CN103943862A - Binary layered lithium ion battery cathode material coated with phosphate and preparing method thereof - Google Patents
Binary layered lithium ion battery cathode material coated with phosphate and preparing method thereof Download PDFInfo
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- CN103943862A CN103943862A CN201310023489.XA CN201310023489A CN103943862A CN 103943862 A CN103943862 A CN 103943862A CN 201310023489 A CN201310023489 A CN 201310023489A CN 103943862 A CN103943862 A CN 103943862A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of lithium ion batteries, and provides a binary layered lithium ion battery cathode material coated with a phosphate and a preparing method thereof. The chemical formula of the cathode material is FePO4(AlPO4)/Li<1+x>(Ni0.5Mn0.5)O2, wherein the x is not more than 0.15 and not less than 0. The preparing method is characterized in that: a composite carbonate comprising Na2CO3 and NH4HCO3 is adopted as a precipitating agent to uniformly precipitate nickel and manganese simultaneously so that uniform mixing at the atom level of the two elements is achieved; and the synthetic process is free of inert gas protection. In addition, the synthesized material is coated with the phosphate, thus enhancing rate capability and cycle performance of the material. Raw materials are simple and low in cost. Composition of the product can be accurately controlled through the rate of charge. The product is uniform in particle, smooth in surface, high in specific capacity, and high in rate capability and cycle performance, and is spheroidal.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to the surface coated binary stratiform of a kind of phosphate anode material for lithium-ion batteries and preparation method thereof.
Background technology
Anode material for lithium-ion batteries, the particularly hysteresis of cheapness, environmental protection, high performance anode material for lithium-ion batteries development, has become the key factor that restriction lithium electricity industry further develops.With regard at present with regard to business-like anode material for lithium-ion batteries, the capacity of lithium manganate having spinel structure and LiFePO4 is also too low, LiCoO
2and LiNi
1/3co
1/3mn
1/3o
2although promote to some extent aspect capacity, contain scarcity of resources, the cobalt element that expensive and toxicity is larger.Therefore, people are always at the novel anode material of actively finding a kind of cheap, environment-protecting asepsis, superior performance.
LiNi
0.5mn
0.5o
2being a kind of positive electrode of very attractive, is by LiNiO
2and LiMnO
2by the solid solution Li, Ni, Mn oxide system of formation in 1: 1.This system has had both the advantage of Ni system and Mn based material simultaneously: preparation condition is gentleer, the lower and LiNi of the cost of material
0.5mn
0.5o
2combination property compares LiNiO
2and LiMnO
2improve a lot, as good structural stability and thermal stability.But LiNi
0.5mn
0.5o
2also exist at present some shortcomings, as: 1, synthetic homogeneous phase compound difficulty is large, and conventional high temperature solid state reaction easily forms Li
2mnO
3and cause unreacted NiO dephasign.Although hydroxide coprecipitation step can form the pure phase product that particle diameter is evenly distributed, crystalline form is good, must blanketing with inert gas, increase cost.2, because conductivity is low, thereby high rate performance is poor.LiNi under high voltage
0.5mn
0.5o
2capacity attenuation in charge and discharge process is very fast, and cyclical stability is poor.
Summary of the invention
The LiNi that the object of the invention is to prepare for conventional method
0.5mn
0.5o
2the problem that material exists, has correspondingly proposed following solution:
1, adopt Na
2cO
3+ NH
4hCO
3compound carbonate is precipitation reagent, and nickel, manganese are precipitated out simultaneously uniformly, makes two kinds of elements reach the even mixing on atomic level.MnCO
3be difficult for oxidizedly, building-up process does not need blanketing with inert gas, has overcome the deficiency of hydroxide coprecipitation step;
2, will wash co-precipitation precursor and lithium salts completely and grind in alcohol medium, ensure that precursor mixes with the full and uniform of lithium salts, has ensured batch stability of product;
3, further the material of synthesized is carried out to Phosphate coating, improved high rate performance and the cycle performance of material.
Another object of the present invention is to provide the preparation method of described material.
This anode material for lithium-ion batteries is the surface coated nickel LiMn2O4 of phosphate binary positive electrode, has following chemical general formula FePO
4(AlPO
4)/Li
1+x(Ni
0.5mn
0.5) O
2, wherein 0≤x≤0.15.
