent, wherein the ratio of the acrylic acid to the sum of the amounts of substances of lithium atoms, manganese atoms, nickel atoms and cobalt atoms is 1:0.8, and heating and stirring at 190 ℃ at a stirring speed of 180 revolutions per minute until xerogel is formed;
step S2: the obtained xerogel is heated and calcined to obtain the low-cobalt lithium-rich manganese-based positive electrode material Li 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 Heating at 295 ℃ for 2 hours, calcining at 580 ℃ for 3 hours and 980 ℃ for 9 hours to obtain the low-cobalt lithium-rich manganese-based positive electrode material Li 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 ；
And the phosphorus and lanthanum with the mass ratio of 2% and the mass ratio of 1% are used for common modification to prepare the low-cobalt lithium-rich manganese-based lithium ion battery anode material which is jointly modified by the phosphorus and the lanthanum, and the method specifically comprises the following steps of:
step 1: 7.5g of low-cobalt lithium-rich manganese-based positive electrode material Li is weighed 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 Dispersing 270 mg ammonium phosphate and 286 mg lanthanum acetate in 133.96mL deionized water, uniformly mixing to obtain a uniform solution with the concentration of 0.7mol/L, wherein the molar ratio of the low-cobalt lithium-rich manganese-based positive electrode material to phosphorus atoms and lanthanum atoms is 100:2:1;
step 2: heating and stirring at 85deg.C at stirring speed of 100 r/min until it is dried;
step 3: calcining at 550 ℃ for 2 hours to obtain the low-cobalt lithium-rich manganese-based positive electrode material modified by phosphorus and lanthanum together, which is named as LMNO8.
Example 9
Preparation of the chemical formula Li 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 Phosphorus and lanthanum modified low cobalt lithium-rich manganese-based positive electrode material:
step S1: 18.096g of lithium nitrate, 30.636g of manganese acetate tetrahydrate, 3.635 g nickel nitrate hexahydrate and 3.113 g cobalt acetate tetrahydrate are weighed and dissolved in 320mL of deionized water to obtain a uniform solution with the total concentration of 1.25mol/L, and the molar ratio of lithium atoms to manganese atoms to nickel atoms to cobalt atoms is 20:10:1:1; adding 25.62 g acrylic acid as a complexing agent, wherein the ratio of the acrylic acid to the sum of the amounts of substances of lithium atoms, manganese atoms, nickel atoms and cobalt atoms is 1:1.125, and heating and stirring at 160 ℃ at a stirring speed of 140 revolutions per minute until xerogel is formed;
step S2: the obtained xerogel is heated and calcined to obtain the low-cobalt lithium-rich manganese-based positive electrode material Li 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 Heating at 270 ℃ for 2 hours, calcining at 520 ℃ for 3 hours and at 920 ℃ for 8 hours to obtain the low-cobalt lithium-rich manganese-based positive electrode material Li 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 ；
And the phosphorus with the mass of 3% and the lanthanum with the mass of 1.5% are used for common modification to prepare the low cobalt lithium-rich manganese-based lithium ion battery anode material with the common modification of the phosphorus and the lanthanum, and the method specifically comprises the following steps of:
step 1: 1g of low-cobalt lithium-rich manganese-based positive electrode material Li is weighed 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 48.1 and mg diammonium hydrogen phosphate and 78.9mg lanthanum nitrate hexahydrate are dispersed in 15.85mL absolute ethyl alcohol and uniformly mixed to obtain a uniform solution with the concentration of 0.8mol/L, and the molar ratio of the low-cobalt lithium-rich manganese-based positive electrode material to phosphorus atoms and lanthanum atoms is 100:3:1.5;
step 2: heating and stirring at 60deg.C and stirring speed of 300 r/min until it is dried;
step 3: calcining at 400 ℃ for 5 hours to obtain the low-cobalt lithium-rich manganese-based positive electrode material modified by phosphorus and lanthanum together, which is named as LMNO9.