The surface coated binary stratiform of described phosphate method for preparing anode material of lithium-ion battery, comprises the steps:
(1) water miscible nickel salt, manganese salt are dissolved in deionized water for 1: 1 in molar ratio, are made into the solution that concentration of metal ions is 0.25～1.0mol/L;
(2) Na that compound concentration is 0.5～2.0mol/L
2cO
3+ NH
4hCO
3compound carbonate solution and concentration are the ammoniacal liquor of 2.0mol/L;
(3) NH that the soluble ferric iron salt that compound concentration is 0.05～0.4mol/L or aluminum salt solution and concentration are 0.05～0.4mol/L
4h
2pO
4or (NH
4)
2hPO
4solution;
(4) by the nickel manganese solution, the Na2CO that prepare respectively in step (1) (2) (3)
3+ NH
4hCO
3solution and ammoniacal liquor are slowly added drop-wise in the reactor of continuous stirring, and are 8.0～9.5 by the pH value that adjusting drips the speed control solution of ammoniacal liquor, and regulating the rotating speed of blender is 400～600r/min, and reaction temperature is 40～80 DEG C;
(5), to the material vigorous stirring in reactor in step (4) 6～10 hours, reacted rear one-tenth and continued ageing and within 5～10 hours, obtain light blue precipitation.By sedimentation and filtration, washing and the dry nickel manganese compound carbonate precursor that obtains.
(6) in order to ensure to join the even of lithium, precursor and Li source compound are ground evenly in alcohol medium, and in 80 DEG C of vacuum drying chambers dry 12 hours, then pre-burning 6 hours at 400～600 DEG C, the precipitation precursor and the Li source compound that make are decomposed into oxide completely.It is fully contacted the mixed oxide ball milling, the compressing tablet that after pre-burning, obtain, finally adopt high temp. sectional calcining manners: 700 DEG C of insulations continue to be warming up to 900 DEG C of constant temperature 6 hours afterwards in 6 hours, and heating rate is 3～5 DEG C/min.Quenching, crosses 300 mesh sieves, obtains the Li that crystal formation is intact
1+x(Ni
0.5mn
0.5) O
2material, wherein 0≤x≤0.15.
(7) get a certain amount of step (6) products therefrom and be scattered in deionized water and form suspension-turbid liquid, under high degree of agitation, add the soluble ferric iron salt or the aluminum salt solution that measure ratio, NH that simultaneously will metering ratio
4h
2pO
4or (NH
4)
2hPO
4solution dropwise splashes into, high degree of agitation 4～8 hours.Filter, wash, in 80 DEG C of vacuum drying chambers, be dried 12 hours, then at 400～600 DEG C, calcine 4～6 hours, cooling with stove, obtain the spherical Li of the surface coated class of phosphate
1+x(Ni
0.5mn
0.5) O
2material, wherein 0≤x≤0.15.
Further, the described Na of step (2)
2cO
3+ NH
4hCO
3in compound carbonate solution, Na
2cO
3with NH
4hCO
3mol ratio is 1: 2.
Further, the described Na of step (4)
2cO
3+ NH
4hCO
3compound carbonate solution phase is 1.1～1.3 for the excess coefficient of nickel manganese mixed solution.
Further, described nickel salt is at least one in nickel nitrate, nickel acetate, nickelous sulfate, nickel chloride; Described manganese salt is at least one in manganese nitrate, manganese acetate, manganese sulfate, manganese chloride; Described lithium salts is one or more the mixture in lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate.Soluble ferric iron salt is the one in ferric nitrate, iron chloride; Aluminum soluble salt is the one in aluminum nitrate, aluminium chloride.
Further, the described phosphatic covering amount of step (7) is: FePO
4(AlPO
4)/Li
1+x(Ni
0.5mn
0.5) O
2mass ratio be 0.5%-2.0%.
Further, step (6) (7) resulting materials has class spherical morphology, and particle diameter is between 200～400nm.
Beneficial effect of the present invention:
(1) coprecipitation method of the present invention has overcome the deficiency of hydroxide coprecipitation step in the past, and the positive electrode of preparation has class spherical morphology and particle is nano-scale, and particle diameter is evenly distributed, smooth surface, good crystallinity.
(2) this material, taking nickel, manganese as basis, has been abandoned expensive cobalt element completely, and cost is lower, and the popularization of environmental protection and electric automobile is had to larger realistic meaning.
(3) adopt environmental protection, at a low price, stable phosphate is coating layer, improved conductivity, and high rate performance is promoted to some extent; Further suppress reacting between positive electrode and electrolyte, slowed down the rate of decay of capacity, improved cycle performance.
The prepared Phosphate coating material of the present invention (in 2.5～4.6V voltage range) first discharge specific capacity under 55 DEG C, 0.1C is 220.0mAh/g left and right, and after 50 circulations, capability retention is 95.7% left and right.
Brief description of the drawings
Fig. 1 is the prepared coated 1.0%FePO of the embodiment of the present invention two
4li
1.1(Ni
0.5mn
0.5) O
2sEM collection of illustrative plates.
Fig. 2 is the prepared coated 1.0%FePO of the embodiment of the present invention two
4li
1.1(Ni
0.5mn
0.5) O
2first charge-discharge capacity curve figure.
Fig. 3 is the prepared Li of the embodiment of the present invention two
1.1(Ni
0.5mn
0.5) O
2with coated 1.0%FePO
4li
1.1(Ni
0.5mn
0.5) O
2circulation ratio comparison diagram, wherein curve A, B are respectively Li
1.1(Ni
0.5mn
0.5) O
2, coated 1.0%FePO
4li
1.1(Ni
0.5mn
0.5) O
2.
Fig. 4 is the prepared Li of the embodiment of the present invention six
1.15(Ni
0.5mn
0.5) O
2sEM collection of illustrative plates.
Fig. 5 is the prepared coated 2.0%AlPO of the embodiment of the present invention six
4li
1.15(Ni
05mn
0.5) O
2first charge-discharge capacity curve figure.
Fig. 6 is the prepared Li of the embodiment of the present invention six
1.15(Ni
0.5mn
0.5) O
2with coated 2.0%AlPO
4li
1.15(Ni
0.5mn
0.5) O
2circulation ratio comparison diagram, wherein curve A, B are respectively Li
1.15(Ni
0.5mn
0.5) O
2, coated 2.0%AlPO
4li
1.15(Ni
0.5mn
0.5) O
2.
Embodiment
Below in conjunction with concrete drawings and Examples, the invention will be further described, and it does not also limit the present invention in any way.
The embodiment mono-coated 0.5%FePO in surface
4li (Ni
0.5mn
0.5) O
2
(1) by 0.1mol Ni (CH
3cOOH)
24H
2o, 0.1mol Mn (CH
3cOOH)
24H
2o is dissolved in 800mL deionized water, forms the solution of 0.25mol/L; By 0.11mol Na
2cO
3and 0.22molNH
4hCO
3be dissolved in 660mL deionized water, form the solution (compound carbonate excess coefficient is 1.1) of 0.5mol/L; By 0.1340gFe (NO
3)
39H
2o is dissolved in the solution that forms 0.066mol/L in 5mL deionized water; By 0.0375g NH
4h
2pO
4be dissolved in the solution that forms 0.066mol/L in 5mL deionized water.
(2) by nickel manganese solution, the Na of preparation in step (1)
2cO
3+ NH
4hCO
3solution is slowly evenly added drop-wise in the reactor of continuous stirring, and the pH value that drips the ammoniacal liquor regulator solution of 2.0mol/L is 8.0, regulating the rotating speed of blender is 400r/min, and reaction temperature is 40 DEG C, in 6 hours reaction time, then continue ageing and within 5 hours, obtain light blue precipitation.By sedimentation and filtration, washing with dryly obtain light blue nickel manganese compound carbonate precursor.
(3) above nickel manganese carbonate precursor and 0.2molLiOH are ground evenly in alcohol medium, and in 80 DEG C of vacuum drying chambers dry 12 hours to then pre-burning 6 hours at 500 DEG C.By the mixed oxide ball milling, the compressing tablet that obtain after pre-burning, finally after 700 DEG C are incubated 6 hours, continue to be warming up to 900 DEG C of constant temperature 6 hours, heating rate is 3 DEG C/min.Quenching, crosses 300 mesh sieves, obtains the Li (Ni that crystal formation is intact
0.5mn
0.5) O
2.
(4) get 10g step (3) products therefrom and be scattered in and in deionized water, form suspension-turbid liquid, under high degree of agitation dropwise by the Fe (NO in step (1)
3)
39H
2o and NH
4h
2pO
4solution adds, high degree of agitation 4 hours.Filter, wash, in 80 DEG C of vacuum drying chambers, be dried 12 hours, then at 400 DEG C, calcine 4 hours, cooling with stove, obtain the coated 0.5%FePO in surface
4li (Ni
0.5mn
0.5) O
2material.