From fig. 1 to 2, the low-cobalt lithium-rich manganese-based cathode materials prepared in examples 1 to 4 show the best electrochemical performance, and thus the low-cobalt lithium-rich manganese-based cathode materials prepared in example 3 are all prepared by the following phosphorus lanthanum co-modified low-cobalt lithium-rich manganese-based cathode materials based on the proportion of example 3 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 And (3) performing phosphorus lanthanum co-modification to prepare the phosphorus and lanthanum co-modified low-cobalt lithium-rich manganese-based anode material.
Analysis of electrochemical cycle performance graphs of examples 1-9, as can be obtained from fig. 2, the cobalt-free and nickel-free low-cobalt lithium-rich manganese-based positive electrode materials prepared in examples 1 and 2 have the same specific discharge capacity and cycle performance at the same current density after being assembled into a lithium ion battery, and compared with examples 3 and 4, ions composed of two elements of Ni and Co are important in changing the local structure of lattice oxygen in the lithium-rich material; the nickel-containing compound and cobalt-containing compound required for the preparation of example 4 were relatively small, and the discharge specific capacity and cycle performance of example 3 were more excellent, although the economic cost was low. As shown in fig. 3, when the low cobalt lithium-rich material with Mn: ni: co: =10:1:1 is Co-modified by using phosphorus with a mass amount of 1.5% and lanthanum with a mass amount of 0.5% at the same time, the first charge-discharge efficiency, specific discharge capacity and cycle stability are all greatly improved compared with those of the material before the modification. In addition, fig. 4 to 7 are respectively comparison graphs of electrochemical performances of examples 5 to 9, and in comparison, in example 5, electrochemical performances of a product obtained by Co-modifying a low cobalt lithium-rich material with Mn: ni: co: =10:1:1 with phosphorus in an amount of 1.5% and lanthanum in an amount of 0.5% of the substance are optimal. In FIGS. 1 to 7, the data before the specific capacity peak is cyclic data at a current density of 25mAh/g, and the data after the specific capacity peak is cyclic data at a current density of 250 mAh/g.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention are included in the protection scope of the present invention.

Claims (1)

1. The preparation method of the phosphorus and lanthanum co-modified low-cobalt lithium-rich manganese-based lithium ion battery anode material is characterized by comprising the following steps of:
step S1: 60.255g of lithium acetate dihydrate, 68.931g of manganese acetate tetrahydrate, 6.998g of nickel acetate tetrahydrate and 7.00g of cobalt acetate tetrahydrate are weighed and dissolved in 1000mL of deionized water to obtain a uniform solution with the total concentration of 0.9mol/L, and the molar ratio of lithium atoms to manganese atoms to nickel atoms to cobalt atoms is 20:10:1:1; 54.045g of acrylic acid is added as a complexing agent, the ratio of the acrylic acid to the sum of the amounts of substances of lithium atoms, manganese atoms, nickel atoms and cobalt atoms is 1:1.2, and the mixture is heated and stirred at 160 ℃ and a stirring speed of 125 revolutions per minute until xerogel is formed;
step S2: heating and calcining the obtained xerogel for 3 hours at the temperature of 250 ℃, and calcining for 3 hours at the temperature of 500 ℃ and 10 hours at the temperature of 900 ℃ to obtain the low-cobalt lithium-rich manganese-based positive electrode material Li 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 ；
And the phosphorus with the mass of 1.5% and the lanthanum with the mass of 0.5% are used for common modification to prepare the low-cobalt lithium-rich manganese-based lithium ion battery anode material with the common modification of the phosphorus and the lanthanum, and the method specifically comprises the following steps of:
step 1: 1.25g of low-cobalt lithium-rich manganese-based positive electrode material Li is weighed 1.25 Mn 0.625 Ni 0.0625 Co 0.0625 O 2 29.9mg of diammonium hydrogen phosphate and 32.7mg of lanthanum nitrate hexahydrate are dispersed in 30.93mL of absolute ethyl alcohol and uniformly mixed to obtain a uniform solution with the concentration of 0.5mol/L, and the molar ratio of the low-cobalt lithium-rich manganese-based positive electrode material to phosphorus atoms and lanthanum atoms is 100:1.5:0.5;
step 2: heating and stirring at 65deg.C and stirring speed of 300 r/min until it is dried;
step 3: calcining at 400 ℃ for 5 hours to obtain the low-cobalt lithium-rich manganese-based anode material modified by phosphorus and lanthanum.
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