The embodiment 2 coated 1.0%FePO in surface
4li
1.1(Ni
0.5mn
0.5) O
2
(1) by 0.1mol Ni (CH
3cOOH)
24H
2o, 0.1mol Mn (CH
3cOOH)
24H
2o is dissolved in 400mL deionized water, forms the solution of 0.5mol/L; By 0.12mol Na
2cO
3and 0.24molNH
4hCO
3be dissolved in 300mL deionized water, form the solution (compound carbonate excess coefficient is 1.2) of 1.2mol/L; By 0.2680gFe (NO
3)
39H
2o is dissolved in the solution that forms 0.132mol/L in 5mL deionized water; By 0.0750g NH
4h
2pO
4be dissolved in the solution that forms 0.132mol/L in 5mL deionized water.
(2) by nickel manganese solution, the Na of preparation in step (1)
2cO
3+ NH
4hCO
3solution is slowly evenly added drop-wise in the reactor of continuous stirring, and the pH value that drips the ammoniacal liquor regulator solution of 2.0mol/L is 8.0, regulating the rotating speed of blender is 500r/min, and reaction temperature is 60 DEG C, in 6 hours reaction time, then continue ageing and within 6 hours, obtain light blue precipitation.By sedimentation and filtration, washing with dryly obtain light blue nickel manganese compound carbonate precursor.
(3) by above nickel manganese carbonate precursor and 0.11molLi
2cO
3in alcohol medium, grind evenly, and in 80 DEG C of vacuum drying chambers dry 12 hours then pre-burning 6 hours at 500 DEG C.By the mixed oxide ball milling, the compressing tablet that obtain after pre-burning, finally after 700 DEG C are incubated 6 hours, continue to be warming up to 900 DEG C of constant temperature 6 hours, heating rate is 5 DEG C/min.Quenching, crosses 300 mesh sieves, obtains the Li that crystal formation is intact
1.1(Ni
0.5mn
0.5) O
2.
(4) get 10g step (3) products therefrom and be scattered in and in deionized water, form suspension-turbid liquid, under high degree of agitation dropwise by the Fe (NO in step (1)
3)
39H
2o and NH
4h
2pO
4solution adds, high degree of agitation 6 hours.Filter, wash, in 80 DEG C of vacuum drying chambers, be dried 12 hours, then at 500 DEG C, calcine 5 hours, cooling with stove, obtain the coated 1.0%FePO in surface
4li
1.1(Ni
0.5mn
0.5) O
2material.
Material prepared by the present embodiment is assembled into button cell and carries out constant current charge-discharge test, and as shown in Figure 1, in 2.5～4.6V voltage range, first discharge specific capacity and coulomb efficiency are respectively 227.03mAh/g (0.1C) and 94.6% at 55 DEG C.Fig. 2 is the SEM figure of this material, can find out that this material is class spherical, and particle is less, and particle diameter is distributed between 200～400nm.In Fig. 3, curve A, B are respectively Li1.1 (Ni
0.5mn
0.5) O
2with the coated 1.0%FePO in surface
4li
1.1(Ni
0.5mn
0.5) O
2circulation ratio curve at 55 DEG C, 0.5C, under 1C and 2C different multiplying, discharge capacity is respectively 89.8%, 83.1%, 76.1% under 0.1C (taking curve B as example) first.
The embodiment 3 coated 2.0%FePO in surface
4li
1.1(Ni
0.5mn
0.5) O
2
(1) by 0.1mol Ni (NO
3)
26H
2o, 0.1mol Mn (NO
3)
26H
2o is dissolved in 400mL deionized water, forms the solution of 0.5mol/L; By 0.11molNa
2cO
3and 0.22molNH
4hCO
3be dissolved in 200mL deionized water, form the solution (compound carbonate excess coefficient is 1.1) of 1.65mol/L; By 0.3575gFeCl
36H
2o is dissolved in the solution that forms 0.264mol/L in 5mL deionized water; By 0.1750g (NH
4)
2hPO
4be dissolved in the solution that forms 0.264mol/L in 5mL deionized water.
(2) by nickel manganese solution, the Na of preparation in step (1)
2cO
3+ NH
4hCO
3solution is slowly evenly added drop-wise in the reactor of continuous stirring, and the pH value that drips the ammoniacal liquor regulator solution of 2.0mol/L is 8.5, regulating the rotating speed of blender is 500r/min, and reaction temperature is 60 DEG C, in 8 hours reaction time, then continue ageing and within 8 hours, obtain light blue precipitation.By sedimentation and filtration, washing with dryly obtain light blue nickel manganese compound carbonate precursor.
(3) by above nickel manganese carbonate precursor and 0.22molLiNO
3in alcohol medium, grind evenly, and in 80 DEG C of vacuum drying chambers dry 12 hours then pre-burning 6 hours at 500 DEG C.By the mixed oxide ball milling, the compressing tablet that obtain after pre-burning, finally after 700 DEG C are incubated 6 hours, continue to be warming up to 900 DEG C of constant temperature 6 hours, heating rate is 5 DEG C/min.Quenching, crosses 300 mesh sieves, obtains the Li that crystal formation is intact
1.1(Ni
0.5mn
05) O
2.
(4) get 10g step (3) products therefrom and be scattered in and in deionized water, form suspension-turbid liquid, under high degree of agitation dropwise by the FeCl in step (1)
36H
2o and (NH
4)
2hPO
4solution adds, high degree of agitation 6 hours.Filter, wash, in 80 DEG C of vacuum drying chambers, be dried 12 hours, then at 500 DEG C, calcine 5 hours, cooling with stove, obtain the coated 2.0%FePO in surface
4li
11(Ni
0.5mn
0.5) O
2material.
The embodiment 4 coated 2.0%FePO in surface
4li
1.15(Ni
0.5mn
0.5) O
2
(1) by 0.1molNiSO
44H
2o, 0.1molMnSO
4h
2o is dissolved in 200mL deionized water, forms the solution of 1.0mol/L; By 0.13molNa
2cO
3and 0.26molNH
4hCO
3be dissolved in 200mL deionized water, form the solution (compound carbonate excess coefficient is 1.3) of 1.95mol/L; By 0.3575gFeCl
36H
2o is dissolved in the solution that forms 0.264mol/L in 5mL deionized water; By 0.1750g (NH
4)
2hPO
4be dissolved in the solution that forms 0.264mol/L in 5mL deionized water.
(2) by nickel manganese solution, the Na of preparation in step (1)
2cO
3+ NH
4hCO
3solution is slowly evenly added drop-wise in the reactor of continuous stirring, and the pH value that drips the ammoniacal liquor regulator solution of 2.0mol/L is 9.0, regulating the rotating speed of blender is 600r/min, and reaction temperature is 80 DEG C, in 10 hours reaction time, then continue ageing and within 10 hours, obtain light blue precipitation.By sedimentation and filtration, washing with dryly obtain light blue nickel manganese compound carbonate precursor.
(3) by above nickel manganese carbonate precursor and 0.23molCH
3cOOLi grinds evenly in alcohol medium, and in 80 DEG C of vacuum drying chambers dry 12 hours, then pre-burning 6 hours at 500 DEG C.By the mixed oxide ball milling, the compressing tablet that obtain after pre-burning, finally after 700 DEG C are incubated 6 hours, continue to be warming up to 900 DEG C of constant temperature 6 hours, heating rate is 5 DEG C/min.Quenching, crosses 300 mesh sieves, obtains the Li that crystal formation is intact
1. 15(Ni
0.5mn
0.5) O
2.
(4) get 10g step (3) products therefrom and be scattered in and in deionized water, form suspension-turbid liquid, under high degree of agitation dropwise by the FeCl in step (1)
36H
2o and (NH
4)
2hPO
4solution adds, high degree of agitation 6 hours.Filter, wash, in 80 DEG C of vacuum drying chambers, be dried 12 hours, then at 600 DEG C, calcine 6 hours, cooling with stove, obtain the coated 2.0%FePO in surface
4li
1.15(Ni
0.5mn
0.5) O
2material.
The embodiment 5 coated 1.0%AlPO in surface
4li
105(Ni
0.5mn
05) O
2
(1) by 0.1mol Ni (CH
3cOOH)
24H
2o, 0.1mol Mn (CH
3cOOH)
24H
2o is dissolved in 400mL deionized water, forms the solution of 0.5mol/L; By 0.12mol Na
2cO
3and 0.24molNH
4hCO
3be dissolved in 200mL deionized water, form the solution (compound carbonate excess coefficient is 1.1) of 1.8mol/L; By 0.3075gAl (NO
3)
39H
2o is dissolved in the solution that forms 0.164mol/L in 5mL deionized water; By 0.1075g (NH
4)
2hPO
4be dissolved in the solution that forms 0.164mol/L in 5mL deionized water.
(2) by nickel manganese solution, the Na of preparation in step (1)
2cO
3+ NH
4hCO
3solution is slowly evenly added drop-wise in the reactor of continuous stirring, and the pH value that drips the ammoniacal liquor regulator solution of 2.0mol/L is 9.0, regulating the rotating speed of blender is 500r/min, and reaction temperature is 60 DEG C, reaction time 6h, then continues ageing 6h and obtains light blue precipitation.By sedimentation and filtration, washing with dryly obtain light blue nickel manganese compound carbonate precursor.
(3) by above nickel manganese carbonate precursor and 0.105mol Li
2cO
3in alcohol medium, grind evenly, and in 80 DEG C of vacuum drying chambers, be dried 12 hours, then pre-burning hour at 500 DEG C.By the mixed oxide ball milling, the compressing tablet that obtain after pre-burning, finally after 700 DEG C are incubated 6 hours, continue to be warming up to 900 DEG C of constant temperature 6 hours, heating rate is 5 DEG C/min.Quenching, crosses 300 mesh sieves, obtains the Li that crystal formation is intact
1.1(Ni
0.5mn
0.5) O
2.
(4) get 10g step (3) products therefrom and be scattered in and in deionized water, form suspension-turbid liquid, under high degree of agitation dropwise by the Al (NO in step (1)
3)
39H
2o and (NH
4)
2hPO
4solution adds, high degree of agitation 6 hours.Filter, wash, in 80 DEG C of vacuum drying chambers, be dried 12 hours, then at 500 DEG C, calcine 5 hours, cooling with stove, obtain the coated 1.0%AlPO in surface
4li
1.1(Ni
0.5mn
0.5) O
2material.
The embodiment 6 coated 2.0%AlPO in surface
4li
1.15(Ni
0.5mn
0.5) O
2
(1) by 0.1mol NiCl
26H
2o, 0.1molMnCl
24H
2o is dissolved in 200mL deionized water, forms the solution of 1.0mol/L; By 0.13mol Na
2cO
3with 0.26mol NH
4hCO
3be dissolved in 300mL deionized water, form the solution (compound carbonate excess coefficient is 1.3) of 1.3mol/L; By 0.2187gAlCl
3be dissolved in the solution that forms 0.328mol/L in 5mL deionized water; By 0.1886gNH
4h
2pO
4be dissolved in the solution that forms 0.328mol/L in 5mL deionized water.
(2) by nickel manganese solution, the Na of preparation in step (1)
2cO
3+ NH
4hCO
3solution is slowly evenly added drop-wise in the reactor of continuous stirring, and the pH value that drips the ammoniacal liquor regulator solution of 2.0mol/L is 9.5, regulating the rotating speed of blender is 600r/min, and reaction temperature is 60 DEG C, in 6 hours reaction time, then continue ageing and within 6 hours, obtain light blue precipitation.By sedimentation and filtration, washing with dryly obtain light blue nickel manganese compound carbonate precursor.
(3) above nickel manganese carbonate precursor and 0.23mol LiOH are ground evenly in alcohol medium, and in 80 DEG C of vacuum drying chambers dry 12 hours to then pre-burning 6 hours at 500 DEG C.By the mixed oxide ball milling, the compressing tablet that obtain after pre-burning, finally after 700 DEG C are incubated 6 hours, continue to be warming up to 900 DEG C of constant temperature 6 hours, heating rate is 5 DEG C/min.Quenching, crosses 300 mesh sieves, obtains the Li that crystal formation is intact
1.1(Ni
0.5mn
0.5) O
2.
(4) get 10g step (3) products therefrom and be scattered in and in deionized water, form suspension-turbid liquid, under high degree of agitation dropwise by the AlCl in step (1)
3and NH
4h
2pO
4solution adds, high degree of agitation 6 hours.Filter, wash, in 80 DEG C of vacuum drying chambers, be dried 12 hours, then at 500 DEG C, calcine 5 hours, cooling with stove, obtain the coated 2.0%AlPO in surface
4li
1.1(Ni
0.5mn
0.5) O
2material.
Material prepared by the present embodiment is assembled into button cell and carries out constant current charge-discharge test, and as shown in Figure 5, in 2.5～4.6V voltage range, first discharge specific capacity and coulomb efficiency are respectively 216.34mAh/g (0.1C) and 93.0% at 55 DEG C.To be class spherical for this material as can be seen from Figure 4, and particle is less, and particle diameter is distributed between 200～400nm.Curve A, B Li respectively in Fig. 6
1.15(Ni
0.5mn
0.5) O
2with the coated 2.0%AlPO in surface
4li
1.15(Ni
0.5mn
0.5) O
2circulation ratio curve at 55 DEG C, 0.5C, under 1C and 2C different multiplying, discharge capacity is respectively 91.1%, 84.5%, 78.3% under 0.1C (taking curve B as example) first.
Claims (9)
1. the surface coated binary stratiform of phosphate anode material for lithium-ion batteries, is characterized in that: have following chemical general formula FePO
4(AlPO
4)/Li
1+x(Ni
0.5mn
0.5) O
2, wherein 0≤x≤0.15.
2. the preparation method of the surface coated binary stratiform of phosphate anode material for lithium-ion batteries described in claim 1, is characterized in that, comprises the steps:
(1) water miscible nickel salt, manganese salt are dissolved in deionized water for 1: 1 in molar ratio, are made into the solution that concentration of metal ions is 0.25～1.0mol/L;
(2) Na that compound concentration is 0.5～2.0mol/L
2cO
3+ NH
4hCO
3compound carbonate solution and concentration are the ammoniacal liquor of 2.0mol/L;
(3) NH that the soluble ferric iron salt that compound concentration is 0.01～0.05mol/L or aluminum salt solution and concentration are 0.01～0.05mol/L
4h
2pO
4or (NH
4)
2hPO
4solution;
(4) by the nickel manganese solution, the Na that prepare respectively in step (1) (2) (3)
2cO
3+ NH
4hCO
3solution and ammoniacal liquor are slowly added drop-wise in the reactor of continuous stirring, and drip the pH value of the speed control solution of ammoniacal liquor by adjusting, regulate rotating speed and the reaction temperature of blender.Vigorous stirring 6～10 hours, has reacted rear continuation ageing 5～10 hours.By sedimentation and filtration, washing and the dry nickel manganese compound carbonate precursor that obtains.
(5) precursor and Li source compound are ground evenly in alcohol medium, and in 80 DEG C of vacuum drying chambers, be dried 12 hours, pre-burning 6 hours.Ball milling, compressing tablet, high-temperature calcination, quenching, crosses 300 mesh sieves, obtains the Li that crystal formation is intact
1+x(Ni
0.5mn
0.5) O
2material, wherein 0≤x≤0.15.
(6) get a certain amount of step (5) products therefrom and be scattered in deionized water, under stirring, add the soluble ferric iron salt or the aluminum salt solution that measure ratio, simultaneously by the NH of metering ratio
4h
2pO
4or (NH
4)
2hPO
4solution dropwise splashes into, vigorous stirring 4～8 hours.Filter, wash, in 80 DEG C of vacuum drying chambers, be dried 12 hours, then at 400～600 DEG C, calcine 6 hours, cooling with stove, obtain the spherical Li of the surface coated class of phosphate
1+x(Mi
0.5mn
0.5) O
2material, wherein 0≤x≤0.15.
3. the surface coated method for preparing anode material of lithium-ion battery of phosphate according to claim 2, is characterized in that: the described nickel salt of step (1) is at least one in nickel nitrate, nickel acetate, nickelous sulfate, nickel chloride; Described manganese salt is at least one in manganese nitrate, manganese acetate, manganese sulfate, manganese chloride.
4. method according to claim 2, is characterized in that: the described Na of step (2)
2cO
3+ NH
4hCO
3in compound carbonate solution, Na
2cO
3with NH
4hCO
3mol ratio is 1: 2.
5. method according to claim 2, is characterized in that: the described soluble ferric iron salt of step (3) is the one in ferric nitrate, iron chloride; Aluminum soluble salt is the one in aluminum nitrate, aluminium chloride.
6. method according to claim 2, is characterized in that: the described Na of step (4)
2cO
3+ NH
4hCO
3compound carbonate solution phase is 1.1～1.3 for the excess coefficient of nickel manganese mixed solution.Described pH value is 8.0～9.5, and the rotating speed of blender is 400～600r/min, and reaction temperature is 40～80 DEG C.
7. method according to claim 2, is characterized in that: the described lithium salts of step (5) is one or more the mixture in lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate.
8. method according to claim 2, it is characterized in that: the described calcined temperature of step (5) is 400～600 DEG C, high-temperature calcination mode is: 700 DEG C of insulations continue to be warming up to 900 DEG C of constant temperature 6 hours afterwards in 6 hours, and heating rate is 3～5 DEG C/min.
9. method according to claim 2, is characterized in that: the described phosphatic covering amount of step (6) is: FePO
4(AlPO
4)/Li
1+x(Ni
0.5mn
0.5) O
2mass ratio be 0.5%～2.0%.
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Cited By (9)
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| CN106328933A (en) * | 2015-06-30 | 2017-01-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Phosphate-coated lithium-rich layered positive electrode material and preparation method and application thereof |
| CN108807949A (en) * | 2018-08-07 | 2018-11-13 | 浙江美都海创锂电科技有限公司 | A kind of preparation method of high nickel lithium manganate cathode material |
| CN109980188A (en) * | 2017-12-27 | 2019-07-05 | 荆门市格林美新材料有限公司 | A kind of nickel-cobalt lithium manganate cathode material and preparation method thereof coating aluminum phosphate |
| CN109980189A (en) * | 2017-12-27 | 2019-07-05 | 荆门市格林美新材料有限公司 | A kind of nickel cobalt lithium aluminate cathode material and preparation method thereof coating aluminum phosphate |
| CN110265658A (en) * | 2019-06-03 | 2019-09-20 | 湖北锂诺新能源科技有限公司 | A kind of aluminum phosphate coats the preparation method of rich lithium ruthenium Base Metal oxyfluoride positive electrode |
| CN112002905A (en) * | 2020-08-26 | 2020-11-27 | 中南大学 | Titanium lanthanum lithium phosphate modified cobalt-free cathode material and preparation method thereof |
| CN114744188A (en) * | 2022-06-13 | 2022-07-12 | 河南科隆新能源股份有限公司 | Lithium ion battery anode material with non-hollow porous structure and preparation method and application thereof |
| CN117393739A (en) * | 2023-12-06 | 2024-01-12 | 河南科隆新能源股份有限公司 | Aluminum phosphate double-modified high-nickel cobalt-free polycrystalline positive electrode material and preparation method thereof |
| EP4092787A4 (en) * | 2020-01-17 | 2024-04-10 | Svolt Energy Tech Co Ltd | Cobalt-free layered positive electrode material and method for preparing same, and lithium-ion battery |
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| CN106328933A (en) * | 2015-06-30 | 2017-01-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Phosphate-coated lithium-rich layered positive electrode material and preparation method and application thereof |
| CN109980188A (en) * | 2017-12-27 | 2019-07-05 | 荆门市格林美新材料有限公司 | A kind of nickel-cobalt lithium manganate cathode material and preparation method thereof coating aluminum phosphate |
| CN109980189A (en) * | 2017-12-27 | 2019-07-05 | 荆门市格林美新材料有限公司 | A kind of nickel cobalt lithium aluminate cathode material and preparation method thereof coating aluminum phosphate |
| CN108807949A (en) * | 2018-08-07 | 2018-11-13 | 浙江美都海创锂电科技有限公司 | A kind of preparation method of high nickel lithium manganate cathode material |
| CN110265658A (en) * | 2019-06-03 | 2019-09-20 | 湖北锂诺新能源科技有限公司 | A kind of aluminum phosphate coats the preparation method of rich lithium ruthenium Base Metal oxyfluoride positive electrode |
| EP4092787A4 (en) * | 2020-01-17 | 2024-04-10 | Svolt Energy Tech Co Ltd | Cobalt-free layered positive electrode material and method for preparing same, and lithium-ion battery |
| CN112002905A (en) * | 2020-08-26 | 2020-11-27 | 中南大学 | Titanium lanthanum lithium phosphate modified cobalt-free cathode material and preparation method thereof |
| CN114744188A (en) * | 2022-06-13 | 2022-07-12 | 河南科隆新能源股份有限公司 | Lithium ion battery anode material with non-hollow porous structure and preparation method and application thereof |
| CN117393739A (en) * | 2023-12-06 | 2024-01-12 | 河南科隆新能源股份有限公司 | Aluminum phosphate double-modified high-nickel cobalt-free polycrystalline positive electrode material and preparation method thereof |
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